WO2019160355A1 - Film touch sensor and structural body for film touch sensor - Google Patents

Film touch sensor and structural body for film touch sensor Download PDF

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Publication number
WO2019160355A1
WO2019160355A1 PCT/KR2019/001826 KR2019001826W WO2019160355A1 WO 2019160355 A1 WO2019160355 A1 WO 2019160355A1 KR 2019001826 W KR2019001826 W KR 2019001826W WO 2019160355 A1 WO2019160355 A1 WO 2019160355A1
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group
substituted
unsubstituted
formula
film
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PCT/KR2019/001826
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French (fr)
Korean (ko)
Inventor
조성훈
김상국
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동우화인켐 주식회사
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Publication of WO2019160355A1 publication Critical patent/WO2019160355A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/42Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/06Interconnection of layers permitting easy separation
    • GPHYSICS
    • G06COMPUTING; CALCULATING OR COUNTING
    • G06FELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00Input 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
    • G06F3/01Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/20Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206Insulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/306Resistant to heat
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/748Releasability
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/20Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208Touch screens
    • GPHYSICS
    • G06COMPUTING; CALCULATING OR COUNTING
    • G06FELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04102Flexible digitiser, i.e. constructional details for allowing the whole digitising part of a device to be flexed or rolled like a sheet of paper

Definitions

  • the present invention relates to a film touch sensor and a structure for a film touch sensor.
  • an ultra-thin flexible display that achieves ultra-light weight, low power, and improved portability has attracted attention as a next-generation display, and development of a touch sensor applicable to such a display has been required.
  • a flexible display means a display manufactured on a flexible substrate that can bend, bend, or roll without loss of properties, and technologies are being developed in the form of flexible LCDs, flexible OLEDs, and electronic paper.
  • a touch sensor having excellent bending and resilience and excellent flexibility and elasticity is required.
  • the wiring board which contains the wiring embedded in the transparent resin base material is proposed.
  • a wiring forming step of forming a metal wiring on the substrate a lamination step of forming a transparent resin substrate by coating and drying a transparent resin solution to cover the metal wiring, and a peeling step of peeling the transparent resin substrate from the substrate.
  • an inorganic releasing material such as an organic releasing agent such as a silicone resin or a fluororesin, a diamond like carbon thin film (DLC) thin film or a zirconium oxide thin film is preliminarily formed on the surface of the substrate. Forming method is used.
  • the method proposed in Korean Patent No. 10-1191865 includes a sacrificial layer, a metal wiring, and a metal layer, which may be removed by light or a solvent in the manufacturing of a flexible substrate having a metal wiring embedded therein. After the polymer material (flexible substrate) is formed on the substrate, the metal wiring and the polymer material (flexible substrate) are peeled off from the substrate by removing the sacrificial layer using light or a solvent.
  • the present invention is excellent in peelability on the carrier substrate, and proceeds the process by forming a separation layer formed of a specific component that prevents electrode damage and crack generation, when separated from the carrier substrate to be used as a wiring coating layer It is an object to provide a film touch sensor and a structure for a film touch sensor.
  • the present invention implements a touch sensor on a carrier substrate, a film touch sensor and a film touch sensor that can secure a fine pitch and heat resistance, which are impossible in a process of implementing a touch sensor directly on a film substrate, and can diversify the film substrate. Its purpose is to provide a structure.
  • the present invention proceeds by forming a separation layer of a specific component with controlled peel force and thickness on the carrier substrate, and does not remove the separation layer even after separation from the carrier substrate, there is no separate layer removal process And to provide a structure for a film touch sensor.
  • the present invention has easy peelability, can withstand heating up to 150 ° C, preferably can withstand heating up to 230 ° C, and is also resistant to solvents used in photoresist solutions, and is an alkaline developer It is an object of the present invention to provide a film touch sensor and a structure for a film touch sensor including a separation layer that can withstand.
  • Separation layer An electrode pattern layer formed on the separation layer, the electrode pattern layer including a sensing electrode and a pad electrode formed at one end of the sensing electrode; And an insulating layer formed on the electrode pattern layer and covering part or all of the electrode pattern layer, wherein the separation layer contains an alcoholic secondary or tertiary OH group or a phenolic OH group.
  • a chain polymer having a side chain having a group and a crosslinking agent wherein the chain polymer includes a unit derived from at least one monomer selected from a monomer represented by Formula 1 and a monomer represented by Formula 2 below It is formed of a resin composition,
  • the crosslinking agent is a triazine compound, its condensate and mixtures thereof; Glycoluril compounds, their condensates, and mixtures thereof; And an imidazolidinone-based compound, a condensate thereof, and a mixture thereof.
  • R 1a is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl group and substituted or unsubstituted alkenyl group,
  • L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
  • L 2 is O or NH
  • R 2a , R 3a and R 4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon group,
  • R 2a , R 3a and R 4a is a substituted or unsubstituted alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group,
  • R 1a is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl group and substituted or unsubstituted alkenyl group,
  • L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
  • R 5a to R 14a are each independently selected from the group consisting of hydrogen, a hydroxy group, and a functional group represented by the following formula (3), or one to form a ring, provided that at least one of R 5a to R 14a or a substituent of the ring is Hydroxy group)
  • R 15a is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic. Selected from the group consisting of flags)
  • L 1 is selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group, the film touch sensor.
  • R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
  • L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
  • R 19a is selected from the group consisting of a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group)
  • cross-linking agent is selected from the group consisting of triazine-based compound, triazine-based compound condensate, and mixtures thereof, film touch sensor.
  • any one of the R 5a to R 14a is a hydroxyl group, the rest is hydrogen, the film touch sensor.
  • R 14a is a hydroxy group, the film touch sensor.
  • crosslinking agent is selected from the group consisting of glycouril-based compounds, glycouril-based compounds, and mixtures thereof, the film touch sensor.
  • the film touch sensor is a compound represented by the following formula B-2, the film touch sensor:
  • cross-linking agent is a compound represented by the following formula B-3
  • film touch sensor
  • the film touch sensor In the above 1, wherein the curable resin composition is provided as a solution, the film touch sensor.
  • the crosslinking agent includes a compound selected from the group consisting of compounds represented by the following Chemical Formulas 7, 9 and 10 and their respective condensates, the film touch sensor:
  • R 1b is a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 25 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 25 carbon atoms, substituted with 4 to 25 carbon atoms, or It is selected from the group consisting of an unsubstituted hetero aromatic group, and a disubstituted amine represented by the formula (8),
  • R 2b , R 3b , R 4b and R 5b are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms)
  • R 6b and R 7b are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.
  • R 8b , R 9b , R 10b and R 11b are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.
  • R 12b and R 13b are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms,
  • R 14b and R 15b are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms)
  • the condensate in the crosslinking agent comprises at least one of a dimer, a trimer and a quaternary or higher polymer of the compound represented by Formula 7, Formula 9 or Formula 10, film touch sensor.
  • the film touch sensor In the above 24, wherein the crosslinking agent will have a weight average polymerization degree of 1.3 to 1.8 for the compound represented by the formula 7, Formula 9 or Formula 10, respectively, the film touch sensor.
  • R 1b is selected from the group consisting of a substituted or unsubstituted aromatic group having 6 to 25 carbon atoms, a disubstituted amine represented by the following formula (11),
  • R 2b to R 13b are each independently a substituted or unsubstituted alkyl having 1 to 10 carbon atoms
  • the curable resin composition further comprises an acid catalyst, film touch sensor.
  • curable resin composition further comprises at least one selected from the group consisting of surfactants, fillers, additives and blowing agents, film touch sensor.
  • curable resin composition further comprises a surfactant, film touch sensor.
  • the curable resin composition has a curability that is cured by heating for 1 minute at 150 °C, film touch sensor.
  • the film touch sensor further comprises a protective layer formed between the separation layer and the electrode pattern layer, the film touch sensor.
  • the electrode pattern layer is formed of at least one selected from the group consisting of metal, metal nanowires, metal oxides, carbon nanotubes, graphene, conductive polymers and conductive inks, film touch sensor.
  • the functional film layer is at least one functional film selected from the group consisting of a transparent film, a retardation film, an isotropic film, a protective film, a polarizer, a polarizer, and a barrier film.
  • the functional film layer is a film having a functional coating layer formed on the base film
  • the functional coating layer comprises a coating organic film layer, a coating retardation layer, a coating polarizer layer or a coating alignment film layer, Film touch sensor.
  • crosslinking agent is fully or partially alkoxymethylated melamine, fully or partially alkoxymethylated guanamine, fully or partially alkoxymethylated acetoguanamine, or fully or partially alkoxymethylated benzoguanamine, and fully or partially alkoxymethylated Will be selected from the group consisting of glycoluril, the method of manufacturing a touch sensor film.
  • carrier substrate A separation layer formed on the carrier substrate; An electrode pattern layer formed on the separation layer, the electrode pattern layer including a sensing electrode and a pad electrode formed at one end of the sensing electrode; An insulating layer formed on the electrode pattern layer and covering a part or the entirety of the electrode pattern layer; and including a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group.
  • a chain polymer and a crosslinking agent wherein the chain polymer is formed of a curable resin composition comprising a unit derived from at least one monomer selected from a monomer represented by Formula 1 and a monomer represented by Formula 2 below
  • the crosslinking agent may include a triazine compound, a condensate thereof, and a mixture thereof; Glycoluril compounds, their condensates, and mixtures thereof; And an imidazolidinone-based compound, a condensate thereof, and a mixture thereof.
  • R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group,
  • L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
  • L 2 is O or NH
  • R 2a , R 3a and R 4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon group,
  • R 2a , R 3a and R 4a is a substituted or unsubstituted alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group,
  • R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group,
  • L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
  • R 5a to R 14a are each independently selected from the group consisting of hydrogen, a hydroxy group, and a functional group represented by the following general formula (C), or one to form a ring, provided that at least one of R 5a to R 14a or a substituent of the ring is Hydroxy group)
  • R 15a is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic Selected from the group consisting of flags)
  • the film touch sensor structure further comprises a protective layer formed between the separation layer and the electrode pattern layer.
  • the present invention can increase the efficiency of the touch sensor manufacturing process by forming an insulating layer used as a planarization layer, an adhesive layer or a substrate layer on the transparent conductive film pattern.
  • the present invention is excellent in peelability on the carrier substrate, and proceeds the process by forming a separation layer of a specific component that prevents electrode damage and crack generation, and when separated from the carrier substrate so that the separation layer is used as a wiring coating layer Increase efficiency and productivity.
  • a process for implementing a touch sensor on a carrier substrate may be performed to ensure fine pitch and heat resistance, and to diversify the film substrate.
  • the present invention does not perform a separate separation layer removal process after separation from the carrier substrate, thereby simplifying the process and solving the problem applied to the touch sensor region in the removal process.
  • the present invention can suppress curl generation occurring in the film touch sensor after separation from the carrier substrate.
  • the present invention may include a separation layer thin film (eg, several hundred nm thick) that can be easily peeled off without difficulty by applying a specific curable resin composition to a carrier substrate and curing the carrier substrate.
  • the separation layer thin film thus formed on the substrate can withstand heating up to 150 ° C, preferably can withstand heating up to 230 ° C, furthermore, is resistant to the solvent used in the photoresist solution, and is an alkaline developer. Since it can endure, it can be advantageously used as a resin base film for circuit manufacture by the photolithography method.
  • the separation layer thin film formed according to the present invention has easy peelability even after heating at such a temperature
  • the separation layer thin film can be provided to a circuit fabrication process including a high temperature firing step, compared to the conventional thin film. It is advantageous for the preservation of properties and can be easily peeled off from the substrate even after fabrication of the circuit, thereby providing a touch sensor or a touch sensor structure having excellent peel force characteristics and crack suppression characteristics.
  • 1 to 4 are structural cross-sectional views of a film touch sensor according to an embodiment of the present invention.
  • 5A to 5F are cross-sectional views illustrating a method of manufacturing a film touch sensor according to the present invention.
  • 6A and 6B are cross-sectional views illustrating a method of manufacturing a film touch sensor according to the present invention.
  • FIG. 7A and 7B are cross-sectional views illustrating a method of manufacturing a film touch sensor according to the present invention.
  • FIG. 8 is a structural cross-sectional view of a film touch sensor according to an embodiment of the present invention.
  • One embodiment of the invention the separation layer; An electrode pattern layer formed on the separation layer, the electrode pattern layer including a sensing electrode and a pad electrode formed at one end of the sensing electrode; And an insulating layer formed on the electrode pattern layer and covering a part or all of the electrode pattern layer, wherein the separation layer includes an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group.
  • a chain polymer having a branched side chain and a crosslinking agent wherein (a) the side chain contains 3 to 30 carbon atoms and includes at least one saturated or unsaturated hydrocarbon group, or further includes at least one aromatic group And, by including a bond selected from the group consisting of -COO-, -O-, and -CO- connecting between the carbon atoms, excellent peelability on the carrier substrate, preventing electrode damage and cracks Forming a separation layer of a specific component and proceeding a touch sensor formation process, and when separated from the carrier substrate, the separation layer is used as a wiring coating layer to implement a touch sensor directly on the film substrate A fixed three (fine pitch) can not be in the process, it is possible to ensure heat resistance, diversify film substrate.
  • the present invention is excellent in peelability on the carrier substrate, forming a separation layer to prevent electrode damage and cracks to proceed the touch sensor forming process, to form an insulating layer to use as an adhesive layer for subsequent film adhesion, It can be used as an optical (film) layer or a planarization layer.
  • the insulating layer used as the planarization layer prevents the corrosion of the electrode pattern and the surface is planarized, thereby suppressing the occurrence of microbubbles during adhesion to the film substrate through an adhesive or an adhesive.
  • the repeating unit, compound or resin represented by the formula means a representative formula including the isomer.
  • each repeating unit represented by the first and second resins should not be construed as limited as indicated, and the sub-repeating units in parentheses may be freely positioned at any position of the chain within a predetermined mole% range. That is, the parentheses of each repeating unit are represented by one block to express mol%, but each sub-repeating unit may be positioned in blocks or separately, without limitation, if it is in the resin.
  • heat resistance means that the film obtained by curing the curable resin composition can withstand heating up to 150 ° C, preferably it can withstand heating up to 230 ° C and does not substantially cause decomposition or other deterioration.
  • the temperature of 230 ° C is a high temperature sufficient to be used as a firing temperature in the production of electronic circuits by the photolithography method.
  • the term "peelable film” means that a film formed by coating and curing a substrate, particularly a glass substrate, can be easily peeled off from the substrate without breaking the film (that is, without difficulty). "Is the nature of such a film.
  • a suitable glass substrate such as a soda glass substrate and an alkali free glass substrate, is mentioned, for example. Soda glass substrates are particularly preferred examples.
  • the "separation layer” is not limited in width.
  • the preferred thickness is 200 to 400 nm, for example about 300 nm, which corresponds to the current thinning request for electronic components, and the performance of the separation layer itself is not limited to this thickness range. Therefore, the thickness of the separation layer described herein is arbitrary.
  • side chain refers to a structural moiety branched from the main chain
  • main chain refers to a chain composed of atoms connected in the one-dimensional direction of a monomer unit which is repeated in the structure of the polymer.
  • the polymer is a polymer of (meth) acrylate
  • “-COO-” which is a part involved in the formation of an ester bond in each monomer
  • the notation of "(meth) acrylate” denotes acrylate and methacrylate without distinction.
  • alkyl refers to a monovalent group resulting from the removal of one hydrogen atom from an aliphatic hydrocarbon (alkane) such as methane, ethane, propane, and is generally represented by C n H 2n + 1 (n is a positive integer). Alkyl may be straight or branched. As an alkyl (C 1-4 alkyl) group having 1 to 4 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec- Although a butyl group etc. are mentioned, this invention is not limited only to this illustration.
  • alkyl (C 1-6 alkyl) group having 1 to 6 carbon atoms for example, an alkyl group having 1 to 4 carbon atoms, tert-butyl group, sec-butyl group, n-pentyl group, isoamyl group, Although n-hexyl group, isohexyl group, cyclohexyl group, etc. are mentioned, This invention is not limited only to this illustration.
  • an alkyl (C 1-10 alkyl) group having 1 to 10 carbon atoms for example, an alkyl group having 1 to 6 carbon atoms, n-octyl group, n-nonyl group, n-decanyl group, etc. may be mentioned. The present invention is not limited only to these examples.
  • an "alkenyl group” refers to a monovalent group formed by removing one hydrogen atom from an aliphatic hydrocarbon (alkene) containing at least one double bond such as ethene, propene, butene, and is generally represented by C m H 2m-1 . (M is an integer of 2 or more). Alkenyl groups can be straight or branched. Examples of the alkenyl group having 2 to 6 carbon atoms include ethenyl group, 1-propenyl group, 2-propenyl group, butenyl group, pentenyl group, hexenyl group, and the like, but the present invention is limited to these examples. It is not.
  • alkenyl groups having 2 to 10 carbon atoms examples include alkenyl groups, heptenyl groups, octenyl groups, nonenyl groups, and dekenyl groups having 2 to 6 carbon atoms, but the present invention is not limited to these examples. .
  • alkynyl group refers to a monovalent group resulting from the removal of one hydrogen atom from an aliphatic hydrocarbon (alkyne) containing at least one triple bond such as ethine (acetylene), propene, butene, and generally C m H 2m-3 (M is an integer of 2 or more).
  • Alkynyl groups can be straight or branched. Examples of the alkynyl group having 2 to 6 carbon atoms include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, and the like, but the present invention is not limited to these examples. no.
  • alkynyl group having 2 to 10 carbon atoms examples include, for example, an alkynyl group having 2 to 6 carbon atoms, heptynyl group, octynyl group, noninyl group, and decinyl group, but the present invention is not limited to these examples. no.
  • an "alkylene group” refers to a divalent group resulting from the loss of two hydrogen atoms from an aliphatic hydrocarbon (alkane) such as methane, ethane, or propane, and can generally be expressed as- (C m H 2m )-(m is an amount Integer).
  • alkane aliphatic hydrocarbon
  • the alkylene group group may be straight or branched chain.
  • alkylene group having 1 to 10 carbon atoms examples include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, tert-butylene group, n-pentylene group, n -Hexylene group, isohexylene group and the like, but the present invention is not limited only to these examples.
  • the alkylene group is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, still more preferably a methylene group and an ethylene group, even more preferably Preferably an ethylene group.
  • alkenylene group refers to a divalent group resulting from the loss of two hydrogen atoms in an aliphatic hydrocarbon (alkene) containing at least one double bond, such as ethenylene, propenylene, butenylene, and generally-(C m H2 m-2 )-(m is an integer of 2 or more). Alkenylene groups may be straight or branched.
  • alkenylene group having 2 to 10 carbon atoms for example, an ethenylene group, n-propenylene group, isophenylene group, n-butenylene group, isobutenylene group, n-pentenylene group, n-hexenylene group And an isohexenylene group, but the present invention is not limited only to these examples.
  • the alkenylene group may preferably be an alkenylene group having 2 to 6 carbon atoms, more preferably an alkenylene group having 2 to 4 carbon atoms, and more preferably an ethenylene group or an n-propenylene group. And even more preferably may be an ethenylene group.
  • alkoxy refers to a monovalent group resulting from the loss of a hydrogen atom of an hydroxy group of an alcohol, and can generally be expressed as C n H 2n + 1 O-(n is an integer of 1 or more).
  • the alkoxy group having 1 to 6 carbon atoms is, for example, methoxy, ethoxy, n-propyl oxy group, isopropyl oxy group, n-butyl oxy group, isobutyl oxy group, tert-butyloxy group, sec-butyl
  • An oxy group, n-pentyloxy group, iso amyl oxy group, n-hexyloxy group, isohexyloxy group, etc. are mentioned, but this invention is not limited only to this illustration.
  • haloalkyl group refers to an alkyl group in which one or a plurality of hydrogen atoms of the alkyl group are substituted with halogen atoms.
  • perhalogenated alkyl refers to an alkyl group in which all hydrogen atoms of the alkyl group are substituted with halogen atoms.
  • haloalkyl group having 1 to 6 carbon atoms examples include trifluoromethyl group, trifluoroethyl, perfluoroethyltrifluoro n-propyl group, perfluoro n-propyl group, trifluoroisopropyl group, Perfluoroisopropyl group, trifluoro n-butyl group, perfluoro n-butyl group, trifluoroisobutyl group, perfluoro isobutyl group, trifluoro tert-butyl group, perfluoro tert- Butyl group, trifluoro n-pentyl group, perfluoro n-pentyl group, trifluoro n-hexyl group, perfluoro n-hexyl group, etc. can be mentioned, but this invention is not limited only to this illustration. .
  • cycloalkyl group means a monocyclic or polycyclic saturated hydrocarbon group, and includes a crosslinked structure.
  • C 3-12 cycloalkyl group means a cyclic alkyl group having 3 to 12 carbon atoms.
  • Specific examples of the "C 6-12 cycloalkyl group” include cyclohexyl group, cycloheptyl group, cyclooctyl group, adamantyl group, isobonyl group and the like.
  • a "C 3-12 cycloalkyl group” a cyclopropyl group, cyclobutyl group, pentyl group, C 6-12 cycloalkyl group, etc. are mentioned.
  • a C 6-12 cycloalkyl group is mentioned.
  • cycloalkenyl group means a monocyclic or polycyclic unsaturated hydrocarbon group including a double bond, and includes a crosslinked structure.
  • C 3-12 cyclo alkenyl group means a cyclic alkenyl group having 3 to 12 carbon atoms.
  • C 6-12 cyclo alkenyl group 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cykuronenyl group, etc. Can be mentioned.
  • cycloalkyl group a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a C 6-12 cyclo alkenyl group, etc. are mentioned.
  • the cyclo alkenyl group may preferably be a C 6-12 cyclo alkenyl group.
  • hydrocarbon group refers to a monovalent group resulting from the loss of one hydrogen atom in a compound consisting solely of carbon and hydrogen.
  • Hydrocarbon radicals include the above “alkyl groups”, “alkenyl groups”, “alkylene groups”, “alkenylene groups”, “cycloalkyl groups”, “cyclo alkenyl groups”, “aromatic groups”, “alicyclic groups” and the like.
  • Hydrocarbon groups can be saturated or unsaturated. Hydrocarbon groups are classified into chain hydrocarbon groups and cyclic hydrocarbon radicals according to the method of bonding carbon, and the cyclic hydrocarbon groups can be further divided into alicyclic hydrocarbon groups and aromatic hydrocarbon radicals.
  • saturated or unsaturated hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, dicyclo pentadienyl, decarinyl, adamantyl, butenyl, hexenyl, cyclo Hexenyl, decyl and other side chains include, but are not limited to, various linear, branched, monocyclic, condensed ring bases within the limits of the number of carbon atoms. Each group may be a divalent or more group depending on the bonding relationship with the other group when not located at the terminal.
  • aromatic group refers to a group resulting from the departure of one hydrogen atom bonded to an aromatic hydrocarbon ring.
  • aromatic group refers to a group resulting from the departure of one hydrogen atom bonded to an aromatic hydrocarbon ring.
  • a phenyl group (C 6 H 5- ) in benzene, a tolyl group (CH 3 C 6 H 4- ) in toluene, a xylenyl group ((CH 3 ) 2 C 6 H 3- ) in xylene, naph in naphthalene Til group (C 10 H 8- ) is induced.
  • heteromatic group used herein means a monocyclic or polycyclic hetero atom-containing aromatic group, and the functional group may have one or more heteroatoms of the same or different kind selected from a nitrogen atom, a sulfur atom and an oxygen atom (eg, For example, 1 to 4) can be included.
  • aromatic group also includes “heteroaromatic group”.
  • aromatic groups include carbocyclic aromatic groups (monocyclic and condensed ring groups) such as phenyl, biphenyl, naphthyl and the like and heteroaromatic groups (monocyclic groups and condensed) such as pyridyl, pyrimidinyl, quinolinyl, triazinyl, etc. Ring groups) and each aromatic group may be a divalent or more group depending on the bonding relationship with other groups when not located at the terminal.
  • carbocyclic aromatic groups monocyclic and condensed ring groups
  • heteroaromatic groups monocyclic groups and condensed
  • pyridyl pyrimidinyl
  • quinolinyl quinolinyl
  • triazinyl triazinyl
  • groups having saturated or unsaturated hydrocarbon chain moieties that form rings together with the aromatic ring moiety eg, tetrahydronaphthyl or dihydronaphthyl as understood by bonding to aromatic groups and saturated or unsaturated hydrocarbon groups. do.
  • alicyclic (group) refers to a moiety (or functional group) resulting from the departure of one hydrogen atom bonded to a ring having no aromaticity, consisting of only carbon and hydrogen.
  • the alicyclic group includes the cycloalkyl group and the cyclo alkenyl group.
  • the alicyclic group may be saturated or unsaturated. Examples of saturated or unsaturated alicyclic groups include various monocyclic, condensed cyclic groups within the limits of the number of carbon atoms of cyclohexyl, dicyclopentadienyl, decarinyl, adamantyl, cyclohexenyl and other side chains. It is not limited to this.
  • Each group may be a divalent or more group depending on the bonding relationship with the other group when not located at the terminal.
  • substitution refers to the conversion of a specific substituent radical, one or more hydrogens, into a radical in a given structure.
  • the number of basic substituents defined herein is not particularly limited as long as it can be substituted, and means one or more.
  • the description of each group also applies when the functional group is a part or substituent of another group except the case mentioned especially.
  • the substituent content that does not specifically specify the term substitution means an unsubstituted substituent.
  • substitution or unsubstitution in this specification was used by the expression which may be substituted.
  • Substituted alkyl group "substituted alkenyl group”, “substituted alkynyl group”, “substituted cycloalkyl group”, “substituted cycloalkenyl group”, “substituted hydrocarbon group”, “substituted aromatic group”, “substituted heteroaromatic group”, " Examples of substituents to the criteria described herein, including “substituted alkylene groups”, “substituted alkenylene groups”, “groups with substituted or unsubstituted secondary or tertiary hydroxyl groups” and “substituted adamantyl groups” halogen, hydroxy, C 1-10 alkyl group, C 1 ⁇ 10 alkoxy group, C 2-10 alkenyl, C 6-12 cycloalkyl, C 6-12 cycloalkenyl group, C 1-10 haloalkyl group, C 2- 10 haloalkenyl group, C 6-18 hydro
  • Preferred examples of the substituent include a hydroxy group, C 6-18 hydrocarbon group, C 1-10 alkyl, C 6-12 aromatic group-substituted C 1-10 alkyl, C 6-12 A C 1-10 alkyl group substituted by a hydrocarbon, an ester C 6-18 hydrocarbon group substituted by group, C 1-10 alkyl group substituted by ester group, ester group (-COO- or -O-CO-), ester group substituted by C 6-12 hydrocarbon group, C 6-12 aromatic group substituted with an ester group, C 2-10 alkenyl, C 6-12 aromatic group substituted C 2-10 alkenyl group, a C 2-10 alkenyl substituted with C 6-12 hydrocarbon group, a C 1-10 alkoxy group, C 6-12 cycloalkyl group, C 6-12 cyclo alkenyl group, and more specific examples thereof may be a benzoyloxy group, a phenyl group, a cyclohexyl group, a cyclo hex
  • the acrylic monomer to which carbon to be formed is replaced is pointed out.
  • R 1 , R 3 , R 4 , R 5 and R 1a are as defined in the preferred Example (2-1) curable resin composition described below.
  • the alcoholic secondary or tertiary OH-containing group herein refers to a functional group containing one or two or more alcoholic secondary or tertiary OH groups.
  • the alcoholic secondary or tertiary OH-containing groups therefore also include the alcoholic secondary or tertiary OH groups themselves.
  • Substituted or unsubstituted in the substituted or unsubstituted alcoholic secondary or tertiary OH-containing group includes one or two or more alcoholic secondary or tertiary OH groups, and the part other than the corresponding OH group is substituted or substituted. It is not shown, and does not show whether the said OH group is substituted or unsubstituted.
  • the phenolic OH-containing group herein refers to a functional group containing one or two or more phenolic OH groups.
  • Substituted or unsubstituted in the substituted or unsubstituted phenolic OH-containing group indicates that one or two or more phenolic OH groups are included, and the portion other than the hydroxy group is substituted or unsubstituted, It does not indicate that it is not substituted.
  • solvate means a compound or salt thereof that further comprises a solvent in a maintenance or indefinite amount bound by non-covalent intermolecular forces that are not particularly rejected. If the solvent is water, the solvate is a hydrate.
  • 1 to 4 are structural cross-sectional views of a film touch sensor according to an embodiment of the present invention.
  • the film touch sensor may include a separation layer 20, a protection layer 30, an electrode pattern layer 40, and an insulating layer.
  • the film touch sensor according to example embodiments may further include an adhesive layer 60 and / or an optical film 100.
  • the separation layer 20 which concerns on this invention can contain the cured resin film formed from the following curable resin composition.
  • the curable resin composition includes a chain polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group; And a crosslinking agent;
  • the side chain includes -COO-,-containing from 3 to 30 carbon atoms, containing at least one saturated or unsaturated hydrocarbon group, or further containing at least one aromatic group, and connecting the carbon atoms;
  • O-, and -CO- may comprise a bond selected from the group consisting of
  • the said crosslinking agent is a triazine type compound, its condensate, and mixtures thereof; Glycoluril compounds, their condensates, and mixtures thereof; And imidazolidinone-based compounds, condensates thereof, and mixtures thereof.
  • the separation layer of the present invention may be referred to as a thermosetting resin composition cured by heat treatment.
  • the chain polymer which is one of the components of the curable resin composition of this invention is equipped with the side chain which has an alcoholic secondary or tertiary OH containing group or phenolic OH containing group.
  • the number of carbon atoms contained in the side chain having an alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group of the chain polymer is preferably 3 to 30.
  • the number of hydroxyl groups in the side chain having an alcoholic secondary or tertiary OH containing group or a phenolic OH containing group may be one or two or more.
  • Said side chain consists of at least 1 saturated or unsaturated hydrocarbon group of carbon atoms, or further contains at least 1 aromatic group.
  • the side chain may contain one or two or more bonds selected from the group consisting of -COO-, -O- and -CO-.
  • the saturated or unsaturated hydrocarbon group constituting the side chain may be, for example, one group alone or may occupy all carbon atoms in the side chain, and a plurality of saturated or unsaturated carbon groups may be composed of -COO-, -O-, and -CO-. It may be connected through a combination selected from.
  • the saturated or unsaturated hydrocarbon group and the aromatic group may be directly bonded, or may be connected via a bond selected from the group consisting of -COO-, -O- and -CO-. do.
  • the side chain alcoholic secondary and tertiary OH-containing groups or phenolic OH-containing groups are applied by the curable resin composition of the present invention on a glass substrate and cured to form a separation layer, which is separated from the substrate even after firing.
  • This is a decisive factor in making it sustainable.
  • the alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group of the side chain is bonded to the alicyclic portion of the side chain, and the alicyclic portion of the side chain can also maintain the peeling property of the separation layer. It is a decisive factor.
  • Chain polymers having such side chains include suitable crosslinking agents, in particular triazine-based compounds, their condensates and mixtures thereof; Glycoluril compounds, their condensates, and mixtures thereof; And when hardened
  • the chain polymer having the side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group is more preferably an unsubstituted or ⁇ -substituted (meth) acrylic monomer, an unsubstituted or ⁇ -substituted vinyl. At least one selected from the group consisting of an ester monomer, an unsubstituted or ⁇ -substituted vinyl ether monomer, and an unsubstituted or ⁇ -substituted vinyl monomer other than the above may be included as a monomer.
  • the chain polymer having the side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group is more preferably a (meth) acrylate monomer, a vinyl ester monomer, or a vinyl ether system. It consists of including at least 1 sort (s) of a monomer and other vinyl-type monomers as a monomer unit.
  • It has 3 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, even more preferably 3 to 20 carbon atoms, and has an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group, and at least one It may comprise a saturated or unsaturated hydrocarbon group, or may further comprise at least one aromatic group, and may have a bond selected from the group consisting of —COO—, —O—, and —CO—, which connects carbon atoms. It includes a monomer selected from the group consisting of compounds represented by).
  • examples of the saturated or unsaturated hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, dicyclopentadienyl, decarinyl, adamantyl, butenyl, hexenyl And cyclohexenyl, decyl, and other linear, branched, monocyclic, and condensed cyclic groups within the limits of the number of carbon atoms in the side chain, but are not limited thereto.
  • each group When each group is not located at the terminal, it may contribute more than bivalent according to the bonding relationship with another group.
  • aromatic group examples include carbocyclic aromatic groups (monocyclic and condensed cyclic groups) such as phenyl, biphenylyl, naphthyl and the like, and heteroaromatic groups such as pyridyl, pyrimidinyl, quinolinyl, triazinyl (monocyclic groups and Condensed cyclic group), and each aromatic group may be a divalent or more group depending on the bonding relationship with other groups.
  • carbocyclic aromatic groups monocyclic and condensed cyclic groups
  • heteroaromatic groups such as pyridyl, pyrimidinyl, quinolinyl, triazinyl (monocyclic groups and Condensed cyclic group)
  • each aromatic group may be a divalent or more group depending on the bonding relationship with other groups.
  • a group having a saturated or unsaturated hydrocarbon chain portion which forms a ring together with an aromatic ring portion is a combination of an aromatic group and a saturated or unsaturated hydrocarbon group.
  • the alcoholic secondary or tertiary hydroxy group is a hydroxy group substituted with a hydrogen atom on any secondary or tertiary carbon atom of the saturated or unsaturated hydrocarbon group constituting the side chain.
  • the hydroxyl group of the side chain of the chain polymer is preferably an alcoholic secondary or tertiary OH group or a phenolic OH group, and more preferably bonded to an alicyclic group constituting part or all of the side chain.
  • the side chain polymer of the present invention may include a monomer represented by the following formula (1).
  • R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
  • L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
  • L 2 is O or NH
  • R 2a , R 3a and R 4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon group,
  • R 2a , R 3a and R 4a is a substituted or unsubstituted alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group,
  • the side chain polymer of the present invention is selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group R 1a in Formula 1, L1 is selected from the group consisting of a single bond and a substituted or unsubstituted alkylene group.
  • R 2a , R 3a and R 4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon radical, wherein at least one of R 2a , R 3a and R 4a is an alcoholic secondary or tertiary OH It may include a monomer selected from the group consisting of a containing group, a phenolic OH-containing group, a substituted or unsubstituted alcoholic secondary or tertiary OH-containing hydrocarbon radical, and a phenolic OH-containing hydrocarbon radical.
  • R 1a is selected from the group consisting of hydrogen and an unsubstituted alkyl group
  • L1 is selected from the group consisting of a single bond and an unsubstituted alkylene group
  • R 2a , R 3a And R 4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon radical, wherein at least one of R 2a , R 3a and R 4a contains an alcoholic secondary or tertiary OH-containing group, containing phenolic OH Groups, substituted or unsubstituted alcoholic secondary or tertiary OH-containing hydrocarbon radicals and phenolic OH-containing hydrocarbon radicals, the other two being independently of one another hydrogen and substituted or unsubstituted hydrocarbon radicals It may include a monomer unit selected from.
  • the side chain polymer of the present invention may include a monomer represented by the following formula (2).
  • R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
  • L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
  • R 5a to R 14a are each independently selected from the group consisting of hydrogen, a hydroxy group, and a functional group represented by the following formula (3), or one to form a ring,
  • At least one of the substituents of R 5a to R 14a or the ring may be a hydroxy group.
  • R 15a is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group. It may be selected from the group consisting of.
  • the side chain polymer of the present invention is selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group R 1a in Formula 2
  • L1 is selected from the group consisting of a single bond and a substituted or unsubstituted alkylene group
  • R 5a to R 14a are each independently selected from the group consisting of hydrogen, a hydroxy group, and a functional group represented by Formula 3, or become one to form a ring, wherein at least one of R 5a to R 14a or a substituent of the ring is Hydroxy group
  • R 15a in Formula 3 is a monomer selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group It may include.
  • the side chain polymer of the present invention is selected from the group consisting of hydrogen and an unsubstituted alkyl group R 1a in Formula 2, L1 is selected from the group consisting of a single bond and an unsubstituted alkylene group, R 5a to In R 14a , R 7a is a hydroxy group, R 9a is a functional group represented by Formula 3 above, otherwise, it is hydrogen or R 5a to R 14a become one to form a ring substituted with one hydroxy group, and in Formula 3 R 15a may include a monomer selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, and a substituted or unsubstituted phenyl group. More preferably, the ring substituted with one hydroxy group may
  • the side chain polymer of the present invention may include a monomer represented by the following formula (4).
  • R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
  • L 2 is selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group
  • R 16a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl group
  • R 17a may be selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl group.
  • the side chain polymer of the present invention is selected from the group consisting of hydrogen and substituted or unsubstituted alkyl group R 1a in Formula 4, L1 is selected from a substituted or unsubstituted alkylene group, R 16a is substituted or It may be selected from an unsubstituted alkyl group, R 17a may include a monomer selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group.
  • the side chain polymer of the present invention may include a monomer represented by the following formula (5).
  • R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group
  • L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group
  • R 18a may comprise a monomer which is an adamantyl group substituted with at least one hydroxy group.
  • R 1a in Formula 5 is selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group
  • L1 is selected from a single bond and a substituted or unsubstituted alkylene group
  • R 18a May include a monomer which is an adamantyl group substituted with at least one hydroxy group.
  • the side chain polymer of the present invention may include a monomer represented by the following formula (6).
  • R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group
  • L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group
  • R 19a may be selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted halo alkyl group and a substituted or unsubstituted cyclo alkenyl group.
  • R 1a in Formula 6 is selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group
  • L1 is selected from a single bond and a substituted or unsubstituted alkylene group
  • R 19a May include a monomer selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted cyclo alkenyl group.
  • R 19a in Chemical Formula 6 may be a substituted or unsubstituted adamantyl group.
  • R 1a in the monomer unit may be hydrogen or methyl, more preferably R 1a may be methyl.
  • Preferred side chains having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group of the chain polymer of the present invention include the followings, but such OH groups may be included. It doesn't work.
  • AO-CO-type (A represents the remainder of the side chain. The same below.) Side chain: 2-hydroxyethoxycarbonyl, 2-hydroxypropoxycarbonyl, 4- (hydroxymethyl) cyclohex Silmethoxycarbonyl, 2-hydroxy-3- (cyclohexylcarbonyloxy) propoxycarbonyl, 3-benzoyloxy-2-hydroxypropoxycarbonyl, 4-benzoyloxy-3-hydroxycyclohexylme Methoxycarbonyl, 3-hydroxy-1-adamantyloxycarbonyl, 2-hydroxycyclohexyloxycarbonyl, 4-undecanoyloxy-3-hydroxycyclohexylmethoxycarbonyl, 4-buta Noyloxy-3-hydroxycyclohexylmethoxycarbonyl and the like.
  • A-CO-O-type side chain 2-hydroxypropylcarbonyloxy, 2-hydroxy-3- (cyclohexylcarbonyloxy) propylcarbonyloxy, 3-benzoyloxy-2-hydroxypropyl Carbonyloxy, 4-benzoyloxy-3-hydroxycyclohexylmethylcarbonyloxy, 3-hydroxy-1-adamantylcarbonyloxy, 2-hydroxycyclohexoxycarbonyloxy, 4-undecano Yloxy-3-hydroxycyclohexylmethylcarbonyloxy, 4-butanoyloxy-3-hydroxycyclohexylmethylcarbonyloxy and the like.
  • Preferred examples of the monomer which gives these side chains to the chain polymer include, but are not limited to the following.
  • the chain polymer of the present invention has no hydroxyl group and unsubstituted or ⁇ -substituted having 1 to 15 carbon atoms in the side chain.
  • (Meth) acrylic monomer, unsubstituted or ⁇ -substituted vinyl ester monomer, unsubstituted or ⁇ -substituted vinyl ether monomer, and at least one of other unsubstituted or ⁇ -substituted vinyl monomer may be included as an additional monomer unit have.
  • R 9 and R 10 have, independently of each other, having 3 to 15 carbon atoms, It does not have a hydroxy group, comprises at least one saturated or unsaturated hydrocarbon group, or further comprises at least one aromatic group, a carbon source .
  • the chain polymer of the present invention is a (meth) acrylic monomer having 1 to 15 carbon atoms in the side chain without having a hydroxyl group in addition to the monomer having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group.
  • a vinyl ester monomer, a vinyl ether monomer, and at least one of other vinyl monomers may be included as an additional monomer unit.
  • C 4 HO 3 -R 11 and C 4 H 2 NO 2 -R 12 (wherein C 4 HO 3 -represents a maleic anhydride group, C 4 H 2 NO 2 -represents a maleimide group, and R 11 and R 12 independently of each other, a hydrogen atom or a carbon number of 1 to 15 carbon atoms, having no alcoholic secondary or tertiary OH group or phenolic OH group, including at least one saturated or unsaturated hydrocarbon group, or further comprising at least one aromatic group, and containing carbon atoms It may have a bond selected from the group consisting of -COO-, -O- and -CO- to connect between, and the hydrocarbon group or aromatic group may have an amino group) can be selected from the group consisting of compounds represented by have.
  • Preferable examples of the monomer unit having no hydroxyl group include, but are not limited to the following.
  • vinyl esters such as vinyl acetate, vinyl butyrate, vinyl pentanate, vinyl hexanoate, vinyl ester of cyclohexanecarboxylic acid, vinyl ester of benzoic acid, vinyl ester of cyclopentadienylcarboxylic acid and vinyl nonanoic acid .
  • vinyl derivatives such as 1-butene, 4-ethoxy-1-butene, 1-pentene, 1-hexene, vinylcyclohexane, styrene, vinyltoluene, 1-nonene and 3-phenylpropene.
  • Maleic anhydride derivatives such as maleic anhydride, methylmaleic anhydride, butylmaleic anhydride, hexylmaleic anhydride, cyclohexylmaleic anhydride, phenylmaleic anhydride and octylmaleic anhydride.
  • maleimide derivatives such as maleimide, methyl maleimide, ethyl maleimide, butyl maleimide, hexyl maleimide, cyclohexyl maleimide, phenyl maleimide, benzyl maleimide and octyl maleimide.
  • the linear polymer of the present invention may be a homopolymer of monomer units, and may be a copolymer including two, three or four or more kinds of monomer units, but at least one of the monomer units of the copolymer is an alcoholic agent. It is a monomer which has a secondary or tertiary OH containing group or a phenolic OH containing group.
  • the copolymer comprises a monomer having at least one alcoholic secondary or tertiary OH containing group or a phenolic OH containing group and an additional monomer having no at least one hydroxyl group.
  • the proportion of the monomeric unit having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group is preferably 30 to 100 mol%, more preferably 50 to 100 mol%. More preferably, it is 60-100 mol%, More preferably, it is 80-100 mol%, Especially preferably, it is 90-100 mol%.
  • the chain polymer is produced by using a raw material monomer and polymerized by a conventional method using, for example, a conventional radical polymerization catalyst such as 2,2'-azobisisobutyronitrile (AIBN). can do.
  • a conventional radical polymerization catalyst such as 2,2'-azobisisobutyronitrile (AIBN).
  • AIBN 2,2'-azobisisobutyronitrile
  • the molecular weight of the linear polymer is usually in the range of 10000 to 100000 (measured by gel filtration chromatography), but is not particularly limited to this range.
  • a triazine crosslinking agent As a crosslinking agent in curable resin composition of this invention, a triazine crosslinking agent, a glycoluril crosslinking agent, or an imidazolidinone type crosslinking agent is preferable. More specifically, triazine compounds, their condensates and mixtures thereof; Glycoluril compounds, their condensates, and mixtures thereof; And imidazolidinone compounds, condensates thereof, and mixtures thereof.
  • crosslinkers include fully or partially alkoxy (eg methoxy, ethoxy) methylated melamines, their condensates and mixtures thereof; Fully or partially alkoxy (eg methoxy, ethoxy) methylated guanamine, its condensates and mixtures thereof; Fully or partially alkoxy (eg methoxy, ethoxy) methylated acetoguanamine, condensates thereof and mixtures thereof; Fully or partially alkoxymethylated benzoguanamine, condensates thereof and mixtures thereof; Fully or partially alkoxy (eg methoxy, ethoxy) methylated glycuril condensates thereof and mixtures thereof; Full or partial alkoxy (eg methoxy, ethoxy) methylated imidazolidinones, condensates thereof and mixtures thereof; and the like. It is preferable here that "alkoxy" has 1 to 4 carbon atoms.
  • crosslinking agent More specifically, for example, hexamethoxymethylmelamine, hexaethoxymethylmelamine, tetramethoxymethylmethylolmelamine, tetramethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylguanamine, Tetramethoxymethylacetoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine, tetramethylolbenzoguanamine, 1,3,4,6-tetrakis ( Methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 4,5-dihydroxy-1,3-dimethoxy methyl-2-imidazolidinone, 4, 5-dimethoxy-1,3-dimethoxymethyl-2-imidazolidinone and the like, but are not limited thereto.
  • the crosslinking agent may be selected from the group consisting of a compound represented by the following Formula 7, a condensate thereof, and a mixture thereof.
  • R 1b is a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 25 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 25 carbon atoms, substituted or unsubstituted carbon atoms at 4 to 25 carbon atoms.
  • Ring heteroaromatic group, and a disubstituted amine represented by the following formula (8);
  • R 2b , R 3b , R 4b and R 5b may be independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.
  • R 6b and R 7b may be independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.
  • R 1b of Formula 7 is a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 25 carbon atoms, and a disubstituted amine represented by Formula 8
  • R 2b to R 7b may be each independently selected from a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, condensates thereof, and mixtures thereof.
  • the crosslinking agent may be selected from the group consisting of a compound represented by the following formula (9), a condensate thereof, and a mixture thereof.
  • R 8b to R 11b may be independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.
  • the crosslinking agent of the present invention may be a compound selected from R 8b to R 11b of Formula 9 independently from a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a condensate thereof and a mixture thereof.
  • the crosslinking agent may be selected from the group consisting of a compound represented by the following Chemical Formula 10, a condensate thereof, and a mixture thereof.
  • R 12b and R 13b are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, and R 14b and R 15b are independent from each other And hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.
  • the crosslinking agent of the present invention R 12b and R 13b of Formula 10 are independently selected from a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and R 14b and R 15b are each independently hydrogen, C 1 It may be selected from the group consisting of compounds selected from substituted or unsubstituted alkyl group of 10 to 10, a condensate thereof and mixtures thereof.
  • R 14b and R 15b may be hydrogen.
  • crosslinking agent of the present invention may be selected from the group consisting of compounds represented or listed in the following structural formula, condensates thereof and mixtures thereof:
  • Hexamethoxymethylmelamine Hexabutoxymethylmelamine; 1,3,4,6-tetrakis (methoxymethyl) glycoluril; 1,3,4,6-tetrakis (butoxymethyl) glycoluril; Tetramethoxymethylbenzoguanamine; 4,5-dihydroxy-1,3-bis (alkoxymethyl) imidazolidin-2-one.
  • the condensate in the crosslinking agent may preferably include a polymer of compounds represented by Formula 7, 9 or 10, and more preferably at least 1 of a dimer, trimer and quaternary higher order polymer of the compounds. May include a dog.
  • the crosslinking agent preferably has a weight average degree of polymerization of 1 or more with respect to the compounds represented by Formula 7, 9 or 10, more preferably 1 to 1.8, more preferably 1.3 to 1.8, especially 1.5 It is preferred to have an average degree of polymerization, but is not limited thereto.
  • the weight average degree of polymerization of the condensate of the compound is 1, it means that the condensate is the compound itself.
  • the weight average degree of polymerization is preferably 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 3, 4 or greater, and more preferably 1.3, 1.4, 1.5, 1.6, 1.7 , 1.8, and more preferably 1.5.
  • the mass ratio of the chain polymer and the crosslinking agent is, for example, 1: 0.03 to 1: 2, preferably 1: 0.05 to 1: 2, 1: 0.05 to 1: 1, 1: 0.03 to 1: 1, more preferably 1: 0.09 to 1: 1, 1: 0.1 to 1: 0.5, more preferably 1: 0.09 to 1: 0.3, 1: 0.1 to 1: 0.3.
  • the curable resin composition also includes an acid catalyst.
  • the acid catalyst is included as necessary as a polymerization catalyst for the reaction between the monomer and the crosslinking agent.
  • the said acid catalyst can use suitably the conventional thing as a polymerization catalyst.
  • the acid catalyst may be a compound selected from the group consisting of Bronsted acid, Lewis acid and mixtures thereof, or may be a salt or solvate thereof.
  • the acid catalyst for example, dinonyl naphthalene disulfonic acid, dinonyl naphthalene (mono) sulfonic acid, dodecyl benzene sulfonic acid, p-toluene sulfonic acid (PTS), proton acids such as phosphoric acid, sulfuric acid and acetic acid, and acid eido
  • thermal acid generators such as SI-100L, SI-150L, SI-60L, and SI-80L (Samshin Chemical Co., Ltd.), or salts or solvates thereof may be mentioned, but are not limited thereto. It doesn't work.
  • the acid catalyst is a compound selected from the group consisting of p-toluene sulfonic acid (PTS), dodecyl benzene sulfonic acid, and a thermal acid generator acid A. SI-100L (Samshin Chemical Co., Ltd.), or a salt thereof, Or solvates thereof. More preferably, the acid catalyst may be pyridinium-p-toluenesulfonic acid, p-toluene sulfonic acid or a hydrate thereof.
  • the mass ratio of the chain polymer, the crosslinking agent and the acid catalyst is preferably 1: 0.03: 0.05 to 1: 2: 0.1, more preferably. 1: 0.05: 0.05 to 1: 2: 0.1, more preferably 1: 0.09: 0.05 to 1: 1: 0.08.
  • the curable resin composition may be diluted to an appropriate concentration with a solvent.
  • a solvent such as glass, there is no problem in formation of a uniform coating film by drying.
  • a common aprotic solvent can be selected suitably, and can be used.
  • propylene glycol monomethyl ether is a suitable solvent, but it is not limited to this. Dilution with a solvent is for handling convenience in the polymerization reaction of a monomer, the application
  • the present invention may include a cured resin film formed by curing the curable resin composition of the above (2-1) as a separation layer.
  • this invention can provide the easily peelable separation layer which hardens curable resin composition of said (2-1) in film form on the board
  • the separation layer formed by the curable resin film of the present invention not only has "heat resistance” defined in the present specification, but also has a peeling property even after heat treatment in a heat resistant temperature range.
  • the curable resin composition of the present invention typically applies a chain polymer, a crosslinking agent, and a solution in which an acid catalyst is further dissolved in a solvent, if necessary, onto a glass substrate (preferably soda lime glass), followed by heat treatment (100 ° C. to 230 ° C. for 1 minute).
  • a glass substrate preferably soda lime glass
  • curing can form the transparent peeling thin film of the peelable separation layer of several hundred nm thickness (preferably about 200 nm-about 300 nm).
  • the hydroxyl group and the crosslinking agent of the side chain of the chain polymer are peelable films for curing shrinkage upon crosslinking by heating.
  • a well-known coating method can be used as a method of apply
  • spin coating spinless coating, die coating, spray coating, roll coating, screen coating, slit coating, dip coating and grabar coating may be mentioned.
  • spin coating is mentioned.
  • the separation layer deposited on the substrate can withstand heating up to 150 ° C. and preferably withstand 230 ° C. heating (firing). Moreover, it is resistant to a photoresist solvent, can withstand an alkaline developing solution, and can be advantageously used as a resin base film for circuit fabrication.
  • the separation layer of the present invention has a dissociation property even after heating (firing), and can be used in a circuit fabrication process including a sintering step at a high temperature in comparison with a conventional film, and is advantageous in maintaining the characteristics of a circuit. In addition, it can be easily peeled off from the substrate even after fabrication of the circuit.
  • the separation layer of the present invention can be prepared according to the method described in the following (3) method for producing a separation layer.
  • the peeling force of the separation layer of this invention can be measured, for example through the following measuring method.
  • the curable resin composition of this invention is typically apply
  • a UR-100N-D type is used as a TENSILON RTG-1310 (A & Day) load cell.
  • a niche half tape (24 mm width) was affixed to the separating layer on a glass substrate, and peeling speed is pulled at the constant speed of 300 mm / min, and peeling force is measured by peeling angle 90 degrees.
  • the separation layer of the present invention preferably has a peel force on a soda glass substrate or an alkali free glass substrate of 0.5 N / mm 2 or less.
  • the separation layer of the present invention more preferably has a peel force on a soda glass substrate or an alkali free glass substrate of 0.1 N / mm 2 or less.
  • the separation layer of the present invention more preferably has a peel force on a soda glass substrate or an alkali-free glass substrate of 0.09 N / mm 2 or less.
  • a preferred value for the peel force of the soda glass substrate is 0.5N / mm 2 or less, 0.4N / mm 2 or less, 0.3N / mm 2 or less 0.2N / mm 2 or less 0.1N / mm 2 or less 0.09N / mm 2 or less , 0.08N / mm 2 or less, 0.07N / mm 2 or less, 0.06N / mm 2 or less, 0.05N / mm 2 or less, 0.04N / mm 2 or less, 0.03N / mm 2 or less, 0.02N / mm 2 or less, It is 0.01 N / mm ⁇ 2> or less.
  • a non-preferred values of the peel force of the alkali glass substrate is 5N / mm 2 or less, 0.04N / mm 2 or less, 0.03N / mm 2 or less, 0.02N / mm 2 or less, 0.01N / mm 2 or less.
  • the separation layer may be regarded as having a peeling property.
  • the present invention is a method for producing a separation layer of the curable resin composition of the above (2-1),
  • the manufacturing method may further include (iv) peeling the separation layer formed on the substrate from the substrate.
  • the preparation method can be carried out not only by the method described in the following examples, but also by a method known to those skilled in the art.
  • the method may further include preparing the chain polymer by polymerizing (i ′) at least one raw material monomer before step (i).
  • a method of polymerizing a monomer for example, a bulk polymerization method, a solution neutralization method, an emulsion polymerization method, a suspension polymerization method, etc. may be mentioned, but the present invention is not limited to these examples.
  • the block polymerization method and the solution polymerization method are preferable.
  • the polymerization of the monomer can be carried out by a method such as a radical polymerization method, a living radical polymerization method, an anion polymerization method, a cation polymerization method, an addition polymerization method or a polycondensation method.
  • a solution obtained by dissolving the monomer in a solvent may be added to the solution while stirring the monomer to polymerize the monomer, and the solution obtained by dissolving the polymerization initiator in the solvent.
  • the monomer can be added to the solution while stirring to polymerize the monomer.
  • a solvent is an organic solvent compatible with a monomer.
  • a chain transfer agent for adjusting the molecular weight can be used.
  • a chain transfer agent can be used in mixture with a monomer normally.
  • Examples of the chain transfer agent include 2- (dodecylthiocarbonothioylthio) -2-methylpropionic acid, 2- (dodecylthiocarbonothioylthio) propionic acid, and methyl 2- (dodecylthiocarbono).
  • a polymerization initiator When polymerizing a monomer, it is preferable to use a polymerization initiator.
  • a polymerization initiator for example, a thermal polymerization initiator, a photopolymerization initiator, a redox polymerization initiator, an ATRP (atomic transfer radical polymerization) initiator, an ICAR ATRP initiator, an ARGET ATRP initiator, a RAFT (reversible addition-cleavage chain transfer polymerization) Agent, NMP (polymerization via nitro oxide) agent, a polymer polymerization initiator, etc. are mentioned. These polymerization initiators may be used independently, respectively and may use two or more types together.
  • thermal initiator examples include azo polymerization initiators such as azoisobutyronitrile, methyl azoisobutyrate and azobisdimethylvaleronitrile, peroxide polymerization initiators such as benzoyl peroxide, potassium persulfate and ammonium persulfate. Although these etc. are mentioned, this invention is not limited only to this illustration. These polymerization initiators may be used independently, respectively and may use two or more types together.
  • the quantity of the thermal polymerization initiator is generally about 0.01 to 20 parts by weight per 100 parts by weight of the total monomers.
  • photoinitiator for example, 2-oxoglutaric acid, 1-hydroxy cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl [4- (methyl Thio) phenyl] -2-morpholinopropane-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, benzophenone, 1- [4- (2-hydroxyethoxy ) Phenyl] -2-hydroxy-2-methyl 1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, bis (2,6 -Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like, but the present invention is not limited to this example.
  • These polymerization initiators may be used independently, respectively and may use two or more types together.
  • the quantity of the said photoinitiator is generally about 0.01 weight part-20 weight part per 100 weight part of total monomers.
  • ATRP atomic transfer radical polymerization
  • II iron
  • RAFT reversible addition-cleavage chain transfer polymerization
  • NMP polymerization through nitrooxide
  • polydimethyl siloxane unit containing polymer azo polymerization initiator polyethylene glycol unit containing
  • polymeric polymerization initiators such as a polymeric azo polymerization initiator, etc. can be mentioned, This invention is not limited only to this illustration. These polymerization initiators may be used independently, respectively and may use two or more types together.
  • the quantity of the said polymerization initiator is generally about 0.01 weight part-20 weight part per 100 weight part of total monomers.
  • electron beam polymerization can proceed by irradiating an electron beam to the monomer.
  • the polymerization temperature is about 50 ° C to about 120 ° C.
  • the atmosphere at the time of a polymerization reaction is inert gas atmosphere, such as nitrogen gas, for example.
  • the polymerization reaction time of the monomer varies depending on the polymerization reaction temperature and the like, it cannot be determined uniformly, but is generally about 3 to 20 hours.
  • the substrate in step (ii) of the manufacturing method is preferably a glass substrate, more preferably soda glass (soda lime glass) or alkali-free glass (eg EAGLE-XG, Corning ), And more preferably soda glass.
  • soda glass soda glass
  • alkali-free glass eg EAGLE-XG, Corning
  • a known coating method may be used as a method of applying the curable resin composition to the substrate in step (ii) of the manufacturing method.
  • spin coating die coating, spray coating, roll coating, screen coating, slit coating, dip coating, gravure coating, and the like, but are not limited thereto.
  • it can be applied using spin coating.
  • the composition in step (ii) of the preparation method, preferably, may also comprise an acid catalyst.
  • the curable resin composition coating film includes an acid catalyst because the acid catalyst can act as a polymerization catalyst in the polymerization reaction in step (iii) and promote the reaction. Therefore, in another embodiment, step (i) of the preparation method may further comprise preparing an acid catalyst.
  • the manufacturing method may further comprise the step of heat-treating the curable resin composition coating film in step (iii).
  • heat processing temperature Preferably it is 100 degreeC-230 degreeC, More preferably, 150 degreeC-230 degreeC is mentioned as an example.
  • the heat treatment time is preferably 1 minute or more, more preferably 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours and the like. But is not limited thereto. Particularly preferred heat treatment time is 10 minutes to 2 hours.
  • the separation layer prepared by the manufacturing method may have a property of the separation layer of the above (2-2), and may be a thin film having peelability.
  • the separation layer 20 is formed on the carrier substrate 10, and after forming an electrode pattern layer or the like thereon, is finally separated from the carrier substrate 10.
  • the carrier substrate 10 and separation during the peel force of the separation layer 20 is preferably 0.5N / mm 2 or less, and more preferably 0.1N / mm 2 or less. That is, a material such that the physical force applied when the separation layer 20 and the carrier substrate 10 are separated does not exceed 1 N / mm 2 , preferably 0.5 N / mm 2 , particularly preferably 0.1 N / mm 2 .
  • the separation layer 20 is preferably formed.
  • the separation layer 20 may not be neatly separated upon separation from the carrier substrate, and the separation layer 20 may remain on the carrier substrate.
  • cracks may occur in at least one of the separation layer 20, the protective layer 30, the electrode pattern layer 40, and the insulating layer 50.
  • the curl (curl) caused on the film after peeling the peel force is together more preferably 0.1N / mm 2 or less, if 0.1N / mm 2 or less, the carrier substrate from the separation layer 20 than the side that controllably desirable. Curls do not cause problems in terms of film touch sensor functionality, but it is advantageous to generate less curl because it may lower the process efficiency in processes such as bonding and cutting processes.
  • the thickness of the separation layer 20 is preferably 10 to 1000 nm, more preferably 50 to 500 nm. If the thickness of the separation layer 20 is less than 10 nm, the uniformity during application of the separation layer may be poor, or the electrode pattern may be unevenly formed, or the peeling force may be locally increased to cause tearing, or after separation from the carrier substrate, There is a problem that curl is not controlled. And when the thickness exceeds 1000nm, there is a problem that the peeling force is no longer lowered, there is a problem that the flexibility of the film is lowered.
  • the present invention provides a structure for a film touch sensor having a carrier substrate 10 attached to one surface of the separation layer 20.
  • an electrode pattern layer 40 is formed on the separation layer 20, and the separation layer 20 functions as a coating layer covering the electrode pattern layer 40 after separation from the carrier substrate or the electrode pattern layer. It functions as a protective layer that protects the 40 from external contact.
  • At least one protective layer 30 may be further formed on the separation layer 20. Since the separation layer 20 alone may be difficult to protect the electrode pattern against contact or impact from the outside, one or more protective layers 30 may be formed on the separation layer 20.
  • the protective layer 30 may include at least one of an organic insulating layer and an inorganic insulating layer, and may be formed by a method of coating and curing or deposition.
  • the protective layer may be formed except for a portion where a pad electrode is to be removed or a portion where a pad electrode is to be formed for circuit connection.
  • a pad pattern layer may be formed under the pad electrode, and the protective layer may be formed by coating and patterning the entire top of the separation layer to form the pad pattern layer, or by applying a portion except the part where the pad pattern layer is to be formed. have.
  • the electrode pattern layer 40 is formed on the separation layer 20 or the protection layer 30.
  • the electrode pattern layer 40 includes a sensing electrode SE for detecting whether a touch is detected and a pad electrode PE formed at one end of the sensing electrode.
  • the sensing electrode may include not only an electrode for sensing a touch but also a wiring pattern connected to the electrode.
  • the pad pattern layer may be formed on or under the pad electrode.
  • the pad electrode may be electrically connected to the circuit board through the pad pattern layer, and serves to lower the contact resistance when connected to the circuit board.
  • the pad pattern layer may be formed on the pad electrode, and when the circuit board is bonded in the separation layer direction, the pad pattern layer may be formed below the pad electrode.
  • the pad pattern layer may be omitted if the pad electrode is sufficiently low in contact resistance when connected to the circuit board.
  • the pad pattern layer may be formed of one or more materials selected from metals, metal nanowires, metal oxides, carbon nanotubes, graphene, conductive polymers, and conductive inks.
  • the electrode pattern layer 40 may be formed of one or more materials selected from metals, metal nanowires, metal oxides, carbon nanotubes, graphene, conductive polymers, and conductive inks.
  • the metal may be any one of gold (Au), silver (Ag), copper (Cu), molybdenum (Mo), aluminum, palladium, neodium, and silver-palladium-copper alloy (APC).
  • the metal nanowires may be any one of silver nanowires, copper nanowires, zirconium nanowires, and gold nanowires.
  • the metal oxide is indium tin oxide (ITO), indium zinc oxide (IZO), indium zinc tin oxide (IZTO), aluminum zinc oxide (AZO), gallium zinc oxide (GZO), florin tin oxide (FTO), zinc oxide (ZnO), indium tin oxide-silver-indium tin oxide (ITO-Ag-ITO), indium zinc oxide-silver-indium zinc oxide (IZO-Ag-IZO), indium zinc tin oxide-silver-indium zinc tin oxide ( IZTO-Ag-IZTO) and aluminum zinc oxide-silver-aluminum zinc oxide (AZO-Ag-AZO).
  • the electrode pattern layer 40 may be formed of a carbon-based material including carbon nanotubes (CNT) or graphene.
  • the conductive polymer includes polypyrrole, polythiophene, polyacetylene, PODOT, and polyaniline, and may be formed of such conductive polymer.
  • the conductive ink is an ink in which a metal powder and a curable polymer binder are mixed, and an electrode may be formed using the ink.
  • the electrode pattern layer 40 may be formed of two or more conductive layers in the form of the first electrode layer 41 and the second electrode layer 42 as shown in FIG. 2A.
  • the electrode pattern layer 40 may be formed of one layer of ITO, AgNW (silver nanowire), or a metal mesh.
  • the first electrode layer 41 may be formed of a transparent metal such as ITO.
  • the second electrode layer 42 may be formed of an oxide, and a metal or AgNW may be formed on the ITO electrode layer to further lower the electrical resistance.
  • the electrode pattern layer 40 may further include a third electrode layer 43 formed of a transparent metal oxide such as ITO on the second electrode layer 42 as shown in FIG. 2B.
  • At least one electrode pattern layer made of metal or metal oxide may be included. More specifically, the electrode pattern layer is formed on the separation layer or the protective layer with a conductive layer of a metal or metal oxide, and then further laminated a transparent conductive layer to form an electrode pattern, or one layer on the separation layer or protective layer After the above-mentioned transparent conductive layer is laminated, a conductive layer may be further formed of a metal or a metal oxide to form an electrode pattern. Specific examples of the laminated structure of the electrode pattern is as follows.
  • a structure in which a metal or metal oxide pattern layer is further formed between the separation layer and the electrode pattern layer a structure in which a metal or metal oxide pattern layer is further formed between the electrode pattern layer and the insulating layer, a metal or between the protective layer and the electrode pattern layer
  • the metal oxide pattern layer may be further formed, and may further include at least one electrode pattern layer made of a transparent conductive material.
  • an electrical insulation layer may be formed between the first electrode pattern layer and the second electrode pattern layer, and the second conductive layer may be formed as a bridge electrode by patterning the electrical insulation layer to form a contact hole.
  • the pattern structure of the electrode pattern layer is preferably an electrode pattern structure used in the capacitive method, a mutual capacitance method (self-capacitance) or a self-capacitance method (self-capacitance) may be applied.
  • the grid electrode structure may have a horizontal axis and a vertical axis.
  • the intersection of the horizontal and vertical electrodes may include a bridge electrode, or the horizontal and vertical electrode pattern layers may be formed to be electrically spaced apart from each other.
  • the electrode layer structure may be a method of reading capacitance change by using one electrode at each point.
  • An insulating layer 50 is formed on the electrode pattern layer 40.
  • the insulating layer may serve to prevent corrosion of the electrode pattern and protect the surface of the electrode pattern.
  • the insulating layer 50 is preferably formed to a certain thickness to fill the gap between the electrode and the wiring.
  • the surface opposite to the surface in contact with the electrode pattern layer 40 is preferably formed flat so that the unevenness of the electrode is not exposed.
  • the insulating layer 50 is formed to expose at least a portion of the pad electrode portion to provide a space in which the pad electrode or the pad pattern layer is connected to the circuit board, and to cover all the sensing electrodes to protect the sensing electrode. Can be.
  • the elastic modulus difference in 25 degreeC of the said protective layer 30 and the said insulating layer 50 is 300 Mpa or less. This is to suppress the occurrence of cracks due to the difference in stress solving ability of each layer, the reason for the elastic modulus difference between the protective layer and the insulating layer to be less than 300MPa at 25 °C when the elastic modulus difference exceeds 300MPa, deformation between the two layers This is because cracks occur due to an imbalance in energy and stress resolving ability.
  • the reason for measuring the elastic modulus difference at 25 °C is because the crack should not occur in the environment used by the user.
  • the insulating layer is not particularly limited as long as it is an organic insulating material satisfying that the difference in elastic modulus from the protective layer is 300 Mpa or less, but the insulating layer is preferably a thermosetting or UV curing organic polymer.
  • the insulating layer may be formed of one or more materials selected from materials, such as an epoxy compound, an acrylic compound, and a melanin compound.
  • the insulating layer may also be formed of one or more materials selected from curable prepolymers, curable polymers, and plastic polymers, in terms of material form.
  • the insulating layer 50 may itself serve as an optical film.
  • the film is made of a varnish-type material, and the varnish-type material is polysilicon or polyimide such as polydimethylsiloxane (PDMS), polyorganosiloxane (POS), or the like. It may be formed of one or more materials selected from materials such as polyurethane-based, such as spandex.
  • the insulating layer 50 may be formed using an inorganic material such as silicon oxide (SiOx), and in this case, the insulating layer 50 may be formed by deposition, sputtering, or the like.
  • the pad electrode may be electrically connected to the circuit board.
  • the circuit board may be a flexible printed circuit board (FPCB) as an example, and serves to electrically connect the touch control circuit and the film touch sensor of the present invention.
  • FPCB flexible printed circuit board
  • An electrode corresponding to the pad electrode is formed at one end of the circuit board, and the pad electrode and the circuit board may be electrically connected by the conductive adhesive.
  • the film touch sensor may be connected to the circuit board through at least a part of the open area on the pad electrode, or through the separation layer.
  • a pad pattern layer made of a material having a low resistance may be formed on or below the pad electrode, and in this case, the circuit board may be connected to the pad electrode through the pad pattern layer.
  • the separation layer An electrode pattern layer formed on the separation layer, the electrode pattern layer including a sensing electrode and a pad electrode formed at one end of the sensing electrode; An insulating layer formed on the electrode pattern and covering a part or all of the electrode pattern layer; An optical film formed directly on the insulating layer; Characterized in that it comprises a.
  • the insulating layer 50 may itself function as an adhesive layer made of an adhesive or an adhesive.
  • This insulating layer may be formed including one or more materials selected from the group consisting of polyester, polyether, polyurethane, epoxy, silicone and acrylic.
  • the optical film 100 may be directly bonded on the insulating layer 50.
  • the optical film 100 may be a transparent film or a polarizing plate.
  • polyester-based resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, and polybutylene terephthalate; Cellulose resins such as diacetyl cellulose and triacetyl cellulose; Polycarbonate resins; Acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene resins such as polystyrene and acrylonitrile-styrene copolymers; Polyolefin-based resins such as polyethylene, polypropylene, cyclo-based or norbornene-structured polyolefins, ethylene-propylene copolymers; Vinyl chloride-based resins; Amide resins such as nylon and aromatic polyamides; Imide resin; Polyether sulfone resin; Sulfone resins; Polyether ether ketone resins;
  • thermosetting resin or ultraviolet curable resin such as (meth) acrylic-type, urethane type, acrylurethane type, epoxy type, and silicone type
  • the thickness of such a transparent film can be determined suitably, it is about 1-500 micrometers generally from the point of workability, thinness, etc., such as strength and handleability. 1-300 micrometers is especially preferable, and 5-200 micrometers is more preferable.
  • Such a transparent film may contain a suitable one or more additives.
  • a ultraviolet absorber, antioxidant, a lubricant, a plasticizer, a mold release agent, a coloring agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment, a coloring agent, etc. are mentioned, for example.
  • the transparent film may have a structure including various functional layers such as a hard coating layer, an antireflection layer, and a gas barrier layer on one or both surfaces of the film, and the functional layer is not limited to the above-described ones. It may include.
  • the transparent film may be surface treated.
  • Such surface treatments include dry treatments such as plasma treatments, corona treatments, primer treatments, and chemical treatments such as alkali treatments including saponification treatments.
  • the transparent film may be an isotropic film, a retardation film or a protective film.
  • in-plane retardation [(nx-ny) ⁇ d], nx, ny is the major refractive index in the film plane, d is the film thickness
  • nx, ny is the major refractive index in the film plane
  • d is the film thickness
  • the thickness direction Retardation [(nx + ny) / 2-nz) ⁇ d, nx, ny is the major refractive index in the film plane, nz is the refractive index in the film thickness direction
  • d is the film thickness
  • Retardation film is a film manufactured by the method of uniaxial stretching, biaxial stretching, polymer coating, liquid crystal coating of polymer film, and is generally used for improving and adjusting optical characteristics such as viewing angle compensation, color improvement, light leakage improvement, color taste control of display. do.
  • the type of retardation film includes a wave plate such as 1/2 or 1/4, a positive C plate, a negative C plate, a positive A plate, a negative A plate, and a biaxial wave plate.
  • the protective film may be a film including an adhesive layer on at least one surface of a film made of a polymer resin, or a film having a self-adhesive property such as polypropylene, and may be used for protecting the touch sensor surface and improving processability.
  • a polarizing plate As a polarizing plate, a well-known thing used for a display panel can be used.
  • a polyvinyl alcohol film is drawn to form a protective layer on at least one surface of a polarizer dyed with iodine or a dichroic dye, a liquid crystal is oriented so as to have a polarizer performance, and a polyvinyl alcohol on a transparent film And those made by coating an orientation resin such as the like and stretching and dyeing the same, but are not limited thereto.
  • the separation layer An electrode pattern layer formed on the separation layer, the electrode pattern layer including a sensing electrode and a pad electrode formed at one end of the sensing electrode; An insulating layer formed on the electrode pattern and covering a part or all of the electrode pattern layer; An adhesive layer formed on the insulating layer; An optical film formed on the adhesive layer; Characterized in that it comprises a.
  • the optical film may be further included on the insulating layer 50.
  • a separate adhesive layer 60 may be formed between the insulating layer 50 and the optical film 100 to thereby be bonded.
  • the adhesive layer 60 is formed of an adhesive or an adhesive, and may be either a thermosetting type or a UV curing type.
  • the adhesive or pressure-sensitive adhesive used for bonding the optical film 100 is preferably polyester, polyether, polyurethane, epoxy, silicone, or acrylic material.
  • 5A to 5F are cross-sectional views illustrating a process of manufacturing a film touch sensor according to a first embodiment of the present invention, and a method of manufacturing the film touch sensor according to the present invention will be described in detail with reference to the drawings.
  • a chain polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group and a crosslinking agent are mixed on the carrier substrate 10, and applied to a separation layer ( 20).
  • the side chain is -COO containing 3 to 30 carbon atoms, containing at least one saturated or unsaturated hydrocarbon group, or further comprises at least one aromatic group, and -COO to connect between the carbon atoms May include a bond selected from the group consisting of-, -O-, and -CO-,
  • the crosslinking agent may be formed of a curable resin composition selected from a triazine crosslinking agent or a glycuril crosslinking agent.
  • a known coating method can be used as a method of applying the separation layer.
  • the curing process for forming the separation layer 20 may be used by heat curing or UV curing alone, or a combination of thermosetting and UV curing.
  • the carrier substrate 10 is preferably a glass substrate, but is not limited to the glass substrate and other substrates may be used as the carrier substrate 10. However, a material having heat resistance that does not deform even at high temperatures, that is, maintains flatness, is preferable to withstand the process temperature at the time of electrode formation.
  • the protective layer 30 is formed by applying an organic insulating layer on the separation layer 20 formed on the carrier substrate 10.
  • the protective layer 30 may be removed by patterning or the like to form a pad pattern layer for circuit connection, or may be applied except for a portion where the pad pattern layer is to be formed.
  • the pad pattern layer for connection with a circuit board can be formed in the part in which the protective layer is not formed, it demonstrates that there is no pad pattern layer in this Example.
  • Electrode pattern layer is then formed on the protective layer 30.
  • the electrode pattern layer will be described as having a single layer laminated structure.
  • an ITO transparent electrode layer is formed as a transparent conductive layer as shown in FIG. 5C, and a photosensitive resist (not shown) is formed thereon. Thereafter, the electrode pattern layer 40 is formed by selectively patterning the photolithography process as illustrated in FIG. 5D.
  • the transparent conductive layer is a sputtering process such as chemical vapor deposition (CVD), physical vapor deposition (PVD), plasma enhanced chemical vapor deposition (PECVD), screen printing, gravure printing, reverse offset, and reverse offset.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • PECVD plasma enhanced chemical vapor deposition
  • screen printing gravure printing
  • reverse offset reverse offset
  • reverse offset reverse offset
  • Printing process such as ink jet, dry or wet plating process
  • an electrode pattern layer may be formed by placing a mask having a desired electrode pattern shape on the substrate and performing a sputtering process.
  • a conductive layer may be formed over the entire surface by the film forming method, and an electrode pattern may be formed using a photolithography method.
  • a negative type photosensitive resist or a positive type photosensitive resist may be used, and after completing the patterning process, the photosensitive resist may remain on the electrode pattern layer 40 as necessary and be removed. You may be.
  • a positive photosensitive resist is used to describe the structure removed on the electrode pattern after the patterning process.
  • the insulating layer 50 is formed to cover the electrode pattern layer 40.
  • the thickness of the insulating layer 50 is equal to or thicker than the thickness of the electrode so that the top surface of the insulating layer is formed to have a flat shape. That is, an insulating material having proper viscoelasticity should be used so that the unevenness of the electrode is not transferred.
  • a liquid material that becomes an insulating layer is coated on the electrode pattern layer, and an insulating layer is formed through a coating film forming step.
  • a well-known coating method can be used here as a method of apply
  • the insulating layer coating may be performed by at least one of thermal curing, UV curing, thermal drying, vacuum drying, and the like, and is selected according to the characteristics of the insulating layer material.
  • the insulating layer can itself function as a support. In this case, since the insulating layer functions as an optical film, there is no need to attach an additional optical film. If the top surface of the insulating layer is not flat, the insulating layer is impossible to play the role of the optical film due to irregularities. When the optical film is additionally attached on the insulating layer, uniform bonding is impossible and a problem occurs that the performance of the touch sensor is degraded.
  • the insulating layer 50 is formed to expose at least a portion of the pad electrode portion to provide a space in which the pad electrode or the pad pattern layer is connected to the circuit board, and to cover all the sensing electrodes to protect the sensing electrode. Can be.
  • the method of forming the insulating layer 50 so that the pad electrode is exposed may be formed by coating and patterning the insulating layer to cover the upper part of the electrode pattern layer or by applying the insulating layer except the pad electrode region to expose the pad electrode. There is a method to form.
  • the pad pattern layer may be formed after the insulating layer is formed. In this embodiment, a structure without the pad pattern layer will be described.
  • step (c) and carrier substrate removal step of separating the separation layer from the carrier substrate may be performed in any order.
  • the separation layer 20 on which the electrode is formed is separated from the carrier substrate 10 used for the process of manufacturing the touch sensor as shown in FIG. 5F.
  • the separation layer 20 is separated using a method of peeling from the carrier substrate 10.
  • the peeling method is a method of lift-off or peel-off, but is not limited thereto.
  • the size of the force applied during the peeling force may vary depending on the peel force of the separation layer, 1N / mm 2 or less are preferred and, 0.5N / mm 2 or less are more preferable and, 0.1N / mm 2 or less is more than desirable.
  • the peeling force exceeds 1 N / mm 2 , a problem may occur in that the film touch sensor is torn during peeling from the carrier substrate. Excessive force is applied to the film touch sensor so that the film touch sensor is deformed and cannot function as a device. Can be.
  • a film touch sensor and a circuit board can be bonded together, it can bond with a circuit board using a conductive adhesive at this time.
  • a conductive adhesive means that conductive fillers, such as silver, copper, nickel, carbon, aluminum, plating, are disperse
  • the circuit board may be bonded before or after separating the carrier board and the touch sensor.
  • the laminate structure is formed to expose a part of the pad electrode in at least one of the insulating layer coating step, the insulating layer coating step, and the optical film attachment step, or a separate structure
  • the stacking structure may be formed to expose a portion of the pad electrode through the patterning step.
  • the circuit board is bonded to the exposed pad electrode and separated from the carrier substrate.
  • the pad pattern layer is formed on the pad electrode, the circuit board is bonded to the pad pattern layer and the substrate is separated.
  • the pad substrate When the circuit board is bonded after separation from the carrier substrate, the pad substrate may be bonded to the pad electrode through the separation layer in the separation layer direction, wherein a pad pattern layer may be formed under the pad electrode, in which case the circuit board may be padded. It is connected to the pad electrode through the pattern layer.
  • the circuit board may be bonded to the pad electrode or the pad pattern layer exposed in the insulating layer or the optical film direction.
  • the method of connecting through the pad pattern layer when the circuit board is connected with the pad electrode is to lower the contact resistance between the circuit board and the pad electrode and may be selectively applied according to the manufacturing process and the product specification.
  • FIGS. 6A and 6B are cross-sectional views illustrating a method of manufacturing the film touch sensor according to the present invention, with reference to this, a second embodiment of the method of manufacturing the film touch sensor according to the present invention will be described.
  • the process of forming the isolation layer 20 on the carrier substrate 10 and forming the electrode pattern layer 40 and the insulating layer 50 after forming the protective layer 30 is substantially the same as in the first embodiment. .
  • the optical film 100 may be attached on the insulating layer 50. Since the insulating layer includes the function of the adhesive layer, the optical film 100 is directly bonded to the insulating layer as shown in FIG. 6A.
  • the pressure conditions for attaching the optical film to the insulating layer in the step of bonding the optical film is a condition of 1 to 200kg / cm 2 , preferably 10 to 100kg / cm 2 conditions. .
  • the separation layer is separated using a method of peeling from the carrier substrate 10 as shown in FIG. 6B. Thereafter, the circuit board is bonded to the pad electrode or the pad pattern layer.
  • FIG. 7A and 7B are cross-sectional views illustrating a method of manufacturing the film touch sensor according to the present invention, with reference to this, a third embodiment of the method of manufacturing the film touch sensor according to the present invention will be described.
  • the adhesive layer 60 is formed on the insulating layer 50 to attach the optical film 100.
  • the adhesive layer 60 may be formed by first coating or bonding to one surface of the optical film 100, or may attach the optical film 100 by coating or bonding an adhesive layer on an upper surface of the insulating layer.
  • an adhesive layer was formed on an insulating layer to show a laminated structure in which an optical film was bonded.
  • the separation layer is separated using a method of peeling from the carrier substrate 10. Thereafter, the circuit board is bonded to the pad electrode or the pad pattern layer.
  • the separation layer An electrode pattern layer formed on the separation layer, the electrode pattern layer including a sensing electrode and a pad electrode formed at one end of the sensing electrode; And an insulating layer formed on the electrode pattern and covering a part or the whole of the electrode pattern layer, wherein the insulating layer is formed on the opposite side on which the electrode pattern layer of the separation layer is formed through an adhesive or an adhesive. It may further include a functional film layer 80.
  • An adhesive layer 70 may be further included between the separation layer 20 and the functional film layer 80, and the adhesive layer 70 may be formed of an adhesive or an adhesive, wherein the adhesive or the adhesive is known in the art.
  • the adhesive or adhesive may be used without particular limitation, but the adhesive or adhesive may be an adhesive or adhesive of at least one of a thermosetting type and a UV curing type.
  • the functional film layer 80 may be a functional film layer known in the art without particular limitation, but may be a film having a functional coating layer formed on a functional film or a base film, and at least one film selected from the group consisting of Alternatively, the coating layer may be formed in a single layer or multiple layers.
  • the functional film may be a transparent film, a retardation film, an isotropic film, a protective film, a polarizer, a polarizer, a barrier film, and the like
  • the barrier film may be a single layer film, and at least one inorganic film and an organic film on the base film. It may be a multilayered film.
  • multilayer barrier film examples include inorganic film / COP (Cyclo-olefin Polymer) film / inorganic film / organic film, inorganic film / hard coating / COP film / hard coating / inorganic film, inorganic film / hard coating / TAC ( Triacetyl cellulose) film / hard coating / inorganic film / organic film, organic film / hard coating / TAC film / hard coating / inorganic film / organic film and the like.
  • COP Cyclo-olefin Polymer
  • TAC Triacetyl cellulose
  • the functional coating layer may be coating layers having the same function as the above-described functional film, and may be, for example, a coating organic film layer, a coating retardation layer, a coating polarizer layer, or a coating alignment film layer.
  • a film known in the art may be applied without particular limitation, and the above-described functional film may be used.
  • the functional film layer 80 may be a film selected from the same group as the optical film 100, used with the optical film 100 as needed, or in the lower portion of the separation layer without the optical film 100
  • the electrode pattern layer 40 may be further protected from external number or expansion stress applied thereto. It can provide a desirable effect in that it can.
  • the adhesive layer 70 may be formed by first coating or bonding one surface of the functional film layer 80 or by coating or bonding the adhesive layer on the bottom surface of the separation layer 20 to attach the functional film layer 80.
  • the film touch sensor manufactured according to the present invention may be used to be disposed so that the functional film layer is positioned at the viewer side when the film touch sensor is bonded to the display panel, and may be arranged to be attached to the display panel.
  • Such a film touch sensor and a manufacturing method thereof according to the present invention implements a touch sensor on a carrier substrate, thereby securing a fine pitch and heat resistance, which are impossible in a process of implementing a touch sensor directly on a film substrate, and diversifying the film substrate. It is to be done. That is, the optical film and the functional film layer which are weak in heat resistance can also be used because they are bonded after electrode formation.
  • the efficiency of the process may be improved by attaching the circuit board to the pad pattern layer after separation from the carrier substrate or before separation without removing the separation layer formed on the carrier substrate.
  • a polymer As a component of the curable resin composition, a polymer was prepared as follows.
  • 2-hydroxypropyl methacrylate of the following Chemical Formula 1-1 was used as a monomer, and 100 parts by mass thereof were dissolved in propylene glycol monomethyl ether (PGME) so as to be 30% by mass. It heated up to 80 degreeC, blowing in nitrogen gas to the obtained solution, 5 mol% of 2,2'- azobisisobutyronitrile (AIBN) was added with respect to monomer total amount, and reaction was performed at 80 degreeC for 8 hours, and the polymer A was carried out. -1 was obtained. It was 25,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • PGME propylene glycol monomethyl ether
  • Polymer A-2 was obtained in the same manner as in Production Example 1 except that 3-benzoyloxy-2-hydroxypropyl methacrylate of the following formula 1-2 was used as a monomer. It was 22000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-3 was obtained in the same manner as in Production Example 1 except that 4-benzoyloxy-3-hydroxycyclohexylmethyl methacrylate of the following formula 1-3 was used as a monomer. It was 32,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-4 was obtained in the same manner as in Production Example 1 except that 1,3-adamantyldiol monomethacrylate of the formula (1-4) was used as a monomer. It was 18,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-5 was obtained in the same manner as in Production Example 1 except that 2-hydroxycyclohexyl methacrylate of the formula (1-5) was used as a monomer. It was 36,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-6 was obtained in the same manner as in Production Example 1 except that 2-hydroxyethyl methacrylate of the following Chemical Formula 1-6 was used as the monomer. It was 42,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-7 was obtained in the same manner as in Production Example 1 except that 4- (hydroxymethyl) cyclohexylmethylmethacrylate of the formula (1-7) was used as a monomer. It was 18,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • 2-hydroxypropyl methacrylate and n-butyl acrylate of the general formula (1-1) were used as monomers, and 50 parts by mass of these were dissolved in propylene glycol monomethyl ether (PGME) so that the total was 30% by mass. It heated up to 80 degreeC, blowing in nitrogen gas to the obtained solution, 5 mol% of 2,2'- azobisisobutyronitrile (AIBN) was added with respect to monomer total amount, and reaction was performed at 80 degreeC for 8 hours, and the polymer A was carried out. Got -8. It was 18,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • PGME propylene glycol monomethyl ether
  • Polymer A-9 was obtained in the same manner as in Production Example 8 except that 2-hydroxypropyl methacrylate and methyl methacrylate of Formula 1-1 were used as monomers. It was 25,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-10 was obtained in the same manner as in Production Example 8 except that 2-hydroxypropyl methacrylate and styrene represented by Chemical Formula 1-1 were used as monomers. It was 22,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-11 was obtained in the same manner as in Production Example 8 except that 4-benzoyloxy-3-hydroxycyclohexylmethyl methacrylate and dicyclopentadienyl methacrylate of the formula 1-3 were used as monomers. It was 35,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-12 was obtained in the same manner as in Production Example 8 except that 2-hydroxycyclohexyl methacrylate and dicyclopentadienyl methacrylate of the formula (1-5) were used as monomers. It was 25,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-13 was obtained in the same manner as in Production Example 8 except for using 2-hydroxyethyl methacrylate and butyl acrylate of Formula 1-6 as monomers. It was 38,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-14 was obtained in the same manner as in Production Example 8 except that 2-hydroxyethyl methacrylate and methyl methacrylate of Formula 1-6 were used as monomers. It was 36,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-15 was obtained in the same manner as in Production Example 8 except that 2-hydroxyethyl methacrylate and dicyclopentadienyl methacrylate of the formula (1-6) were used as the monomers. It was 39,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-17 of Chemical Formula 1-9-1 was obtained in the same manner as in Production Example 1 except that 4-adamantanecarboxyoxy-3-hydroxycyclohexylmethyl methacrylate of Chemical Formula 1-9 was used as a monomer. . It was 31,700 when the average molecular weight (MW) of the A-17 polymer was measured by the gel filtration chromatography.
  • Polymer A-18 of the following formula was obtained in the same manner as in Production Example 8 except that 2-hydroxycyclohexyl methacrylate of the formula (1-5) was used as the monomer. It was 25,500 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-19 of formula 1-10-1 was obtained in the same manner as in Preparation Example 1 except that 3-hydroxyadamantyl methyl-2-methacrylate of formula 1-10 was used as a monomer. It was 35,700 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • the polymer of Formula 1-12-1 in the same manner as in Production Example 1 except that 4- (2-cyclohexylacetyl) oxy-3-hydroxycyclohexanemethyl 2-methacrylate of Formula 1-12 was used as a monomer. A-21 was obtained. It was 30,700 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-22 of the following formula was obtained in the same manner as in Production Example 8 except that 2-hydroxycyclohexyl methacrylate and benzyl methacrylate of the formula (1-5) were used as the monomers. It was 32,700 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • Polymer A-24 of the following formula was obtained in the same manner as in Production Example 8 except that methyl methacrylate, glycidyl methacrylate and dicyclopentadienyl methacrylate were used as monomers. It was 35,700 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
  • curable resin compositions of this invention were manufactured as follows, apply
  • Test Example Evaluation of physical properties of the separation layers of Examples 1 to 19 and Comparative Examples 1 to 6
  • peel force The magnitude of the force (peel force) required to peel the film touch sensors of the Experimental and Comparative Examples from the glass was measured quantitatively by the following method.
  • TENSILON RTG-1310 A & Day Co., Ltd.
  • load cell type UR-100N-D load cell type UR-100N-D as measuring equipment.
  • the speed is measured by peeling force at a constant speed of 300 mm / min and the values are shown in Table 1 below. Peel force of Examples 1 to 16 was expressed by three decimal places, and the rest was displayed to two decimal places.
  • the peeling forces of Comparative Examples 1 to 6 were 2.2 to 8.7 N / mm 2 (soda glass substrate) and 3.2 to 9.2 N / mm 2 (EAGLE-XG substrate), while Examples 1 to 16 were used.
  • the peel force of was 0.013 to 0.078 N / mm 2 (soda glass substrate) and 0.028 to 0.085 N / mm 2 (EAGLE-XG substrate), which was two orders of magnitude smaller than the comparative example.
  • the film touch sensor of the comparative example was damaged due to the high peel force, the film touch sensor or the substrate was broken, and each film touch sensor of the example could be easily peeled off without difficulty.
  • the peeling force at the time of baking a cured resin thin film was measured by assuming the baking process at the time of circuit preparation by the patterning using the photolithography method or the printing method on the cured resin thin film in the same way as said 2 above. That is, about Example 12, 17-24, and the comparative example 7, the cured resin thin film formed on the soda glass board
  • Example 12 0.03 0.03
  • Example 17 0.04 0.04
  • Example 18 0.04 0.04
  • Example 19 0.04 0.04
  • Example 20 0.04 0.04
  • Example 21 0.05 0.05
  • Example 22 0.07 0.07
  • Example 23 0.08 0.08
  • Example 24 0.05 0.05 Comparative Example 7 3.8 3.8
  • Substrate Soda glass (coated on the tinned surface)
  • Peel test conditions Peel test was carried out with niche half tape (24 mm width).
  • the polymer used was polymer A-3.
  • the crosslinking agents used are shown in Table 4.
  • MW-30 is hexamethoxymethylmelamine of the formula (B-1) (Nikarakku MW-30, Samwha Chemical Co., Ltd.)
  • MW-30LF is hexamethoxymethylmelamine (low glass formaldehyde) Product) (Nikarakku MW-30LF, Samwha Chemical Co., Ltd.)
  • MX-270 is 1,3,4,6-tetrakis (methoxymethyl) glycoluril of the formula (B-2) (Nikarakku MW) -270, Samhwa Chemical Co., Ltd.
  • the weight ratio (wt%) of the polymer, the crosslinking agent and the acid catalyst was changed, and the peel force of the prepared separation layer was measured. That is, for Examples 28 to 38 and Comparative Examples 11 to 15, a solution prepared using a polymer, a crosslinking agent, and an acid catalyst at a weight ratio shown in Table 6 was applied onto a soda glass substrate, and baked at 230 ° C. for 20 minutes. Except for the formation of the separation layer in the same manner as in Example 1, and then by measuring the peel force of each according to the apparatus and method described in the above 1 was compared. The results are shown in Table 6.
  • Example 11 Polymer Crosslinking agent Acid catalyst content (wt%) Peel force (N / mm 2 ) ingredient Content (wt%) ingredient Content (wt%) Comparative Example 11 A-3 90 B-1 5 5 5.23 Comparative Example 12 A-3 87 B-1 8 5 2.12 Example 28 A-3 85 B-1 10 5 0.02 Example 29 A-3 63 B-1 32 5 0.03 Example 30 A-3 45 B-1 50 5 0.02 Comparative Example 13 A-3 90 B-2 5 5 5.20 Comparative Example 14 A-3 94 B-2 One 5 7.90 Example 31 A-3 87 B-2 8 5 0.02 Example 32 A-3 85 B-2 10 5 0.03 Comparative Example 15 A-5 94 B-2 One 5 8.39 Example 33 A-5 92 B-2 3 5 0.06 Example 34 A-5 90 B-2 5 5 0.02 Example 35 A-5 87 B-2 8 5 0.03 Example 36 A-5 85 B-2 10 5 0.02 Example 37 A-16 70 B-1 25 5 0.02 Example 38 A-17 70 B-1 25 5 0.02
  • the crosslinking agent B-1 exhibited dissociation property when the content was 10% by weight or more based on the total amount of the polymer, the crosslinking agent and the acid catalyst (Examples 28 to 30), and the crosslinking agent B-2 was a polymer.
  • the peeling property was expressed (Examples 33 to 38).
  • Example 8 of Table 5 when the polymer / crosslinking agent mixture ratio was 90/10, no dissociation property was observed.
  • Example 28 of Table 6 of Table 6 which was about the same mixing ratio (85/10) using an acid catalyst, Peelability was expressed. Therefore, it can be said that the peeling property easily appears when the acid catalyst is added.

Abstract

The present invention relates to a film touch sensor and a structural body for a film touch sensor for which a process is proceeded by forming a separation layer formed of a certain ingredient on a carrier substrate and in which an insulation layer used as a planarization layer, an adhesive layer, or a base layer is formed on a transparent conductive film pattern.

Description

필름 터치 센서 및 필름 터치 센서용 구조체Film touch sensor and structure for film touch sensor
본 발명은 필름 터치 센서 및 필름 터치 센서용 구조체에 관한 것이다.The present invention relates to a film touch sensor and a structure for a film touch sensor.
터치입력방식이 차세대 입력방식으로 각광받으면서 좀 더 다양한 전자기기에 터치입력방식을 도입하려는 시도들이 이루어지고 있으며, 따라서 다양한 환경에 적용할 수 있고 정확한 터치인식이 가능한 터치 센서에 대한 연구개발도 활발히 이루어지고 있다.As the touch input method has been spotlighted as the next generation input method, attempts have been made to introduce touch input methods to a wider variety of electronic devices. Therefore, research and development on touch sensors that can be applied to various environments and enable accurate touch recognition have been actively made. ought.
예를 들어, 터치 방식의 디스플레이를 갖는 전자기기의 경우 초경량, 저전력을 달성하고 휴대성이 향상된 초박막의 유연성 디스플레이가 차세대 디스플레이로 주목을 받으면서 이러한 디스플레이에 적용 가능한 터치 센서의 개발이 요구되어 왔다.For example, in the case of an electronic device having a touch type display, an ultra-thin flexible display that achieves ultra-light weight, low power, and improved portability has attracted attention as a next-generation display, and development of a touch sensor applicable to such a display has been required.
유연성 디스플레이란 특성의 손실 없이 휘거나 구부리거나 말 수 있는 유연한 기판상에 제작된 디스플레이를 의미하며, 유연성 LCD, 유연성 OLED 및 전자종이와 같은 형태로 기술개발이 진행 중에 있다.A flexible display means a display manufactured on a flexible substrate that can bend, bend, or roll without loss of properties, and technologies are being developed in the form of flexible LCDs, flexible OLEDs, and electronic paper.
이러한 유연성 디스플레이에 터치입력방식을 적용하기 위해서는 휘어짐 및 복원력이 우수하고, 유연성 및 신축성이 뛰어난 터치 센서가 요구된다.In order to apply a touch input method to such a flexible display, a touch sensor having excellent bending and resilience and excellent flexibility and elasticity is required.
이와 같은 유연성 디스플레이의 제조를 위한 필름 터치 센서에 있어서 투명 수지 기재 중에 매설된 배선을 포함하는 배선 기판이 제시되고 있다.In the film touch sensor for manufacturing such a flexible display, the wiring board which contains the wiring embedded in the transparent resin base material is proposed.
기판 상에 금속배선을 형성하는 배선형성공정과, 상기 금속배선을 덮도록 투명 수지 용액을 도포 건조하여 투명 수지 기재를 형성하는 적층공정 및 상기 기판으로부터 투명 수지 기재를 박리시키는 박리공정을 포함하는 것이다.A wiring forming step of forming a metal wiring on the substrate, a lamination step of forming a transparent resin substrate by coating and drying a transparent resin solution to cover the metal wiring, and a peeling step of peeling the transparent resin substrate from the substrate. .
이와 같은 제조 방법에서는 박리공정을 원활하게 수행하기 위하여, 실리콘 수지나 불소수지와 같은 유기 박리제, 다이아몬드 라이크 카본(Diamond Like Carbon, DLC) 박막, 산화 지르코늄 박막 등의 무기 박리재를 기판의 표면에 미리 형성시키는 방법을 사용한다.In such a manufacturing method, in order to perform the peeling process smoothly, an inorganic releasing material such as an organic releasing agent such as a silicone resin or a fluororesin, a diamond like carbon thin film (DLC) thin film or a zirconium oxide thin film is preliminarily formed on the surface of the substrate. Forming method is used.
그러나 무기 박리제를 이용하는 경우, 기판으로부터 기재 및 금속 배선을 박리시킬 때, 배선 및 기재의 박리가 원활하게 진행되지 않아 기판 표면에 금속 배선 및 기재의 일부가 잔류하는 문제가 있으며, 박리제로 사용된 유기 물질이 배선 및 기재의 표면에 묻어 나오는 문제가 있다.However, in the case of using the inorganic release agent, when the substrate and the metal wiring are peeled off from the substrate, there is a problem that the peeling of the wiring and the substrate does not proceed smoothly and some of the metal wiring and the substrate remain on the surface of the substrate. There is a problem that the material adheres to the surface of the wiring and the substrate.
즉, 박리제를 이용하더라도 배선기판의 금속배선을 기판으로부터 완벽하게 박리시킬 수 없는 문제가 있다.In other words, even if a release agent is used, there is a problem that the metal wiring of the wiring board cannot be completely peeled from the board.
이러한 문제를 해결하기 위하여 대한민국 등록특허 제10-1191865호에서 제시되고 있는 방법은, 금속배선이 매립된 형태의 유연기판을 제조하는 단계에서 빛이나 용매에 의해 제거될 수 있는 희생층, 금속배선 및 고분자 물질(유연기판)을 기판상에 형성시킨 후, 빛이나 용매를 이용하여 희생층을 제거함으로써 금속 배선 및 고분자 물질(유연기판)을 기판으로부터 박리시킨다.In order to solve this problem, the method proposed in Korean Patent No. 10-1191865 includes a sacrificial layer, a metal wiring, and a metal layer, which may be removed by light or a solvent in the manufacturing of a flexible substrate having a metal wiring embedded therein. After the polymer material (flexible substrate) is formed on the substrate, the metal wiring and the polymer material (flexible substrate) are peeled off from the substrate by removing the sacrificial layer using light or a solvent.
하지만, 이와 같은 방법은 대형 사이즈에서의 희생층 제거 공정이 어렵고, 고온공정이 불가능하여 다양한 필름기재를 사용할 수 없는 문제가 있다.However, this method is difficult to remove the sacrificial layer in a large size, there is a problem that can not use a variety of film substrates because the high temperature process is impossible.
본 발명은 캐리어 기판 상에 박리성이 우수하며, 전극손상 및 크랙 발생을 방지하는 특정성분으로 형성되는 분리층을 형성하여 공정을 진행하고, 캐리어 기판과 분리되면 분리층이 배선 피복층으로 사용되도록 하는 필름 터치 센서 및 필름 터치 센서용 구조체를 제공하는데 그 목적이 있다.The present invention is excellent in peelability on the carrier substrate, and proceeds the process by forming a separation layer formed of a specific component that prevents electrode damage and crack generation, when separated from the carrier substrate to be used as a wiring coating layer It is an object to provide a film touch sensor and a structure for a film touch sensor.
본 발명은 캐리어 기판 상에서 터치 센서를 구현하므로 필름 기재 상에서 직접 터치 센서를 구현하는 공정에서는 불가능한 고정세(fine pitch), 내열성을 확보하고, 필름 기재를 다변화할 수 있도록 한 필름 터치 센서 및 필름 터치 센서용 구조체를 제공하는데 그 목적이 있다.Since the present invention implements a touch sensor on a carrier substrate, a film touch sensor and a film touch sensor that can secure a fine pitch and heat resistance, which are impossible in a process of implementing a touch sensor directly on a film substrate, and can diversify the film substrate. Its purpose is to provide a structure.
본 발명은 캐리어 기판 상에 박리력과 두께가 제어된 특정 성분의 분리층을 형성하여 공정을 진행하고, 캐리어 기판과의 분리 이후에도 분리층을 제거하지 않아 별도의 분리층 제거 공정이 없는 필름 터치 센서 및 필름 터치 센서용 구조체를 제공하는데 그 목적이 있다.The present invention proceeds by forming a separation layer of a specific component with controlled peel force and thickness on the carrier substrate, and does not remove the separation layer even after separation from the carrier substrate, there is no separate layer removal process And to provide a structure for a film touch sensor.
본 발명은 이(easy)박리성을 가지며, 150℃까지의 가열에 견딜 수 있고, 바람직하게는 230℃의 가열에도 견딜 수 있으며, 나아가서는 포토레지스트 용액에 이용되는 용제에 내성을 가지며, 알칼리성 현상액에도 견딜 수 있는 분리층을 포함하는 필름 터치 센서 및 필름 터치 센서용 구조체를 제공하는데 그 목적이 있다.The present invention has easy peelability, can withstand heating up to 150 ° C, preferably can withstand heating up to 230 ° C, and is also resistant to solvents used in photoresist solutions, and is an alkaline developer It is an object of the present invention to provide a film touch sensor and a structure for a film touch sensor including a separation layer that can withstand.
1. 분리층; 상기 분리층 상에 형성되되, 센싱 전극 및 상기 센싱 전극의 일단에 형성되는 패드 전극을 포함하는 전극 패턴층; 및 상기 전극 패턴층 상부에 형성되며 상기 전극 패턴층의 일부 또는 전부를 덮도록 형성되는 절연층;을 포함하며, 상기 분리층은, 알코올성 제2급 또는 제3급 OH기 또는 페놀성 OH기 함유기를 가진 측쇄를 구비한 쇄상 폴리머 및 가교제를 포함하고, 상기 쇄상 폴리머는 하기 화학식 1로 표시되는 모노머 및 하기 화학식 2로 표시되는 모노머 중에서 선택되는 적어도 하나의 모노머로부터 유래된 단위를 포함하는 것인 경화성 수지 조성물로 형성되며, 상기 가교제는, 트리아진계 화합물, 그 축합체 및 이들의 혼합물; 글리콜우릴계 화합물, 그 축합체 및 이들의 혼합물; 및 이미다졸리디논계 화합물, 그 축합체 및 이들의 혼합물로 이루어진 군에서 선택되는 것인, 필름 터치 센서:1. Separation layer; An electrode pattern layer formed on the separation layer, the electrode pattern layer including a sensing electrode and a pad electrode formed at one end of the sensing electrode; And an insulating layer formed on the electrode pattern layer and covering part or all of the electrode pattern layer, wherein the separation layer contains an alcoholic secondary or tertiary OH group or a phenolic OH group. A chain polymer having a side chain having a group and a crosslinking agent, wherein the chain polymer includes a unit derived from at least one monomer selected from a monomer represented by Formula 1 and a monomer represented by Formula 2 below It is formed of a resin composition, The crosslinking agent is a triazine compound, its condensate and mixtures thereof; Glycoluril compounds, their condensates, and mixtures thereof; And an imidazolidinone-based compound, a condensate thereof, and a mixture thereof.
[화학식 1][Formula 1]
Figure PCTKR2019001826-appb-I000001
Figure PCTKR2019001826-appb-I000001
(화학식 1 중, R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고, (Formula 1, R 1a is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl group and substituted or unsubstituted alkenyl group,
L1은 단일결합, 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고,L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
L2는 O 또는 NH이고,L 2 is O or NH,
R2a, R3a 및 R4a는 서로 독립적으로 수소, 및 치환 또는 비치환 탄화수소기로 이루어진 군에서 선택되고, R 2a , R 3a and R 4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon group,
단 R2a, R3a 및 R4a 중 적어도 1개는 치환 또는 비치환의 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기거나,Provided that at least one of R 2a , R 3a and R 4a is a substituted or unsubstituted alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group,
혹은 R2a, R3a 및 R4a 중 적어도 2개가 하나가 되어, 알코올성 제2급 또는 제3급 OH 또는 페놀성 OH를 포함하는, 치환 또는 비치환 시클로알킬기, 치환 또는 비치환 시클로알케닐기, 치환 또는 비치환 방향족기, 치환 또는 비치환 헤테로 방향족기, 및 이들을 포함하는 다환임)Or a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, substituted with at least two of R 2a , R 3a and R 4a and containing an alcoholic secondary or tertiary OH or phenolic OH Or an unsubstituted aromatic group, a substituted or unsubstituted hetero aromatic group, and a polycyclic including them)
[화학식 2][Formula 2]
Figure PCTKR2019001826-appb-I000002
Figure PCTKR2019001826-appb-I000002
(화학식 2 중, R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고,(Formula 2, R 1a is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl group and substituted or unsubstituted alkenyl group,
L1은 단일결합, 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고,L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
R5a 내지 R14a는 서로 독립적으로 수소, 히드록시기 및 하기 화학식 3으로 표시되는 작용기로 이루어진 군 중에서 선택되거나, 또는 하나가 되어 환을 형성하되, 단 R5a 내지 R14a 또는 상기 환의 치환기 중 적어도 하나는 히드록시기임)R 5a to R 14a are each independently selected from the group consisting of hydrogen, a hydroxy group, and a functional group represented by the following formula (3), or one to form a ring, provided that at least one of R 5a to R 14a or a substituent of the ring is Hydroxy group)
[화학식 3][Formula 3]
Figure PCTKR2019001826-appb-I000003
Figure PCTKR2019001826-appb-I000003
(화학식 3 중, R15a는 치환 또는 비치환 알킬기, 치환 또는 비치환 알케닐기, 치환 또는 비치환 시클로알킬기, 치환 또는 비치환 시클로알케닐기, 치환 또는 비치환 방향족기, 및 치환 또는 비치환 헤테로 방향족기로 이루어진 군에서 선택됨)In Formula 3, R 15a is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic. Selected from the group consisting of flags)
2. 위 1에 있어서, 상기 L1은 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되는, 필름 터치 센서.2. In the above 1, wherein L 1 is selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group, the film touch sensor.
3. 위 1에 있어서, 상기 L1은 치환 또는 비치환 알킬렌기인, 필름 터치 센서.3. In the above 1, wherein L 1 is a substituted or unsubstituted alkylene group, the touch sensor film.
4. 위 1에 있어서, 상기 L1은 메틸렌기인, 필름 터치 센서.4. In the above 1, wherein L 1 is a methylene group, the film touch sensor.
5. 위 1에 있어서, 상기 쇄상 폴리머는 하기 화학식 6으로 표시되는 모노머 단위를 포함하는, 필름 터치 센서:5. In the above 1, wherein the chain polymer comprises a monomer unit represented by the following formula (6), film touch sensor:
[화학식 6][Formula 6]
Figure PCTKR2019001826-appb-I000004
Figure PCTKR2019001826-appb-I000004
(화학식 6 중,(In formula 6,
R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고,R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
L1은 단일결합, 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고,L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
R19a는 치환 또는 비치환 시클로알킬기, 치환 또는 비치환 시클로알케닐기, 치환 또는 비치환 방향족기, 및 치환 또는 비치환 헤테로 방향족기로 이루어진 군에서 선택됨)R 19a is selected from the group consisting of a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group)
6. 위 5에 있어서, 상기 L1은 치환 또는 비치환 알킬렌기인, 필름 터치 센서.6. In the above 5, wherein L 1 is a substituted or unsubstituted alkylene group, the touch sensor film.
7. 위 5에 있어서, 상기 L1은 메틸렌기인, 필름 터치 센서.7. In the above 5, wherein L 1 is a methylene group, the film touch sensor.
8. 위 5에 있어서, 상기 R19a는 페닐기인, 필름 터치 센서.8. In the above 5, wherein R 19a is a phenyl group, the film touch sensor.
9. 위 1에 있어서, 상기 가교제는 트리아진계 화합물, 트리아진계 화합물의 축합체 및 이들의 혼합물로 이루어진 군에서 선택되는, 필름 터치 센서.9. In the above 1, wherein the cross-linking agent is selected from the group consisting of triazine-based compound, triazine-based compound condensate, and mixtures thereof, film touch sensor.
10. 위 1에 있어서, 상기 가교제는 하기 화학식 B-1으로 표시되는 화합물인, 필름 터치 센서:10. In the above 1, wherein the crosslinking agent is a compound represented by the following formula B-1, film touch sensor:
[화학식 B-1][Formula B-1]
Figure PCTKR2019001826-appb-I000005
Figure PCTKR2019001826-appb-I000005
11. 위 1에 있어서, 상기 L1은 단일 결합인, 필름 터치 센서.11. The film touch sensor according to the above 1, wherein L 1 is a single bond.
12. 위 1에 있어서, 상기 R5a 내지 R14a 중 어느 2개 이상이 히드록시기이고, 나머지는 수소인, 필름 터치 센서.12. In the above 1, wherein any two or more of the R 5a to R 14a is a hydroxy group, the remainder is hydrogen, the film touch sensor.
13. 위 1에 있어서, 상기 R5a 내지 R14a 중 어느 하나가 히드록시기이고, 나머지는 수소인, 필름 터치 센서.13. In the above 1, wherein any one of the R 5a to R 14a is a hydroxyl group, the rest is hydrogen, the film touch sensor.
14. 위 1에 있어서, 상기 R5a 내지 R13a는 수소이고, R14a는 히드록시기인, 필름 터치 센서. 14. In the above 1, wherein R 5a to R 13a is hydrogen, R 14a is a hydroxy group, the film touch sensor.
15. 위 1에 있어서, 상기 가교제는 글리코우릴계 화합물, 글리코우릴계 화합물의 축합체 및 이들의 혼합물로 이루어진 군에서 선택되는, 필름 터치 센서.15. The method according to the above 1, wherein the crosslinking agent is selected from the group consisting of glycouril-based compounds, glycouril-based compounds, and mixtures thereof, the film touch sensor.
16. 위 1에 있어서, 상기 가교제는 하기 화학식 B-2로 표시되는 화합물인, 필름 터치 센서:16. In the above 1, wherein the crosslinking agent is a compound represented by the following formula B-2, the film touch sensor:
[화학식 B-2][Formula B-2]
Figure PCTKR2019001826-appb-I000006
Figure PCTKR2019001826-appb-I000006
17. 위 1에 있어서, 상기 가교제는 하기 화학식 B-3으로 표시되는 화합물인, 필름 터치 센서:17. In the above 1, wherein the cross-linking agent is a compound represented by the following formula B-3, film touch sensor:
[화학식 B-3][Formula B-3]
Figure PCTKR2019001826-appb-I000007
Figure PCTKR2019001826-appb-I000007
18. 위 1에 있어서, 상기 경화성 수지 조성물은 용액으로 제공되는, 필름 터치 센서. 18. In the above 1, wherein the curable resin composition is provided as a solution, the film touch sensor.
19. 위 18에 있어서, 상기 용액의 용매는 알코올을 포함하는, 필름 터치 센서.19. The touch sensor of claim 18, wherein the solvent of the solution comprises an alcohol.
20. 위 19에 있어서, 상기 알코올은 1급 알코올을 포함하는, 필름 터치 센서.20. The method according to the above 19, wherein the alcohol comprises a primary alcohol, film touch sensor.
21. 위 19에 있어서, 상기 알코올은 에탄올을 포함하는, 필름 터치 센서.21. The film touch sensor according to the above 19, wherein the alcohol comprises ethanol.
22. 위 19에 있어서, 상기 알코올의 함량은 상기 용매 중량 중 10 중량% 이상으로 존재하는, 필름 터치 센서.22. The method according to the above 19, wherein the alcohol content is present in more than 10% by weight of the solvent weight, the film touch sensor.
23. 위 1에 있어서, 상기 가교제는, 완전 또는 부분 알콕시메틸화 멜라민, 그 축합체 및 이들의 혼합물; 완전 또는 부분 알콕시메틸화 구아나민, 그 축합체 및 이들의 혼합물; 완전 또는 부분 알콕시메틸화 아세토구아나민, 그 축합체 및 이들의 혼합물; 완전 또는 부분 알콕시메틸화 벤조구아나민, 그 축합체 및 이들의 혼합물; 완전 또는 부분 알콕시메틸화 글리콜우릴, 그 축합체 및 이들의 혼합물; 및 완전 또는 부분 알콕시메틸화 이미다졸리디논, 그 축합체 및 이들의 혼합물;로 이루어진 군에서 선택된 것을 포함하는, 필름 터치 센서.23. The method according to the above 1, wherein the crosslinking agent, a full or partial alkoxymethylated melamine, its condensate and mixtures thereof; Fully or partially alkoxymethylated guanamines, their condensates and mixtures thereof; Fully or partially alkoxymethylated acetoguanamine, its condensates and mixtures thereof; Fully or partially alkoxymethylated benzoguanamine, condensates thereof and mixtures thereof; Fully or partially alkoxymethylated glycolurils, their condensates and mixtures thereof; And fully or partially alkoxymethylated imidazolidinone, condensates thereof, and mixtures thereof.
24. 위 1에 있어서, 상기 가교제는 하기 화학식 7, 9 및 10으로 표시되는 화합물 및 이들의 각 축합체로 이루어진 군에서 선택된 것을 포함하는, 필름 터치 센서:24. The method according to 1 above, wherein the crosslinking agent includes a compound selected from the group consisting of compounds represented by the following Chemical Formulas 7, 9 and 10 and their respective condensates, the film touch sensor:
[화학식 7][Formula 7]
Figure PCTKR2019001826-appb-I000008
Figure PCTKR2019001826-appb-I000008
(화학식 7 중, R1b는 탄소수 1 내지 25의 치환 또는 비치환 알킬기, 탄소수 2 내지 25의 치환 또는 비치환 알케닐기, 탄소수 6 내지 25의 치환 또는 비치환 방향족기, 탄소수 4 내지 25의 치환 또는 비치환 헤테로 방향족기, 및 하기 화학식 8로 표시되는 2치환 아민으로 이루어진 군에서 선택되고, In Formula 7, R 1b is a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 25 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 25 carbon atoms, substituted with 4 to 25 carbon atoms, or It is selected from the group consisting of an unsubstituted hetero aromatic group, and a disubstituted amine represented by the formula (8),
R2b, R3b, R4b 및 R5b 는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기, 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택됨)R 2b , R 3b , R 4b and R 5b are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms)
[화학식 8][Formula 8]
Figure PCTKR2019001826-appb-I000009
Figure PCTKR2019001826-appb-I000009
(화학식 8 중, R6b 및 R7b 는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기, 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택됨)(In Formula 8, R 6b and R 7b are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.)
[화학식 9][Formula 9]
Figure PCTKR2019001826-appb-I000010
Figure PCTKR2019001826-appb-I000010
(화학식 9 중, R8b, R9b, R10b 및 R11b는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기, 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택됨)(In Formula 9, R 8b , R 9b , R 10b and R 11b are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.)
[화학식 10][Formula 10]
Figure PCTKR2019001826-appb-I000011
Figure PCTKR2019001826-appb-I000011
(화학식 10 중, R12b 및 R13b는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기, 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고,In Formula 10, R 12b and R 13b are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms,
R14b 및 R15b는 서로 독립적으로 수소, 탄소수 1 내지 10의 치환 또는 비치환 알킬기, 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택됨)R 14b and R 15b are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms)
25. 위 24에 있어서, 상기 가교제 중 축합체는 상기 화학식 7, 화학식 9 또는 화학식 10으로 표시되는 화합물의 중합체를 포함하는, 필름 터치 센서.25. The method according to the above 24, wherein the condensate in the crosslinking agent comprises a polymer of the compound represented by Formula 7, Formula 9 or Formula 10, film touch sensor.
26. 위 24에 있어서, 상기 가교제 중 축합체는 상기 화학식 7, 화학식 9 또는 화학식 10로 표시되는 화합물의 2량체, 3량체 및 4차 이상의 고차 중합체 중 적어도 1개를 포함하는, 필름 터치 센서.26. The method according to the above 24, wherein the condensate in the crosslinking agent comprises at least one of a dimer, a trimer and a quaternary or higher polymer of the compound represented by Formula 7, Formula 9 or Formula 10, film touch sensor.
27. 위 24에 있어서, 상기 가교제는 상기 화학식 7, 화학식 9 또는 화학식 10으로 표시되는 화합물에 대해 1.3 내지 1.8의 중량평균 중합도를 각각 가지는 것인, 필름 터치 센서.27. In the above 24, wherein the crosslinking agent will have a weight average polymerization degree of 1.3 to 1.8 for the compound represented by the formula 7, Formula 9 or Formula 10, respectively, the film touch sensor.
28. 위 24에 있어서, 28. The above 24,
R1b는 탄소수 6 내지 25의 치환 또는 비치환 방향족기, 하기 화학식 11로 표시되는 2치환 아민으로 이루어진 군에서 선택되고,R 1b is selected from the group consisting of a substituted or unsubstituted aromatic group having 6 to 25 carbon atoms, a disubstituted amine represented by the following formula (11),
R2b 내지 R13b 는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬이고,R 2b to R 13b are each independently a substituted or unsubstituted alkyl having 1 to 10 carbon atoms,
R14b 및 R15b는 서로 독립적으로 수소인, 터치 필름 센서:Touch film sensors wherein R 14b and R 15b are independently of each other hydrogen:
[화학식 11][Formula 11]
Figure PCTKR2019001826-appb-I000012
Figure PCTKR2019001826-appb-I000012
29. 위 1에 있어서, 상기 쇄상 폴리머와 상기 가교제의 질량비는 1: 0.05 내지 1:2인, 필름 터치 센서.29. The method according to the above 1, wherein the mass ratio of the chain polymer and the crosslinking agent is 1: 0.05 to 1: 2, the film touch sensor.
30. 위 1에 있어서, 상기 경화성 수지 조성물은 산 촉매를 더 포함하는, 필름 터치 센서.30. In the above 1, wherein the curable resin composition further comprises an acid catalyst, film touch sensor.
31. 위 30에 있어서, 상기 산 촉매는 브뢴스테드산, 루이스산 및 이들의 혼합물, 이들의 염 및 이들의 용매화물로 이루어진 군에서 선택되는, 필름 터치 센서.31. The film touch sensor according to the above 30, wherein the acid catalyst is selected from the group consisting of Bronsted acid, Lewis acid and mixtures thereof, salts thereof and solvates thereof.
32. 위 1에 있어서, 상기 경화성 수지 조성물은 계면 활성제, 필러, 첨가제 및 발포제로 이루어진 군에서 선택된 적어도 하나를 더 포함하는, 필름 터치 센서.32. The method of 1 above, wherein the curable resin composition further comprises at least one selected from the group consisting of surfactants, fillers, additives and blowing agents, film touch sensor.
33. 위 1에 있어서, 상기 경화성 수지 조성물은 계면 활성제를 더 포함하는, 필름 터치 센서.33. The method of 1 above, wherein the curable resin composition further comprises a surfactant, film touch sensor.
34. 위 1에 있어서, 상기 경화성 수지 조성물은 발포제를 더 포함하는, 필름 터치 센서.34. The method of 1 above, wherein the curable resin composition further comprises a foaming agent, the film touch sensor.
35. 위 1에 있어서, 상기 경화성 수지 조성물은 150℃에서 1분의 가열에 의해 경화되는 경화성을 가지는, 필름 터치 센서.35. In the above 1, wherein the curable resin composition has a curability that is cured by heating for 1 minute at 150 ℃, film touch sensor.
36. 위 1에 있어서, 분리층은 400nm에서 99%의 이상의 투과율(%T) 및 0.1 이하의 b*을 가지는, 필름 터치 센서.36. The touch sensor of 1 above, wherein the separation layer has a transmittance (% T) of 99% or more at 400 nm and a b * of 0.1 or less.
37. 위 1에 있어서, 상기 분리층은 230℃ 내지 300℃의 내열성을 가지는, 필름 터치 센서.37. In the above 1, wherein the separation layer has a heat resistance of 230 ℃ to 300 ℃, film touch sensor.
38. 위 1에 있어서, 상기 분리층은 230℃ 내지 260℃의 1 내지 2시간, 내열성을 가지는, 필름 터치 센서.38. The above 1, wherein the separation layer has a heat resistance of 1 to 2 hours, 230 ℃ to 260 ℃, film touch sensor.
39. 위 1에 있어서, 상기 분리층은 230℃에서 8시간 이상, 내열성을 가지는, 필름 터치 센서.39. The method of 1 above, wherein the separation layer has a heat resistance of 8 hours or more at 230 ℃, film touch sensor.
40. 위 1에 있어서, 상기 분리층은 230℃에서 1 내지 2시간, 내열성을 가지는, 필름 터치 센서.40. The method of 1 above, wherein the separation layer has a heat resistance of 1 to 2 hours at 230 ℃, film touch sensor.
41. 위 1에 있어서, 상기 분리층은 소다 유리제 기판 또는 무알칼리 유리제 기판에서 0.5N/mm2 이하의 박리력을 가지는, 필름 터치 센서.41. The touch sensor of 1 above, wherein the separation layer has a peel force of 0.5 N / mm 2 or less on a soda glass substrate or an alkali free glass substrate.
42. 위 1에 있어서, 상기 분리층은 소다 유리제 기판 또는 무알칼리 유리제 기판에서 0.1N/mm2 이하의 박리력을 가지는, 필름 터치 센서.42. The touch sensor of 1 above, wherein the separation layer has a peel force of 0.1 N / mm 2 or less on a soda glass substrate or an alkali free glass substrate.
43. 위 1에 있어서, 상기 필름 터치 센서는 상기 분리층과 상기 전극 패턴층 사이에 형성되는 보호층을 더 포함하는, 필름 터치 센서.43. The method of 1 above, wherein the film touch sensor further comprises a protective layer formed between the separation layer and the electrode pattern layer, the film touch sensor.
44. 위 1에 있어서, 상기 절연층의 상부에 배치되는 광학필름을 더 포함하는, 필름 터치 센서.44. The touch sensor according to the above 1, further comprising an optical film disposed on the insulating layer.
45. 위 1에 있어서, 상기 전극 패턴층은 금속, 금속나노와이어, 금속산화물, 탄소나노튜브, 그래 핀, 전도성 고분자 및 도전성 잉크로 이루어진 군에서 선택된 적어도 하나로 형성된, 필름 터치 센서.45. The method of 1 above, wherein the electrode pattern layer is formed of at least one selected from the group consisting of metal, metal nanowires, metal oxides, carbon nanotubes, graphene, conductive polymers and conductive inks, film touch sensor.
46. 위 1에 있어서, 상기 분리층의 상기 전극 패턴층이 형성되는 반대 면에 점착제 또는 접착제를 매개로 형성되는 기능성 필름층을 더 포함하는, 필름 터치 센서.46. The method according to the above 1, further comprising a functional film layer formed via a pressure-sensitive adhesive or an adhesive on the opposite side on which the electrode pattern layer of the separation layer is formed.
47. 위 46에 있어서, 상기 기능성 필름층은 투명 필름, 위상차 필름, 등방성 필름, 보호 필름, 편광판, 편광자, 배리어 필름으로 이루어진 군에서 선택된 적어도 하나의 기능성 필름인, 필름 터치 센서.47. The touch sensor of claim 46, wherein the functional film layer is at least one functional film selected from the group consisting of a transparent film, a retardation film, an isotropic film, a protective film, a polarizer, a polarizer, and a barrier film.
48. 위 46에 있어서, 상기 기능성 필름층은 기재 필름 상에 기능성 코팅층이 형성된 필름이고, 상기 기능성 코팅층은 코팅형 유기막층, 코팅형 위상차층, 코팅형 편광자층 또는 코팅형 배향막층을 포함하는, 필름 터치 센서.48. The method according to the above 46, wherein the functional film layer is a film having a functional coating layer formed on the base film, the functional coating layer comprises a coating organic film layer, a coating retardation layer, a coating polarizer layer or a coating alignment film layer, Film touch sensor.
49. (i) 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 갖는 측쇄를 포함하는 쇄상 폴리머와 가교제를 준비하는 단계; (ii) 상기 쇄상 폴리머와 상기 가교제를 포함하는 경화성 수지 조성물을 기판 상에 도포하여 경화성 수지 조성물 도막을 형성하는 단계; 및 (iii) 상기 경화성 수지 조성물 도막에서 중합 반응을 시켜 경화시킴으로써 분리층을 형성하는 단계;를 포함하는, 필름 터치 센서의 제조방법.49. (i) preparing a chain polymer comprising a side chain having an alcoholic secondary or tertiary OH containing group or a phenolic OH containing group and a crosslinking agent; (ii) applying a curable resin composition comprising the chain polymer and the crosslinking agent onto a substrate to form a curable resin composition coating film; And (iii) forming a separation layer by performing a polymerization reaction on the curable resin composition coating film to cure the film.
50. 위 49에 있어서, 상기 제조방법은 (iv) 상기 기판 상에 형성되어 있는 상기 분리층을 상기 기판에서 박리하는 단계를 더 포함하는 필름 터치 센서의 제조방법.50. The method of claim 49, wherein the manufacturing method further comprises the step of (iv) peeling the separation layer formed on the substrate from the substrate.
51. 위 49에 있어서, 상기 쇄상 폴리머를 구성하는 모노머 단위에서 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 포함하는 모노머 단위가 차지하는 비율은 30 내지 100몰%인, 필름 터치 센서의 제조방법.51. The film touch according to 49 above, wherein the ratio of monomer units including alcoholic secondary or tertiary OH-containing groups or phenolic OH-containing groups in the monomer units constituting the chain polymer is 30 to 100 mol%. Method of manufacturing the sensor.
52. 위 49에 있어서, 상기 가교제는 완전 또는 부분 알콕시메틸화 멜라민, 완전 또는 부분 알콕시메틸화 구아나민, 완전 또는 부분 알콕시메틸화 아세토구아나민, 또는 완전 또는 부분 알콕시메틸화 벤조구아나민, 및 완전 또는 부분 알콕시메틸화 글리콜우릴로 이루어진 군에서 선택되는 것인, 필름 터치 센서의 제조방법.52. The method of 49 above, wherein the crosslinking agent is fully or partially alkoxymethylated melamine, fully or partially alkoxymethylated guanamine, fully or partially alkoxymethylated acetoguanamine, or fully or partially alkoxymethylated benzoguanamine, and fully or partially alkoxymethylated Will be selected from the group consisting of glycoluril, the method of manufacturing a touch sensor film.
53. 위 49에 있어서, 상기 쇄상 폴리머와 상기 가교제의 질량비는 1: 0.05 내지 1:2인, 필름 터치 센서 제조방법.53. The method of claim 49, wherein the mass ratio of the chain polymer and the crosslinking agent is 1: 0.05 to 1: 2, the film touch sensor manufacturing method.
54. 캐리어 기판; 상기 캐리어 기판 상에 형성되는 분리층; 상기 분리층 상에 형성되되, 센싱 전극 및 상기 센싱 전극의 일단에 형성되는 패드 전극을 포함하는 전극 패턴층; 상기 전극 패턴층 상부에 형성되며 상기 전극 패턴층의 일부 또는 전부를 덮도록 형성되는 절연층;을 포함하며, 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 측쇄를 구비한 쇄상 폴리머 및 가교제를 포함하고, 상기 쇄상 폴리머는 하기 화학식 1로 표시되는 모노머 및 하기 화학식 2로 표시되는 모노머 중에서 선택되는 적어도 하나의 모노머로부터 유래된 단위를 포함하는 것인 경화성 수지 조성물로 형성되며, 상기 가교제는, 트리아진계 화합물, 그 축합체 및 이들의 혼합물; 글리콜우릴계 화합물, 그 축합체 및 이들의 혼합물; 및 이미다졸리디논계 화합물, 그 축합체 및 이들의 혼합물로 이루어진 군에서 선택되는 것인, 필름 터치 센서용 구조체:54. carrier substrate; A separation layer formed on the carrier substrate; An electrode pattern layer formed on the separation layer, the electrode pattern layer including a sensing electrode and a pad electrode formed at one end of the sensing electrode; An insulating layer formed on the electrode pattern layer and covering a part or the entirety of the electrode pattern layer; and including a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group. A chain polymer and a crosslinking agent, wherein the chain polymer is formed of a curable resin composition comprising a unit derived from at least one monomer selected from a monomer represented by Formula 1 and a monomer represented by Formula 2 below, The crosslinking agent may include a triazine compound, a condensate thereof, and a mixture thereof; Glycoluril compounds, their condensates, and mixtures thereof; And an imidazolidinone-based compound, a condensate thereof, and a mixture thereof.
[화학식 A][Formula A]
Figure PCTKR2019001826-appb-I000013
Figure PCTKR2019001826-appb-I000013
(화학식 A 중, R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고,In Formula A, R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group,
L1은 단일결합, 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고,L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
L2는 O 또는 NH이고,L 2 is O or NH,
R2a, R3a 및 R4a는 서로 독립적으로 수소, 및 치환 또는 비치환 탄화수소기로 이루어진 군에서 선택되고, R 2a , R 3a and R 4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon group,
단 R2a, R3a 및 R4a 중 적어도 1개는 치환 또는 비치환의 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기거나,Provided that at least one of R 2a , R 3a and R 4a is a substituted or unsubstituted alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group,
혹은 R2a, R3a 및 R4a 중 적어도 2개가 하나가 되어, 알코올성 제2급 또는 제3급 OH 또는 페놀성 OH를 포함하는, 치환 또는 비치환 시클로알킬기, 치환 또는 비치환 시클로알케닐기, 치환 또는 비치환 방향족기, 치환 또는 비치환 헤테로 방향족기, 및 이들을 포함하는 다환임)Or a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, substituted with at least two of R 2a , R 3a and R 4a and containing an alcoholic secondary or tertiary OH or phenolic OH Or an unsubstituted aromatic group, a substituted or unsubstituted hetero aromatic group, and a polycyclic including them)
[화학식 B][Formula B]
Figure PCTKR2019001826-appb-I000014
Figure PCTKR2019001826-appb-I000014
(화학식 11 중, R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고,In Formula 11, R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group,
L1은 단일결합, 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고,L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
R5a 내지 R14a는 서로 독립적으로 수소, 히드록시기 및 하기 화학식 C로 표시되는 작용기로 이루어진 군 중에서 선택되거나, 또는 하나가 되어 환을 형성하되, 단 R5a 내지 R14a 또는 상기 환의 치환기 중 적어도 하나는 히드록시기임)R 5a to R 14a are each independently selected from the group consisting of hydrogen, a hydroxy group, and a functional group represented by the following general formula (C), or one to form a ring, provided that at least one of R 5a to R 14a or a substituent of the ring is Hydroxy group)
[화학식 C][Formula C]
Figure PCTKR2019001826-appb-I000015
Figure PCTKR2019001826-appb-I000015
(화학식 C 중, R15a는 치환 또는 비치환 알킬기, 치환 또는 비치환 알케닐기, 치환 또는 비치환 시클로알킬기, 치환 또는 비치환 시클로알케닐기, 치환 또는 비치환 방향족기, 및 치환 또는 비치환 헤테로 방향족기로 이루어진 군에서 선택됨)In Formula C, R 15a is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic Selected from the group consisting of flags)
55. 위 54에 있어서, 상기 필름 터치 센서용 구조체는 상기 분리층과 상기 전극 패턴층 사이에 형성되는 보호층을 더 포함하는, 필름 터치 센서용 구조체.55. The structure of claim 54, wherein the film touch sensor structure further comprises a protective layer formed between the separation layer and the electrode pattern layer.
본 발명은 투명 전도막 패턴 상에 평탄화층 또는 접착층 또는 기재층으로 사용되는 절연층을 형성하여 터치 센서 제조 공정의 효율성을 높일 수 있다.The present invention can increase the efficiency of the touch sensor manufacturing process by forming an insulating layer used as a planarization layer, an adhesive layer or a substrate layer on the transparent conductive film pattern.
본 발명은 캐리어 기판 상에 박리성이 우수하며, 전극손상 및 크랙 발생을 방지하는 특정성분의 분리층을 형성하여 공정을 진행하고, 캐리어 기판과 분리되면 분리층이 배선 피복층으로 사용되도록 하여 공정의 효율성 및 생산성을 높일 수 있다.The present invention is excellent in peelability on the carrier substrate, and proceeds the process by forming a separation layer of a specific component that prevents electrode damage and crack generation, and when separated from the carrier substrate so that the separation layer is used as a wiring coating layer Increase efficiency and productivity.
본 발명은 캐리어 기판 상에서 터치 센서를 구현하기 위한 공정을 진행하여 고정세(fine pitch), 내열성을 확보하고, 필름 기재를 다변화할 수 있다.According to the present invention, a process for implementing a touch sensor on a carrier substrate may be performed to ensure fine pitch and heat resistance, and to diversify the film substrate.
본 발명은 캐리어 기판과의 분리 이후에 별도의 분리층 제거 공정을 하지 않아 공정을 단순화하고 제거 공정에서 터치 센서 영역에 가해지는 문제를 해결할 수 있다.The present invention does not perform a separate separation layer removal process after separation from the carrier substrate, thereby simplifying the process and solving the problem applied to the touch sensor region in the removal process.
본 발명은 캐리어 기판과의 분리 이후에 필름 터치 센서에 발생하는 컬(Curl) 발생을 억제할 수 있다.The present invention can suppress curl generation occurring in the film touch sensor after separation from the carrier substrate.
본 발명은 특정한 경화성 수지 조성물을 캐리어 기판에 도포하여 경화시킴으로써, 무리 없이 용이하게 박리할 수 있는 분리층 박막(예를 들면 수백nm 두께)을 포함할 수 있다. 또한, 이렇게 기판 상에 성막된 분리층 박막은 150℃까지의 가열에 견딜 수 있고, 바람직하게는 230℃의 가열에도 견딜 수 있으며, 나아가서는 포토레지스트 용액에 이용되는 용제에 내성을 가지며, 알칼리성 현상액에도 견딜 수 있으므로, 포토리소그라피 법에 의한 회로 제작을 위한 수지제 베이스 필름으로서 유리하게 사용될 수 있다. 아울러, 본 발명에 따라 형성된 분리층 박막은 그러한 온도에서 가열 후에도 이(easy)박리성을 가지고 있기 때문에, 박막임에도 불구하고 종래에 비해 고온의 소성 단계를 포함한 회로 제작 프로세스에 제공할 수 있어 회로의 특성 보존에 유리하며, 또 회로 제작 후에도 기판으로부터 무리 없이 용이하게 박리될 수 있어 박리력 특성 및 크랙 억제 특성이 우수한 터치 센서 또는 터치 센서 구조체를 제공할 수 있다.The present invention may include a separation layer thin film (eg, several hundred nm thick) that can be easily peeled off without difficulty by applying a specific curable resin composition to a carrier substrate and curing the carrier substrate. In addition, the separation layer thin film thus formed on the substrate can withstand heating up to 150 ° C, preferably can withstand heating up to 230 ° C, furthermore, is resistant to the solvent used in the photoresist solution, and is an alkaline developer. Since it can endure, it can be advantageously used as a resin base film for circuit manufacture by the photolithography method. In addition, since the separation layer thin film formed according to the present invention has easy peelability even after heating at such a temperature, the separation layer thin film can be provided to a circuit fabrication process including a high temperature firing step, compared to the conventional thin film. It is advantageous for the preservation of properties and can be easily peeled off from the substrate even after fabrication of the circuit, thereby providing a touch sensor or a touch sensor structure having excellent peel force characteristics and crack suppression characteristics.
도 1 내지 도 4는 본 발명의 일 실시예에 따른 필름 터치 센서의 구조 단면도이다.1 to 4 are structural cross-sectional views of a film touch sensor according to an embodiment of the present invention.
도 5a 내지 도 5f는 본 발명에 따른 필름 터치 센서의 제조 방법의 제1 실시예에 따른 공정 단면도이다.5A to 5F are cross-sectional views illustrating a method of manufacturing a film touch sensor according to the present invention.
도 6a 및 도 6b는 본 발명에 따른 필름 터치 센서의 제조 방법의 제2 실시예에 따른 공정 단면도이다.6A and 6B are cross-sectional views illustrating a method of manufacturing a film touch sensor according to the present invention.
도 7a 및 도 7b는 본 발명에 따른 필름 터치 센서의 제조 방법의 제3 실시예에 따른 공정 단면도이다.7A and 7B are cross-sectional views illustrating a method of manufacturing a film touch sensor according to the present invention.
도 8은 본 발명의 일 실시예에 따른 필름 터치 센서의 구조 단면도이다.8 is a structural cross-sectional view of a film touch sensor according to an embodiment of the present invention.
본 발명의 일 실시형태는 분리층; 상기 분리층 상에 형성되되, 센싱 전극 및 상기 센싱 전극의 일단에 형성되는 패드 전극을 포함하는 전극 패턴층; 상기 전극 패턴층 상부에 형성되며 상기 전극 패턴층의 일부 또는 전부를 덮도록 형성되는 절연층;을 포함하며, 상기 분리층은, 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 측쇄를 구비한 쇄상 폴리머 및 가교제를 포함하고, (a) 상기 측쇄는, 탄소원자 3 내지 30개를 포함하고, 적어도 1개의 포화 또는 불포화의 탄화수소기를 포함하거나, 또는 적어도 1개의 방향족기를 더 포함하고, 탄소원자 사이를 연결하는 -COO-, -O-, 및 -CO-로 이루어진 군에서 선택된 결합을 포함할 수 있음으로써, 캐리어 기판 상에 박리성이 우수하며, 전극손상 및 크랙 발생을 방지하는 특정성분의 분리층을 형성하고 터치 센서 형성 공정을 진행하고, 캐리어 기판과 분리되면 분리층이 배선 피복층으로 사용되도록 하여 필름 기재 상에서 직접 터치 센서를 구현하는 공정에서는 불가능한 고정세(fine pitch), 내열성을 확보하고, 필름 기재를 다변화할 수 있다.One embodiment of the invention the separation layer; An electrode pattern layer formed on the separation layer, the electrode pattern layer including a sensing electrode and a pad electrode formed at one end of the sensing electrode; And an insulating layer formed on the electrode pattern layer and covering a part or all of the electrode pattern layer, wherein the separation layer includes an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group. A chain polymer having a branched side chain and a crosslinking agent, wherein (a) the side chain contains 3 to 30 carbon atoms and includes at least one saturated or unsaturated hydrocarbon group, or further includes at least one aromatic group And, by including a bond selected from the group consisting of -COO-, -O-, and -CO- connecting between the carbon atoms, excellent peelability on the carrier substrate, preventing electrode damage and cracks Forming a separation layer of a specific component and proceeding a touch sensor formation process, and when separated from the carrier substrate, the separation layer is used as a wiring coating layer to implement a touch sensor directly on the film substrate A fixed three (fine pitch) can not be in the process, it is possible to ensure heat resistance, diversify film substrate.
본 발명은 캐리어 기판 상에 박리성이 우수하며, 전극손상 및 크랙 발생을 방지하는 분리층을 형성하여 터치 센서 형성 공정을 진행하고, 절연층을 형성하여 이후의 필름 접착을 위한 접착층으로 사용하거나, 광학(필름)층 또는 평탄화층으로 사용할 수 있도록 한 것이다. 평탄화층으로 사용되는 절연층은 전극 패턴의 부식을 막고 표면이 평탄화되어, 점착제 또는 접착제를 통한 필름 기재와의 접착 시 미세기포 발생을 억제할 수 있다.The present invention is excellent in peelability on the carrier substrate, forming a separation layer to prevent electrode damage and cracks to proceed the touch sensor forming process, to form an insulating layer to use as an adhesive layer for subsequent film adhesion, It can be used as an optical (film) layer or a planarization layer. The insulating layer used as the planarization layer prevents the corrosion of the electrode pattern and the surface is planarized, thereby suppressing the occurrence of microbubbles during adhesion to the film substrate through an adhesive or an adhesive.
본 발명에 있어서, 화학식으로 표시되는 반복 단위, 화합물 또는 수지의 이성질체가 있는 경우에는, 해당 식으로 표시되는 반복 단위, 화합물 또는 수지는 그 이성질체까지 포함하는 대표 화학식을 의미한다.In the present invention, when there is an isomer of a repeating unit, compound or resin represented by the formula, the repeating unit, compound or resin represented by the formula means a representative formula including the isomer.
본 발명에 있어서, 상기 제1 및 2 수지에서 표시되는 각 반복 단위는 표시된 그대로 한정해서 해석되어서는 안되며, 괄호 내의 서브 반복 단위가 정해진 몰% 범위 내에서 사슬의 어느 위치에라도 자유롭게 위치할 수 있다. 즉, 각 반복 단위의 괄호는 몰%를 표현하기 위해 하나의 블록으로 표시되었으나, 각 서브 반복 단위는 해당 수지 내라면 제한 없이 블록으로 또는 각각 분리되어 위치될 수 있다.In the present invention, each repeating unit represented by the first and second resins should not be construed as limited as indicated, and the sub-repeating units in parentheses may be freely positioned at any position of the chain within a predetermined mole% range. That is, the parentheses of each repeating unit are represented by one block to express mol%, but each sub-repeating unit may be positioned in blocks or separately, without limitation, if it is in the resin.
(1) 용어의 정의(1) Definition of terms
본 명세서에서 "내열성"이란, 경화성 수지 조성물을 경화시켜서 얻어지는 막에 대해 150℃까지의 가열에 견딜 수 있고, 바람직하게는 230℃의 가열에도 견딜 수 있어 실질적으로 분해, 그 밖의 열화를 일으키지 않는 것을 말한다. 230℃라는 온도는 포토리소그라피법에 의한 전자 회로 제작에 있어서, 소성 온도로 이용하기에 충분한 고온이다.As used herein, "heat resistance" means that the film obtained by curing the curable resin composition can withstand heating up to 150 ° C, preferably it can withstand heating up to 230 ° C and does not substantially cause decomposition or other deterioration. Say. The temperature of 230 ° C is a high temperature sufficient to be used as a firing temperature in the production of electronic circuits by the photolithography method.
본 명세서에서 "이박리막"이란, 기판, 특히 유리 기판에 대한 도포·경화에 의해 형성된 막이, 기판으로부터 막을 파손시키지 않고(즉, 무리 없이) 용이하게 박리할 수 있는 것을 말하며, "이박리성"이란 그러한 막의 성질을 말한다. 유리 기판으로는, 예를 들면 소다 유리제 기판, 무알칼리 유리제 기판 등, 적절한 유리 기판을 들 수 있다. 소다 유리제 기판은 특히 바람직한 일례이다.As used herein, the term "peelable film" means that a film formed by coating and curing a substrate, particularly a glass substrate, can be easily peeled off from the substrate without breaking the film (that is, without difficulty). "Is the nature of such a film. As a glass substrate, a suitable glass substrate, such as a soda glass substrate and an alkali free glass substrate, is mentioned, for example. Soda glass substrates are particularly preferred examples.
본 명세서에서 "분리층"은 그 폭은 한정되지 않는다. 회로 제작을 위한 베이스 필름으로 사용할 경우 바람직한 두께는 200 내지 400nm, 예를 들면 약 300nm인데, 이는 전자 부품으로 할 경우 현재의 박막화 요청에 대응한 것이며, 분리층 자체의 성능은 이 두께범위에 한정되지 않으므로, 본 명세서에 기재된 분리층의 두께는 임의이다.As used herein, the "separation layer" is not limited in width. When used as a base film for circuit fabrication, the preferred thickness is 200 to 400 nm, for example about 300 nm, which corresponds to the current thinning request for electronic components, and the performance of the separation layer itself is not limited to this thickness range. Therefore, the thickness of the separation layer described herein is arbitrary.
본 명세서에서 "측쇄"란 말은 주쇄에서 분기한 구조 부분을 말하며, "주쇄"란 폴리머의 구조 중에서 반복되는 모노머 단위의 1차원 방향으로 연결되어 있는 원자로 이루어진 사슬을 말한다. 따라서, 예를 들면 폴리머가 (메타)아크릴레이트의 중합체인 경우, 각 모노머에 있어서 에스테르 결합의 형성에 관여하고 있는 부분인 "-COO-"는 "측쇄"의 일부에 포함된다. 한편 "(메타)아크릴레이트"의 표기는 아크릴레이트 및 메타크릴레이트를 구별 없이 나타낸다.As used herein, the term "side chain" refers to a structural moiety branched from the main chain, and the term "main chain" refers to a chain composed of atoms connected in the one-dimensional direction of a monomer unit which is repeated in the structure of the polymer. Thus, for example, when the polymer is a polymer of (meth) acrylate, "-COO-", which is a part involved in the formation of an ester bond in each monomer, is included in a part of the "side chain". On the other hand, the notation of "(meth) acrylate" denotes acrylate and methacrylate without distinction.
본 명세서에서 "-O-"및 "-CO-"는 그들이 "-COO-"의 구성 부분 인 경우를 포함한다. 덧붙여 "-COO-"는 에스테르의 양단의 기초가 고정되어 있지 않은 경우의 에스테르를 나타내며, "-COO-" 및 "-O-CO-"모두를 포함한다. 그러나 에스테르의 양단의 기초가 고정되어있는 경우에는 "- COO-"며 "-O-CO-"과는 구별하여 사용된다.As used herein, "-O-" and "-CO-" include the case where they are part of "-COO-". In addition, "-COO-" represents the ester in the case where the base of both ends of an ester is not fixed, and contains both "-COO-" and "-O-CO-". However, if the base of both ends of the ester is fixed, "-COO-" and "-O-CO-" is used separately.
본 명세서에서 "알킬"은 메탄, 에탄, 프로판과 같은 지방족 탄화수소 (알칸)로부터 수소 원자 하나 제거되어 생기는 1가의 기를 말하며, 일반적으로 CnH2n+1로 표현된다(n은 양의 정수). 알킬은 직쇄 또는 측쇄일 수 있다. 탄소 원자 수 1 내지 4의 알킬(C1~4 알킬)기로서, 예를 들어 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, 이소부틸기, tert-부틸기, sec-부틸기 등을 들 수 있지만, 본 발명은 이러한 예시에만 한정되는 것은 아니다. 탄소 원자 수 1 내지 6의 알킬(C1~6 알킬)기로서, 예를 들면, 탄소 원자 수 1 내지 4의 알킬기, tert-부틸기, sec-부틸기, n-펜틸기, 이소아밀 기, n-헥실기, 이소헥실기, 시클로헥실기 등을 들 수 있지만, 본 발명은 이러한 예시에만 한정되는 것은 아니다. 탄소 원자 수 1 내지 10의 알킬(C1~10 알킬)기로서, 예를 들면, 탄소 원자 수 1 내지 6의 알킬기, n-옥틸기, n-노닐기, n-데카닐기 등을 들 수 있지만, 본 발명은 이러한 예시에만 한정되는 것은 아니다.As used herein, "alkyl" refers to a monovalent group resulting from the removal of one hydrogen atom from an aliphatic hydrocarbon (alkane) such as methane, ethane, propane, and is generally represented by C n H 2n + 1 (n is a positive integer). Alkyl may be straight or branched. As an alkyl (C 1-4 alkyl) group having 1 to 4 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec- Although a butyl group etc. are mentioned, this invention is not limited only to this illustration. As an alkyl (C 1-6 alkyl) group having 1 to 6 carbon atoms, for example, an alkyl group having 1 to 4 carbon atoms, tert-butyl group, sec-butyl group, n-pentyl group, isoamyl group, Although n-hexyl group, isohexyl group, cyclohexyl group, etc. are mentioned, This invention is not limited only to this illustration. As an alkyl (C 1-10 alkyl) group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 6 carbon atoms, n-octyl group, n-nonyl group, n-decanyl group, etc. may be mentioned. The present invention is not limited only to these examples.
본 명세서에서 "알케닐기"는 에텐, 프로펜, 부텐과 같은 이중 결합을 적어도 하나 함유하는 지방족 탄화수소(알켄)에서 수소 원자 하나 제거되어 생기는 1가의 기를 말하며, 일반적으로 CmH2m-1로 표시된다(m은 2 이상의 정수). 알케닐기은 직쇄 또는 측쇄일 수있다. 탄소 원자 수 2 내지 6의 알케닐기로서는 예를 들면, 에테닐기, 1-프로페닐기, 2-프로페닐기, 부테닐기, 펜테닐기, 헥세닐기 등을 들 수 있지만, 본 발명은 이러한 예시에만 한정되는 것은 아니다. 탄소 원자 수 2 내지 10의 알케닐기로서는 예를 들면 탄소 원자 수 2 내지 6의 알케닐기, 헵테닐기, 옥테닐기, 노네닐기, 데케닐기 등을 들 수 있지만, 본 발명은 이러한 예시에만 한정되는 것은 아니다.As used herein, an "alkenyl group" refers to a monovalent group formed by removing one hydrogen atom from an aliphatic hydrocarbon (alkene) containing at least one double bond such as ethene, propene, butene, and is generally represented by C m H 2m-1 . (M is an integer of 2 or more). Alkenyl groups can be straight or branched. Examples of the alkenyl group having 2 to 6 carbon atoms include ethenyl group, 1-propenyl group, 2-propenyl group, butenyl group, pentenyl group, hexenyl group, and the like, but the present invention is limited to these examples. It is not. Examples of alkenyl groups having 2 to 10 carbon atoms include alkenyl groups, heptenyl groups, octenyl groups, nonenyl groups, and dekenyl groups having 2 to 6 carbon atoms, but the present invention is not limited to these examples. .
본 명세서에서 "알키닐기"는 에틴(아세틸렌), 프로핀, 부틴 같은 삼중 결합을 적어도 하나 함유하는 지방족 탄화수소(알킨)에서 수소 원자 하나 제거되어 생기는 1가의 기를 말하며, 일반적으로 CmH2m-3으로 표시된다(m은 2 이상의 정수). 알키닐기는 직쇄 또는 측쇄 일 수있다. 탄소 원자 수 2 내지 6의 알키닐기로 예를 들어, 에티닐기, 1-프로피닐기, 2- 프로피닐기, 부티닐기, 펜티닐기, 헥시닐기 등을 들 수 있지만, 본 발명은 이러한 예시에만 한정 되는 것은 아니다. 탄소 원자 수 2 내지 10의 알키닐기로서, 예를 들어 탄소 원자 수 2 내지 6의 알키닐기, 헵티닐기, 옥티닐기, 노니닐기, 데시닐기 등을들 수 있지만, 본 발명은 이러한 예시에만 한정되는 것은 아니다.As used herein, "alkynyl group" refers to a monovalent group resulting from the removal of one hydrogen atom from an aliphatic hydrocarbon (alkyne) containing at least one triple bond such as ethine (acetylene), propene, butene, and generally C m H 2m-3 (M is an integer of 2 or more). Alkynyl groups can be straight or branched. Examples of the alkynyl group having 2 to 6 carbon atoms include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, and the like, but the present invention is not limited to these examples. no. Examples of the alkynyl group having 2 to 10 carbon atoms include, for example, an alkynyl group having 2 to 6 carbon atoms, heptynyl group, octynyl group, noninyl group, and decinyl group, but the present invention is not limited to these examples. no.
본 명세서에서 "알킬렌기"는 메탄, 에탄, 프로판과 같은 지방족 탄화수소(알칸)로부터 수소 원자 두개를 잃어 생기는 2가의 기를 말하며, 일반적으로 - (CmH2m) - 으로 표현할 수 있다(m은 양의 정수). 알킬렌기 그룹은 직쇄 또는 측쇄일 수 있다. 탄소 원자 수 1 내지 10의 알킬 렌기로서는, 예를 들면, 메틸렌기, 에틸렌기, n-프로필렌기, 이소 프로필렌기, n-부틸렌기, 이소부틸렌기, tert-부틸렌기, n-펜틸렌기, n- 헥실렌기, 이소헥실렌기 등을들 수 있지만, 본 발명은 이러한 예시에만 한정되는 것은 아니다. 상기 알킬렌기는 탄소 원자 수 1 내지 6의 알킬렌기인 것이 바람직하고, 보다 바람직하게는 탄소 원자 수 1 내지 4의 알킬렌기일 수 있고, 더욱 바람직하게는, 메틸렌기 및 에틸렌기일 수 있고, 더욱더 바람직하게는 에틸렌기일 수 있다.As used herein, an "alkylene group" refers to a divalent group resulting from the loss of two hydrogen atoms from an aliphatic hydrocarbon (alkane) such as methane, ethane, or propane, and can generally be expressed as- (C m H 2m )-(m is an amount Integer). The alkylene group group may be straight or branched chain. Examples of the alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, tert-butylene group, n-pentylene group, n -Hexylene group, isohexylene group and the like, but the present invention is not limited only to these examples. The alkylene group is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, still more preferably a methylene group and an ethylene group, even more preferably Preferably an ethylene group.
본 명세서에서 "알케닐렌기"는 에테닐렌, 프로페닐렌, 부테닐렌 같은 이중 결합을 적어도 하나 함유하는 지방족 탄화수소(알켄)에서 수소 원자 두개를 잃어 생기는 2가의 기를 말하며, 일반적으로 - (CmH2m-2) -로 표현할 수 있다(m은 2 이상의 정수). 알케닐렌기는 직쇄 또는 측쇄일 수있다. 탄소 원자 수 2 내지 10의 알케닐렌기로서, 예를 들어 에테닐렌기, n- 프로페닐렌기, 이소페닐렌기, n-부테닐렌기, 이소부테닐렌기, n-펜테닐렌기, n-헥세닐렌기, 이소헥세닐렌기 등을 들 수 있으나, 본 발명은 이러한 예시에만 한정되는 것은 아니다. 상기 알케닐렌기는 바람직하게는 탄소 원자 수 2 내지 6 알케닐렌기일 수 있고, 보다 바람직하게는 탄소 원자 수 2 내지 4의 알케닐렌기일 수 있고, 더욱 바람직하게는 에테닐렌기 또는 n-프로페닐렌기일 수 있고, 더욱더 바람직하게는 에테닐렌기일 수 있다.As used herein, "alkenylene group" refers to a divalent group resulting from the loss of two hydrogen atoms in an aliphatic hydrocarbon (alkene) containing at least one double bond, such as ethenylene, propenylene, butenylene, and generally-(C m H2 m-2 )-(m is an integer of 2 or more). Alkenylene groups may be straight or branched. As an alkenylene group having 2 to 10 carbon atoms, for example, an ethenylene group, n-propenylene group, isophenylene group, n-butenylene group, isobutenylene group, n-pentenylene group, n-hexenylene group And an isohexenylene group, but the present invention is not limited only to these examples. The alkenylene group may preferably be an alkenylene group having 2 to 6 carbon atoms, more preferably an alkenylene group having 2 to 4 carbon atoms, and more preferably an ethenylene group or an n-propenylene group. And even more preferably may be an ethenylene group.
본 명세서에서 "알콕시"는 알콜의 히드록시기의 수소 원자가 손실되어 발생하는 1가의 기를 말하며, 일반적으로 CnH2n+1O -로 표현할 수 있다(n은 1 이상의 정수). 탄소 원자 수 1 내지 6의 알콕시기는 예를 들면, 메톡시, 에톡시, n-프로필 옥시기, 이소프로필 옥시기, n-부틸 옥시기, 이소 부틸 옥시기, tert-부틸옥시기, sec-부틸옥시기, n-펜틸옥시기, 이소 아밀 옥시기, n-헥실옥시기, 이소헥실옥시기 등을 들 수 있으나, 본 발명은 이러한 예시에만 한정되는 것은 아니다.As used herein, "alkoxy" refers to a monovalent group resulting from the loss of a hydrogen atom of an hydroxy group of an alcohol, and can generally be expressed as C n H 2n + 1 O-(n is an integer of 1 or more). The alkoxy group having 1 to 6 carbon atoms is, for example, methoxy, ethoxy, n-propyl oxy group, isopropyl oxy group, n-butyl oxy group, isobutyl oxy group, tert-butyloxy group, sec-butyl An oxy group, n-pentyloxy group, iso amyl oxy group, n-hexyloxy group, isohexyloxy group, etc. are mentioned, but this invention is not limited only to this illustration.
본 명세서에서 "할로알킬기"는 상기 알킬기의 1개 또는 복수 개의 수소 원자가 할로겐 원자로 치환된 알킬기를 말한다. 또한 "퍼할로겐화 알킬"은 상기 알킬기의 모든 수소 원자가 할로겐 원자로 치환된 알킬기를 말한다. 탄소수 1 내지 6의 할로알킬기로서, 예를 들면, 트리플루오로 메틸기, 트리플루오로에틸, 퍼플루오로에틸트리플루오로 n-프로필기, 퍼플루오로 n-프로필기, 트리플루오로이소프로필기, 퍼플루오로이소프로필 기, 트리플루오로 n-부틸기, 퍼플루오로 n-부틸기, 트리플루오로이소 부틸기, 퍼플루오로 이소부틸기, 트리플루오로 tert-부틸기, 퍼플루오로 tert-부틸기, 트리플루오로 n-펜틸기, 퍼플루오로 n-펜틸기, 트리플루오로 n-헥실기, 퍼플루오로 n-헥실기 등을들 수 있으나, 본 발명은 이러한 예시에만 한정되는 것은 아니다.As used herein, "haloalkyl group" refers to an alkyl group in which one or a plurality of hydrogen atoms of the alkyl group are substituted with halogen atoms. In addition, "perhalogenated alkyl" refers to an alkyl group in which all hydrogen atoms of the alkyl group are substituted with halogen atoms. Examples of the haloalkyl group having 1 to 6 carbon atoms include trifluoromethyl group, trifluoroethyl, perfluoroethyltrifluoro n-propyl group, perfluoro n-propyl group, trifluoroisopropyl group, Perfluoroisopropyl group, trifluoro n-butyl group, perfluoro n-butyl group, trifluoroisobutyl group, perfluoro isobutyl group, trifluoro tert-butyl group, perfluoro tert- Butyl group, trifluoro n-pentyl group, perfluoro n-pentyl group, trifluoro n-hexyl group, perfluoro n-hexyl group, etc. can be mentioned, but this invention is not limited only to this illustration. .
본 명세서에서 "시클로 알킬기"은 단환 또는 다환식 포화 탄화수소기를 의미하고, 가교된 구조의 것도 포함된다. 예를 들어, "C3-12 시클로 알킬기"는 탄소 원자 수가 3 내지 12의 고리 형 알킬기를 의미한다. 구체적인 예로서 "C6-12 시클로 알킬기"의 경우에는 시클로 헥실기, 시클로 헵틸기, 사이클로 옥틸기, 아다만틸기, 이소보닐기 등을 들 수있다. "C3-12 시클로 알킬기"의 경우에는 시클로 프로필기, 시클로부틸기, 펜틸기, C6-12 시클로 알킬기 등을 들 수있다. 상기 시클로 알킬기로는 바람직하게는, C6-12 시클로 알킬기를 들 수있다.As used herein, "cycloalkyl group" means a monocyclic or polycyclic saturated hydrocarbon group, and includes a crosslinked structure. For example, "C 3-12 cycloalkyl group" means a cyclic alkyl group having 3 to 12 carbon atoms. Specific examples of the "C 6-12 cycloalkyl group" include cyclohexyl group, cycloheptyl group, cyclooctyl group, adamantyl group, isobonyl group and the like. In the case of a "C 3-12 cycloalkyl group", a cyclopropyl group, cyclobutyl group, pentyl group, C 6-12 cycloalkyl group, etc. are mentioned. As said cycloalkyl group, Preferably, a C 6-12 cycloalkyl group is mentioned.
본 명세서에서 "시클로 알케닐기"는 이중결합을 포함하는 단환 또는 다환식 불포화 탄화수소기를 의미하며, 가교된 구조의 것도 포함된다. 예를 들어, "C3-12 시클로 알케닐기"는 탄소 원자 수 3 내지 12의 고리형 알케닐기을 의미한다. 구체적인 예로서 "C6-12 시클로 알케닐기"의 경우에는 1-시클로헥세닐기, 2-시클로헥세닐기, 3-시클로헥세닐기, 시클로 헵테닐기, 시클로옥테닐기, 시쿠로노네닐기 등을 들 수 있다. "C3-12 시클로 알킬기"의 경우에는 시클로프로페닐기, 시클로부테닐기, 시클로펜테닐기, C6-12 시클로 알케닐기 등을 들 수있다. 상기 시클로 알케닐기는 바람직하게는, C6-12 시클로 알케닐기일 수 있다.As used herein, "cycloalkenyl group" means a monocyclic or polycyclic unsaturated hydrocarbon group including a double bond, and includes a crosslinked structure. For example, "C 3-12 cyclo alkenyl group" means a cyclic alkenyl group having 3 to 12 carbon atoms. As a specific example, in the case of the "C 6-12 cyclo alkenyl group", 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cykuronenyl group, etc. Can be mentioned. In the case of a "C 3-12 cycloalkyl group", a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a C 6-12 cyclo alkenyl group, etc. are mentioned. The cyclo alkenyl group may preferably be a C 6-12 cyclo alkenyl group.
본 명세서에서 "탄화수소기"는 탄소와 수소만으로 구성되는 화합물에서 수소 원자 하나를 잃어 생기는 1가의 기를 말한다. 탄화수소 라디칼은 상기 "알킬기", "알케닐기", "알킬렌기", "알케닐렌기", "시클로 알킬기", "시클로 알케닐기", "방향족기", "지환족기" 등을 포함한다. 탄화수소 기는 포화 또는 불포화 일 수 있다. 탄화수소기는 탄소의 결합 방법에 따라 사슬형 탄화수소 기와 환식 탄화수소 라디칼로 분류되어, 환식 탄화수소 기는 추가로 지환식 탄화수소기와 방향족 탄화수소 라디칼로 나뉠 수 있다. 포화 또는 불포화 탄화수소 기의 예로는 메틸, 에틸, n-프로필, 이소프로필, 부틸, 펜틸, 헥실, 시클로헥실, 디사이클로 펜타다이엔일, 데카리닐, 아다만틸, 부테닐, 헥세닐, 시클로 헥세닐, 데실 및 기타 측쇄에 탄소 원자 수의 한도 범위 내에서 다양한 직쇄상, 분지 쇄상, 단환상, 축합 고리의 기반 등을 들 수 있으나, 이들에 한정되지 않는다. 그 각 그룹은 말단에 위치하지 않은 경우에는 다른 그룹과의 결합 관계에 따라 2가 이상의 기일 수있다.As used herein, the term "hydrocarbon group" refers to a monovalent group resulting from the loss of one hydrogen atom in a compound consisting solely of carbon and hydrogen. Hydrocarbon radicals include the above "alkyl groups", "alkenyl groups", "alkylene groups", "alkenylene groups", "cycloalkyl groups", "cyclo alkenyl groups", "aromatic groups", "alicyclic groups" and the like. Hydrocarbon groups can be saturated or unsaturated. Hydrocarbon groups are classified into chain hydrocarbon groups and cyclic hydrocarbon radicals according to the method of bonding carbon, and the cyclic hydrocarbon groups can be further divided into alicyclic hydrocarbon groups and aromatic hydrocarbon radicals. Examples of saturated or unsaturated hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, dicyclo pentadienyl, decarinyl, adamantyl, butenyl, hexenyl, cyclo Hexenyl, decyl and other side chains include, but are not limited to, various linear, branched, monocyclic, condensed ring bases within the limits of the number of carbon atoms. Each group may be a divalent or more group depending on the bonding relationship with the other group when not located at the terminal.
본 명세서에서 "방향족기"는 방향족 탄화수소 고리에 결합하는 수소 원자가 1개 이탈하여 생기는 기를 말한다. 예를 들어, 벤젠에서 페닐기 (C6H5-), 톨루엔에서 톨릴기(CH3C6H4-), 크실렌에서 크실레닐기((CH3)2C6H3-), 나프탈렌에서 나프틸기(C10H8-)가 유도된다. 또한 본 명세서에서 "헤테로 방향족기"는 단환식 또는 다환식의 헤테로 원자 함유 방향족기를 의미하고 상기 작용기는 질소 원자, 황 원자 및 산소 원자로부터 선택되는 동종 또는 이종의 헤테로 원자를 1 개 이상(예를 들어 1 ~ 4 개) 포함할 수 있다. 상기 "방향족기"는 또한 "헤테로 방향족기"를 포함한다. 방향족 기의 예로는 페닐, 비페닐, 나프틸 등과 같은 탄소환식 방향족기(단환기 및 축합 고리기) 및 피리딜, 피리미디닐, 퀴놀리닐, 트리아지닐 등의 헤테로 방향족 기(단환기 및 축합고리기)를 들 수 있고 각 방향족기는 말단에 위치하지 않은 경우에는 다른 그룹과의 결합 관계에 따라 2가 이상의 기일 수 있다. 또한 본 명세서에서 방향족 고리 부분과 함께 고리를 형성하는 포화 또는 불포화 탄화수소 사슬 부분을 갖는 기(예를 들면, 테트라하이드로나프틸 또는 디하이드로나프틸)는 방향족 기 및 포화 또는 불포화 탄화수소 기와의 결합으로 파악한다.As used herein, the term "aromatic group" refers to a group resulting from the departure of one hydrogen atom bonded to an aromatic hydrocarbon ring. For example, a phenyl group (C 6 H 5- ) in benzene, a tolyl group (CH 3 C 6 H 4- ) in toluene, a xylenyl group ((CH 3 ) 2 C 6 H 3- ) in xylene, naph in naphthalene Til group (C 10 H 8- ) is induced. In addition, the term "heteroaromatic group" used herein means a monocyclic or polycyclic hetero atom-containing aromatic group, and the functional group may have one or more heteroatoms of the same or different kind selected from a nitrogen atom, a sulfur atom and an oxygen atom (eg, For example, 1 to 4) can be included. Said "aromatic group" also includes "heteroaromatic group". Examples of aromatic groups include carbocyclic aromatic groups (monocyclic and condensed ring groups) such as phenyl, biphenyl, naphthyl and the like and heteroaromatic groups (monocyclic groups and condensed) such as pyridyl, pyrimidinyl, quinolinyl, triazinyl, etc. Ring groups) and each aromatic group may be a divalent or more group depending on the bonding relationship with other groups when not located at the terminal. Also used herein are groups having saturated or unsaturated hydrocarbon chain moieties that form rings together with the aromatic ring moiety (eg, tetrahydronaphthyl or dihydronaphthyl) as understood by bonding to aromatic groups and saturated or unsaturated hydrocarbon groups. do.
본 명세서에서 "지환식(기)"는 탄소와 수소만으로 구성된, 방향족 성이없는 고리에 결합하는 수소 원자가 1 개 이탈하여 생기는 부분(또는 작용기)을 말한다. 지환식 기는 상기 시클로 알킬기 및 시클로 알케닐기를 포함한다. 지환식기는 포화 또는 불포화 일 수있다. 포화 또는 불포화 지환식기의 예로는 시클로헥실, 디시클로펜타다이엔일, 데카리닐, 아다만틸, 시클로 헥세닐 및 기타 측쇄의 탄소 원자 수의 한도 범위 내에서 다양한 단 환상, 축합 고리 모양기가 있으나, 이에 한정되지 않는다. 그 각 그룹은 말단에 위치하지 않은 경우에는 다른 그룹과의 결합 관계에 따라 2가 이상의 기일 수있다.As used herein, "alicyclic (group)" refers to a moiety (or functional group) resulting from the departure of one hydrogen atom bonded to a ring having no aromaticity, consisting of only carbon and hydrogen. The alicyclic group includes the cycloalkyl group and the cyclo alkenyl group. The alicyclic group may be saturated or unsaturated. Examples of saturated or unsaturated alicyclic groups include various monocyclic, condensed cyclic groups within the limits of the number of carbon atoms of cyclohexyl, dicyclopentadienyl, decarinyl, adamantyl, cyclohexenyl and other side chains. It is not limited to this. Each group may be a divalent or more group depending on the bonding relationship with the other group when not located at the terminal.
일반적으로 용어 "치환"는 특정 치환기 라디칼, 주어진 구조에서 하나 이상의 수소를 라디칼로 바꾼 것을 가리킨다. 본 명세서에서 정의된 기본의 치환기의 수는 치환 가능하다면 특별히 제한은 없으며, 1이상을 의미한다. 또한 특별히 언급한 경우를 제외하고 각 그룹의 설명은 그 작용기가 다른 기의 일부 또는 치환기인 경우에도 해당한다. 또한, 본 명세서에서 치환이라는 용어를 특히 명시하지 않은 치환기 내용은 치환되지 않은 치환기를 의미한다. 또한, 본 명세서에서 어구 치환 또는 비치환은 치환되어 있어도 좋다는 표현으로 사용하였다.In general, the term “substitution” refers to the conversion of a specific substituent radical, one or more hydrogens, into a radical in a given structure. The number of basic substituents defined herein is not particularly limited as long as it can be substituted, and means one or more. In addition, the description of each group also applies when the functional group is a part or substituent of another group except the case mentioned especially. Also, in the specification, the substituent content that does not specifically specify the term substitution means an unsubstituted substituent. In addition, the phrase substitution or unsubstitution in this specification was used by the expression which may be substituted.
"치환 알킬기", "치환 알케닐기", "치환 알키닐기", "치환 시클로 알킬기", "치환 시클로알케닐기", "치환 탄화수소기", "치환 방향족기", "치환 헤테로 방향족기", "치환 알킬렌기", "치환 알케닐렌기", "치환 또는 비치환 제2급 또는 제3급 히드록시기를 가진기" 및 "치환 아다만틸기"를 포함하는 본원 명세서에 기재의 기준에 치환기의 예로는 할로겐, 히드록시, C1-10 알킬기, C1 ~ 10 알콕시기, C2-10 알케닐기, C6-12 시클로 알킬기, C6-12 시클로 알케닐기 , C1-10 할로알킬기, C2-10 할로알케닐기, C6-18 탄화수소기, C6-18 방향족기, C6-18 헤테로 방향족기, C6-12 방향족기로 치환 된 C1-10 알킬기, C6-12 탄화수소기로 치환된 C1-10 알킬기, C6-12 방향족기로 치환된 C2-10 알케닐기, C6-12 탄화수소기로 치환된 C2-10 알케닐기, -CN, 옥소기(=O) -O(CH2)2O-, -OC(CH3)2O-, -OCH2O-, -O-, 에스테르기(-COO- 또는 -O-CO-), C6-12 탄화수소기로 치환된 에스테르기, C6-12 방향족기로 치환된 에스테르기, 에스테르기로 치환된 C6-18 탄화수소기, 에스테르기로 치환된 C1-10 알킬기, C1-6 알킬렌기, C2-6 알케닐렌기 등을 들 수 있으나, 본 발명은 이러한 예시에만 한정되는 것은 아니다. 상기 치환기의 바람직한 예로는 히드록시기, C6-18 탄화수소기, C1-10 알킬기, C6-12 방향족기로 치환된 C1-10 알킬기, C6-12 탄화수소기로 치환된 C1-10 알킬기, 에스테르기로 치환된 C6-18 탄화수소기, 에스테르기로 치환된 C1-10 알킬기, 에스테르기 (-COO- 또는 -O-CO-), C6-12 탄화수소기로 치환된 에스테르기, C6-12 방향족기로 치환된 에스테르기, C2-10 알케닐기, C6-12 방향족기로 치환된 C2-10 알케닐기, C6-12 탄화수소기로 치환된 C2-10 알케닐기, C1-10 알콕시메틸기, C6-12 시클로 알킬기, C6-12 시클로 알케닐기를 들 수 있으며, 보다 구체적인 예로는 벤조일 옥시 기, 페닐기, 시클로 헥실기, 시클로 헥세닐기, 아다만틸기, 히드록시기로 치환된 아다만틸기를들 수있다."Substituted alkyl group", "substituted alkenyl group", "substituted alkynyl group", "substituted cycloalkyl group", "substituted cycloalkenyl group", "substituted hydrocarbon group", "substituted aromatic group", "substituted heteroaromatic group", " Examples of substituents to the criteria described herein, including "substituted alkylene groups", "substituted alkenylene groups", "groups with substituted or unsubstituted secondary or tertiary hydroxyl groups" and "substituted adamantyl groups" halogen, hydroxy, C 1-10 alkyl group, C 1 ~ 10 alkoxy group, C 2-10 alkenyl, C 6-12 cycloalkyl, C 6-12 cycloalkenyl group, C 1-10 haloalkyl group, C 2- 10 haloalkenyl group, C 6-18 hydrocarbon group, C 6-18 aromatic group, C 6-18 heteroaromatic group, C 1-10 alkyl group substituted with C 6-12 aromatic group, C 6-12 hydrocarbon group substituted 1-10 alkyl, C 6-12 aromatic a C 2-10 alkenyl group, a C 2-10 alkenyl group, -CN, an oxo group (= O) substituted with a C 6-12 hydrocarbon group substituted with a -O (CH 2) 2 O-, -OC (CH 3 ) 2 O-, -OCH 2 O-,- O-, ester group (-COO- or -O-CO-), ester group substituted with C 6-12 hydrocarbon group, ester group substituted with C 6-12 aromatic group, C 6-18 hydrocarbon group substituted with ester group, C 1-10 alkyl group, C 1-6 alkylene group, C 2-6 alkenylene group substituted with an ester group, and the like, but the present invention is not limited only to these examples. Preferred examples of the substituent include a hydroxy group, C 6-18 hydrocarbon group, C 1-10 alkyl, C 6-12 aromatic group-substituted C 1-10 alkyl, C 6-12 A C 1-10 alkyl group substituted by a hydrocarbon, an ester C 6-18 hydrocarbon group substituted by group, C 1-10 alkyl group substituted by ester group, ester group (-COO- or -O-CO-), ester group substituted by C 6-12 hydrocarbon group, C 6-12 aromatic group substituted with an ester group, C 2-10 alkenyl, C 6-12 aromatic group substituted C 2-10 alkenyl group, a C 2-10 alkenyl substituted with C 6-12 hydrocarbon group, a C 1-10 alkoxy group, C 6-12 cycloalkyl group, C 6-12 cyclo alkenyl group, and more specific examples thereof may be a benzoyloxy group, a phenyl group, a cyclohexyl group, a cyclo hexenyl group, an adamantyl group, or an adamantyl group substituted with a hydroxy group. Can be heard.
본 명세서에서 "α치환 (메타)아크릴계 모노머"는 CH2=C(R1a)-COO-R1에 도시 된 바와 같이, 에스테르 기 -COO- 탄소의 바로 옆(α위치)의 이중결합을 형성하는 탄소가 대체되는 아크릴계 모노머를 가리킨다. 마찬가지로, "α치환 비닐 에스테르 계 단량체"는 CH2=C(R1a)-O-CO-R3에서 나타낸 바와 같이, 에스테르기 -O-CO- 산소의 바로 옆(α위치)의 이중 결합을 형성하는 탄소가 대체되는 아크릴계 모노머를 가리킨다. "α치환 비닐에테르계 모노머"는 CH2=C(R1a)-O-R4에 도시 된 바와 같이, 에테르기 -O- 산소의 바로 옆(α위치)의 이중결합을 형성하는 탄소가 대체되는 아크릴계 모노머를 가리킨다. "α치환 비닐계 모노머"는 CH2=C(R1a)-R5에 도시된 바와 같이, 비닐기의 말단 탄소가 아닌 내부 탄소가 대체되는 아크릴계 모노머를 가리킨다. R1, R3, R4, R5 및 R1a는 후술하는 바람직한 실시 예 (2-1) 경화성 수지 조성물에서 정의 된 바와 같다.As used herein, an "α-substituted (meth) acrylic monomer" forms a double bond next to the ester group -COO-carbon, as shown in CH 2 = C (R 1a ) -COO-R 1 . Refers to an acrylic monomer in which carbon is replaced. Similarly, "α-substituted vinyl ester monomer" refers to a double bond immediately next to the ester group -O-CO- oxygen (α position), as shown in CH 2 = C (R 1a ) -O-CO-R 3 . The acrylic monomer to which carbon to be formed is replaced is pointed out. "Al Substituted Vinyl Ether Monomer" is an acrylic based carbon which forms a double bond next to the ether group -O- oxygen (α position), as shown in CH 2 = C (R 1a ) -OR 4 Point to monomer. "α-substituted vinyl monomer" refers to an acrylic monomer in which internal carbon, not terminal carbon of a vinyl group, is replaced, as shown in CH 2 = C (R 1a ) -R 5 . R 1 , R 3 , R 4 , R 5 and R 1a are as defined in the preferred Example (2-1) curable resin composition described below.
본 명세서에서 알코올성 제2급 또는 제3급 OH 함유기는 알코올성 제2급 또는 제3급 OH기를 1개 또는 2개 이상 함유하는 작용기를 나타낸다. 따라서 알코올성 제2급 또는 제3급 OH 함유기는 알코올성 제2급 또는 제3급 OH기 자체도 포함한다. 치환 또는 비치환 알코올성 제2급 또는 제3급 OH 함유기에서 치환 또는 비치환은 알코올성 제2급 또는 제3급 OH기를 1개 또는 2개 이상 포함하면서 해당 OH기 이외의 부분이 치환되어 있는지 또는 치환되지 않은 것을 나타내는 것이지, 상기 OH기가 치환되어 있는지 또는 치환되지 않은 것을 나타내는 것은 아니다.The alcoholic secondary or tertiary OH-containing group herein refers to a functional group containing one or two or more alcoholic secondary or tertiary OH groups. The alcoholic secondary or tertiary OH-containing groups therefore also include the alcoholic secondary or tertiary OH groups themselves. Substituted or unsubstituted in the substituted or unsubstituted alcoholic secondary or tertiary OH-containing group includes one or two or more alcoholic secondary or tertiary OH groups, and the part other than the corresponding OH group is substituted or substituted. It is not shown, and does not show whether the said OH group is substituted or unsubstituted.
본 명세서에서 페놀성 OH 함유기는 페놀성 OH기를 1개 또는 2개 이상 함유하는 작용기를 나타낸다. 따라서 페놀성 OH 함유기는 또는 페놀성 OH기 자체도 포함한다. 치환 또는 비치환 페놀성 OH 함유기에서 치환 또는 비치환은 페놀성 OH기를 1개 또는 2개 이상 포함하면서 해당 히드록시기 이외의 부분이 치환되어 있는지 또는 치환되지 않은 것을 나타내는 것이지, 상기 OH기가 치환되어 있는지 또는 치환되지 않은 것을 나타내는 것은 아니다.The phenolic OH-containing group herein refers to a functional group containing one or two or more phenolic OH groups. The phenolic OH containing group or thus also includes the phenolic OH group itself. Substituted or unsubstituted in the substituted or unsubstituted phenolic OH-containing group indicates that one or two or more phenolic OH groups are included, and the portion other than the hydroxy group is substituted or unsubstituted, It does not indicate that it is not substituted.
본 명세서에서 "용매화물"은 특별히 거절하지 않는 비공유 분자간 힘에 의해 결합 된 정비 또는 부정비의 양의 용매를 더 포함하는 화합물 또는 그의 염을 의미한다. 용매가 물이면, 상기 용매화물은 수화물이다.As used herein, "solvate" means a compound or salt thereof that further comprises a solvent in a maintenance or indefinite amount bound by non-covalent intermolecular forces that are not particularly rejected. If the solvent is water, the solvate is a hydrate.
본 명세서에서 "또는"는 문장 중에 열거 된 사항의 "하나 이상의"을 채용 할 때 사용된다. "혹은"도 마찬가지이다. 본 명세서에서 "두 값의 범위"라고 명기 한 경우, 그 범위는 두 값 자체도 포함한다. 따라서 범위를 나타내는 'X ~ Y'는 'X 이상, Y 이하"을 의미한다. 또한 특별한 고지가 없는 한, 「무게」와 「질량」, 「중량%」또는 "wt%"와 "질량%"는 각각 동의어로 취급한다. "약"이라는 표현은 특히 거절하지 않는 10 %의 허용 오차를 가지고 측정 값 인 경우는 유효 숫자 또는 표시되는 숫자 1 자리 아래 자리를 반올림하여 얻어지는 모든 범위의 수치를 말한다.As used herein, "or" is used when employing "one or more" of the matters listed in the sentence. The same is true of "or". When specified herein as "range of two values", the range also includes the two values themselves. Therefore, the range "X to Y" means "X or more and Y or less" and "Weight" and "mass", "wt%" or "wt%" and "mass%" unless otherwise specified. The terms "about" refer to all ranges of values obtained by rounding the significant digits or one digit below the displayed digit, especially if the measurement value has a tolerance of 10% which does not reject.
(2) 바람직한 실시형태의 설명(2) Description of Preferred Embodiments
이하, 도면을 참조하여 본 발명의 구체적인 실시형태를 설명하기로 한다. 그러나 이는 예시에 불과하며 본 발명은 이에 제한되지 않는다. 따라서 발명이 속하는 분야에서 통상의 지식을 가진 사람(이하 '당업자'라 함)은 본 명세서의 기재를 참작하여, 본 발명의 범위 내에서 적절하게 수정할 수 있음은 분명하다. 또한, 본 발명의 실시예는 단독 또는 혼합하여 사용될 수 있다.Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. However, this is only an example and the present invention is not limited thereto. Therefore, it is clear that a person of ordinary skill in the art to which the invention pertains (hereinafter referred to as a person skilled in the art) may appropriately modify the present invention in consideration of the description herein. In addition, embodiments of the present invention may be used alone or in combination.
도 1 내지 도 4는 본 발명의 일 실시예에 따른 필름 터치 센서의 구조 단면도이다.1 to 4 are structural cross-sectional views of a film touch sensor according to an embodiment of the present invention.
도 1 및 도 2를 참조하면, 예시적인 실시예들에 따른 필름 터치 센서는 분리층(20), 보호층(30), 전극 패턴층(40) 및 절연층을 포함할 수 있다.1 and 2, the film touch sensor according to example embodiments may include a separation layer 20, a protection layer 30, an electrode pattern layer 40, and an insulating layer.
도 3 및 도 4를 참조하면, 예시적인 실시예들에 따른 필름 터치 센서는 접착층(60) 및/또는 광학필름(100)을 더 포함할 수 있다.3 and 4, the film touch sensor according to example embodiments may further include an adhesive layer 60 and / or an optical film 100.
(2-1) 경화성 수지 조성물(2-1) curable resin composition
본 발명에 따른 분리층(20)은, 하기 경화성 수지 조성물로 형성되는 경화 수지막을 포함할 수 있다.The separation layer 20 which concerns on this invention can contain the cured resin film formed from the following curable resin composition.
경화성 수지 조성물은 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 측쇄를 구비한 쇄상 폴리머; 및 가교제;를 포함하며,The curable resin composition includes a chain polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group; And a crosslinking agent;
(a) 상기 측쇄는, 탄소원자 3 내지 30개를 포함하고, 적어도 1개의 포화 또는 불포화의 탄화수소기를 포함하거나, 또는 적어도 1개의 방향족기를 더 포함하고, 탄소원자 사이를 연결하는 -COO-, -O-, 및 -CO-로 이루어진 군에서 선택된 결합을 포함할 수 있고,(a) The side chain includes -COO-,-containing from 3 to 30 carbon atoms, containing at least one saturated or unsaturated hydrocarbon group, or further containing at least one aromatic group, and connecting the carbon atoms; O-, and -CO- may comprise a bond selected from the group consisting of
필요에 따라, (b) 상기 가교제는, 트리아진계 화합물, 그 축합체 및 이들의 혼합물; 글리콜우릴계 화합물, 그 축합체 및 이들의 혼합물; 및 이미다졸리디논계 화합물, 그 축합체 및 이들의 혼합물로 이루어진 군에서 선택될 수 있다.If necessary, (b) the said crosslinking agent is a triazine type compound, its condensate, and mixtures thereof; Glycoluril compounds, their condensates, and mixtures thereof; And imidazolidinone-based compounds, condensates thereof, and mixtures thereof.
본 발명의 분리층은 가열처리에 의해 경화되는 열경화성 수지 조성물이라 할 수 있다.The separation layer of the present invention may be referred to as a thermosetting resin composition cured by heat treatment.
본 발명의 경화성 수지 조성물의 구성요소 중 하나인 쇄상 폴리머는, 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 측쇄를 구비한다.The chain polymer which is one of the components of the curable resin composition of this invention is equipped with the side chain which has an alcoholic secondary or tertiary OH containing group or phenolic OH containing group.
본 발명에서 쇄상 폴리머의 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 측쇄에 포함되는 탄소 원자수는 바람직하게는 3 내지 30개이다. 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 측쇄에서 상기 히드록실기의 개수는 1개 또는 2개 이상일 수 있다.In the present invention, the number of carbon atoms contained in the side chain having an alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group of the chain polymer is preferably 3 to 30. The number of hydroxyl groups in the side chain having an alcoholic secondary or tertiary OH containing group or a phenolic OH containing group may be one or two or more.
상기의 측쇄는 탄소원자 적어도 1개의 포화 또는 불포화 탄화수소기를 포함해서 이루어지거나, 또는 적어도 1개의 방향족기를 더 포함해서 이루어진다. 상기 측쇄는 -COO-, -O- 및 -CO-로 이루어진 군에서 선택된 결합을 1개 또는 2개 이상 포함하고 있어도 된다. 측쇄를 구성하는 포화 또는 불포화 탄화수소기는, 예를 들면 1개 단독으로 측쇄의 모든 탄소원자를 차지해도 되고, 또 복수의 포화 또는 불포화 탄소기가 상호간에 -COO-, -O- 및 -CO-로 이루어진 군에서 선택된 결합을 통해 연결한 것이어도 된다. 측쇄가 포화 또는 불포화 탄화수소기에 더해 방향족기를 포함할 경우, 포화 또는 불포화 탄화수소기와 방향족기는 직접 결합해 있어도 되고, 또한 -COO-, -O- 및 -CO-로 이루어진 군에서 선택된 결합을 통해 연결되어 있어도 된다.Said side chain consists of at least 1 saturated or unsaturated hydrocarbon group of carbon atoms, or further contains at least 1 aromatic group. The side chain may contain one or two or more bonds selected from the group consisting of -COO-, -O- and -CO-. The saturated or unsaturated hydrocarbon group constituting the side chain may be, for example, one group alone or may occupy all carbon atoms in the side chain, and a plurality of saturated or unsaturated carbon groups may be composed of -COO-, -O-, and -CO-. It may be connected through a combination selected from. When the side chain contains an aromatic group in addition to a saturated or unsaturated hydrocarbon group, the saturated or unsaturated hydrocarbon group and the aromatic group may be directly bonded, or may be connected via a bond selected from the group consisting of -COO-, -O- and -CO-. do.
본 발명에서 측쇄의 알코올성 제2급 및 제3급 OH 함유기 또는 페놀성 OH 함유기는 본 발명의 경화성 수지 조성물을 유리 기판상에 도포하여 경화시켜서 성막한 분리층이, 소성 후에도 기판으로부터 이박리성을 유지 가능하도록 하는데 실질적인 결정적 요소이다. 또한, 측쇄의 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기가 측쇄의 지환식 부분에 결합하는 것이 더욱 바람직하고, 측쇄의 지환식 부분도 분리층의 이박리성을 유지할 수 있는데 실질적인 결정적 요인이다. 이러한 측쇄를 구비한 쇄상 폴리머는 적절한 가교제, 특히 트리아진계 화합물, 그 축합체 및 이들의 혼합물; 글리콜우릴계 화합물, 그 축합체 및 이들의 혼합물; 및 이미다졸리디논계 화합물, 그 축합체 및 이들의 혼합물로 이루어진 군에서 선택된 것의 수지 조성물로 경화시켰을 때, 내열성의 이박리막을 제공할 수 있다.In the present invention, the side chain alcoholic secondary and tertiary OH-containing groups or phenolic OH-containing groups are applied by the curable resin composition of the present invention on a glass substrate and cured to form a separation layer, which is separated from the substrate even after firing. This is a decisive factor in making it sustainable. In addition, it is more preferable that the alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group of the side chain is bonded to the alicyclic portion of the side chain, and the alicyclic portion of the side chain can also maintain the peeling property of the separation layer. It is a decisive factor. Chain polymers having such side chains include suitable crosslinking agents, in particular triazine-based compounds, their condensates and mixtures thereof; Glycoluril compounds, their condensates, and mixtures thereof; And when hardened | cured with the resin composition of what was chosen from the group which consists of an imidazolidinone type compound, its condensate, and mixtures thereof, a heat resistant peeling film can be provided.
본 발명에서 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 상기 측쇄를 갖춘 쇄상 폴리머는, 보다 바람직하게는 비치환 또는 α치환 (메타)아크릴계 모노머, 비치환 또는 α치환 비닐에스테르계 단량체, 비치환 또는 α치환 비닐에테르계 모노머 및 상기 이외의 비치환 또는 α치환 비닐계 모노머로 이루어진 군에서 선택된 적어도 1종을 모노머 로 포함할 수 있다.In the present invention, the chain polymer having the side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group is more preferably an unsubstituted or α-substituted (meth) acrylic monomer, an unsubstituted or α-substituted vinyl. At least one selected from the group consisting of an ester monomer, an unsubstituted or α-substituted vinyl ether monomer, and an unsubstituted or α-substituted vinyl monomer other than the above may be included as a monomer.
본 발명에서 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 상기 측쇄를 구비한 쇄상 폴리머는, 보다 바람직하게는 (메타)아크릴레이트계 모노머, 비닐에스테르계 모노머, 비닐에테르계 모노머, 상기 외의 비닐계 모노머 중 적어도 1종을 모노머 단위로 포함해서 이루어지는 것이다.In the present invention, the chain polymer having the side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group is more preferably a (meth) acrylate monomer, a vinyl ester monomer, or a vinyl ether system. It consists of including at least 1 sort (s) of a monomer and other vinyl-type monomers as a monomer unit.
바람직하게는 본 발명의 쇄상 고분자는 CH2=C(R1a)-COO-R1, CH2=C(R1a)-O-CO-R3, CH2=C(R1a)-O-R4 및 CH2=C(R1a)-R5 (여기서, R1, R3, R4 및 R5는 서로 독립적으로 각 비닐기에 에스테르 결합을 통해 결합해 있을 경우에는 상기 에스테르 결합 구성 탄소원자를 포함해서 탄소원자 3 내지 30개, 더욱 바람직하게는 3 내지 25개, 더욱더 바람직하게는 3 내지 20개를 가지며, 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가지고 있으며, 적어도 1개의 포화 또는 불포화 탄화수소기를 포함해서 이루어지거나, 또는 적어도 1개의 방향족기를 더 포함해서 이루어지며, 탄소원자 사이를 연결하는 -COO-, -O- 및 -CO-로 이루어진 군에서 선택된 결합을 가지고 있을 수 있다)로 표시되는 화합물로 이루어진 군에서 선택되는 모노머를 포함한다.Preferably, the chain polymer of the present invention is CH 2 = C (R 1a ) -COO-R 1 , CH 2 = C (R 1a ) -O-CO-R 3 , CH 2 = C (R 1a ) -OR 4 And CH 2 = C (R 1a ) -R 5 , wherein R 1 , R 3 , R 4 and R 5 independently of each other include the ester bond constituent carbon atoms when they are bonded to each vinyl group through an ester bond. It has 3 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, even more preferably 3 to 20 carbon atoms, and has an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group, and at least one It may comprise a saturated or unsaturated hydrocarbon group, or may further comprise at least one aromatic group, and may have a bond selected from the group consisting of —COO—, —O—, and —CO—, which connects carbon atoms. It includes a monomer selected from the group consisting of compounds represented by).
보다 바람직하게는, 본 발명의 쇄상 폴리머는 CH2=CH-COO-R1, CH2=C(CH3)-COO-R2, CH2=CH-O-CO-R3, CH2=CH-0-R4 및 CH2=CH-R5 (여기서, R1, R2, R3, R4 및 R5는 서로 독립적으로, 각 비닐기에 에스테르 결합을 통해 결합해 있을 경우에는 상기 에스테르 결합 구성 탄소원자를 포함해서 탄소원자 3 내지 30개, 더욱 바람직하게는 3 내지 25개, 더욱더 바람직하게는 3 내지 20개를 가지며, 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가지고 있으며, 적어도 1개의 포화 또는 불포화 탄화수소기를 포함해서 이루어지거나, 또는 적어도 1개의 방향족기를 더 포함해서 이루어지며, 탄소원자 사이를 연결하는 -COO-, -O- 및 -CO-로 이루어진 군에서 선택된 결합을 가지고 있을 수 있다)로 표시되는 화합물로 이루어진 군에서 선택된 모노머 단위를 포함해서 이루어진다.More preferably, the chain polymer of the present invention is CH 2 = CH-COO-R 1 , CH 2 = C (CH 3 ) -COO-R 2 , CH 2 = CH-O-CO-R 3 , CH 2 = CH-0-R 4 and CH 2 = CH-R 5 (wherein R 1 , R 2 , R 3 , R 4 and R 5 are independently of each other, the ester when each vinyl group is bonded via an ester bond) Groups having 3 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, even more preferably 3 to 20 carbon atoms, including constituent carbon atoms, and an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group It has at least one saturated or unsaturated hydrocarbon group, or further comprises at least one aromatic group, selected from the group consisting of -COO-, -O- and -CO- which connects the carbon atoms Comprising monomer units selected from the group consisting of compounds It is broken.
상기에서, 포화 또는 불포화 탄화수소기의 예로는 메틸, 에틸, n-프로필, 이소프로필, 부틸, 펜틸, 헥실, 시클로헥실, 디시클로펜타디에닐, 데카리닐, 아다만틸, 부테닐, 헥세닐, 시클로헥세닐, 데실, 그 밖에 측쇄의 탄소수의 한도범위 내에서 다양한 직쇄상, 분기쇄상, 단환상, 축합환상의 기를 들 수 있으나, 이에 한정되지 않는다. 그들 각 기는 말단에 위치해 있지 않을 경우에는, 다른 기와의 결합 관계에 따라서 2가 이상을 기여도 된다. 방향족기의 예로는, 페닐, 비페닐릴, 나프틸 등과 같은 탄소환식 방향족기(단환기 및 축합환기) 및 피리딜, 피리미디닐, 퀴놀리닐, 트리아지닐 등의 헤테로 방향족기(단환기 및 축합환기)를 들 수 있고, 각 방향족기에 대해서도 말단에 위치해 있지 않은 경우에는 다른 기와의 결합 관계에 따라서 2가 이상의 기일 수있다. 한편, 본 명세서에서, 방향환 부분과 함께 환을 형성하는 포화 또는 불포화의 탄화수소쇄 부분을 가진 기(예를 들면 테트라히드로나프틸 또는 디히드로나프틸)는 방향족기와 포화 또는 불포화 탄화수소기와의 결합으로 파악한다. In the above, examples of the saturated or unsaturated hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, dicyclopentadienyl, decarinyl, adamantyl, butenyl, hexenyl And cyclohexenyl, decyl, and other linear, branched, monocyclic, and condensed cyclic groups within the limits of the number of carbon atoms in the side chain, but are not limited thereto. When each group is not located at the terminal, it may contribute more than bivalent according to the bonding relationship with another group. Examples of the aromatic group include carbocyclic aromatic groups (monocyclic and condensed cyclic groups) such as phenyl, biphenylyl, naphthyl and the like, and heteroaromatic groups such as pyridyl, pyrimidinyl, quinolinyl, triazinyl (monocyclic groups and Condensed cyclic group), and each aromatic group may be a divalent or more group depending on the bonding relationship with other groups. On the other hand, in the present specification, a group having a saturated or unsaturated hydrocarbon chain portion which forms a ring together with an aromatic ring portion (for example, tetrahydronaphthyl or dihydronaphthyl) is a combination of an aromatic group and a saturated or unsaturated hydrocarbon group. Figure out.
본 발명에서, 알코올성 제2급 또는 제3급 히드록시기는 상기 측쇄를 구성하는 포화 또는 불포화 탄화수소기의 어느 제2급 또는 제3급 탄소원자상의 수소원자를 치환한 히드록시기이다.In the present invention, the alcoholic secondary or tertiary hydroxy group is a hydroxy group substituted with a hydrogen atom on any secondary or tertiary carbon atom of the saturated or unsaturated hydrocarbon group constituting the side chain.
쇄상 고분자의 측쇄의 히드록시기는 알코올성 제2급 또는 제3급 OH기 또는 페놀성 OH기인 것이 바람직하고, 상기 측쇄의 일부 또는 전부를 구성하는 지환식기에 결합되는 것이 더욱 바람직하다.The hydroxyl group of the side chain of the chain polymer is preferably an alcoholic secondary or tertiary OH group or a phenolic OH group, and more preferably bonded to an alicyclic group constituting part or all of the side chain.
보다 바람직하게는, 본 발명의 측쇄 모양 폴리머는 하기 화학식 1 로 표시되는 모노머를 포함할 수 있다.More preferably, the side chain polymer of the present invention may include a monomer represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2019001826-appb-I000016
Figure PCTKR2019001826-appb-I000016
화학식 1에서, R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고,In formula 1, R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
L1은 단일결합, 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고,L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
L2는 O 또는 NH이고,L 2 is O or NH,
R2a, R3a 및 R4a는 서로 독립적으로 수소, 및 치환 또는 비치환 탄화수소기로 이루어진 군에서 선택되고, R 2a , R 3a and R 4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon group,
단 R2a, R3a 및 R4a 중 적어도 1개는 치환 또는 비치환의 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기거나,Provided that at least one of R 2a , R 3a and R 4a is a substituted or unsubstituted alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group,
혹은 R2a, R3a 및 R4a 중 적어도 2개가 하나가 되어, 알코올성 제2급 또는 제3급 OH 또는 페놀성 OH를 포함하는, 치환 또는 비치환 시클로알킬기, 치환 또는 비치환 시클로알케닐기, 치환 또는 비치환 방향족기, 치환 또는 비치환 헤테로 방향족기, 및 이들을 포함하는 다환일 수 있다.Or a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, substituted with at least two of R 2a , R 3a and R 4a and containing an alcoholic secondary or tertiary OH or phenolic OH Or an unsubstituted aromatic group, a substituted or unsubstituted hetero aromatic group, and a polycyclic including them.
더욱 바람직하게는, 본 발명의 측쇄 모양 폴리머는 상기 화학식 1 중 R1a가 수소 및 치환 또는 비치환 알킬기로 이루어진 군에서 선택되고, L1은 단일 결합, 및 치환 또는 비치환 알킬렌기로 이루어진 군에서 선택되고, R2a, R3a 및 R4a는 서로 독립적으로 수소 및 치환 또는 비치환 탄화수소 라디칼로 이루어진 군으로부터 선택되되, R2a, R3a 및 R4a 중 적어도 하나는 알코올성 제2급 또는 제3급 OH 함유기, 페놀성 OH 함유기, 치환 또는 비치환의 알코올성 제2급 또는 제3급 OH 함유 탄화수소 라디칼 및 페놀성 OH 함유 탄화수소 라디칼로 이루어진 군에서 선택되는 모노머를 포함할 수 있다.More preferably, the side chain polymer of the present invention is selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group R 1a in Formula 1, L1 is selected from the group consisting of a single bond and a substituted or unsubstituted alkylene group. R 2a , R 3a and R 4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon radical, wherein at least one of R 2a , R 3a and R 4a is an alcoholic secondary or tertiary OH It may include a monomer selected from the group consisting of a containing group, a phenolic OH-containing group, a substituted or unsubstituted alcoholic secondary or tertiary OH-containing hydrocarbon radical, and a phenolic OH-containing hydrocarbon radical.
더욱 바람직하게는 본 발명의 측쇄 모양 폴리머는 상기 화학식 1 중 R1a는 수소 및 비치환 알킬기로 이루어진 군에서 선택되고, L1은 단일결합 및 비치환 알킬렌기 이루어진 군에서 선택되고, R2a, R3a 및 R4a는 서로 독립적으로 수소 및 치환 또는 비치환 탄화수소 라디칼로 이루어진 군에서 선택되되, R2a, R3a 및 R4a 중 적어도 하나는 알코올성 제2급 또는 제3급 OH 함유기, 페놀성 OH 함유기, 치환 또는 비치환의 알코올성 제2급 또는 제3급 OH 함유 탄화수소 라디칼 및 페놀성 OH 함유 탄화수소 라디칼로 이루어진 군에서 선택되고, 다른 2개는 서로 독립적으로 수소 및 치환 또는 비치환 탄화수소 라디칼로 이루어진 군에서 선택되는 단량체 단위를 포함할 수 있다.More preferably, in the side chain polymer of the present invention, in Formula 1, R 1a is selected from the group consisting of hydrogen and an unsubstituted alkyl group, L1 is selected from the group consisting of a single bond and an unsubstituted alkylene group, and R 2a , R 3a And R 4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon radical, wherein at least one of R 2a , R 3a and R 4a contains an alcoholic secondary or tertiary OH-containing group, containing phenolic OH Groups, substituted or unsubstituted alcoholic secondary or tertiary OH-containing hydrocarbon radicals and phenolic OH-containing hydrocarbon radicals, the other two being independently of one another hydrogen and substituted or unsubstituted hydrocarbon radicals It may include a monomer unit selected from.
보다 바람직하게는, 본 발명의 측쇄 모양 폴리머는 하기 화학식 2 로 표시되는 모노머를 포함할 수 있다.More preferably, the side chain polymer of the present invention may include a monomer represented by the following formula (2).
[화학식 2][Formula 2]
Figure PCTKR2019001826-appb-I000017
Figure PCTKR2019001826-appb-I000017
화학식 2 에서,In Formula 2,
R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고,R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
L1은 단일결합, 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고,L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
R5a 내지 R14a는 서로 독립적으로 수소, 히드록시기 및 하기 화학식 3으로 표시되는 작용기로 이루어진 군 중에서 선택되거나, 또는 하나가 되어 환을 형성하되, R 5a to R 14a are each independently selected from the group consisting of hydrogen, a hydroxy group, and a functional group represented by the following formula (3), or one to form a ring,
R5a 내지 R14a 또는 상기 환의 치환기 중 적어도 하나는 히드록시기일 수 있다.At least one of the substituents of R 5a to R 14a or the ring may be a hydroxy group.
[화학식 3][Formula 3]
Figure PCTKR2019001826-appb-I000018
Figure PCTKR2019001826-appb-I000018
화학식 3 에서, R15a는 치환 또는 비치환 알킬기, 치환 또는 비치환 알케닐기, 치환 또는 비치환 시클로알킬기, 치환 또는 비치환 시클로알케닐기, 치환 또는 비치환 방향족기, 및 치환 또는 비치환 헤테로 방향족기로 이루어진 군에서 선택될 수 있다.In formula (3), R 15a is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group. It may be selected from the group consisting of.
더욱 바람직하게는, 본 발명의 측쇄 모양 폴리머는 상기 화학식 2 중 R1a가 수소 및 치환 또는 비치환 알킬기로 이루어진 군에서 선택되고, L1은 단일결합 및 치환 또는 비치환 알킬렌기로 이루어진 군에서 선택되고, R5a 내지 R14a는 서로 독립적으로 수소, 히드록시기 및 상기 화학식 3으로 표시되는 작용기로 이루어진 군 중에서 선택되거나, 또는 하나가 되어 환을 형성하되, R5a 내지 R14a 또는 상기 환의 치환기 중 적어도 하나는 히드록시기이고, 상기 화학식 3 중 R15a는 치환 또는 비치환 알킬기, 치환 또는 비치환 알케닐기, 치환 또는 비치환 시클로알킬기, 치환 또는 비치환 시클로알케닐기, 치환 또는 비치환 방향족기로 이루어진 군에서 선택되는 모노머를 포함할 수 있다.More preferably, the side chain polymer of the present invention is selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group R 1a in Formula 2, L1 is selected from the group consisting of a single bond and a substituted or unsubstituted alkylene group R 5a to R 14a are each independently selected from the group consisting of hydrogen, a hydroxy group, and a functional group represented by Formula 3, or become one to form a ring, wherein at least one of R 5a to R 14a or a substituent of the ring is Hydroxy group, R 15a in Formula 3 is a monomer selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group It may include.
더욱 바람직하게는, 본 발명의 측쇄 모양 폴리머는 상기 화학식 2 중 R1a가 수소 및 비치환 알킬기로 이루어진 군에서 선택되고, L1은 단일결합 및 비치환 알킬렌기로 이루어진 군에서 선택되고, R5a 내지 R14a 중 R7a가 히드록시기이고, R9a가 상기 화학식 3으로 표시되는 작용기이며, 그 외에는 수소이거나 또는 R5a 내지 R14a가 하나가 되어 1개의 히드록시기로 치환된 환을 형성하고, 상기 화학식 3 중 R15a는 치환 또는 비치환 알킬기, 치환 또는 비치환 알케닐기, 치환 또는 비치환 시클로알킬기, 치환 또는 비치환 시클로알케닐기 및 치환 또는 비치환 페닐기로 이루어진 군에서 선택되는 모노머를 포함할 수 있다. 보다 바람직하게는, 상기 1개의 히드록시기로 치환된 환은 적어도 1개의 히드록시기로 치환된 아다만탄일 수 있다.More preferably, the side chain polymer of the present invention is selected from the group consisting of hydrogen and an unsubstituted alkyl group R 1a in Formula 2, L1 is selected from the group consisting of a single bond and an unsubstituted alkylene group, R 5a to In R 14a , R 7a is a hydroxy group, R 9a is a functional group represented by Formula 3 above, otherwise, it is hydrogen or R 5a to R 14a become one to form a ring substituted with one hydroxy group, and in Formula 3 R 15a may include a monomer selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, and a substituted or unsubstituted phenyl group. More preferably, the ring substituted with one hydroxy group may be adamantane substituted with at least one hydroxy group.
보다 바람직하게는, 본 발명의 측쇄 모양 폴리머는 하기 화학식 4로 표시되는 모노머를 포함할 수 있다.More preferably, the side chain polymer of the present invention may include a monomer represented by the following formula (4).
[화학식 4][Formula 4]
Figure PCTKR2019001826-appb-I000019
Figure PCTKR2019001826-appb-I000019
화학식 4 에서,In Formula 4,
R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고,R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
L2는 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고, R16a는 치환 또는 비치환 알킬기, 치환 또는 비치환 알케닐기 및 치환 또는 비치환 알키닐기로 이루어진 군에서 선택되고, R17a는 수소, 치환 또는 비치환 알킬기, 치환 또는 비치환 알케닐기 및 치환 또는 비치환 알키닐기로 이루어진 군에서 선택될 수 있다.L 2 is selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group, and R 16a is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl group. R 17a may be selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl group.
더욱 바람직하게는, 본 발명의 측쇄 모양 폴리머는 상기 화학식 4 중 R1a가 수소 및 치환 또는 비치환 알킬기로 이루어진 군에서 선택되고, L1은 치환 또는 비치환 알킬렌기에서 선택되고, R16a는 치환 또는 비치환 알킬기에서 선택되고, R17a는 수소 및 치환 또는 비치환 알킬기로 이루어진 군에서 선택된 모노머를 포함할 수 있다.More preferably, the side chain polymer of the present invention is selected from the group consisting of hydrogen and substituted or unsubstituted alkyl group R 1a in Formula 4, L1 is selected from a substituted or unsubstituted alkylene group, R 16a is substituted or It may be selected from an unsubstituted alkyl group, R 17a may include a monomer selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group.
보다 바람직하게는, 본 발명의 측쇄 모양 폴리머는 하기 화학식 5로 표시되는 모노머를 포함할 수 있다.More preferably, the side chain polymer of the present invention may include a monomer represented by the following formula (5).
[화학식 5][Formula 5]
Figure PCTKR2019001826-appb-I000020
Figure PCTKR2019001826-appb-I000020
화학식 5 에서,In Formula 5,
R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고, L1은 단일결합, 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고, R18a는 적어도 1개의 히드록시기로 치환된 아다만틸기인 모노머를 포함할 수 있다.R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group, L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group, R 18a may comprise a monomer which is an adamantyl group substituted with at least one hydroxy group.
더욱 바람직하게는, 본 발명의 측쇄 모양 폴리머는 상기 화학식 5 중 R1a가 수소 및 치환 또는 비치환 알킬기로 이루어진 군에서 선택되고, L1은 단일결합 및 치환 또는 비치환 알킬렌기에서 선택되고, R18a는 적어도 1개의 히드록시기로 치환된 아다만틸기인 모노머를 포함할 수 있다.More preferably, in the side chain polymer of the present invention, R 1a in Formula 5 is selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group, L1 is selected from a single bond and a substituted or unsubstituted alkylene group, and R 18a May include a monomer which is an adamantyl group substituted with at least one hydroxy group.
보다 바람직하게는, 본 발명의 측쇄 모양 폴리머는 하기 화학식 6으로 표시되는 모노머를 포함할 수 있다.More preferably, the side chain polymer of the present invention may include a monomer represented by the following formula (6).
[화학식 6][Formula 6]
Figure PCTKR2019001826-appb-I000021
Figure PCTKR2019001826-appb-I000021
화학식 6 에서,In Chemical Formula 6,
R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고, L1은 단일결합, 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고, R19a는 치환 또는 비치환 알킬기, 치환 또는 비치환 알케닐기, 치환 또는 비치환 시킬로 알킬기 및 치환 또는 비치환 시클로 알케닐기로 이루어진 군에서 선택될 수 있다.R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group, L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group, R 19a may be selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted halo alkyl group and a substituted or unsubstituted cyclo alkenyl group.
더욱 바람직하게는, 본 발명의 측쇄 모양 폴리머는 상기 화학식 6 중 R1a가 수소 및 치환 또는 비치환 알킬기로 이루어진 군에서 선택되고, L1은 단일결합 및 치환 또는 비치환 알킬렌기에서 선택되고, R19a는 치환 또는 비치환 알킬기, 치환 또는 비치환 알케닐기, 치환 또는 비치환 시클로 알킬기 및 치환 또는 비치환 시클로 알케닐기로 이루어진 군에서 선택되는 모노머를 포함할 수있다. More preferably, in the side chain polymer of the present invention, R 1a in Formula 6 is selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group, L1 is selected from a single bond and a substituted or unsubstituted alkylene group, and R 19a May include a monomer selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted cyclo alkenyl group.
더욱 바람직하게는 상기 화학식 6 중 R19a는 치환 또는 비치환 아다만틸기일 수 있다.More preferably, R 19a in Chemical Formula 6 may be a substituted or unsubstituted adamantyl group.
바람직하게는, 상기 모노머 단위에서 R1a는 수소 또는 메틸일 수 있고, 보다 바람직하게는 상기 R1a는 메틸일 수 있다.Preferably, R 1a in the monomer unit may be hydrogen or methyl, more preferably R 1a may be methyl.
본 발명의 쇄상 폴리머의 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 바람직한 측쇄에는 다음의 것이 포함되나, 그러한 OH기를 가지면 되므로, 열거한 내용은 어디까지나 예시이며, 이에 한정되지 않는다.Preferred side chains having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group of the chain polymer of the present invention include the followings, but such OH groups may be included. It doesn't work.
(1a) A-O-CO-형(A는 측쇄의 잔부를 나타낸다. 이하 동일.) 측쇄: 2-히드록시에톡시카보닐, 2-히드록시프로폭시카르보닐, 4-(히드록시메틸)시클로헥실메톡시카보닐, 2-히드록시-3-(시클로헥실카르보닐옥시)프로폭시카르보닐, 3-벤조일옥시-2-히드록시프로폭시카르보닐, 4-벤조일옥시-3-히드록시시클로헥실메톡시카르보닐, 3-히드록시-1-아다만틸옥시카르보닐, 2-히드록시시클로헥실옥시카르보닐, 4-운데카노일옥시-3-히드록시시클로헥실메톡시카르보닐, 4-부타노일옥시-3-히드록시시클로헥실메톡시카르보닐 등.(1a) AO-CO-type (A represents the remainder of the side chain. The same below.) Side chain: 2-hydroxyethoxycarbonyl, 2-hydroxypropoxycarbonyl, 4- (hydroxymethyl) cyclohex Silmethoxycarbonyl, 2-hydroxy-3- (cyclohexylcarbonyloxy) propoxycarbonyl, 3-benzoyloxy-2-hydroxypropoxycarbonyl, 4-benzoyloxy-3-hydroxycyclohexylme Methoxycarbonyl, 3-hydroxy-1-adamantyloxycarbonyl, 2-hydroxycyclohexyloxycarbonyl, 4-undecanoyloxy-3-hydroxycyclohexylmethoxycarbonyl, 4-buta Noyloxy-3-hydroxycyclohexylmethoxycarbonyl and the like.
(2a) A-CO-O-형 측쇄: 2-히드록시프로필카르보닐옥시, 2-히드록시-3-(시클로헥실카르보닐옥시)프로필카르보닐옥시, 3-벤조일옥시-2-히드록시프로필카르보닐옥시, 4-벤조일옥시-3-히드록시시클로헥실메틸카르보닐옥시, 3-히드록시-1-아다만틸카르보닐옥시, 2-히드록시시클로헥시록시카르보닐옥시, 4-운데카노일옥시-3-히드록시시클로헥실메틸카르보닐옥시, 4-부타노일옥시-3-히드록시시클로헥실메틸카르보닐옥시 등.(2a) A-CO-O-type side chain: 2-hydroxypropylcarbonyloxy, 2-hydroxy-3- (cyclohexylcarbonyloxy) propylcarbonyloxy, 3-benzoyloxy-2-hydroxypropyl Carbonyloxy, 4-benzoyloxy-3-hydroxycyclohexylmethylcarbonyloxy, 3-hydroxy-1-adamantylcarbonyloxy, 2-hydroxycyclohexoxycarbonyloxy, 4-undecano Yloxy-3-hydroxycyclohexylmethylcarbonyloxy, 4-butanoyloxy-3-hydroxycyclohexylmethylcarbonyloxy and the like.
(3a) A-O-형 측쇄: 2-히드록시프로폭시, 2-히드록시-3-(시클로헥실카르보닐옥시)프로폭시, 3-벤조일옥시-2-히드록시프로폭시, 4-벤조일옥시-3-히드록시시클로헥실메톡시, 3-히드록시-1-아다만틸옥시, 2-히드록시시클로헥시록시, 4-운데카노일옥시-3-히드록시시클로헥실메톡시, 4-부타노일옥시-3-히드록시시클로헥실메톡시 등.(3a) AO-type side chains: 2-hydroxypropoxy, 2-hydroxy-3- (cyclohexylcarbonyloxy) propoxy, 3-benzoyloxy-2-hydroxypropoxy, 4-benzoyloxy-3 -Hydroxycyclohexylmethoxy, 3-hydroxy-1-adamantyloxy, 2-hydroxycyclohexoxyoxy, 4-undecanoyloxy-3-hydroxycyclohexylmethoxy, 4-butanoyloxy -3-hydroxycyclohexylmethoxy and the like.
(4a) 기타: 2-히드록시프로필, 2-히드록시-3-(시클로헥실카르보닐옥시)프로필, 3-벤조일옥시-2-히드록시프로필, 4-벤조일옥시-3-히드록시시클로헥실메틸, 3-히드록시-1-아다만틸, 2-히드록시시클로헥실, 4-운데카노일옥시-3-히드록시시클로헥실메틸, 4-부타노일옥시-3-히드록시시클로헥실메틸 등.(4a) Others: 2-hydroxypropyl, 2-hydroxy-3- (cyclohexylcarbonyloxy) propyl, 3-benzoyloxy-2-hydroxypropyl, 4-benzoyloxy-3-hydroxycyclohexylmethyl , 3-hydroxy-1-adamantyl, 2-hydroxycyclohexyl, 4-undecanoyloxy-3-hydroxycyclohexylmethyl, 4-butanoyloxy-3-hydroxycyclohexylmethyl and the like.
쇄상 폴리머에 이들 측쇄를 부여하는 모노머의 바람직한 예로는 이하의 것을 들 수 있으나, 이에 한정되지 않는다.Preferred examples of the monomer which gives these side chains to the chain polymer include, but are not limited to the following.
(1b) 2-히드록시프로필(메타)아크릴레이트, 2-히드록시-3-(시클로헥실카르보닐옥시)프로필(메타)아크릴레이트, 3-벤조일옥시-2-히드록시프로필(메타)아크릴레이트, 4-벤조일옥시-3-히드록시시클로헥실메틸(메타)아크릴레이트, 1,3-아다만틸디올모노(메타)아크릴레이트 및 2-히드록시시클로헥실(메타)아크릴레이트, 4-운데카노일옥시-3-히드록시시클로헥실메틸(메타)아크릴레이트, 4-부타노일옥시-3-히드록시시클로헥실메틸(메타)아크릴레이트 등의(메타)아크릴레이트.(1b) 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3- (cyclohexylcarbonyloxy) propyl (meth) acrylate, 3-benzoyloxy-2-hydroxypropyl (meth) acrylate , 4-benzoyloxy-3-hydroxycyclohexylmethyl (meth) acrylate, 1,3-adamantyldiol mono (meth) acrylate and 2-hydroxycyclohexyl (meth) acrylate, 4-undecano (Meth) acrylates, such as yloxy-3-hydroxycyclohexylmethyl (meth) acrylate and 4-butanoyloxy-3-hydroxycyclohexylmethyl (meth) acrylate.
(2b) 2-히드록시부탄산 비닐에스테르, 2-히드록시-3-(시클로헥실카르보닐옥시)부탄산 비닐에스테르, 3-벤조일옥시-2-히드록시부탄산 비닐에스테르, 4-벤조일옥시-3-히드록시시클로헥실아세트산 비닐에스테르, 3-히드록시-1-아다만틸카르본산 비닐에스테르, 2-히드록시시클로헥시록실카르본산 비닐에스테르, 4-운데카노일옥시-3-히드록시시클로헥실아세트산 비닐에스테르, 4-부타노일옥시-3-히드록시시클로헥실아세트산 비닐에스테르 등의 비닐에스테르.(2b) 2-hydroxybutanoic acid vinyl ester, 2-hydroxy-3- (cyclohexylcarbonyloxy) butanoic acid vinyl ester, 3-benzoyloxy-2-hydroxybutanoic acid vinyl ester, 4-benzoyloxy- 3-hydroxycyclohexyl acetate vinyl ester, 3-hydroxy-1-adamantyl carboxylic acid vinyl ester, 2-hydroxycyclohexyl carboxylic acid vinyl ester, 4-undecanoyloxy-3-hydroxycyclo Vinyl esters such as hexyl acetate vinyl ester and 4-butanoyloxy-3-hydroxycyclohexyl acetate vinyl ester.
(3b) 2-히드록시프로필비닐에테르, 2-히드록시-3-(시클로헥실카르보닐옥시)프로필비닐에테르, 3-벤조일옥시-2-히드록시프로필비닐에테르, 4-벤조일옥시-3-히드록시시클로헥실메틸비닐에테르, 3-히드록시-1-아다만틸비닐에테르, 2-히드록시시클로헥실비닐에테르, 4-운데카노일옥시-3-히드록시시클로헥실메틸에테르, 4-부타노일옥시-3-히드록시시클로헥실메틸에테르 등의 비닐에테르.(3b) 2-hydroxypropyl vinyl ether, 2-hydroxy-3- (cyclohexylcarbonyloxy) propyl vinyl ether, 3-benzoyloxy-2-hydroxypropyl vinyl ether, 4-benzoyloxy-3-hydroxy Hydroxycyclohexyl methyl vinyl ether, 3-hydroxy-1-adamantyl vinyl ether, 2-hydroxycyclohexyl vinyl ether, 4-undecanoyloxy-3-hydroxycyclohexyl methyl ether, 4-butanoyloxy Vinyl ether, such as 3-hydroxycyclohexyl methyl ether.
(4b) 1-펜텐-4-올, 4-히드록시-5-(시클로헥실카르보닐옥시)-1-펜텐, 5-벤조일옥시-4-히드록시-1-펜텐, 3-(4-벤조일옥시-3-히드록시시클로헥실)-1-프로펜, (3-히드록시-1-아다만틸)에텐, (2-히드록시시클로헥실)에텐, 3-(4-운데카노일옥시-3-히드록시시클로헥실)-1-프로펜, 3-(4-부타노일옥시-3-히드록시시클로헥실)-1-프로펜 등의 비닐모노머.(4b) 1-penten-4-ol, 4-hydroxy-5- (cyclohexylcarbonyloxy) -1-pentene, 5-benzoyloxy-4-hydroxy-1-pentene, 3- (4-benzoyl Oxy-3-hydroxycyclohexyl) -1-propene, (3-hydroxy-1-adamantyl) ethene, (2-hydroxycyclohexyl) ethene, 3- (4-undecanoyloxy-3 Vinyl monomers such as -hydroxycyclohexyl) -1-propene and 3- (4-butanoyloxy-3-hydroxycyclohexyl) -1-propene.
(5b) 상기 (1a) 내지 (4a)를 각각 치환기로 가지는 무수 말레산 및 말레이미드.(5b) Maleic anhydride and maleimide each having the above (1a) to (4a) as a substituent.
본 발명의 쇄상 폴리머는, 상기의 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 모노머에 더해, 히드록실기를 갖지 않고 측쇄의 탄소수가 1 내지 15인 비치환 또는 α치환 (메타)아크릴계 모노머, 비치환 또는 α치환 비닐에스테르계 모노머, 비치환 또는 α치환 비닐에테르계 모노머 및 이들 외의 비치환 또는 α치환 비닐계 모노머 중 적어도 1종을 추가 모노머 단위로 포함해서 이루어지는 것일 수 있다. 그러한 추가 모노머 단위는 바람직하게는 CH2=C(R1a)-COO-R6, CH2=C(R1a)-COO-R7, CH2=C(R1a)-O-CO-R8,(여기서, R6, R7 및 R8은 서로 독립적으로, 탄소원자 1 내지 15개를 가지며, 히드록실기를 갖지 않고, 적어도 1개의 포화 또는 불포화 탄화수소기를 포함해서 이루어지거나, 또는 적어도 1개의 방향족기를 더 포함해서 이루어지며, 탄소원자 사이를 연결하는 -COO-, -O- 및 -CO-로 이루어진 군에서 선택된 결합을 가지고 있을 수 있고, 상기 탄화수소기 또는 방향족기는 아미노기를 가질 수 있다.), CH2=C(R1a)-0-R9, CH2=C(R1a)-R10 (여기서, R9 및 R10은 서로 독립적으로, 탄소원자 3 내지 15개를 가지며, 히드록실기를 갖지 않고, 적어도 1개의 포화 또는 불포화 탄화수소기를 포함해서 이루어지거나, 또는 적어도 1개의 방향족기를 더 포함해서 이루어지며, 탄소원자 사이를 연결하는 -COO-, -O- 및 -CO-로 이루어진 군에서 선택된 결합을 가지고 있을 수 있고, 상기 탄화수소기 또는 방향족기는 아미노기를 가질 수 있다.), C4(R1a)O3-R11 및 C4(R1a)HNO2-R12 (여기서, C4(R1a)O3-는 무수 말레산기를 나타내고, C4(R1a)HNO2-는 말레이미드기를 나타내고, R11 및 R12는 서로 독립적으로, 수소원자이거나 또는 탄소원자수 1 내지 15개를 가지며, 알코올성 제2급 또는 제3급 OH기 또는 페놀성 OH기를 갖지 않고, 적어도 1개의 포화 또는 불포화 탄화수소기를 포함해서 이루어지거나, 또는 적어도 1개의 방향족기를 더 포함해서 이루어지며, 탄소원자 사이를 연결하는 -COO-, -O- 및 -CO-로 이루어진 군에서 선택된 결합을 가지고 있을 수 있고, 상기 탄화수소기 또는 방향족기는 아미노기를 가질 수 있다.)로 표시되는 화합물로 이루어진 군에서 선택할 수 있다.In addition to the above-mentioned alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group, the chain polymer of the present invention has no hydroxyl group and unsubstituted or α-substituted having 1 to 15 carbon atoms in the side chain. (Meth) acrylic monomer, unsubstituted or α-substituted vinyl ester monomer, unsubstituted or α-substituted vinyl ether monomer, and at least one of other unsubstituted or α-substituted vinyl monomer may be included as an additional monomer unit have. Such further monomeric units are preferably CH 2 = C (R 1a ) -COO-R 6 , CH 2 = C (R 1a ) -COO-R 7 , CH 2 = C (R 1a ) -O-CO-R 8 , (wherein R 6 , R 7 and R 8 independently of one another have 1 to 15 carbon atoms, have no hydroxyl group, comprise at least one saturated or unsaturated hydrocarbon group, or at least 1 It further comprises two aromatic groups, may have a bond selected from the group consisting of -COO-, -O- and -CO- connecting between the carbon atoms, the hydrocarbon group or aromatic group may have an amino group. ), CH 2 = C (R 1a ) -0-R 9 , CH 2 = C (R 1a ) -R 10 (wherein R 9 and R 10 have, independently of each other, having 3 to 15 carbon atoms, It does not have a hydroxy group, comprises at least one saturated or unsaturated hydrocarbon group, or further comprises at least one aromatic group, a carbon source . It is possible to have a combination selected from the group consisting of -COO-, -O- and -CO- connecting the said hydrocarbon group or an aromatic group may have an amino group), C 4 (R 1a) O 3 - R 11 and C 4 (R 1a ) HNO 2 —R 12 wherein C 4 (R 1a ) O 3 − represents a maleic anhydride group, C 4 (R 1a ) HNO 2 − represents a maleimide group, and R 11 And R 12 independently of each other, have a hydrogen atom or 1 to 15 carbon atoms, do not have an alcoholic secondary or tertiary OH group or phenolic OH group, and comprises at least one saturated or unsaturated hydrocarbon group Or at least one aromatic group, and may have a bond selected from the group consisting of —COO—, —O—, and —CO— that connects carbon atoms, and the hydrocarbon or aromatic group is an amino group. It may have a compound represented by You can choose from the military.
본 발명의 쇄상 폴리머는, 상기의 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 모노머에 더해, 히드록실기를 갖지 않고 측쇄의 탄소수가 1 내지 15인 (메타)아크릴계 모노머, 비닐에스테르계 모노머, 비닐에테르계 모노머 및 이들 외의 비닐계 모노머 중 적어도 1종을 추가 모노머 단위로 포함해서 이루어지는 것일 수 있다. 그러한 추가 모노머 단위는 바람직하게는 CH2=CH-COO-R6, CH2=C(CH3) -COO-R7, CH2=CH-O-CO-R8,(여기서, R6, R7 및 R8은 서로 독립적으로, 탄소원자 1 내지 15개를 가지며, 히드록실기를 갖지 않고, 적어도 1개의 포화 또는 불포화 탄화수소기를 포함해서 이루어지거나, 또는 적어도 1개의 방향족기를 더 포함해서 이루어지며, 탄소원자 사이를 연결하는 -COO-, -O- 및 -CO-로 이루어진 군에서 선택된 결합을 가지고 있을 수 있고, 상기 탄화수소기 또는 방향족기는 아미노기를 가질 수 있다.), CH2=CH-0-R9, CH2=CH-R10 (여기서, R9 및 R10은 서로 독립적으로, 탄소원자 3 내지 15개를 가지며, 히드록실기를 갖지 않고, 적어도 1개의 포화 또는 불포화 탄화수소기를 포함해서 이루어지거나, 또는 적어도 1개의 방향족기를 더 포함해서 이루어지며, 탄소원자 사이를 연결하는 -COO-, -O- 및 -CO-로 이루어진 군에서 선택된 결합을 가지고 있을 수 있고, 상기 탄화수소기 또는 방향족기는 아미노기를 가질 수 있다.), C4HO3-R11 및 C4H2NO2-R12 (여기서, C4HO3-는 무수 말레산기를 나타내고, C4H2NO2-는 말레이미드기를 나타내고, R11 및 R12는 서로 독립적으로, 수소원자이거나 또는 탄소원자수 1 내지 15개를 가지며, 알코올성 제2급 또는 제3급 OH기 또는 페놀성 OH기를 갖지 않고, 적어도 1개의 포화 또는 불포화 탄화수소기를 포함해서 이루어지거나, 또는 적어도 1개의 방향족기를 더 포함해서 이루어지며, 탄소원자 사이를 연결하는 -COO-, -O- 및 -CO-로 이루어진 군에서 선택된 결합을 가지고 있을 수 있고, 상기 탄화수소기 또는 방향족기는 아미노기를 가질 수 있다.)로 표시되는 화합물로 이루어진 군에서 선택할 수 있다.The chain polymer of the present invention is a (meth) acrylic monomer having 1 to 15 carbon atoms in the side chain without having a hydroxyl group in addition to the monomer having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group. , A vinyl ester monomer, a vinyl ether monomer, and at least one of other vinyl monomers may be included as an additional monomer unit. Such further monomeric units are preferably CH 2 = CH-COO-R 6 , CH 2 = C (CH 3 ) -COO-R 7 , CH 2 = CH-O-CO-R 8 , wherein R 6 , R 7 and R 8 independently of each other, having 1 to 15 carbon atoms, do not have a hydroxyl group, comprises at least one saturated or unsaturated hydrocarbon group, or further comprises at least one aromatic group May have a bond selected from the group consisting of —COO—, —O—, and —CO— that connects carbon atoms, and the hydrocarbon or aromatic group may have an amino group.), CH 2 = CH-0 —R 9 , CH 2 ═CH—R 10 wherein R 9 and R 10 independently of one another have 3 to 15 carbon atoms, have no hydroxyl group, and include at least one saturated or unsaturated hydrocarbon group Or at least one aromatic group, and connect carbon atoms. And may have a bond selected from the group consisting of -COO-, -O- and -CO-, wherein the hydrocarbon group or the aromatic group may have an amino group.), C 4 HO 3 -R 11 and C 4 H 2 NO 2 -R 12 (wherein C 4 HO 3 -represents a maleic anhydride group, C 4 H 2 NO 2 -represents a maleimide group, and R 11 and R 12 independently of each other, a hydrogen atom or a carbon number of 1 to 15 carbon atoms, having no alcoholic secondary or tertiary OH group or phenolic OH group, including at least one saturated or unsaturated hydrocarbon group, or further comprising at least one aromatic group, and containing carbon atoms It may have a bond selected from the group consisting of -COO-, -O- and -CO- to connect between, and the hydrocarbon group or aromatic group may have an amino group) can be selected from the group consisting of compounds represented by have.
상기의 히드록실기를 갖지 않는 모노머 단위의 바람직한 예로는 이하의 것을 들 수 있으나, 이에 한정되지 않는다.Preferable examples of the monomer unit having no hydroxyl group include, but are not limited to the following.
(1) 메틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 글리시딜(메타)아크릴레이트, 부틸(메타)아크릴레이트, 에톡시에틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, 테트라히드로푸르푸릴(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 페닐(메타)아크릴레이트, 디시클로펜타디에닐(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 벤질(메타)아크릴레이트, N,N-디메틸아미노에틸(메타)아크릴레이트, N,N-디메틸아미노프로필(메타)아크릴레이트 등의 (메타)아크릴레이트.(1) Methyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, butyl (meth) acrylate, ethoxyethyl (meth) acrylate, pentyl (meth) acrylate, tetra Hydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, octyl (meth) acrylate, benzyl (meth) acrylate, N (Meth) acrylates, such as N, dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.
(2) 아세트산 비닐에스테르, 부탄산 비닐에스테르, 펜탄산 비닐에스테르, 헥산산 비닐에스테르, 시클로헥산카르본산 비닐에스테르, 안식향산 비닐에스테르, 시클로펜타디에닐카르본산 비닐에스테르, 노난산 비닐에스테르 등의 비닐에스테르.(2) vinyl esters such as vinyl acetate, vinyl butyrate, vinyl pentanate, vinyl hexanoate, vinyl ester of cyclohexanecarboxylic acid, vinyl ester of benzoic acid, vinyl ester of cyclopentadienylcarboxylic acid and vinyl nonanoic acid .
(3) 프로필비닐에테르, 부틸비닐에테르, 에톡시에틸비닐에테르, 글리시딜비닐에테르, 펜틸비닐에테르, 테트라히드로푸르푸릴비닐에테르, 시클로헥실비닐에테르, 페닐비닐에테르, 시클로펜타디에닐비닐에테르, 옥틸비닐에테르, 벤질비닐에테르, 2-(비닐옥시)에틸디메틸아민, 3-(비닐옥시)프로필 디메틸아민 등의 비닐에테르.(3) propyl vinyl ether, butyl vinyl ether, ethoxy ethyl vinyl ether, glycidyl vinyl ether, pentyl vinyl ether, tetrahydrofurfuryl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether, cyclopentadienyl vinyl ether, Vinyl ethers such as octyl vinyl ether, benzyl vinyl ether, 2- (vinyloxy) ethyldimethylamine, and 3- (vinyloxy) propyl dimethylamine.
(4) 1-부텐, 4-에톡시-1-부텐, 1-펜텐, 1-헥센, 비닐시클로헥산, 스티렌, 비닐톨루엔, 1-노넨, 3-페닐프로펜 등의 비닐 유도체.(4) vinyl derivatives such as 1-butene, 4-ethoxy-1-butene, 1-pentene, 1-hexene, vinylcyclohexane, styrene, vinyltoluene, 1-nonene and 3-phenylpropene.
(5) 말레산 무수물, 메틸말레산 무수물, 부틸말레산 무수물, 헥실말레산 무수물, 시클로헥실말레산 무수물, 페닐말레산 무수물, 옥틸말레산 무수물 등의 말레산 무수물 유도체.(5) Maleic anhydride derivatives such as maleic anhydride, methylmaleic anhydride, butylmaleic anhydride, hexylmaleic anhydride, cyclohexylmaleic anhydride, phenylmaleic anhydride and octylmaleic anhydride.
(6) 말레이미드, 메틸말레이미드, 에틸말레이미드, 부틸말레이미드, 헥실말레이미드, 시클로헥실말레이미드, 페닐말레이미드, 벤질말레이미드, 옥틸말레이미드 등의 말레이미드 유도체.(6) maleimide derivatives such as maleimide, methyl maleimide, ethyl maleimide, butyl maleimide, hexyl maleimide, cyclohexyl maleimide, phenyl maleimide, benzyl maleimide and octyl maleimide.
본 발명의 쇄상 폴리머는 모노머 단위의 단독 중합체이어도 좋고, 2종, 3종 또는 4종 이상의 종류의 모노머 단위를 포함하는 공중합체일 수 있으나, 상기 공중합체의 상기 모노머 단위의 최소 1종은 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 모노머이다. 바람직하게는 상기 공중합체는 1종 이상의 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 갖는 모노머와 적어도 1종의 히드록시기를 갖지 않는 추가 모노머를 포함한다.The linear polymer of the present invention may be a homopolymer of monomer units, and may be a copolymer including two, three or four or more kinds of monomer units, but at least one of the monomer units of the copolymer is an alcoholic agent. It is a monomer which has a secondary or tertiary OH containing group or a phenolic OH containing group. Preferably the copolymer comprises a monomer having at least one alcoholic secondary or tertiary OH containing group or a phenolic OH containing group and an additional monomer having no at least one hydroxyl group.
본 발명의 쇄상 폴리머 중, 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 모노머 단위가 차지하는 비율은, 바람직하게는 30 내지 100몰%, 보다 바람직하게는 50 내지 100몰%, 보다 바람직하게는 60 내지 100몰%, 더욱 바람직하게는 80 내지 100몰%, 특히 바람직하게는 90 내지 100몰%이다.In the chain polymer of the present invention, the proportion of the monomeric unit having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group is preferably 30 to 100 mol%, more preferably 50 to 100 mol%. More preferably, it is 60-100 mol%, More preferably, it is 80-100 mol%, Especially preferably, it is 90-100 mol%.
본 발명에서 쇄상 폴리머는, 그 원료 모노머를 이용하여, 통상적인 방법으로, 예를 들어 2,2'-아조비스이소부티로니트릴(AIBN) 등 관용의 라디칼 중합 촉매를 사용하여, 중합 반응시킴으로써 제조할 수 있다. 쇄상 폴리머의 분자량은 10000 내지 100000의 범위(겔 여과 크로마토그래피법에 의한 측정)인 것이 보통 바람직하지만, 특별히 이 범위에 한정되는 것은 아니다.In the present invention, the chain polymer is produced by using a raw material monomer and polymerized by a conventional method using, for example, a conventional radical polymerization catalyst such as 2,2'-azobisisobutyronitrile (AIBN). can do. The molecular weight of the linear polymer is usually in the range of 10000 to 100000 (measured by gel filtration chromatography), but is not particularly limited to this range.
본 발명의 경화성 수지 조성물에서의 가교제로는 트리아진계 가교제, 글리콜우릴계 가교제 또는 이미다졸리디논계 가교제가 바람직하다. 보다 구체적으로는 트리아진계 화합물, 그 축합체 및 이들의 혼합물; 글리콜우릴계 화합물, 그 축합체 및 이들의 혼합물; 및 이미다졸리디논계 화합물, 그 축합체 및 이들의 혼합물로 이루어진 군에서 선택되는 것이 바람직하다. As a crosslinking agent in curable resin composition of this invention, a triazine crosslinking agent, a glycoluril crosslinking agent, or an imidazolidinone type crosslinking agent is preferable. More specifically, triazine compounds, their condensates and mixtures thereof; Glycoluril compounds, their condensates, and mixtures thereof; And imidazolidinone compounds, condensates thereof, and mixtures thereof.
이들 가교제의 바람직한 구체예로는, 완전 또는 부분 알콕시(예를 들면 메톡시, 에톡시) 메틸화 멜라민, 그 축합체 및 이들의 혼합물; 완전 또는 부분 알콕시(예를 들면 메톡시, 에톡시) 메틸화 구아나민, 그 축합체 및 이들의 혼합물; 완전 또는 부분 알콕시(예를 들면 메톡시, 에톡시) 메틸화 아세토구아나민, 그 축합체 및 이들의 혼합물; 완전 또는 부분 알콕시메틸화 벤조구아나민, 그 축합체 및 이들의 혼합물; 완전 또는 부분 알콕시(예를 들면 메톡시, 에톡시) 메틸화 글리코루릴 그 축합체 및 이들의 혼합물; 완전 또는 부분 알콕시(예를 들면 메톡시, 에톡시) 메틸화 이미다졸리디논, 그 축합체 및 이들의 혼합물로 이루어진 군에서 선택된 것;을 들 수 있다. 여기서 "알콕시"는 탄소 수 1 내지 4인 것이 바람직하다. Preferred embodiments of these crosslinkers include fully or partially alkoxy (eg methoxy, ethoxy) methylated melamines, their condensates and mixtures thereof; Fully or partially alkoxy (eg methoxy, ethoxy) methylated guanamine, its condensates and mixtures thereof; Fully or partially alkoxy (eg methoxy, ethoxy) methylated acetoguanamine, condensates thereof and mixtures thereof; Fully or partially alkoxymethylated benzoguanamine, condensates thereof and mixtures thereof; Fully or partially alkoxy (eg methoxy, ethoxy) methylated glycuril condensates thereof and mixtures thereof; Full or partial alkoxy (eg methoxy, ethoxy) methylated imidazolidinones, condensates thereof and mixtures thereof; and the like. It is preferable here that "alkoxy" has 1 to 4 carbon atoms.
그러한 가교제로서, 보다 구체적으로 예를 들면, 헥사메톡시메틸멜라민, 헥사에톡시메틸멜라민, 테트라메톡시메틸메틸올멜라민, 테트라메톡시메틸멜라민, 헥사부톡시메틸멜라민, 테트라메톡시메틸구아나민, 테트라메톡시메틸아세토구아나민, 테트라메톡시메틸벤조구아나민, 트리메톡시메틸벤조구아나민, 테트라에톡시메틸벤조구아나민, 테트라메틸올벤조구아나민, 1,3,4,6-테트라키스(메톡시메틸)글리코루릴, 1,3,4,6-테트라키스(부톡시메틸)글리코루릴, 4,5-디히드록시-1,3-디메톡시 메틸-2-이미다졸리디논, 4,5-디메톡시-1,3-디메톡시메틸-2-이미다졸리디논 등을 들 수 있으나, 이에 한정되지 않는다.As such a crosslinking agent, More specifically, for example, hexamethoxymethylmelamine, hexaethoxymethylmelamine, tetramethoxymethylmethylolmelamine, tetramethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylguanamine, Tetramethoxymethylacetoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine, tetramethylolbenzoguanamine, 1,3,4,6-tetrakis ( Methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 4,5-dihydroxy-1,3-dimethoxy methyl-2-imidazolidinone, 4, 5-dimethoxy-1,3-dimethoxymethyl-2-imidazolidinone and the like, but are not limited thereto.
일 실시예에 있어서, 바람직하게는 상기 가교제는 하기 화학식 7로 표시되는 화합물, 그 축합체 및 이들의 혼합물로 이루어진 군에서 선택될 수 있다.In one embodiment, preferably, the crosslinking agent may be selected from the group consisting of a compound represented by the following Formula 7, a condensate thereof, and a mixture thereof.
[화학식 7][Formula 7]
Figure PCTKR2019001826-appb-I000022
Figure PCTKR2019001826-appb-I000022
화학식 7 에서, R1b는 탄소수 1 내지 25의 치환 또는 비치환 알킬기, 탄소수 2 내지 25의 치환 또는 비치환 알케닐기, 탄소수 6 내지 25의 치환 또는 비치환 방향족기, 탄소수 4 내지 25의 치환 또는 비치환 헤테로 방향족기, 및 하기 화학식 8로 표시되는 2치환 아민으로 이루어진 군에서 선택되고, In Formula 7, R 1b is a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 25 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 25 carbon atoms, substituted or unsubstituted carbon atoms at 4 to 25 carbon atoms. Ring heteroaromatic group, and a disubstituted amine represented by the following formula (8);
R2b, R3b, R4b 및 R5b 는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기, 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택될 수 있다.R 2b , R 3b , R 4b and R 5b may be independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.
[화학식 8][Formula 8]
Figure PCTKR2019001826-appb-I000023
Figure PCTKR2019001826-appb-I000023
화학식 8 에서, R6b 및 R7b 는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기, 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택될 수 있다.In Formula 8, R 6b and R 7b may be independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.
보다 바람직하게는, 본 발명의 가교제는 상기 화학식 7의 R1b는 탄소수 1 내지 25의 치환 또는 비치환 알킬기, 탄소수 6 내지 25의 치환 또는 비치환 방향족기, 상기 화학식 8로 표시되는 2치환 아민으로 이루어진 군에서 선택되고, R2b 내지 R7b는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기에서 선택되는 화합물, 그 축합체 및 이들의 혼합물일 수 있다.More preferably, the crosslinking agent of the present invention, R 1b of Formula 7 is a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 25 carbon atoms, and a disubstituted amine represented by Formula 8 And R 2b to R 7b may be each independently selected from a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, condensates thereof, and mixtures thereof.
다른 실시예에 있어서, 바람직하게는 상기 가교제는 하기 화학식 9로 표시되는 화합물, 그 축합체 및 이들의 혼합물로 이루어진 군에서 선택될 수 있다.In another embodiment, preferably, the crosslinking agent may be selected from the group consisting of a compound represented by the following formula (9), a condensate thereof, and a mixture thereof.
[화학식 9] [Formula 9]
Figure PCTKR2019001826-appb-I000024
Figure PCTKR2019001826-appb-I000024
화학식 9 에서, R8b 내지 R11b는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택될 수 있다.In Formula 9, R 8b to R 11b may be independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.
보다 바람직하게는, 본 발명의 가교제는 상기 화학식 9의 R8b 내지 R11b는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기에서 선택되는 화합물, 그 축합체 및 이들의 혼합물일 수 있다.More preferably, the crosslinking agent of the present invention may be a compound selected from R 8b to R 11b of Formula 9 independently from a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a condensate thereof and a mixture thereof.
또다른 실시예에 있어서, 바람직하게는 상기 가교제는 하기 화학식 10으로 표시되는 화합물, 그 축합체 및 이들의 혼합물로 이루어진 군에서 선택될 수 있다.In another embodiment, preferably, the crosslinking agent may be selected from the group consisting of a compound represented by the following Chemical Formula 10, a condensate thereof, and a mixture thereof.
[화학식 10][Formula 10]
Figure PCTKR2019001826-appb-I000025
Figure PCTKR2019001826-appb-I000025
화학식 10 에서, R12b 및 R13b는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고, R14b 및 R15b는 서로 독립적으로 수소, 탄소수 1 내지 10의 치환 또는 비치환 알킬기, 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택될 수 있다.In formula (10), R 12b and R 13b are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, and R 14b and R 15b are independent from each other And hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.
보다 바람직하게는, 본 발명의 가교제는 상기 화학식 10의 R12b 및 R13b는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기에서 선택되고, R14b 및 R15b는 서로 독립적으로 수소, 탄소수 1 내지 10의 치환 또는 비치환 알킬기에서 선택되는 화합물, 그 축합체 및 이들의 혼합물로 이루어진 군에서 선택될 수 있다. More preferably, the crosslinking agent of the present invention, R 12b and R 13b of Formula 10 are independently selected from a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and R 14b and R 15b are each independently hydrogen, C 1 It may be selected from the group consisting of compounds selected from substituted or unsubstituted alkyl group of 10 to 10, a condensate thereof and mixtures thereof.
더욱 바람직하게는, 상기 식 10에서 R14b 및 R15b가 수소일 수 있다.More preferably, in Formula 10, R 14b and R 15b may be hydrogen.
본 발명의 가교제의 더욱 바람직한 구체적인 예로는 다음의 구조식에 표시되거나 열거된 화합물, 그 축합체 및 이들의 혼합물로 구성된 군에서 선택될 수 있다:More preferred specific examples of the crosslinking agent of the present invention may be selected from the group consisting of compounds represented or listed in the following structural formula, condensates thereof and mixtures thereof:
Figure PCTKR2019001826-appb-I000026
Figure PCTKR2019001826-appb-I000026
헥사메톡시메틸멜라민; 헥사부톡시메틸멜라민; 1,3,4,6-테트라키스(메톡시메틸)글리콜우릴; 1,3,4,6-테트라키스(부톡시메틸)글리콜우릴; 테트라메톡시메틸벤조구아나민; 4,5-디히드록시-1,3-비스(알콕시메틸)이미다졸리딘-2-온.Hexamethoxymethylmelamine; Hexabutoxymethylmelamine; 1,3,4,6-tetrakis (methoxymethyl) glycoluril; 1,3,4,6-tetrakis (butoxymethyl) glycoluril; Tetramethoxymethylbenzoguanamine; 4,5-dihydroxy-1,3-bis (alkoxymethyl) imidazolidin-2-one.
상기 가교제 중 축합체는, 바람직하게는 상기 화학식 7, 9 또는 10으로 표시되는 화합물들의 중합체를 포함할 수 있으며, 보다 바람직하게는 상기 화합물들의 2량체, 3량체 및 4차 이상의 고차 중합체 중 적어도 1개를 포함할 수 있다.The condensate in the crosslinking agent may preferably include a polymer of compounds represented by Formula 7, 9 or 10, and more preferably at least 1 of a dimer, trimer and quaternary higher order polymer of the compounds. May include a dog.
상기 가교제는 상기 화학식 7, 9 또는 10으로 표시되는 화합물들에 대해 1 이상의 중량평균 중합도를 가지는 것이 바람직하며, 보다 바람직하게는 1 내지 1.8, 더 바람직하게는 1.3 내지 1.8, 특별하게는 1.5의 중량 평균 중합도를 갖는 것이 바람직하나, 이에 한정되지 않는다.The crosslinking agent preferably has a weight average degree of polymerization of 1 or more with respect to the compounds represented by Formula 7, 9 or 10, more preferably 1 to 1.8, more preferably 1.3 to 1.8, especially 1.5 It is preferred to have an average degree of polymerization, but is not limited thereto.
상기 화합물의 상기 축합체의 중량 평균 중합도가 1인 경우, 그 축합체는 그 화합물 자체임을 의미한다. 상기 중량 평균 중합도는 바람직하게는 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 3, 4 또는 그보다 큰 값이며, 보다 바람직하게는 1.3, 1.4, 1.5, 1.6, 1.7, 1.8이며, 더욱 바람직하게는 1.5이다.When the weight average degree of polymerization of the condensate of the compound is 1, it means that the condensate is the compound itself. The weight average degree of polymerization is preferably 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 3, 4 or greater, and more preferably 1.3, 1.4, 1.5, 1.6, 1.7 , 1.8, and more preferably 1.5.
본 발명의 일 실시예에 따른 경화성 수지 조성물에서 쇄상 폴리머와 가교제의 질량비는 예를 들어, 1:0.03 내지 1:2, 바람직하게는 1:0.05 내지 1:2, 1:0.05 내지 1:1, 1:0.03 내지 1:1, 더욱 바람직하게는 1:0.09 내지 1:1, 1:0.1 내지 1:0.5, 더욱 바람직하게는 1:0.09 내지 1:0.3, 1:0.1 내지 1:0.3이다.In the curable resin composition according to an embodiment of the present invention, the mass ratio of the chain polymer and the crosslinking agent is, for example, 1: 0.03 to 1: 2, preferably 1: 0.05 to 1: 2, 1: 0.05 to 1: 1, 1: 0.03 to 1: 1, more preferably 1: 0.09 to 1: 1, 1: 0.1 to 1: 0.5, more preferably 1: 0.09 to 1: 0.3, 1: 0.1 to 1: 0.3.
본 발명에있어서, 경화성 수지 조성물은 또한 산 촉매를 포함한다. 상기 산 촉매는 모노머와 가교제 간 반응의 중합 촉매로서 필요에 따라 포함된다. 상기 산 촉매는 중합 촉매로서 관용의 것을 적절히 선택 사용할 수있다. 상기 산 촉매는 브뢴스테드 산, 루이스 산 및 이들의 혼합물로 이루어진 군에서 선택되는 화합물일 수 있으며, 또는 그의 염 또는 그 용매화물일 수 있다. 상기 산 촉매로는, 예를 들면, 디노닐 나프탈렌 디술 폰산, 디노닐 나프탈렌 (모노)술폰산, 도데실 벤젠 술폰산, p-톨루엔 술폰산(PTS), 인산, 황산 및 아세트산 등 양성자 산, 및 산에이도 SI-100L, SI-150L, SI-60L 및 SI-80L(삼신화학공업(주)) 등의 열 산 발생 제로 이루어진 군에서 선택되는 화합물, 또는 그 염 또는 그 용매화물을 들 수 있지만, 이에 한정되지 않는다. 바람직하게는 상기 산 촉매는 p-톨루엔 술폰산(PTS), 도데실 벤젠 술폰산 및 열 산 발생제 산에이도 SI-100L (삼신화학공업 (주))로 이루어진 군에서 선택되는 화합물, 또는 그 염, 또는 그 용매화물일 수 있다. 보다 바람직하게는 상기 산 촉매는 피리디니움-p-톨루엔술폰산, p-톨루엔 술폰산 또는 그 수화물일 수 있다.In the present invention, the curable resin composition also includes an acid catalyst. The acid catalyst is included as necessary as a polymerization catalyst for the reaction between the monomer and the crosslinking agent. The said acid catalyst can use suitably the conventional thing as a polymerization catalyst. The acid catalyst may be a compound selected from the group consisting of Bronsted acid, Lewis acid and mixtures thereof, or may be a salt or solvate thereof. As the acid catalyst, for example, dinonyl naphthalene disulfonic acid, dinonyl naphthalene (mono) sulfonic acid, dodecyl benzene sulfonic acid, p-toluene sulfonic acid (PTS), proton acids such as phosphoric acid, sulfuric acid and acetic acid, and acid eido Compounds selected from the group consisting of thermal acid generators such as SI-100L, SI-150L, SI-60L, and SI-80L (Samshin Chemical Co., Ltd.), or salts or solvates thereof may be mentioned, but are not limited thereto. It doesn't work. Preferably, the acid catalyst is a compound selected from the group consisting of p-toluene sulfonic acid (PTS), dodecyl benzene sulfonic acid, and a thermal acid generator acid A. SI-100L (Samshin Chemical Co., Ltd.), or a salt thereof, Or solvates thereof. More preferably, the acid catalyst may be pyridinium-p-toluenesulfonic acid, p-toluene sulfonic acid or a hydrate thereof.
본 발명의 일 실시예에 따른 경화성 수지 조성물이 산 촉매를 더 포함하는 경우, 상기 쇄상 폴리머와 가교제 및 산 촉매의 질량비는 바람직하게는 1:0.03:0.05 내지 1:2:0.1, 보다 바람직하게는 1:0.05:0.05 내지 1:2:0.1, 더욱 바람직하게는 1:0.09:0.05 내지 1:1:0.08일 수 있다.When the curable resin composition according to an embodiment of the present invention further includes an acid catalyst, the mass ratio of the chain polymer, the crosslinking agent and the acid catalyst is preferably 1: 0.03: 0.05 to 1: 2: 0.1, more preferably. 1: 0.05: 0.05 to 1: 2: 0.1, more preferably 1: 0.09: 0.05 to 1: 1: 0.08.
본 발명에서, 경화성 수지 조성물은 용제에 의해 적절한 농도로 희석된 것일 수 있다. 비점이 너무 낮거나 높거나 해서 경화성 수지 조성물을 유리제 등의 기판에 경화성 수지 조성물을 도포한 후 건조에 의한 균일한 도막 형성에 문제가 없는 한, 관용되는 비프로톤 용매를 적절히 선택해서 사용할 수 있다. 예를 들면, 프로필렌글리콜모노메틸에테르는 적합한 용제이나, 이에 한정되지 않는다. 용제에 의한 희석은 모노머의 중합 반응시나, 가교제, 촉매를 첨가한 경화성 수지 조성물의 도포 시 등에서의 취급 편의를 위한 것이므로 희석 정도에 특별한 상한, 하한은 없다.In the present invention, the curable resin composition may be diluted to an appropriate concentration with a solvent. As long as a boiling point is too low or high, and a curable resin composition is apply | coated to the board | substrate, such as glass, there is no problem in formation of a uniform coating film by drying, A common aprotic solvent can be selected suitably, and can be used. For example, propylene glycol monomethyl ether is a suitable solvent, but it is not limited to this. Dilution with a solvent is for handling convenience in the polymerization reaction of a monomer, the application | coating of curable resin composition which added the crosslinking agent, a catalyst, etc., and there is no special upper limit and a minimum in dilution degree.
(2-2) 분리층(경화수지막)(2-2) Separation layer (cured resin film)
본 발명은 상기 (2-1)의 경화성 수지 조성물을 경화시켜 형성한 경화수지막을 분리층으로 포함할 수 있다.The present invention may include a cured resin film formed by curing the curable resin composition of the above (2-1) as a separation layer.
또한, 본 발명은 상기 (2-1)의 경화성 수지 조성물을 기판 표면상에 막 형태로 경화시켜 이루어지는, 이박리성 분리층을 제공할 수 있다.Moreover, this invention can provide the easily peelable separation layer which hardens curable resin composition of said (2-1) in film form on the board | substrate surface.
본 발명의 경화성 수지막에 의해 형성되는 분리층은 본 명세서에서 정의된 "내열성"을 갖춤과 동시에, 내열성인 온도 범위에서 가열 처리 후에도 이박리성을 가진다.The separation layer formed by the curable resin film of the present invention not only has "heat resistance" defined in the present specification, but also has a peeling property even after heat treatment in a heat resistant temperature range.
본 발명의 경화성 수지 조성물은 대표적으로 쇄상 고분자, 가교제 및 필요에 따라 산 촉매를 더 용제에 용해한 용액을 유리 기판(바람직하게는 소다 라임 유리) 위에 도포하고, 열처리(100℃ 내지 230℃, 1 분 이상)하여 경화시킴으로써, 수백 nm 두께(바람직하게는 약 200nm 내지 약 300nm의 두께)의 이박리성 분리층을 투명 박막으로 성막할 수 있다. 이론에 구속되는 것을 바라지 않으나, 구조적으로는 쇄상 고분자의 측쇄의 히드록시기와 가교제가 가열에 의해 가교시 경화 수축에 박리 가능한 필름이다.The curable resin composition of the present invention typically applies a chain polymer, a crosslinking agent, and a solution in which an acid catalyst is further dissolved in a solvent, if necessary, onto a glass substrate (preferably soda lime glass), followed by heat treatment (100 ° C. to 230 ° C. for 1 minute). The above-mentioned) hardening | curing can form the transparent peeling thin film of the peelable separation layer of several hundred nm thickness (preferably about 200 nm-about 300 nm). Although not wishing to be bound by theory, structurally, the hydroxyl group and the crosslinking agent of the side chain of the chain polymer are peelable films for curing shrinkage upon crosslinking by heating.
Figure PCTKR2019001826-appb-I000027
Figure PCTKR2019001826-appb-I000027
상기 유리 기판에 조성물을 도포하는 방법으로는 공지의 코팅 방법을 사용할 수 있다. 예를 들면, 스핀 코팅, 스핀리스 코팅, 다이 코팅, 스프레이 코팅, 롤 코팅, 스크린 코팅, 슬릿 코팅, 딥 코팅 및 그라이바 고팅 등을 들 수 있다. 바람직하게는 스핀 코팅을 들 수 있다.A well-known coating method can be used as a method of apply | coating a composition to the said glass substrate. For example, spin coating, spinless coating, die coating, spray coating, roll coating, screen coating, slit coating, dip coating and grabar coating may be mentioned. Preferably spin coating is mentioned.
기판 상에 증착된 분리층은 150℃까지 가열을 견디고, 바람직하게는 230℃ 가열(소성)에 견딜 수 있다. 또한, 포토 레지스트 용제에 내성이 있고, 알칼리성 현상 용액에 견딜 수 있어, 회로 제작을 위한 수지베이스 필름으로 유리하게 사용할 수 있다. 또한, 본 발명의 분리층은 가열(소성) 후에도 이박리성을 가지고 있어, 박막임에도 불구하고 기존에 비해 고온에서의 소성 단계를 포함하는 회로 제작 프로세스에 사용 가능하여, 회로의 특성 유지에 유리하며, 또한 회로 제작 후에도 기재에서 무리없이 쉽게 박리 가능하다.The separation layer deposited on the substrate can withstand heating up to 150 ° C. and preferably withstand 230 ° C. heating (firing). Moreover, it is resistant to a photoresist solvent, can withstand an alkaline developing solution, and can be advantageously used as a resin base film for circuit fabrication. In addition, the separation layer of the present invention has a dissociation property even after heating (firing), and can be used in a circuit fabrication process including a sintering step at a high temperature in comparison with a conventional film, and is advantageous in maintaining the characteristics of a circuit. In addition, it can be easily peeled off from the substrate even after fabrication of the circuit.
본 발명의 분리층은 하기 (3) 분리층 제조방법에 기재된 방법에 따라 제조될 수 있다.The separation layer of the present invention can be prepared according to the method described in the following (3) method for producing a separation layer.
본 발명의 분리층의 박리력은, 예를 들어 다음의 측정 방법을 통해 측정할 수 있다. 본 발명의 경화성 수지 조성물을, 대표적으로, 쇄상 고분자, 가교제 및 필요에 따라 산 촉매를 더욱 용제에 용해한 용액을 유리 기판(바람직하게는 소다 라임 유리) 위에 도포하고, 열처리(100℃ 내지 230℃, 1 분 이상)하여 경화시킴으로써, 유리 기판 상에 분리층을 형성한다. 측정 장치로서, 예를 들면, TENSILON RTG-1310(㈜ A&데이) 로드셀로 UR-100N-D형을 이용한다. 유리 기판 상의 분리층에 니치 반 테이프(24mm폭)를 붙여, 박리 각도 90°로 박리속도는 300mm/분의 일정한 속도로 당겨 박리력을 측정한다.The peeling force of the separation layer of this invention can be measured, for example through the following measuring method. The curable resin composition of this invention is typically apply | coated on a glass substrate (preferably soda lime glass) the linear polymer, the crosslinking agent, and the solution which melt | dissolved the acid catalyst further in the solvent as needed, and heat-processing (100-230 degreeC, 1 minute or more) and hardening | curing, a separation layer is formed on a glass substrate. As a measuring device, for example, a UR-100N-D type is used as a TENSILON RTG-1310 (A & Day) load cell. A niche half tape (24 mm width) was affixed to the separating layer on a glass substrate, and peeling speed is pulled at the constant speed of 300 mm / min, and peeling force is measured by peeling angle 90 degrees.
본 발명의 분리층은, 바람직하게는, 0.5N/mm2 이하의 소다 유리기판 또는 무 알칼리 유리기판에서의 박리력을 갖는다. 본 발명의 분리층은 더욱 바람직하게는 0.1N/mm2 이하의 소다 유리 기판 또는 무 알칼리 유리기판에서의 박리력을 갖는다. 본 발명의 분리층은 더욱 바람직하게는 0.09N/mm2 이하의 소다 유리기판 또는 무 알칼리 유리기판에서의 박리력을 갖는다. The separation layer of the present invention preferably has a peel force on a soda glass substrate or an alkali free glass substrate of 0.5 N / mm 2 or less. The separation layer of the present invention more preferably has a peel force on a soda glass substrate or an alkali free glass substrate of 0.1 N / mm 2 or less. The separation layer of the present invention more preferably has a peel force on a soda glass substrate or an alkali-free glass substrate of 0.09 N / mm 2 or less.
소다 유리기판에서의 박리력의 바람직한 값으로는 0.5N/mm2 이하, 0.4N /mm2 이하, 0.3N/mm2 이하 0.2N/mm2 이하 0.1N/mm2 이하 0.09N/mm2 이하, 0.08N/mm2 이하, 0.07N/mm2 이하, 0.06N/mm2 이하, 0.05N/mm2 이하, 0.04N/mm2 이하, 0.03N/mm2 이하, 0.02N/mm2 이하, 0.01N/mm2 이하가 있다. A preferred value for the peel force of the soda glass substrate is 0.5N / mm 2 or less, 0.4N / mm 2 or less, 0.3N / mm 2 or less 0.2N / mm 2 or less 0.1N / mm 2 or less 0.09N / mm 2 or less , 0.08N / mm 2 or less, 0.07N / mm 2 or less, 0.06N / mm 2 or less, 0.05N / mm 2 or less, 0.04N / mm 2 or less, 0.03N / mm 2 or less, 0.02N / mm 2 or less, It is 0.01 N / mm <2> or less.
무 알칼리 유리 기판에서의 박리력의 바람직한 값으로는 5N/mm2 이하, 0.04N/mm2 이하, 0.03N/mm2 이하, 0.02N/mm2 이하, 0.01N/mm2 이하이다. A non-preferred values of the peel force of the alkali glass substrate is 5N / mm 2 or less, 0.04N / mm 2 or less, 0.03N / mm 2 or less, 0.02N / mm 2 or less, 0.01N / mm 2 or less.
소다 유리 기판 또는 무 알칼리 유리기판에서의 상기 박리력이 0.5N/mm2 이하인 경우 상기 분리층은 이박리성을 갖춘 것으로 간주할 수 있다.When the peeling force in a soda glass substrate or an alkali free glass substrate is 0.5 N / mm 2 or less, the separation layer may be regarded as having a peeling property.
(3) 분리층의 제조방법(3) Manufacturing method of separation layer
일부 실시예에 있어서, 본 발명은 상기 (2-1)의 경화성 수지 조성물의 분리층 제조 방법으로서, In some embodiments, the present invention is a method for producing a separation layer of the curable resin composition of the above (2-1),
(i) 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 갖는 측쇄를 포함하는 상기 쇄상 폴리머와 상기 가교제를 준비하는 단계;(i) preparing the chain polymer and the crosslinking agent comprising a side chain having an alcoholic secondary or tertiary OH containing group or a phenolic OH containing group;
(ii) 상기 쇄상 폴리머와 상기 가교제를 포함하는 상기 경화성 수지 조성물을 기판 상에 도포하여 경화성 수지 조성물 도막을 형성하는 단계; 및(ii) applying the curable resin composition containing the chain polymer and the crosslinking agent onto a substrate to form a curable resin composition coating film; And
(iii) 상기 경화성 수지 조성물 도막에서 중합 반응을 시켜 경화시킴으로써 분리층을 형성하는 단계를 포함하는 제조방법을 제공한다.(iii) it provides a manufacturing method comprising the step of forming a separation layer by curing the polymerization reaction in the curable resin composition coating film.
상기 제조방법은 (iv) 상기 기판 상에 형성되어 있는 상기 분리층을 상기 기판에서 박리하는 단계를 더 포함할 수 있다.The manufacturing method may further include (iv) peeling the separation layer formed on the substrate from the substrate.
상기 제조방법은 하기 실시예에 기재된 방법으로 실시될 수 있을 뿐만 아니라, 당업자에게 공지된 방법으로도 실시될 수 있다.The preparation method can be carried out not only by the method described in the following examples, but also by a method known to those skilled in the art.
일부 실시예에 있어서, 상기 제조방법은 (i)단계 전에 (i') 적어도 1종의 원료 모노머를 중합시켜 상기 쇄상 폴리머를 제조하는 단계를 더 포함할 수 있다.In some embodiments, the method may further include preparing the chain polymer by polymerizing (i ′) at least one raw material monomer before step (i).
모노머를 중합시키는 방법으로는, 예를 들어, 괴상중합법, 용액중화법, 유화중합법, 현탁중합법 등을 들 수 있으나, 본 발명은 이러한 예시들에만 한정되는 것은 아니다. 이러한 중합법 중에서는, 괴상중합법 및 용액중합법이 바람직하다.As a method of polymerizing a monomer, for example, a bulk polymerization method, a solution neutralization method, an emulsion polymerization method, a suspension polymerization method, etc. may be mentioned, but the present invention is not limited to these examples. In such a polymerization method, the block polymerization method and the solution polymerization method are preferable.
또한, 모노머의 중합은, 예를 들면, 라디칼 중합법, 리빙 라디칼 중합법, 음이온중합법, 양이온중합법, 부가중합법, 중축합법 등의 방법으로 실시될 수 있다.In addition, the polymerization of the monomer can be carried out by a method such as a radical polymerization method, a living radical polymerization method, an anion polymerization method, a cation polymerization method, an addition polymerization method or a polycondensation method.
모노머를 용액중합법에 의해 중합시키는 경우, 예를 들어, 모노머를 용매에 용해시켜 얻은 용액을 교반하면서 중합개시제를 당해 용액에 첨가하여 모노머를 중합시킬 수 있으며, 중합개시제를 용매에 용해시켜 얻은 용액을 교반하면서 모노머를 당해 용액에 첨가하여 모노머를 중합시킬 수 있다. 용매는 모노머와 상용하는 유기용매인 것이 바람직하다.When the monomer is polymerized by the solution polymerization method, for example, a solution obtained by dissolving the monomer in a solvent may be added to the solution while stirring the monomer to polymerize the monomer, and the solution obtained by dissolving the polymerization initiator in the solvent. The monomer can be added to the solution while stirring to polymerize the monomer. It is preferable that a solvent is an organic solvent compatible with a monomer.
모노머를 중합시킬 때 분자량을 조정하는 연쇄이동제를 사용할 수 있다. 연쇄이동제는, 통상적으로, 모노머와 혼합하여 사용할 수 있다. 연쇄이동제로는, 예를 들면, 2- (도데실티오카르보노티오일티오)-2-메틸프로피온산, 2-(도데실티오카르보노티오일티오) 프로피온산, 메틸 2- (도데실티오카르보노티오일티오)-2-메틸프로피오네이트, 2-(도데실티오카르보노티오일티오)-2-메틸프로피온산 3-아지도-1-프로판올 에스테르, 2-(도데실티오카르보노티오일티오)-2-메틸프로피온산 펜타 플루오로페닐 에스테르, 라우릴메르캅탄, 도데실 메르캅탄, 티오 글리세롤 등의 메르캅탄기 함유 화합물, 차아인산염나트륨, 아황산수소나트륨 등의 무기염 등을 들 수 있지만, 본 발명은 이러한 예시에만 한정되는 것은 아니다. 이러한 연쇄 이동제는 각각 단독으로 사용해도되고, 2 종류 이상을 병용해도 좋다. 연쇄 이동제의 양은 특별히 한정되지 않지만, 일반적으로 전체 모노머 100 중량 부 당 약 0.01 중량부 내지 10 중량부이면 된다.When the monomer is polymerized, a chain transfer agent for adjusting the molecular weight can be used. A chain transfer agent can be used in mixture with a monomer normally. Examples of the chain transfer agent include 2- (dodecylthiocarbonothioylthio) -2-methylpropionic acid, 2- (dodecylthiocarbonothioylthio) propionic acid, and methyl 2- (dodecylthiocarbono). Thioylthio) -2-methylpropionate, 2- (dodecylthiocarbonothioylthio) -2-methylpropionic acid 3-azido-1-propanol ester, 2- (dodecylthiocarbonothioylthio Mercaptan group-containing compounds such as) -2-methylpropionic acid pentafluorophenyl ester, lauryl mercaptan, dodecyl mercaptan, thioglycerol, inorganic salts such as sodium hypophosphite, sodium bisulfite, and the like. The invention is not limited only to this example. These chain transfer agents may be used independently, respectively and may use two or more types together. Although the quantity of a chain transfer agent is not specifically limited, Generally, what is necessary is just about 0.01 weight part-10 weight part per 100 weight part of total monomers.
모노머를 중합시킬 때, 중합 개시제를 이용하는 것이 바람직하다. 중합 개시제로서는, 예를 들어, 열중합 개시제, 광중합 개시제, 레독스(redox) 중합 개시제, ATRP(원자 이동 라디칼 중합)개시제, ICAR ATRP 개시제, ARGET ATRP 개시제, RAFT(가역 추가 - 분열 연쇄 이동 중합)제, NMP (니트로옥사이드를 통해 중합)제, 고분자 중합 개시제 등을 들 수 있다. 이러한 중합 개시제는 각각 단독으로 사용해도되고, 2 종류 이상을 병용해도 좋다.When polymerizing a monomer, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, a thermal polymerization initiator, a photopolymerization initiator, a redox polymerization initiator, an ATRP (atomic transfer radical polymerization) initiator, an ICAR ATRP initiator, an ARGET ATRP initiator, a RAFT (reversible addition-cleavage chain transfer polymerization) Agent, NMP (polymerization via nitro oxide) agent, a polymer polymerization initiator, etc. are mentioned. These polymerization initiators may be used independently, respectively and may use two or more types together.
열 합 개시제로서는, 예를 들면, 아조이소부티로니트릴, 아조이소 부틸산메틸, 아조비스디메틸발레로니트릴 등의 아조계 중합 개시제, 과산화 벤조일, 과황산칼륨, 과황산암모늄 등의 과산화물계 중합 개시제 등을 들 수 있지만, 본 발명은 이러한 예시에만 한정되는 것은 아니다. 이러한 중합 개시제는 각각 단독으로 사용해도되고, 2 종류 이상을 병용해도 좋다.Examples of the thermal initiator include azo polymerization initiators such as azoisobutyronitrile, methyl azoisobutyrate and azobisdimethylvaleronitrile, peroxide polymerization initiators such as benzoyl peroxide, potassium persulfate and ammonium persulfate. Although these etc. are mentioned, this invention is not limited only to this illustration. These polymerization initiators may be used independently, respectively and may use two or more types together.
중합 개시제로서 열중합 개시제를 사용하는 경우, 해당 열중합 개시제의 양은 전체 모노머 100 중량부 당 일반적으로 약 0.01 중량부 내지 20 중량부인 것이 바람직하다.When using a thermal polymerization initiator as a polymerization initiator, it is preferable that the quantity of the thermal polymerization initiator is generally about 0.01 to 20 parts by weight per 100 parts by weight of the total monomers.
광중합 개시제로서는, 예를 들면, 2-옥소글루타릭산, 1-히드록시 시클로헥실페닐케톤, 2-히드록시-2-메틸-1-페닐프로판-1-온, 2-메틸[4-(메틸 티오)페닐]-2-모르포리노프로판-1-온, 2,2-디메톡시-1,2-디페닐에탄-1- 온, 벤조페논, 1-[4-(2-히드록시에톡시)페닐]-2-히드록시-2-메틸 1-프로판-1- 온, 2-벤질-2-디메틸아미노-1-(4-모르포리노페닐) 부탄-1-온, 비스 (2,6-디메톡시벤조일)-2,4,4-트리메틸펜틸포스핀 옥사이드 등을 들 수 있지만, 본 발명은 이러한 예시에만 한정되는 것은 아니다. 이러한 중합 개시제는 각각 단독으로 사용해도 되고, 2 종류 이상을 병용해도 좋다.As a photoinitiator, for example, 2-oxoglutaric acid, 1-hydroxy cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl [4- (methyl Thio) phenyl] -2-morpholinopropane-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, benzophenone, 1- [4- (2-hydroxyethoxy ) Phenyl] -2-hydroxy-2-methyl 1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, bis (2,6 -Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like, but the present invention is not limited to this example. These polymerization initiators may be used independently, respectively and may use two or more types together.
중합 개시제로서 광중합 개시제를 사용하는 경우 당해 광중합 개시제의 양은 전체 단량체 100 중량 부 당 일반적으로 약 0.01 중량부 내지 20 중량부인 것이 바람직하다.When using a photoinitiator as a polymerization initiator, it is preferable that the quantity of the said photoinitiator is generally about 0.01 weight part-20 weight part per 100 weight part of total monomers.
본 발명에서 사용 가능한 다른 중합 개시제로서는, 예를 들면, 과산화수소와 철(II)염, 과황산염 및 아황산수소나트륨 등의 산화 환원 중합 개시제 금속 촉매 하에서 알킬 할라이드를 사용 ATRP(원자 이동 라디칼 중합)개시제 금속과 질소 함유 리간드를 사용 ICAR ATRP 개시제와 ARGET ATRP 개시제, RAFT (가역적부가 - 개열연쇄이동중합)제, NMP (니트로옥사이드를 통해 중합)제, 폴리디메틸 실록산 단위 함유 고분자 아조 중합 개시제, 폴리에틸렌 글리콜 단위 함유 고분자 아조 중합 개시제 등의 고분자 중합 개시제 등을 들 수 있지만, 본 발명은 이러한 예시에만 한정되는 것은 아니다. 이러한 중합 개시제는 각각 단독으로 사용해도 되고, 2 종류 이상을 병용해도 좋다.As another polymerization initiator usable in the present invention, for example, ATRP (atomic transfer radical polymerization) initiator metals using alkyl halides under redox polymerization initiator metal catalysts such as hydrogen peroxide and iron (II) salts, persulfates and sodium hydrogen sulfite Using a nitrogen-containing ligand with ICAR ATRP initiator and ARGET ATRP initiator, RAFT (reversible addition-cleavage chain transfer polymerization) agent, NMP (polymerization through nitrooxide) agent, polydimethyl siloxane unit containing polymer azo polymerization initiator, polyethylene glycol unit containing Although polymeric polymerization initiators, such as a polymeric azo polymerization initiator, etc. can be mentioned, This invention is not limited only to this illustration. These polymerization initiators may be used independently, respectively and may use two or more types together.
중합 개시제로서 상기 사용 가능한 중합 개시제를 사용하는 경우, 해당 중합 개시제의 양은 전체 단량체 100 중량부 당 일반적으로 약 0.01 중량부 내지 20 중량부인 것이 바람직하다.When using the above-mentioned usable polymerization initiator as a polymerization initiator, it is preferable that the quantity of the said polymerization initiator is generally about 0.01 weight part-20 weight part per 100 weight part of total monomers.
일부 실시예에 있어서, 모노머에 전자선을 조사함으로써, 전자선 중합이 진행될 수 있다.In some embodiments, electron beam polymerization can proceed by irradiating an electron beam to the monomer.
모노머를 중합시킬 때의 중합반응 온도 및 분위기에 대해서는 특별히 제한이 없다. 일반적으로 중합반응 온도는 약 50℃ 내지 약 120℃이다. 중합반응시의 분위기는, 예를 들면, 질소 가스 등의 불활성 가스 분위기 인 것이 바람직하다. 또한 모노머의 중합 반응 시간은 중합 반응온도 등에 따라 변하기 때문에 일률적으로는 결정할 수 없지만, 일반적으로 약 3 내지 20시간이다.There is no restriction | limiting in particular about the polymerization reaction temperature and atmosphere at the time of superposing | polymerizing a monomer. Generally, the polymerization temperature is about 50 ° C to about 120 ° C. It is preferable that the atmosphere at the time of a polymerization reaction is inert gas atmosphere, such as nitrogen gas, for example. In addition, since the polymerization reaction time of the monomer varies depending on the polymerization reaction temperature and the like, it cannot be determined uniformly, but is generally about 3 to 20 hours.
일 실시 예에 있어서, 상기 제조 방법의 단계 (ii)에서 상기 기판은 바람직하게는 유리 기판이며, 보다 바람직하게는 소다 유리(소다 라임 유리) 또는 무 알칼리 유리(예를 들면, EAGLE-XG, 코닝)이며, 더욱 바람직하게는 소다 유리이다.In one embodiment, the substrate in step (ii) of the manufacturing method is preferably a glass substrate, more preferably soda glass (soda lime glass) or alkali-free glass (eg EAGLE-XG, Corning ), And more preferably soda glass.
일 실시 예에서, 상기 제조 방법의 단계 (ii)에서 상기 경화성 수지 조성물을 상기 기판에 도포하는 방법으로는 공지의 코팅 방법을 사용할 수있다. 예를 들어, 스핀 코팅, 다이 코팅, 스프레이 코팅, 롤 코팅, 스크린 코팅, 슬릿 코팅, 딥 코팅, 그라비아 코팅 등을들 수 있으나 이에 제한되지 않는다. 바람직하게는 스핀 코팅을 사용하여 도포 할 수 있다.In one embodiment, a known coating method may be used as a method of applying the curable resin composition to the substrate in step (ii) of the manufacturing method. For example, spin coating, die coating, spray coating, roll coating, screen coating, slit coating, dip coating, gravure coating, and the like, but are not limited thereto. Preferably it can be applied using spin coating.
다른 실시예에 있어서, 상기 제조방법의 단계 (ii)에서, 바람직하게는, 상기 조성물이 또한 산 촉매를 포함할 수 있다. 이론에 구속되는 것을 바라지 않지만, 상기 경화성 수지 조성물 도막은 산 촉매를 포함함으로써 산 촉매가 단계 (iii)에서 중합 반응에서 중합 촉매 역할을 하며 반응을 촉진 할 수 있기 때문이다. 따라서 다른 실시 예에서, 상기 제조 방법의 단계 (i)가 산 촉매를 준비하는 단계를 더 포함할 수 있다.In another embodiment, in step (ii) of the preparation method, preferably, the composition may also comprise an acid catalyst. Although not wishing to be bound by theory, the curable resin composition coating film includes an acid catalyst because the acid catalyst can act as a polymerization catalyst in the polymerization reaction in step (iii) and promote the reaction. Therefore, in another embodiment, step (i) of the preparation method may further comprise preparing an acid catalyst.
다른 실시 예에서, 상기 제조 방법은 단계 (iii)에서 상기 경화성 수지 조성물 도막을 가열처리하는 단계를 더 포함할 수 있다. 상기 가열 처리 온도로는 바람직하게는 100℃ 내지 230℃, 보다 바람직하게는 150℃ 내지 230℃를 예시로 들 수 있다. 상기 가열처리 시간은 바람직하게는 1 분 이상, 보다 바람직하게는 10 분, 20 분, 30 분, 40 분, 50 분, 1시간, 2시간, 3시간, 4시간, 5시간, 6시간 등을 들 수 있으나 이에 제한되지 않는다. 특히 바람직한 상기 가열 처리 시간은 10 분 내지 2시간이다.In another embodiment, the manufacturing method may further comprise the step of heat-treating the curable resin composition coating film in step (iii). As said heat processing temperature, Preferably it is 100 degreeC-230 degreeC, More preferably, 150 degreeC-230 degreeC is mentioned as an example. The heat treatment time is preferably 1 minute or more, more preferably 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours and the like. But is not limited thereto. Particularly preferred heat treatment time is 10 minutes to 2 hours.
상기 제조방법에 의해 제조된 분리층은 상기 (2-2)의 분리층의 특성을 가지며, 이박리성을 갖춘 박막일 수 있다.The separation layer prepared by the manufacturing method may have a property of the separation layer of the above (2-2), and may be a thin film having peelability.
(4) 필름 터치 센서 및 필름 터치 센서 구조체(4) film touch sensor and film touch sensor structure
본 실시형태에서 상기 분리층(20)은 캐리어 기판(10)상에 형성 후 그 상부에 전극 패턴층 등을 형성한 후에 최종적으로 캐리어 기판(10)으로부터 분리하게 된다. In the present exemplary embodiment, the separation layer 20 is formed on the carrier substrate 10, and after forming an electrode pattern layer or the like thereon, is finally separated from the carrier substrate 10.
분리층(20)의 캐리어 기판(10)과 분리 시 박리력은 0.5N/mm2 이하인 것이 바람직하며, 0.1N/mm2 이하인 것이 보다 바람직하다. 즉, 분리층(20)과 캐리어 기판(10)의 분리 시에 가해지는 물리적 힘이 1N/mm2, 바람직하게는 0.5N/mm2, 특히 바람직하게는 0.1N/mm2을 넘지 않도록 하는 물질로 분리층(20)이 형성되는 것이 바람직하다.The carrier substrate 10 and separation during the peel force of the separation layer 20 is preferably 0.5N / mm 2 or less, and more preferably 0.1N / mm 2 or less. That is, a material such that the physical force applied when the separation layer 20 and the carrier substrate 10 are separated does not exceed 1 N / mm 2 , preferably 0.5 N / mm 2 , particularly preferably 0.1 N / mm 2 . The separation layer 20 is preferably formed.
분리층(20)의 캐리어 기판(10)과 분리 시 박리력이 1N/mm2 초과인 경우에는 캐리어 기판과의 분리 시 깔끔하게 분리되지 않아, 분리층(20)이 캐리어 기판상에 잔존할 가능성이 있으며, 또한 분리층(20), 보호층(30), 전극 패턴층(40), 절연층(50) 중 한 곳 이상에서 크랙이 생길 가능성도 있기 때문이다.When the separation force of the separation layer 20 from the carrier substrate 10 is greater than 1 N / mm 2 , the separation layer 20 may not be neatly separated upon separation from the carrier substrate, and the separation layer 20 may remain on the carrier substrate. In addition, cracks may occur in at least one of the separation layer 20, the protective layer 30, the electrode pattern layer 40, and the insulating layer 50.
특히, 분리층(20)의 박리력은 0.1N/mm2 이하인 것이 보다 바람직한데, 0.1N/mm2 이하인 경우에는 캐리어 기판으로부터 박리 후에 필름에 발생하는 컬(curl)이 제어 가능하다는 측면에서 보다 바람직하다. 컬(curl)은 필름 터치 센서 기능적 측면에서 문제를 주지 않지만, 접합 공정, 커팅 공정 등의 공정에서 공정효율성을 떨어뜨릴 수 있기 때문에 적게 발생하도록 하는 것이 유리하다.In particular, the curl (curl) caused on the film after peeling the peel force is together more preferably 0.1N / mm 2 or less, if 0.1N / mm 2 or less, the carrier substrate from the separation layer 20 than the side that controllably desirable. Curls do not cause problems in terms of film touch sensor functionality, but it is advantageous to generate less curl because it may lower the process efficiency in processes such as bonding and cutting processes.
여기서, 분리층(20)의 두께는 10 내지 1000nm가 바람직하고, 50 내지 500nm인 것이 보다 바람직하다. 분리층(20)의 두께가 10nm 미만이면 분리층 도포시의 균일성이 떨어져 전극 패턴 형성이 불균일하거나, 국부적으로 박리력이 상승하여 찢겨짐이 발생하거나, 캐리어 기판과 분리 후, 필름 터치 센서에 컬(curl)이 제어되지 않는 문제점이 있다. 그리고 두께가 1000nm를 초과하면 상기 박리력이 더 이상 낮아지지 않는 문제점이 있으며, 필름의 유연성이 저하되는 문제점이 있다.Here, the thickness of the separation layer 20 is preferably 10 to 1000 nm, more preferably 50 to 500 nm. If the thickness of the separation layer 20 is less than 10 nm, the uniformity during application of the separation layer may be poor, or the electrode pattern may be unevenly formed, or the peeling force may be locally increased to cause tearing, or after separation from the carrier substrate, There is a problem that curl is not controlled. And when the thickness exceeds 1000nm, there is a problem that the peeling force is no longer lowered, there is a problem that the flexibility of the film is lowered.
본 발명의 다른 실시형태로서, 캐리어 기판(10)으로부터 분리층(20)에서 분리되지 않을 수도 있다. 이 경우 본 발명은 분리층(20)의 일면에 캐리어 기판(10)이 부착된 필름 터치 센서용 구조체를 제공한다.As another embodiment of the present invention, it may not be separated in the separation layer 20 from the carrier substrate 10. In this case, the present invention provides a structure for a film touch sensor having a carrier substrate 10 attached to one surface of the separation layer 20.
한편, 분리층(20)의 상부에는 전극 패턴층(40)이 형성되는데, 상기 분리층(20)은 캐리어 기판으로부터 분리 후에는 전극 패턴층(40)을 피복하는 피복층의 기능을 하거나 전극 패턴층(40)을 외부의 접촉으로부터 보호하는 보호층의 기능을 하게 된다.Meanwhile, an electrode pattern layer 40 is formed on the separation layer 20, and the separation layer 20 functions as a coating layer covering the electrode pattern layer 40 after separation from the carrier substrate or the electrode pattern layer. It functions as a protective layer that protects the 40 from external contact.
분리층(20)의 상부에는 다시 하나 이상의 보호층(30)이 더 형성될 수 있다. 분리층(20)만으로는 외부로부터의 접촉이나 충격에 대해 전극 패턴을 보호하기 힘들 수 있으므로, 하나 이상의 보호층(30)이 분리층(20)상에 형성될 수 있다.At least one protective layer 30 may be further formed on the separation layer 20. Since the separation layer 20 alone may be difficult to protect the electrode pattern against contact or impact from the outside, one or more protective layers 30 may be formed on the separation layer 20.
보호층(30)은 유기절연막 또는 무기절연막중 적어도 하나를 포함하며, 코팅 및 경화의 방법 또는 증착을 통하여 형성될 수 있다.The protective layer 30 may include at least one of an organic insulating layer and an inorganic insulating layer, and may be formed by a method of coating and curing or deposition.
보호층은 회로 접속을 위하여 패드 전극이 형성될 부분은 제거되거나 패드 전극이 형성될 부분은 제외하고 형성될 수 있다. 또한 패드 전극 하부에 패드 패턴층이 형성될 수도 있는데, 보호층은 패드 패턴층 형성을 위하여 분리층 상부를 전부 덮도록 도포하고 패터닝하거나, 패드 패턴층이 형성될 부분은 제외하고 도포하여 형성될 수 있다.The protective layer may be formed except for a portion where a pad electrode is to be removed or a portion where a pad electrode is to be formed for circuit connection. In addition, a pad pattern layer may be formed under the pad electrode, and the protective layer may be formed by coating and patterning the entire top of the separation layer to form the pad pattern layer, or by applying a portion except the part where the pad pattern layer is to be formed. have.
분리층(20) 또는 보호층(30)의 상부에는 전극 패턴층(40)이 형성된다. 전극 패턴층(40)은 터치 여부를 감지하는 센싱 전극(SE) 및 상기 센싱 전극의 일단에 형성되는 패드 전극(PE)을 포함하여 구성된다. 여기서, 센싱 전극은 터치를 감지하는 전극뿐 아니라, 그 전극에 연결된 배선 패턴을 포함할 수 있다.The electrode pattern layer 40 is formed on the separation layer 20 or the protection layer 30. The electrode pattern layer 40 includes a sensing electrode SE for detecting whether a touch is detected and a pad electrode PE formed at one end of the sensing electrode. Here, the sensing electrode may include not only an electrode for sensing a touch but also a wiring pattern connected to the electrode.
패드 패턴층은 패드 전극의 상부 또는 하부에 형성될 수 있다. 패드 전극은 패드 패턴층을 통하여 회로 기판과 전기적으로 접속될 수 있으며, 회로 기판과 접속 시 접촉저항을 낮추어 주는 역할을 한다. 회로 기판이 절연층 방향에서 접합되는 경우, 패드 전극 상부에 패드 패턴층이 형성되고, 회로기판이 분리층 방향에서 접합되는 경우에는 패드 전극 하부에 패드 패턴층이 형성될 수 있다. 패드 전극이 회로 기판과 접속시 접촉저항이 충분히 낮은 경우 패드 패턴층은 생략될 수 있다.The pad pattern layer may be formed on or under the pad electrode. The pad electrode may be electrically connected to the circuit board through the pad pattern layer, and serves to lower the contact resistance when connected to the circuit board. When the circuit board is bonded in the insulating layer direction, the pad pattern layer may be formed on the pad electrode, and when the circuit board is bonded in the separation layer direction, the pad pattern layer may be formed below the pad electrode. The pad pattern layer may be omitted if the pad electrode is sufficiently low in contact resistance when connected to the circuit board.
패드 패턴층은 금속, 금속나노와이어, 금속산화물, 탄소나노튜브, 그래핀, 전도성 고분자 및 도전성 잉크에서 선택된 하나 이상의 물질로 형성될 수 있다.The pad pattern layer may be formed of one or more materials selected from metals, metal nanowires, metal oxides, carbon nanotubes, graphene, conductive polymers, and conductive inks.
전극 패턴층(40)은 금속, 금속나노와이어, 금속산화물, 탄소나노튜브, 그래핀, 전도성 고분자 및 도전성 잉크에서 선택된 하나 이상의 물질로 형성될 수 있다.The electrode pattern layer 40 may be formed of one or more materials selected from metals, metal nanowires, metal oxides, carbon nanotubes, graphene, conductive polymers, and conductive inks.
여기서, 금속은 금(Au), 은(Ag), 구리(Cu), 몰리브덴(Mo), 알루미늄, 팔라듐, 네오듐, 은-팔라듐-구리합금(APC) 중 어느 하나가 될 수 있다.Here, the metal may be any one of gold (Au), silver (Ag), copper (Cu), molybdenum (Mo), aluminum, palladium, neodium, and silver-palladium-copper alloy (APC).
그리고, 금속나노와이어는 은나노와이어, 구리나노와이어, 지르코늄나노와이어, 금나노와이어 중 어느 하나가 될 수 있다.The metal nanowires may be any one of silver nanowires, copper nanowires, zirconium nanowires, and gold nanowires.
그리고, 금속산화물은 인듐틴옥사이드(ITO), 인듐징크옥사이드(IZO), 인듐징크틴옥사이드(IZTO), 알루미늄징크옥사이드(AZO), 갈륨징크옥사이드(GZO), 플로린틴옥사이드(FTO), 징크옥사이드(ZnO), 인듐틴옥사이드-은-인듐틴옥사이드(ITO-Ag-ITO), 듐징크옥사이드-은-인듐징크옥사이드(IZO-Ag-IZO), 인듐징크틴옥사이드-은-인듐징크틴옥사이드(IZTO-Ag-IZTO) 및 알루미늄징크옥사이드-은-알루미늄징크옥사이드(AZO-Ag-AZO) 중 어느 하나가 될 수 있다.In addition, the metal oxide is indium tin oxide (ITO), indium zinc oxide (IZO), indium zinc tin oxide (IZTO), aluminum zinc oxide (AZO), gallium zinc oxide (GZO), florin tin oxide (FTO), zinc oxide (ZnO), indium tin oxide-silver-indium tin oxide (ITO-Ag-ITO), indium zinc oxide-silver-indium zinc oxide (IZO-Ag-IZO), indium zinc tin oxide-silver-indium zinc tin oxide ( IZTO-Ag-IZTO) and aluminum zinc oxide-silver-aluminum zinc oxide (AZO-Ag-AZO).
또한 전극 패턴층(40)은 탄소나노튜브(CNT) 또는 그래핀 (graphene)을 포함하는 탄소(carbon)계 물질로 형성할 수도 있다.In addition, the electrode pattern layer 40 may be formed of a carbon-based material including carbon nanotubes (CNT) or graphene.
상기 전도성 고분자는 폴리피롤(polypyrrole), 폴리티오펜(polythiophene), 폴리아세틸렌(polyacetylene), 피닷(PEDOT) 및 폴리아닐린(polyaniline)을 포함하며, 이런 전도성 고분자로 형성될 수도 있다.The conductive polymer includes polypyrrole, polythiophene, polyacetylene, PODOT, and polyaniline, and may be formed of such conductive polymer.
상기 도전성 잉크는 금속파우더와 경화성 고분자 바인더가 혼합된 잉크로, 이를 이용하여 전극을 형성할 수도 있다.The conductive ink is an ink in which a metal powder and a curable polymer binder are mixed, and an electrode may be formed using the ink.
상기 전극 패턴층(40)은 전기 저항을 저감시키기 위해 경우에 따라서는 도 2a와 같이 제1 전극층(41) 및 제2 전극층(42)의 형태로 2 이상의 도전층으로 이루어 질 수 있다.In order to reduce the electrical resistance, the electrode pattern layer 40 may be formed of two or more conductive layers in the form of the first electrode layer 41 and the second electrode layer 42 as shown in FIG. 2A.
전극 패턴층(40)은 일 실시예로 ITO, AgNW(은나노와이어), 메탈 메쉬로 1층으로 형성할 수 있으며, 2 이상의 층을 형성하는 경우에는 제1 전극층(41)을 ITO와 같은 투명 금속산화물로 형성하고, 전기적 저항을 더 낮추기 위하여 ITO 전극층 상부에 금속이나 AgNW 등을 이용하여 제2 전극층(42)을 형성할 수 있다. 또한, 필요에 따라서 전극 패턴층(40)은 일 실시예로 도 2b와 같이 제2 전극층(42) 상에 ITO와 같은 투명 금속산화물로 제3 전극층(43)이 더 형성될 수 있다.In one embodiment, the electrode pattern layer 40 may be formed of one layer of ITO, AgNW (silver nanowire), or a metal mesh. In the case of forming two or more layers, the first electrode layer 41 may be formed of a transparent metal such as ITO. The second electrode layer 42 may be formed of an oxide, and a metal or AgNW may be formed on the ITO electrode layer to further lower the electrical resistance. In addition, the electrode pattern layer 40 may further include a third electrode layer 43 formed of a transparent metal oxide such as ITO on the second electrode layer 42 as shown in FIG. 2B.
전극 패턴층(40)의 전기 전도도 향상을 위하여 금속 또는 금속산화물로 이루어진 전극 패턴층을 적어도 1층 이상 포함하여 형성할 수 있다. 보다 상세하게는, 전극 패턴층은 분리층 또는 보호층 상에 금속 또는 금속산화물로 도전층을 형성한 후 추가로 투명 도전층을 적층하여 전극 패턴을 형성하거나, 분리층 또는 보호층 상에 1층 이상의 투명 도전층을 적층한 후 추가로 금속 또는 금속산화물로 도전층을 형성하여 전극 패턴을 형성할 수 있다. 상기 전극 패턴의 적층 구조의 구체적인 예는 다음과 같다. 분리층과 전극 패턴층 사이에 금속 또는 금속산화물 패턴층이 더 형성되는 구조, 전극 패턴층과 절연층 사이에 금속 또는 금속산화물 패턴층이 더 형성되는 구조, 보호층과 전극 패턴층 사이에 금속 또는 금속산화물 패턴층이 더 형성되는 구조일 수 있으며, 또한 투명 도전성 재료로 이루어지는 전극 패턴층을 1층 이상 더 포함할 수 있다.In order to improve the electrical conductivity of the electrode pattern layer 40, at least one electrode pattern layer made of metal or metal oxide may be included. More specifically, the electrode pattern layer is formed on the separation layer or the protective layer with a conductive layer of a metal or metal oxide, and then further laminated a transparent conductive layer to form an electrode pattern, or one layer on the separation layer or protective layer After the above-mentioned transparent conductive layer is laminated, a conductive layer may be further formed of a metal or a metal oxide to form an electrode pattern. Specific examples of the laminated structure of the electrode pattern is as follows. A structure in which a metal or metal oxide pattern layer is further formed between the separation layer and the electrode pattern layer, a structure in which a metal or metal oxide pattern layer is further formed between the electrode pattern layer and the insulating layer, a metal or between the protective layer and the electrode pattern layer The metal oxide pattern layer may be further formed, and may further include at least one electrode pattern layer made of a transparent conductive material.
적용 가능한 전극 패턴층(40)의 적층 구조의 구체적인 예는 다음과 같다.Specific examples of the laminated structure of the applicable electrode pattern layer 40 are as follows.
금속산화물을 적층하고 그 상부에 은나노와이어를 적층하는 구조, 금속산화물을 적층하고 그 상부에 금속을 적층하는 구조, 금속산화물을 적층하고 그 상부에 메탈 메쉬 전극을 적층하는 구조, 은나노와이어를 적층하고 그 상부에 금속산화물을 적층하는 구조, 금속을 적층하고 그 상부에 금속산화물을 적층하는 구조, 메탈 메쉬 전극을 적층하고 그 상부에 금속산화물을 적층하는 구조, 금속산화물을 적층하고 그 상부에 은나노와이어를 적층하고 그 상부에 금속 또는 금속산화물을 더 적층하는 구조, 은나노와이어를 적층하고 그 상부에 금속산화물을 적층하고 그 상부에 금속층을 더 적층하는 구조 등이 있으며, 상기 전극 적층 구조는 터치 센서의 신호처리, 저항을 고려하여 변경할 수 있으며 상기 기재한 적층 구조에 제한되는 것은 아니다.Lamination of metal oxides and lamination of silver nanowires on top of them, lamination of metal oxides and lamination of metals on top of them, lamination of metal oxides and lamination of metal mesh electrodes on top of them, lamination of silver nanowires, A structure for laminating a metal oxide on the top, a structure for laminating a metal and a metal oxide on the top, a structure for laminating a metal mesh electrode and a metal oxide on the top, a metal oxide and a silver nanowire on the top And a structure in which a metal or metal oxide is further stacked on the top, a silver nanowire is laminated, a metal oxide is stacked on the top, and a metal layer is further stacked on the top. It may be changed in consideration of signal processing and resistance, and is not limited to the above-described laminated structure.
전극 패턴층은 제1 전극 패턴층과 제2 전극 패턴층 사이에 전기절연층이 형성될 수 있고, 전기 절연층을 패터닝하여 컨택홀을 형성하여 제2 도전층을 브릿지 전극이 되도록 형성할 수도 있다.In the electrode pattern layer, an electrical insulation layer may be formed between the first electrode pattern layer and the second electrode pattern layer, and the second conductive layer may be formed as a bridge electrode by patterning the electrical insulation layer to form a contact hole. .
또한, 전극 패턴층의 구조를 터치 센서 방식의 관점에서 설명하면 다음과 같다.In addition, the structure of the electrode pattern layer will be described below in terms of the touch sensor method.
전극 패턴층의 패턴 구조는 정전용량 방식에 사용되는 전극 패턴구조가 바람직하며, 상호 정전용량 방식(mutual-capacitance) 또는 셀프 정전용량 방식(self-capacitance)이 적용될 수 있다.The pattern structure of the electrode pattern layer is preferably an electrode pattern structure used in the capacitive method, a mutual capacitance method (self-capacitance) or a self-capacitance method (self-capacitance) may be applied.
상호 정전용량 방식(mutual-capacitance)일 경우, 가로축과 세로축의 격자 전극구조일 수 있다. 가로축과 세로축의 전극의 교차점에는 브릿지 전극을 포함할 수 있으며, 또는, 가로축 전극 패턴층과 세로축 전극 패턴층이 각각 형성되어 전기적으로 이격되는 형태일 수도 있다.In the case of mutual capacitance, the grid electrode structure may have a horizontal axis and a vertical axis. The intersection of the horizontal and vertical electrodes may include a bridge electrode, or the horizontal and vertical electrode pattern layers may be formed to be electrically spaced apart from each other.
셀프 정전용량 방식(self-capacitance)일 경우, 각 지점의 한 개의 전극을 사용해 정전용량 변화를 읽어내는 방식의 전극층 구조일 수 있다.In the case of self-capacitance, the electrode layer structure may be a method of reading capacitance change by using one electrode at each point.
전극 패턴층(40)의 상부에는 절연층(50)이 형성된다. 절연층은 전극 패턴의 부식을 막고 전극 패턴의 표면을 보호하는 역할을 할 수 있다. 절연층(50)은 전극이나 배선의 틈 사이를 메우고 일정한 두께로 형성되는 것이 바람직하다.An insulating layer 50 is formed on the electrode pattern layer 40. The insulating layer may serve to prevent corrosion of the electrode pattern and protect the surface of the electrode pattern. The insulating layer 50 is preferably formed to a certain thickness to fill the gap between the electrode and the wiring.
즉, 전극 패턴층(40)과 접하는 면의 반대편 표면은 전극의 요철이 드러나지 않도록 평탄하게 형성하는 것이 바람직하다.That is, the surface opposite to the surface in contact with the electrode pattern layer 40 is preferably formed flat so that the unevenness of the electrode is not exposed.
여기서, 절연층(50)은 패드 전극이나 패드 패턴층이 회로 기판과 접속되는 공간을 제공하기 위해 패드 전극 부분의 적어도 일부분이 노출되도록 형성하고, 센싱 전극을 보호하기 위해 센싱 전극을 모두 덮도록 형성될 수 있다.Here, the insulating layer 50 is formed to expose at least a portion of the pad electrode portion to provide a space in which the pad electrode or the pad pattern layer is connected to the circuit board, and to cover all the sensing electrodes to protect the sensing electrode. Can be.
상기 보호층(30)과 상기 절연층(50)의 25℃에서의 탄성율 차는 300MPa 이하인 것이 바람직하다. 이는 각층의 스트레스 해소능력 차이에 의한 크랙 발생을 억제하기 위한 것으로, 상기 보호층과 상기 절연층의 탄성율차를 25℃ 에서 300MPa 이하가 되도록 하는 이유는 탄성율 차이가 300MPa을 초과하면, 두 층간의 변형에너지 및 스트레스 해소능력에 불균형이 발생하여 크랙이 발생하기 때문이다.It is preferable that the elastic modulus difference in 25 degreeC of the said protective layer 30 and the said insulating layer 50 is 300 Mpa or less. This is to suppress the occurrence of cracks due to the difference in stress solving ability of each layer, the reason for the elastic modulus difference between the protective layer and the insulating layer to be less than 300MPa at 25 ℃ when the elastic modulus difference exceeds 300MPa, deformation between the two layers This is because cracks occur due to an imbalance in energy and stress resolving ability.
또한, 25℃ 에서의 탄성율 차이를 측정하는 이유는 사용자가 사용하는 환경에서 크랙이 발생하지 않아야 하기 때문이다.In addition, the reason for measuring the elastic modulus difference at 25 ℃ is because the crack should not occur in the environment used by the user.
절연층은 보호층과의 탄성율 차이가 300Mpa 이하가 되는 것을 만족하는 유기절연물질이면 특별히 제한되지 않으나, 절연층은 열경화성 또는 UV경화성 유기고분자인 것이 바람직하다. 절연층은 에폭시 화합물, 아크릴 화합물, 멜라닌 화합물 등 물질에서 선택된 하나 이상의 물질로 형성될 수 있다.The insulating layer is not particularly limited as long as it is an organic insulating material satisfying that the difference in elastic modulus from the protective layer is 300 Mpa or less, but the insulating layer is preferably a thermosetting or UV curing organic polymer. The insulating layer may be formed of one or more materials selected from materials, such as an epoxy compound, an acrylic compound, and a melanin compound.
또한, 절연층은 재료 형태의 관점에서, 경화성 프리폴리머, 경화성 폴리머 및 가소성 폴리머에서 선택된 하나 이상의 물질로 형성될 수 있다.The insulating layer may also be formed of one or more materials selected from curable prepolymers, curable polymers, and plastic polymers, in terms of material form.
절연층(50)은 그 자체가 광학필름의 역할을 할 수 있다. 이 경우 필름화 가능한 바니쉬(varnish) 타입의 재료로 이루어진 것이 바람직하며, 바니쉬타입의 재료는 폴리다이메틸실록산(PDMS: polydimethylsiloxane), 폴리오가노실록산(POS: polyorganosiloxane) 등의 폴리실리콘계 또는 폴리이미드계 또는 스판덱스 등의 폴리우레탄계 등 물질에서 선택된 하나 이상의 물질로 형성될 수 있다.The insulating layer 50 may itself serve as an optical film. In this case, it is preferable that the film is made of a varnish-type material, and the varnish-type material is polysilicon or polyimide such as polydimethylsiloxane (PDMS), polyorganosiloxane (POS), or the like. It may be formed of one or more materials selected from materials such as polyurethane-based, such as spandex.
또한, 절연층(50)은 실리콘산화물(SiOx)등의 무기물을 사용하여 형성될 수도 있으며 이 경우 증착, 스퍼터링 등의 방법으로 형성될 수 있다.In addition, the insulating layer 50 may be formed using an inorganic material such as silicon oxide (SiOx), and in this case, the insulating layer 50 may be formed by deposition, sputtering, or the like.
본 발명의 필름 터치 센서는 패드 전극이 회로기판과 전기적으로 접속될 수 있다.In the film touch sensor of the present invention, the pad electrode may be electrically connected to the circuit board.
회로 기판은 연성 인쇄 회로 기판(FPCB)을 일례로 들 수가 있으며, 터치 제어 회로와 본 발명의 필름 터치 센서를 전기적으로 접속시키는 기능을 한다.The circuit board may be a flexible printed circuit board (FPCB) as an example, and serves to electrically connect the touch control circuit and the film touch sensor of the present invention.
회로 기판의 일단에는 패드 전극과 대응하는 전극이 형성되어 있으며, 도전성 접착제에 의해 패드 전극과 회로기판이 전기적으로 접속될 수 있다. 또한 상기 필름 터치 센서는 패드 전극 상부의 적어도 일부 오픈된 영역을 통해 회로기판과 접속되거나, 분리층을 통하여 회로 기판과 접속될 수 있다. 패드 전극의 상부 또는 하부에는 저항이 낮은 물질로 이루어진 패드 패턴층이 형성될 수 있고, 이 경우 회로 기판은 패드 패턴층을 통하여 패드 전극과 접속될 수 있다.An electrode corresponding to the pad electrode is formed at one end of the circuit board, and the pad electrode and the circuit board may be electrically connected by the conductive adhesive. In addition, the film touch sensor may be connected to the circuit board through at least a part of the open area on the pad electrode, or through the separation layer. A pad pattern layer made of a material having a low resistance may be formed on or below the pad electrode, and in this case, the circuit board may be connected to the pad electrode through the pad pattern layer.
그리고 본 발명에 따른 필름 터치 센서의 또 다른 실시예는 도 3에서와 같이, 분리층; 상기 분리층 상에 형성되되, 센싱 전극 및 상기 센싱 전극의 일단에 형성되는 패드 전극을 포함하는 전극 패턴층; 상기 전극 패턴 상부에 형성되며 상기 전극 패턴층의 일부 또는 전부를 덮도록 형성되는 절연층; 상기 절연층 상에 직접 형성되는 광학필름; 을 포함하는 것을 특징으로 한다.And another embodiment of the film touch sensor according to the present invention, as shown in Figure 3, the separation layer; An electrode pattern layer formed on the separation layer, the electrode pattern layer including a sensing electrode and a pad electrode formed at one end of the sensing electrode; An insulating layer formed on the electrode pattern and covering a part or all of the electrode pattern layer; An optical film formed directly on the insulating layer; Characterized in that it comprises a.
절연층(50)은 그 자체가 점착제나 접착제로 이루어진 접착층의 기능을 할 수 있다. 이 절연층은 폴리에스테르, 폴리에테르, 폴리우레탄, 에폭시, 실리콘 및 아크릴로 이루어진 군에서 선택된 하나 이상의 물질을 포함하여 형성될 수 있다. 또한 절연층(50)이 접착층의 기능을 할 경우, 절연층(50) 상부에 직접 광학필름(100)이 접합될 수도 있다.The insulating layer 50 may itself function as an adhesive layer made of an adhesive or an adhesive. This insulating layer may be formed including one or more materials selected from the group consisting of polyester, polyether, polyurethane, epoxy, silicone and acrylic. In addition, when the insulating layer 50 functions as an adhesive layer, the optical film 100 may be directly bonded on the insulating layer 50.
여기서, 상기 광학필름(100)은 투명필름 또는 편광판이 될 수 있다.Here, the optical film 100 may be a transparent film or a polarizing plate.
투명필름은 투명성, 기계적 강도, 열안정성이 우수한 필름이 사용될 수 있으며, 구체적인 예로는, 폴리에틸렌테레프탈레이트, 폴리에틸렌이소프탈레이트, 폴리에틸렌나프탈레이트, 폴리부틸렌테레프탈레이트 등의 폴리에스테르계 수지; 디아세틸셀룰로오스, 트리아세틸셀룰로오스 등의 셀룰로오스계 수지; 폴리카보네이트계 수지; 폴리메틸(메타)아크릴레이트, 폴리에틸(메타)아크릴레이트 등의 아크릴계 수지; 폴리스티렌, 아크릴로니트릴-스티렌 공중합체 등의 스티렌계 수지; 폴리에틸렌, 폴리프로필렌, 시클로계 또는 노보넨 구조를 갖는 폴리올레핀, 에틸렌-프로필렌 공중합체 등의 폴리올레핀계 수지; 염화비닐계 수지; 나일론, 방향족 폴리아미드 등의 아미드계 수지; 이미드계 수지; 폴리에테르술폰계 수지; 술폰계 수지; 폴리에테르에테르케톤계 수지; 황화 폴리페닐렌계 수지; 비닐알코올계 수지; 염화비닐리덴계 수지; 비닐부티랄계 수지; 알릴레이트계 수지; 폴리옥시메틸렌계 수지; 에폭시계 수지 등과 같은 열가소성 수지로 구성된 필름을 들 수 있으며, 상기 열가소성 수지의 블렌드물로 구성된 필름도 사용할 수 있다. 또한, (메타)아크릴계, 우레탄계, 아크릴우레탄계, 에폭시계, 실리콘계 등의 열경화성 수지 또는 자외선 경화형 수지로 된 필름을 이용할 수도 있다. 이와 같은 투명 필름의 두께는 적절히 결정할 수 있지만, 일반적으로는 강도나 취급성 등의 작업성, 박층성 등의 점에서 1 내지 500㎛ 정도이다. 특히 1 내지 300㎛가 바람직하고, 5 내지 200㎛가 보다 바람직하다.As the transparent film, a film having excellent transparency, mechanical strength and thermal stability may be used. Specific examples thereof include polyester-based resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, and polybutylene terephthalate; Cellulose resins such as diacetyl cellulose and triacetyl cellulose; Polycarbonate resins; Acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene resins such as polystyrene and acrylonitrile-styrene copolymers; Polyolefin-based resins such as polyethylene, polypropylene, cyclo-based or norbornene-structured polyolefins, ethylene-propylene copolymers; Vinyl chloride-based resins; Amide resins such as nylon and aromatic polyamides; Imide resin; Polyether sulfone resin; Sulfone resins; Polyether ether ketone resins; Sulfided polyphenylene resins; Vinyl alcohol-based resins; Vinylidene chloride-based resins; Vinyl butyral resin; Allyl resins; Polyoxymethylene resin; And films composed of thermoplastic resins such as epoxy resins, and the like, and films composed of blends of the above thermoplastic resins may also be used. Moreover, the film of thermosetting resin or ultraviolet curable resin, such as (meth) acrylic-type, urethane type, acrylurethane type, epoxy type, and silicone type, can also be used. Although the thickness of such a transparent film can be determined suitably, it is about 1-500 micrometers generally from the point of workability, thinness, etc., such as strength and handleability. 1-300 micrometers is especially preferable, and 5-200 micrometers is more preferable.
이러한 투명 필름은 적절한 1종 이상의 첨가제가 함유된 것일 수도 있다. 첨가제로는, 예컨대 자외선흡수제, 산화방지제, 윤활제, 가소제, 이형제, 착색방지제, 난연제, 핵제, 대전방지제, 안료, 착색제 등을 들 수 있다. 상기 투명 필름은 필름의 일면 또는 양면에 하드코팅층, 반사방지층, 가스배리어층과 같은 다양한 기능성층을 포함하는 구조일 수 있으며, 기능성층은 전술한 것으로 한정되는 것은 아니며, 용도에 따라 다양한 기능성층을 포함할 수 있다.Such a transparent film may contain a suitable one or more additives. As an additive, a ultraviolet absorber, antioxidant, a lubricant, a plasticizer, a mold release agent, a coloring agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment, a coloring agent, etc. are mentioned, for example. The transparent film may have a structure including various functional layers such as a hard coating layer, an antireflection layer, and a gas barrier layer on one or both surfaces of the film, and the functional layer is not limited to the above-described ones. It may include.
또한, 필요에 따라 투명 필름은 표면 처리된 것일 수 있다. 이러한 표면 처리로는 플라즈마 처리, 코로나 처리, 프라이머 처리 등의 건식 처리, 검화 처리를 포함하는 알칼리 처리 등의 화학 처리 등을 들 수 있다.In addition, if necessary, the transparent film may be surface treated. Such surface treatments include dry treatments such as plasma treatments, corona treatments, primer treatments, and chemical treatments such as alkali treatments including saponification treatments.
또한, 투명필름은 등방성필름, 위상차필름 또는 보호필름(Protective Film)일 수 있다.In addition, the transparent film may be an isotropic film, a retardation film or a protective film.
등방성필름일 경우 면내 위상차(Ro, Ro=[(nx-ny)×d], nx, ny는 필름 평면 내의 주굴절률, d는 필름 두께이다)가 40nm 이하이고, 10nm 이하가 바람직하며, 두께방향 위상차(Rth, Rth=[(nx+ny)/2-nz]×d, nx, ny는 필름 평면 내의 주굴절률, nz는 필름 두께 방향의 굴절률, d는 필름 두께이다)가 -90nm 내지 +75nm 이며, 바람직하게는 -80nm 내지 +60nm, 특히 -70nm 내지 +45nm 가 바람직하다.In the case of an isotropic film, in-plane retardation (Ro, Ro = [(nx-ny) × d], nx, ny is the major refractive index in the film plane, d is the film thickness) is 40 nm or less, preferably 10 nm or less, and the thickness direction Retardation (Rth, Rth = [(nx + ny) / 2-nz) × d, nx, ny is the major refractive index in the film plane, nz is the refractive index in the film thickness direction, d is the film thickness) from -90 nm to +75 nm And preferably -80 nm to +60 nm, particularly -70 nm to +45 nm.
위상차필름은 고분자필름의 일축 연신, 이축 연신, 고분자코팅, 액정코팅의 방법으로 제조된 필름이며, 일반적으로 디스플레이의 시야각보상, 색감개선, 빛샘개선, 색미조절 등의 광학특성 향상 및 조절을 위하여 사용된다.Retardation film is a film manufactured by the method of uniaxial stretching, biaxial stretching, polymer coating, liquid crystal coating of polymer film, and is generally used for improving and adjusting optical characteristics such as viewing angle compensation, color improvement, light leakage improvement, color taste control of display. do.
위상차필름의 종류에는 1/2 이나 1/4 등의 파장판, 양의 C플레이트, 음의 C플레이트, 양의 A플레이트, 음의 A플레이트, 이축성 파장판을 포함한다.The type of retardation film includes a wave plate such as 1/2 or 1/4, a positive C plate, a negative C plate, a positive A plate, a negative A plate, and a biaxial wave plate.
보호필름은 고분자수지로 이루어진 필름의 적어도 일면에 점착층을 포함하는 필름이거나 폴리프로필렌 등의 자가점착성을 가진 필름일 수 있으며, 터치 센서 표면의 보호, 공정성 개선을 위하여 사용될 수 있다.The protective film may be a film including an adhesive layer on at least one surface of a film made of a polymer resin, or a film having a self-adhesive property such as polypropylene, and may be used for protecting the touch sensor surface and improving processability.
편광판은 표시 패널에 사용되는 공지의 것이 사용될 수 있다.As a polarizing plate, a well-known thing used for a display panel can be used.
구체적으로는 폴리비닐알코올 필름을 연신하여 요오드나 이색성 색소를 염색한 편광자의 적어도 일면에 보호층을 설치하여 이루어진 것, 액정을 배향하여 편광자의 성능을 갖도록 하여 만든 것, 투명필름에 폴리비닐알코올 등의 배향성 수지를 코팅하고 이것을 연신 및 염색하여 만든 것을 들 수 있으며, 이에 한정되는 것은 아니다.Specifically, a polyvinyl alcohol film is drawn to form a protective layer on at least one surface of a polarizer dyed with iodine or a dichroic dye, a liquid crystal is oriented so as to have a polarizer performance, and a polyvinyl alcohol on a transparent film And those made by coating an orientation resin such as the like and stretching and dyeing the same, but are not limited thereto.
그리고 본 발명에 따른 필름 터치 센서의 또 다른 실시예는 도 4에서와 같이, 분리층; 상기 분리층 상에 형성되되, 센싱 전극 및 상기 센싱 전극의 일단에 형성되는 패드 전극을 포함하는 전극 패턴층; 상기 전극 패턴 상부에 형성되며 상기 전극 패턴층의 일부 또는 전부를 덮도록 형성되는 절연층; 상기 절연층 상에 형성되는 접착층; 상기 접착층 상에 형성되는 광학필름; 을 포함하는 것을 특징으로 한다.And another embodiment of the film touch sensor according to the present invention, as shown in Figure 4, the separation layer; An electrode pattern layer formed on the separation layer, the electrode pattern layer including a sensing electrode and a pad electrode formed at one end of the sensing electrode; An insulating layer formed on the electrode pattern and covering a part or all of the electrode pattern layer; An adhesive layer formed on the insulating layer; An optical film formed on the adhesive layer; Characterized in that it comprises a.
절연층(50)의 상부에 광학필름을 더 포함할 수 있다. 이 경우 절연층(50)과 광학필름(100)사이에 별도의 접착층(60)을 형성하여 이에 의해 접합될 수 있다. 접착층(60)은 점착제 또는 접착제로 형성되며, 열경화형이나 UV경화형 모두 가능하다.The optical film may be further included on the insulating layer 50. In this case, a separate adhesive layer 60 may be formed between the insulating layer 50 and the optical film 100 to thereby be bonded. The adhesive layer 60 is formed of an adhesive or an adhesive, and may be either a thermosetting type or a UV curing type.
광학필름(100)의 접합에 사용되는 접착제나 점착제는 폴리에스테르, 폴리에테르, 폴리우레탄, 에폭시, 실리콘, 아크릴계 물질인 것이 바람직하다.The adhesive or pressure-sensitive adhesive used for bonding the optical film 100 is preferably polyester, polyether, polyurethane, epoxy, silicone, or acrylic material.
상기와 같은 구조를 갖는 본 발명에 따른 필름 터치 센서의 제조 공정을 도 5a 내지 도 5f를 참조하여 설명하면 다음과 같다.The manufacturing process of the film touch sensor according to the present invention having the above structure will be described with reference to FIGS. 5A to 5F.
도 5a 내지 도 5f는 본 발명에 따른 필름 터치 센서 제조 방법의 제1 실시예에 따른 공정 단면도이며, 이를 참조하여 본 발명에 따른 필름 터치 센서의 제조 방법을 구체적으로 설명한다.5A to 5F are cross-sectional views illustrating a process of manufacturing a film touch sensor according to a first embodiment of the present invention, and a method of manufacturing the film touch sensor according to the present invention will be described in detail with reference to the drawings.
도 5a에 도시된 바와 같이 먼저 캐리어 기판(10)상에 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 측쇄를 구비한 쇄상 폴리머 및 가교제를 혼합하고, 도포하여 분리층(20)을 형성한다.As shown in FIG. 5A, first, a chain polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group and a crosslinking agent are mixed on the carrier substrate 10, and applied to a separation layer ( 20).
구체적으로, (a) 상기 측쇄는, 탄소원자 3 내지 30개를 포함하고, 적어도 1개의 포화 또는 불포화의 탄화수소기를 포함하거나, 또는 적어도 1개의 방향족기를 더 포함하고, 탄소원자 사이를 연결하는 -COO-, -O-, 및 -CO-로 이루어진 군에서 선택된 결합을 포함할 수 있고, Specifically, (a) the side chain is -COO containing 3 to 30 carbon atoms, containing at least one saturated or unsaturated hydrocarbon group, or further comprises at least one aromatic group, and -COO to connect between the carbon atoms May include a bond selected from the group consisting of-, -O-, and -CO-,
필요에 따라, (b) 상기 가교제는, 트리아진계 가교제 또는 글리코루릴계 가교제에서 선택된 것인 경화성 수지 조성물로 형성된 것일 수 있다.If necessary, (b) the crosslinking agent may be formed of a curable resin composition selected from a triazine crosslinking agent or a glycuril crosslinking agent.
여기서 분리층을 도포하는 방법으로는 공지의 코팅 방법을 사용할 수 있다.Here, as a method of applying the separation layer, a known coating method can be used.
예를 들면, 스핀 코팅, 다이 코팅, 스프레이 코팅, 롤 코팅, 스크린 코팅, 슬릿 코팅, 딥 코팅, 그라비아 코팅 등을 들 수 있다.For example, spin coating, die coating, spray coating, roll coating, screen coating, slit coating, dip coating, gravure coating, etc. are mentioned.
분리층(20)을 형성하기 위한 경화 공정은 열경화 또는 UV경화를 단독으로 사용하거나, 열경화 및 UV 경화를 조합하여 사용할 수 있다.The curing process for forming the separation layer 20 may be used by heat curing or UV curing alone, or a combination of thermosetting and UV curing.
캐리어 기판(10)은 글래스 기판이 사용되는 것이 바람직하나, 글래스 기판으로 제한되지 않고 다른 기재도 캐리어 기판(10)으로 사용될 수 있다. 다만, 전극 형성시의 공정 온도를 견딜 수 있도록 고온에서도 변형이 되지 않는, 즉 평탄성을 유지할 수 있는 내열성을 가진 재료가 바람직하다.The carrier substrate 10 is preferably a glass substrate, but is not limited to the glass substrate and other substrates may be used as the carrier substrate 10. However, a material having heat resistance that does not deform even at high temperatures, that is, maintains flatness, is preferable to withstand the process temperature at the time of electrode formation.
이어, 도 5b에서와 같이, 캐리어 기판(10) 상에 형성된 분리층(20) 상에 유기 절연막을 도포하여 보호층(30)을 형성한다.Subsequently, as shown in FIG. 5B, the protective layer 30 is formed by applying an organic insulating layer on the separation layer 20 formed on the carrier substrate 10.
보호층(30)은, 회로 접속을 위한 패드 패턴층 형성을 위하여 패터닝 등의 방법으로 제거되거나, 패드 패턴층이 형성될 부분은 제외하고 도포할 수 있다. 그리고, 보호층이 형성되지 않은 부분에는 회로 기판과의 접속을 위한 패드 패턴층을 형성할 수 있는데, 본 실시예에서는 패드 패턴층이 없는 것을 설명한다.The protective layer 30 may be removed by patterning or the like to form a pad pattern layer for circuit connection, or may be applied except for a portion where the pad pattern layer is to be formed. In addition, although the pad pattern layer for connection with a circuit board can be formed in the part in which the protective layer is not formed, it demonstrates that there is no pad pattern layer in this Example.
그 다음 보호층(30) 상에 전극 패턴층을 형성하는데, 본 실시예에서는 전극 패턴층이 단일층의 적층구조로 된 것을 설명한다.An electrode pattern layer is then formed on the protective layer 30. In this embodiment, the electrode pattern layer will be described as having a single layer laminated structure.
먼저, 도 5c와 같이 투명 도전층으로서, ITO 투명 전극층을 형성하고, 그 위에 감광성 레지스트(미도시)를 형성한다. 이후에 포토리소그래피 공정을 통하여 선택적으로 패터닝하여 도 5d와 같이 전극 패턴층(40)을 형성한다.First, an ITO transparent electrode layer is formed as a transparent conductive layer as shown in FIG. 5C, and a photosensitive resist (not shown) is formed thereon. Thereafter, the electrode pattern layer 40 is formed by selectively patterning the photolithography process as illustrated in FIG. 5D.
상기 투명 도전층은 CVD(Chemical Vapor Deposition), PVD(Physical Vapor Deposition), PECVD(Plasma Enhanced Chemical Vapor Deposition) 등의 스퍼터링(Sputtering)공정, 스크린인쇄, 그라비아(Gravure)인쇄, 리버스오프셋(Reverse Offset), 잉크젯(Ink Jet) 등의 인쇄공정, 건식 또는 습식의 도금 공정을 이용하여The transparent conductive layer is a sputtering process such as chemical vapor deposition (CVD), physical vapor deposition (PVD), plasma enhanced chemical vapor deposition (PECVD), screen printing, gravure printing, reverse offset, and reverse offset. , Printing process such as ink jet, dry or wet plating process
성막할 수 있으며, 스퍼터링공정으로 성막하는 경우에는 원하는 전극 패턴 형상을 갖는 마스크를 기재 위에 배치하고 스퍼터링공정을 실시하여 전극 패턴층을 형성할 수도 있다. 또한 상기의 성막방식으로 전면에 도전층을 형성하고 포토리소그래피 공법을 이용하여 전극 패턴을 형성할 수도 있다.In the case of forming a film by a sputtering process, an electrode pattern layer may be formed by placing a mask having a desired electrode pattern shape on the substrate and performing a sputtering process. In addition, a conductive layer may be formed over the entire surface by the film forming method, and an electrode pattern may be formed using a photolithography method.
감광성 레지스트는 네가티브형(negative type) 감광성 레지스트 또는 포지티브형(positive type) 감광성 레지스트가 사용될 수 있으며, 패터닝과정을 마친 후 감광성 레지스트는 필요에 따라서 전극 패턴층(40)상에 잔존하여도 되고, 제거되어도 된다. 본 실시예에서는 포지티브형 감광성 레지스트를 사용하여, 패터닝과정을 마친 후 전극 패턴상에서 제거된 구조로 된 것을 설명한다.As the photosensitive resist, a negative type photosensitive resist or a positive type photosensitive resist may be used, and after completing the patterning process, the photosensitive resist may remain on the electrode pattern layer 40 as necessary and be removed. You may be. In this embodiment, a positive photosensitive resist is used to describe the structure removed on the electrode pattern after the patterning process.
다음으로, 도 5e와 같이 전극 패턴층(40)이 덮히도록 절연층(50)을 형성한다. 절연층(50)의 두께는 전극의 두께보다 같거나 더 두껍도록 하여 절연층의 상부면이 평탄한 형태를 가지도록 형성한다. 즉, 전극의 요철이 전사되지 않도록 적절한 점탄성을 가진 절연재료를 사용하여야 한다.Next, as shown in FIG. 5E, the insulating layer 50 is formed to cover the electrode pattern layer 40. The thickness of the insulating layer 50 is equal to or thicker than the thickness of the electrode so that the top surface of the insulating layer is formed to have a flat shape. That is, an insulating material having proper viscoelasticity should be used so that the unevenness of the electrode is not transferred.
구체적으로 전극 패턴층 상부에 절연층이 되는 액상의 재료를 도포하고, 도막화단계를 통하여 절연층을 형성한다.Specifically, a liquid material that becomes an insulating layer is coated on the electrode pattern layer, and an insulating layer is formed through a coating film forming step.
여기서 절연층을 도포하는 방법으로는 공지의 코팅 방법을 사용할 수 있다.A well-known coating method can be used here as a method of apply | coating an insulating layer.
예를 들면, 스핀 코팅, 다이 코팅, 스프레이 코팅, 롤 코팅, 스크린 코팅, 슬릿 코팅, 딥 코팅, 그라비아 코팅 등을 들 수 있다.For example, spin coating, die coating, spray coating, roll coating, screen coating, slit coating, dip coating, gravure coating, etc. are mentioned.
절연층 도막화는 열경화, UV경화, 열건조, 진공건조 등의 방법 중 적어도 한가지 방법으로 수행할 수 있으며, 절연층 재료의 특성에 따라 선택된다.The insulating layer coating may be performed by at least one of thermal curing, UV curing, thermal drying, vacuum drying, and the like, and is selected according to the characteristics of the insulating layer material.
절연층은 그 자체로 지지체의 기능을 할 수 있다. 이 경우 절연층이 광학필름의 기능을 하므로 추가로 광학필름을 부착하지 않아도 된다. 절연층의 상부면이 평탄하지 않는 경우, 절연층이 요철로 인하여 광학필름의 역할이 불가능하다. 절연층 상부에 추가로 광학필름을 부착하는 경우 균일한 접합이 불가능하고 터치 센서의 성능이 저하되는 문제점이 발생한다.The insulating layer can itself function as a support. In this case, since the insulating layer functions as an optical film, there is no need to attach an additional optical film. If the top surface of the insulating layer is not flat, the insulating layer is impossible to play the role of the optical film due to irregularities. When the optical film is additionally attached on the insulating layer, uniform bonding is impossible and a problem occurs that the performance of the touch sensor is degraded.
여기서, 절연층(50)은 패드 전극이나 패드 패턴층이 회로 기판과 접속되는 공간을 제공하기 위해 패드 전극 부분의 적어도 일부분이 노출되도록 형성하고, 센싱 전극을 보호하기 위해 센싱 전극을 모두 덮도록 형성될 수 있다.Here, the insulating layer 50 is formed to expose at least a portion of the pad electrode portion to provide a space in which the pad electrode or the pad pattern layer is connected to the circuit board, and to cover all the sensing electrodes to protect the sensing electrode. Can be.
패드 전극이 노출되도록 절연층(50)을 형성하는 방법은, 절연층이 전극 패턴층 상부를 전부 덮도록 도포하고 패터닝하여 형성하는 방법 또는 절연층을 패드 전극이 노출되도록 패드 전극영역은 제외하고 도포하여 형성하는 방법이 있다.The method of forming the insulating layer 50 so that the pad electrode is exposed may be formed by coating and patterning the insulating layer to cover the upper part of the electrode pattern layer or by applying the insulating layer except the pad electrode region to expose the pad electrode. There is a method to form.
절연층 형성 후 패드 패턴층을 형성할 수도 있는데, 본 실시예에서는 패드 패턴층이 없는 구조를 설명한다.The pad pattern layer may be formed after the insulating layer is formed. In this embodiment, a structure without the pad pattern layer will be described.
본 발명의 필름 터치 센서의 제조 방법은 절연층 형성단계 이후에, (a) 상기 절연층상에 광학필름을 부착하는 광학필름 부착단계, (b) 상기 전극 패턴층과 회로 기판을 접합하는 회로 기판 접합단계, 및 (c) 상기 캐리어 기판으로부터 상기 분리층을 분리하는 캐리어 기판 제거단계 중에서 선택된 하나 이상의 단계를를 임의의 순서로 실시할 수 있다.In the manufacturing method of the film touch sensor of the present invention, after the insulating layer forming step, (a) the optical film attaching step of attaching the optical film on the insulating layer, (b) the circuit board bonding for bonding the electrode pattern layer and the circuit board One or more steps selected from step (c) and carrier substrate removal step of separating the separation layer from the carrier substrate may be performed in any order.
상기 (a), (b), (c)단계 중에서 선택된 하나 이상의 단계를 실시하는 구체적인 방법은 하기에서 개별적으로 설명된다.Specific methods for carrying out one or more steps selected from steps (a), (b) and (c) are described separately below.
상기 절연층을 형성한 후, 도 5f 와 같이 터치 센서의 제조 공정을 진행하기 위하여 사용된 캐리어 기판(10)으로부터 전극이 형성된 분리층(20)을 분리한다.After the insulating layer is formed, the separation layer 20 on which the electrode is formed is separated from the carrier substrate 10 used for the process of manufacturing the touch sensor as shown in FIG. 5F.
본 발명에서는 상기 분리층(20)을 캐리어 기판(10)으로부터 박리하는 방법을 사용하여 분리한다.In the present invention, the separation layer 20 is separated using a method of peeling from the carrier substrate 10.
박리하는 방법은 리프트오프(Lift-off) 또는 필오프(Peel-off)의 방법이 있으며 이에 한정되는 것은 아니다.The peeling method is a method of lift-off or peel-off, but is not limited thereto.
이 경우 박리시 가해지는 힘의 크기는 분리층의 박리력에 따라 달라질 수 있으나, 1N/mm2 이하가 바람직하며, 0.5N/ mm2 이하가 보다 바람직하고, 0.1N/mm2 이하가 보다 더 바람직하다. 박리력이 1N/mm2를 초과할 경우, 캐리어 기판으로부터 박리시에 필름 터치 센서가 찢어지는 문제가 발생할 수 있으며, 필름 터치 센서에 과도한 힘이 가해져 필름 터치 센서가 변형되어 디바이스의 기능을 하지 못할 수 있다.In this case, the size of the force applied during the peeling force, but may vary depending on the peel force of the separation layer, 1N / mm 2 or less are preferred and, 0.5N / mm 2 or less are more preferable and, 0.1N / mm 2 or less is more than desirable. When the peeling force exceeds 1 N / mm 2 , a problem may occur in that the film touch sensor is torn during peeling from the carrier substrate. Excessive force is applied to the film touch sensor so that the film touch sensor is deformed and cannot function as a device. Can be.
다음으로, 필름 터치 센서와 회로 기판을 접합할 수 있는데, 이 때 도전성 접착제를 사용하여 회로 기판과 접합할 수 있다.Next, although a film touch sensor and a circuit board can be bonded together, it can bond with a circuit board using a conductive adhesive at this time.
도전성 접착제는, 에폭시, 실리콘, 우레탄, 아크릴, 폴리이미드계 수지 등의 바인더에 은, 구리, 니켈, 카본, 알루미늄, 도금 등의 도전성 필러가 분산되어 있는 것을 말한다.A conductive adhesive means that conductive fillers, such as silver, copper, nickel, carbon, aluminum, plating, are disperse | distributed to binders, such as epoxy, a silicone, urethane, an acryl, and polyimide resin.
회로 기판은 캐리어 기판과 터치 센서를 분리하기 전 또는 분리한 후에 접합이 가능하다.The circuit board may be bonded before or after separating the carrier board and the touch sensor.
캐리어 기판과 분리하기 전에 회로 기판을 접합하는 경우에는, 절연층 도포단계, 절연층 도막화단계 및 광학필름 부착단계 중 적어도 하나의 단계에서 패드 전극의 일부가 노출되도록 적층구조를 형성하거나, 별도의 패터닝단계를 거쳐 패드 전극의 일부가 노출되도록 적층구조를 형성할 수 있다. 그리고 상기 노출된 패드 전극에 회로 기판을 접합하고 캐리어 기판과 분리한다. 패드 전극 상부에 패드 패턴층이 형성되는 경우는 상기 패드 패턴층에 회로 기판을 접합하고 기판을 분리한다.When the circuit board is bonded before separating from the carrier substrate, the laminate structure is formed to expose a part of the pad electrode in at least one of the insulating layer coating step, the insulating layer coating step, and the optical film attachment step, or a separate structure The stacking structure may be formed to expose a portion of the pad electrode through the patterning step. The circuit board is bonded to the exposed pad electrode and separated from the carrier substrate. When the pad pattern layer is formed on the pad electrode, the circuit board is bonded to the pad pattern layer and the substrate is separated.
캐리어 기판과 분리한 후에 회로 기판을 접합하는 경우에는, 분리층 방향에서 분리층을 관통하여 패드 전극과 접합할 수 있는데, 패드 전극 하부에는 패드 패턴층이 형성될 수 있고, 이 경우 회로 기판은 패드 패턴층을 통하여 패드 전극과 접속된다. 또한 회로 기판은 절연층 또는 광학필름방향에서 노출된 패드 전극 또는 패드 패턴층에 접합될 수 있다.When the circuit board is bonded after separation from the carrier substrate, the pad substrate may be bonded to the pad electrode through the separation layer in the separation layer direction, wherein a pad pattern layer may be formed under the pad electrode, in which case the circuit board may be padded. It is connected to the pad electrode through the pattern layer. In addition, the circuit board may be bonded to the pad electrode or the pad pattern layer exposed in the insulating layer or the optical film direction.
회로 기판이 패드 전극과 접속될 때 패드 패턴층을 통하여 접속하는 방법은 회로 기판과 패드 전극의 접촉 저항을 낮추기 위한 것으로 제조 공정 및 제품 사양에 따라 선택적으로 적용될 수 있다.The method of connecting through the pad pattern layer when the circuit board is connected with the pad electrode is to lower the contact resistance between the circuit board and the pad electrode and may be selectively applied according to the manufacturing process and the product specification.
도 6a 및 도 6b는 본 발명에 따른 필름 터치 센서의 제조 방법의 제2 실시예에 따른 공정 단면도이며, 이를 참조하여 본 발명에 따른 필름 터치 센서 제조 방법의 제2 실시예를 설명한다.6A and 6B are cross-sectional views illustrating a method of manufacturing the film touch sensor according to the present invention, with reference to this, a second embodiment of the method of manufacturing the film touch sensor according to the present invention will be described.
캐리어 기판(10)상에 분리층(20)을 형성하고, 보호층(30) 형성 후 전극 패턴층(40)과 절연층(50)을 형성하는 과정은 상기 제1 실시예와 실질적으로 동일하다.The process of forming the isolation layer 20 on the carrier substrate 10 and forming the electrode pattern layer 40 and the insulating layer 50 after forming the protective layer 30 is substantially the same as in the first embodiment. .
다만, 본 발명의 제2 실시예는 절연층(50)의 상부에 광학필름(100)을 부착할 수 있다. 절연층이 접착층의 기능을 포함하고 있어서 도 6a와 같이 절연층 상부에 직접 광학필름(100)을 접합하는 것이 특징이다.However, in the second embodiment of the present invention, the optical film 100 may be attached on the insulating layer 50. Since the insulating layer includes the function of the adhesive layer, the optical film 100 is directly bonded to the insulating layer as shown in FIG. 6A.
이와 같이, 광학필름을 접합하는 단계에서 광학필름을 절연층에 부착하는 압력조건은, 필름에 가해지는 압력이 1 내지 200kg/cm2의 조건이고, 바람직하게는 10 내지 100kg/cm2의 조건이다.As such, the pressure conditions for attaching the optical film to the insulating layer in the step of bonding the optical film, the pressure applied to the film is a condition of 1 to 200kg / cm 2 , preferably 10 to 100kg / cm 2 conditions. .
그 후에 도 6b와 같이 분리층을 캐리어 기판(10)으로부터 박리하는 방법을 사용하여 분리한다. 그 후에 패드 전극 또는 패드 패턴층에 회로 기판을 접합한다.Thereafter, the separation layer is separated using a method of peeling from the carrier substrate 10 as shown in FIG. 6B. Thereafter, the circuit board is bonded to the pad electrode or the pad pattern layer.
도 7a 및 도 7b는 본 발명에 따른 필름 터치 센서의 제조 방법의 제3 실시예에 따른 공정 단면도이며, 이를 참조하여 본 발명에 따른 필름 터치 센서 제조 방법의 제3 실시예를 설명한다.7A and 7B are cross-sectional views illustrating a method of manufacturing the film touch sensor according to the present invention, with reference to this, a third embodiment of the method of manufacturing the film touch sensor according to the present invention will be described.
본 발명의 제3 실시예는 절연층(50)을 형성한 후에, 절연층(50)의 상부에 접착층(60)을 형성하여 광학필름(100)을 부착하는 것이다. 이 경우 접착층(60)은 광학필름(100)의 일면에 먼저 코팅 또는 접합하여 형성하거나, 절연층 상면에 접착층을 코팅 또는 접합하여 광학필름(100)을 부착할 수 있다.According to the third embodiment of the present invention, after the insulating layer 50 is formed, the adhesive layer 60 is formed on the insulating layer 50 to attach the optical film 100. In this case, the adhesive layer 60 may be formed by first coating or bonding to one surface of the optical film 100, or may attach the optical film 100 by coating or bonding an adhesive layer on an upper surface of the insulating layer.
도 7a와 같이, 절연층 상에 접착층을 형성하여 광학필름을 접착한 적층 구조를 나타냈다.As shown in FIG. 7A, an adhesive layer was formed on an insulating layer to show a laminated structure in which an optical film was bonded.
다음으로, 도 7b와 같이 분리층을 캐리어 기판(10)으로부터 박리하는 방법을 사용하여 분리한다. 그 후에 패드 전극 또는 패드 패턴층에 회로 기판을 접합한다.Next, as shown in FIG. 7B, the separation layer is separated using a method of peeling from the carrier substrate 10. Thereafter, the circuit board is bonded to the pad electrode or the pad pattern layer.
그리고 본 발명에 따른 필름 터치 센서의 또 다른 실시예는 도 8에서와 같이, 분리층; 상기 분리층 상에 형성되되, 센싱 전극 및 상기 센싱 전극의 일단에 형성되는 패드 전극을 포함하는 전극 패턴층; 및 상기 전극 패턴 상부에 형성되며 상기 전극 패턴층의 일부 또는 전부를 덮도록 형성되는 절연층;을 포함하며, 상기 분리층의 상기 전극 패턴층이 형성되는 반대 면에 점착제 또는 접착제를 매개로 형성되는 기능성 필름층(80)을 더 포함할 수 있다.And another embodiment of the film touch sensor according to the present invention, as shown in Figure 8, the separation layer; An electrode pattern layer formed on the separation layer, the electrode pattern layer including a sensing electrode and a pad electrode formed at one end of the sensing electrode; And an insulating layer formed on the electrode pattern and covering a part or the whole of the electrode pattern layer, wherein the insulating layer is formed on the opposite side on which the electrode pattern layer of the separation layer is formed through an adhesive or an adhesive. It may further include a functional film layer 80.
상기 분리층(20)과 상기 기능성 필름층(80) 사이에는 접착층(70)이 더 포함될 수 있으며, 상기 접착층(70)은 점착제 또는 접착제로 형성되며, 이 때, 점착제 또는 접착제는 당분야에 공지된 점착제 또는 접착제가 별다른 제한 없이 사용될 수 있으나, 점착제 또는 접착제는 열경화형 및 UV경화형 중 적어도 하나의 방식의 점착제 또는 접착제일 수 있다.An adhesive layer 70 may be further included between the separation layer 20 and the functional film layer 80, and the adhesive layer 70 may be formed of an adhesive or an adhesive, wherein the adhesive or the adhesive is known in the art. The adhesive or adhesive may be used without particular limitation, but the adhesive or adhesive may be an adhesive or adhesive of at least one of a thermosetting type and a UV curing type.
상기 기능성 필름층(80)은 당분야에 공지된 기능성 필름층이 별다른 제한 없이 사용될 수 있으나, 기능성 필름 또는 기재 필름 상에 기능성 코팅층이 형성된 필름일 수 있으며, 이들로 이루어진 군에서 선택된 적어도 하나의 필름 또는 코팅층이 단층 또는 복층으로 형성될 수 있다. 예를 들어, 기능성 필름은 투명 필름, 위상차 필름, 등방성 필름, 보호 필름, 편광판, 편광자, 배리어 필름 등일 수 있고, 배리어 필름은 단층의 필름일 수도 있고, 기재 필름 상에 무기막 및 유기막이 적어도 1층 도포된 복층의 필름일 수도 있다. 복층의 배리어 필름의 예를 들면, 무기막/COP(Cyclo-olefin Polymer)필름/무기막/유기막, 무기막/하드코팅/COP필름/하드코팅/무기막, 무기막/하드코팅/TAC(Triacetyl cellulose)필름/하드코팅/무기막/유기막, 유기막/하드코팅/TAC필름/하드코팅/무기막/유기막 등의 구조를 가질 수 있다.The functional film layer 80 may be a functional film layer known in the art without particular limitation, but may be a film having a functional coating layer formed on a functional film or a base film, and at least one film selected from the group consisting of Alternatively, the coating layer may be formed in a single layer or multiple layers. For example, the functional film may be a transparent film, a retardation film, an isotropic film, a protective film, a polarizer, a polarizer, a barrier film, and the like, the barrier film may be a single layer film, and at least one inorganic film and an organic film on the base film. It may be a multilayered film. Examples of the multilayer barrier film include inorganic film / COP (Cyclo-olefin Polymer) film / inorganic film / organic film, inorganic film / hard coating / COP film / hard coating / inorganic film, inorganic film / hard coating / TAC ( Triacetyl cellulose) film / hard coating / inorganic film / organic film, organic film / hard coating / TAC film / hard coating / inorganic film / organic film and the like.
기능성 코팅층은 전술한 기능성 필름과 같은 기능을 가지는 코팅층들일 수 있으며, 예를 들면 코팅형 유기막층, 코팅형 위상차층, 코팅형 편광자층, 코팅형 배향막층 등일 수 있다. 또한, 기재 필름 당분야에 공지된 필름이 특별한 제한 없이 적용될 수 있으며, 전술한 기능성 필름이 사용될 수도 있다. The functional coating layer may be coating layers having the same function as the above-described functional film, and may be, for example, a coating organic film layer, a coating retardation layer, a coating polarizer layer, or a coating alignment film layer. In addition, a film known in the art may be applied without particular limitation, and the above-described functional film may be used.
한편, 상기 기능성 필름층(80)은 상기 광학필름(100)과 동일한 군에서 선택된 필름일 수 있으며, 필요에 따라 광학필름(100)과 함께 사용되거나, 광학필름(100) 없이 분리층의 하부에 접합될 수 있으며, 상기와 같은 적층 구조에 의해서 본 발명에 의해 제조된 필름 터치 센서를 휘거나 구부리거나 말 경우, 가해지는 외부의 수 또는 팽창 응력으로부터 상기 전극 패턴층(40)을 더욱 보호해 줄 수 있다는 점에서 바람직한 효과를 제공한다.On the other hand, the functional film layer 80 may be a film selected from the same group as the optical film 100, used with the optical film 100 as needed, or in the lower portion of the separation layer without the optical film 100 When the film touch sensor manufactured by the present invention is bent, bent or rolled out by the laminated structure as described above, the electrode pattern layer 40 may be further protected from external number or expansion stress applied thereto. It can provide a desirable effect in that it can.
상기 접착층(70)은 기능성 필름층(80)의 일면에 먼저 코팅 또는 접합하여 형성하거나, 분리층(20) 하면에 접착층을 코팅 또는 접합한 후 기능성 필름층(80)을 부착할 수 있다.The adhesive layer 70 may be formed by first coating or bonding one surface of the functional film layer 80 or by coating or bonding the adhesive layer on the bottom surface of the separation layer 20 to attach the functional film layer 80.
본 발명의 실시예에서 다 설명하진 않았지만, 각층을 적층하는 공정의 순서는 변경될 수 있다.Although not described in the embodiments of the present invention, the order of the processes for laminating each layer may be changed.
본 발명에 의해 제조된 필름 터치 센서는 표시 패널과의 접합 시, 기능성 필름층이 시인 측에 위치하도록 배치되어 사용이 가능하며, 반대로 표시 패널쪽에 부착이 되도록 배치될 수도 있다.The film touch sensor manufactured according to the present invention may be used to be disposed so that the functional film layer is positioned at the viewer side when the film touch sensor is bonded to the display panel, and may be arranged to be attached to the display panel.
이와 같은 본 발명에 따른 필름 터치 센서 및 그의 제조 방법은 캐리어 기판상에서 터치 센서를 구현하므로 필름 기재상에서 직접 터치 센서를 구현하는 공정에서는 불가능한 고정세(fine pitch), 내열성을 확보하고, 필름 기재를 다변화할 수 있도록 한 것이다. 즉 내열성이 약한 광학필름이나 기능성 필름층도 전극 형성 후에 접합을 하게 되기 때문에 사용이 가능한 것이다.Such a film touch sensor and a manufacturing method thereof according to the present invention implements a touch sensor on a carrier substrate, thereby securing a fine pitch and heat resistance, which are impossible in a process of implementing a touch sensor directly on a film substrate, and diversifying the film substrate. It is to be done. That is, the optical film and the functional film layer which are weak in heat resistance can also be used because they are bonded after electrode formation.
또한, 캐리어 기판상에 형성되는 분리층을 제거하지 않고 캐리어 기판과 분리한 이후 또는 분리 이전에 패드 패턴층에 회로 기판을 부착하여 공정의 효율성을 높일 수 있다.In addition, the efficiency of the process may be improved by attaching the circuit board to the pad pattern layer after separation from the carrier substrate or before separation without removing the separation layer formed on the carrier substrate.
또한, 분리층과 절연층 사이에 탄성율이 제어된 보호층을 추가로 형성하여 스트레스 해소능력 차이에 의한 크랙 발생을 억제하며 필름 터치 센서의 컬(Curl)을 방지할 수 있도록 한 것이다.In addition, by forming an additional control layer of the elastic modulus controlled between the separation layer and the insulating layer to suppress the occurrence of cracks due to the stress resolving power difference and to prevent the curl (Curl) of the film touch sensor.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.
제조예 및 합성예Preparation and Synthesis Examples
1. 경화성 수지 조성물의 구성 요소로서 중합체의 제조1. Preparation of Polymer as Component of Curable Resin Composition
경화성 수지 조성물의 구성 요소로서, 다음과 같이 중합체를 제조하였다. As a component of the curable resin composition, a polymer was prepared as follows.
[제조예 1] 중합체 A-1의 제조 Preparation Example 1 Preparation of Polymer A-1
하기 화학식 1-1의 2-히드록시프로필메타크릴레이트를 모노머로 이용하고, 그 100질량부를 프로필렌글리콜모노메틸에테르(PGME)에 30질량%가 되도록 용해시켰다. 얻어진 용액에 질소 가스를 불어넣으면서 80℃까지 승온하고 2,2'-아조비스이소부티로니트릴(AIBN)을 모노머 총량에 대해 5몰% 첨가한 뒤, 80℃에서 8시간 반응을 실시하여 중합체 A-1을 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 25,000이었다.2-hydroxypropyl methacrylate of the following Chemical Formula 1-1 was used as a monomer, and 100 parts by mass thereof were dissolved in propylene glycol monomethyl ether (PGME) so as to be 30% by mass. It heated up to 80 degreeC, blowing in nitrogen gas to the obtained solution, 5 mol% of 2,2'- azobisisobutyronitrile (AIBN) was added with respect to monomer total amount, and reaction was performed at 80 degreeC for 8 hours, and the polymer A was carried out. -1 was obtained. It was 25,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[화학식 1-1][Formula 1-1]
Figure PCTKR2019001826-appb-I000028
Figure PCTKR2019001826-appb-I000028
[제조예 2] 중합체 A-2의 제조Preparation Example 2 Preparation of Polymer A-2
하기 화학식 1-2의 3-벤조일옥시-2-히드록시프로필메타크릴레이트를 모노머로 사용한 것 외에는 제조예 1과 동일하게 해서 중합체 A-2를 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 22000이었다.Polymer A-2 was obtained in the same manner as in Production Example 1 except that 3-benzoyloxy-2-hydroxypropyl methacrylate of the following formula 1-2 was used as a monomer. It was 22000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[화학식 1-2][Formula 1-2]
Figure PCTKR2019001826-appb-I000029
Figure PCTKR2019001826-appb-I000029
[제조예 3] 중합체 A-3의 제조Preparation Example 3 Preparation of Polymer A-3
하기 화학식 1-3의 4-벤조일옥시-3-히드록시시클로헥실메틸메타크릴레이트 를 모노머로 사용한 것 외에는 제조예 1과 동일하게 해서 중합체 A-3를 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 32,000이었다.Polymer A-3 was obtained in the same manner as in Production Example 1 except that 4-benzoyloxy-3-hydroxycyclohexylmethyl methacrylate of the following formula 1-3 was used as a monomer. It was 32,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[화학식 1-3][Formula 1-3]
Figure PCTKR2019001826-appb-I000030
Figure PCTKR2019001826-appb-I000030
[제조예 4] 중합체 A-4의 제조Preparation Example 4 Preparation of Polymer A-4
하기 화학식 1-4의 1,3-아다만틸디올모노메타크릴레이트를 모노머로 사용한 것 외에는 제조예 1과 동일하게 해서 중합체 A-4를 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 18,000이었다.Polymer A-4 was obtained in the same manner as in Production Example 1 except that 1,3-adamantyldiol monomethacrylate of the formula (1-4) was used as a monomer. It was 18,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[화학식 1-4][Formula 1-4]
Figure PCTKR2019001826-appb-I000031
Figure PCTKR2019001826-appb-I000031
[제조예 5] 중합체 A-5Production Example 5 Polymer A-5
하기 화학식 1-5의 2-히드록시시클로헥실메타크릴레이트를 모노머로 사용한 것 외에는 제조예 1과 동일하게 해서 중합체 A-5를 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바 36,000이었다.Polymer A-5 was obtained in the same manner as in Production Example 1 except that 2-hydroxycyclohexyl methacrylate of the formula (1-5) was used as a monomer. It was 36,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[화학식 1-5][Formula 1-5]
Figure PCTKR2019001826-appb-I000032
Figure PCTKR2019001826-appb-I000032
[제조예 6] 중합체 A-6의 제조 Preparation Example 6 Preparation of Polymer A-6
하기 화학식 1-6의 2-히드록시에틸메타크릴레이트를 모노머로 사용한 것 외에는 제조예 1과 동일하게 해서 중합체 A-6을 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 42,000이었다.Polymer A-6 was obtained in the same manner as in Production Example 1 except that 2-hydroxyethyl methacrylate of the following Chemical Formula 1-6 was used as the monomer. It was 42,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[화학식 1-6][Formula 1-6]
Figure PCTKR2019001826-appb-I000033
Figure PCTKR2019001826-appb-I000033
[제조예 7] 중합체 A-7의 제조Preparation Example 7 Preparation of Polymer A-7
하기 화학식 1-7의 4-(히드록시메틸)시클로헥실메틸메타크릴레이트를 모노머로 사용한 것 외에는 제조예 1과 동일하게 해서 중합체 A-7을 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 18,000이었다.Polymer A-7 was obtained in the same manner as in Production Example 1 except that 4- (hydroxymethyl) cyclohexylmethylmethacrylate of the formula (1-7) was used as a monomer. It was 18,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[화학식 1-7][Formula 1-7]
Figure PCTKR2019001826-appb-I000034
Figure PCTKR2019001826-appb-I000034
[제조예 8] 중합체 A-8의 제조Preparation Example 8 Preparation of Polymer A-8
화학식 1-1의 2-히드록시프로필메타크릴레이트 및 n-부틸아크릴레이트를 모노머로 사용하고, 이들 50질량부씩을 프로필렌글리콜모노메틸에테르(PGME)에 합계 30질량%가 되도록 용해시켰다. 얻어진 용액에 질소 가스를 불어넣으면서 80℃까지 승온하고 2,2'-아조비스이소부티로니트릴(AIBN)을 모노머 총량에 대해 5몰% 첨가한 뒤, 80℃에서 8시간 반응을 실시하여 중합체 A-8을 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 18,000이었다.2-hydroxypropyl methacrylate and n-butyl acrylate of the general formula (1-1) were used as monomers, and 50 parts by mass of these were dissolved in propylene glycol monomethyl ether (PGME) so that the total was 30% by mass. It heated up to 80 degreeC, blowing in nitrogen gas to the obtained solution, 5 mol% of 2,2'- azobisisobutyronitrile (AIBN) was added with respect to monomer total amount, and reaction was performed at 80 degreeC for 8 hours, and the polymer A was carried out. Got -8. It was 18,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[제조예 9] 중합체 A-9의 제조Preparation Example 9 Preparation of Polymer A-9
화학식 1-1의 2-히드록시프로필메타크릴레이트 및 메틸메타크릴레이트를 모노머로 사용한 것 외에는 제조예 8과 동일하게 해서 중합체 A-9를 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 25,000이었다.Polymer A-9 was obtained in the same manner as in Production Example 8 except that 2-hydroxypropyl methacrylate and methyl methacrylate of Formula 1-1 were used as monomers. It was 25,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[제조예 10] 중합체 A-10의 제조Preparation Example 10 Preparation of Polymer A-10
화학식 1-1의 2-히드록시프로필메타크릴레이트 및 스티렌을 모노머로 사용한 것 외에는 제조예 8과 동일하게 해서 중합체 A-10을 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 22,000이었다.Polymer A-10 was obtained in the same manner as in Production Example 8 except that 2-hydroxypropyl methacrylate and styrene represented by Chemical Formula 1-1 were used as monomers. It was 22,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[제조예 11] 중합체 A-11의 제조Preparation Example 11 Preparation of Polymer A-11
화학식 1-3의 4-벤조일옥시-3-히드록시시클로헥실메틸메타크릴레이트 및 디시클로펜타디에닐메타크릴레이트를 모노머로 사용한 것 외에는 제조예 8과 동일하게 해서 중합체 A-11을 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바 35,000이었다.Polymer A-11 was obtained in the same manner as in Production Example 8 except that 4-benzoyloxy-3-hydroxycyclohexylmethyl methacrylate and dicyclopentadienyl methacrylate of the formula 1-3 were used as monomers. It was 35,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[제조예 12] 중합체 A-12의 제조Preparation Example 12 Preparation of Polymer A-12
화학식 1-5의 2-히드록시시클로헥실메타크릴레이트 및 디시클로펜타디에닐메타크릴레이트를 모노머로 사용한 것 외에는 제조예 8과 동일하게 해서 중합체 A-12를 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 25,000이었다.Polymer A-12 was obtained in the same manner as in Production Example 8 except that 2-hydroxycyclohexyl methacrylate and dicyclopentadienyl methacrylate of the formula (1-5) were used as monomers. It was 25,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[제조예 13] 중합체 A-13의 제조Preparation Example 13 Preparation of Polymer A-13
화학식 1-6의 2-히드록시에틸메타크릴레이트 및 부틸아크릴레이트를 모노머로 사용한 것 외에는 제조예 8과 동일하게 해서 중합체 A-13을 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바 38,000이었다.Polymer A-13 was obtained in the same manner as in Production Example 8 except for using 2-hydroxyethyl methacrylate and butyl acrylate of Formula 1-6 as monomers. It was 38,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[제조예 14] 중합체 A-14의 제조Preparation Example 14 Preparation of Polymer A-14
화학식 1-6의 2-히드록시에틸메타크릴레이트 및 메틸메타크릴레이트를 모노머로 사용한 것 외에는 제조예 8과 동일하게 해서 중합체 A-14를 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바 36,000이었다.Polymer A-14 was obtained in the same manner as in Production Example 8 except that 2-hydroxyethyl methacrylate and methyl methacrylate of Formula 1-6 were used as monomers. It was 36,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[제조예 15] 중합체 A-15의 제조Preparation Example 15 Preparation of Polymer A-15
화학식 1-6의 2-히드록시에틸메타크릴레이트 및 디시클로펜타디에닐메타크릴레이트를 모노머로 사용한 것 외에는 제조예 8과 동일하게 해서 중합체 A-15를 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바 39,000이었다.Polymer A-15 was obtained in the same manner as in Production Example 8 except that 2-hydroxyethyl methacrylate and dicyclopentadienyl methacrylate of the formula (1-6) were used as the monomers. It was 39,000 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[제조예 16] 중합체 A-16의 제조Preparation Example 16 Preparation of Polymer A-16
하기 화학식 1-8의 4-(4-메톡시페닐프로페노일) 옥시-3-하이드록시클로헥실메틸 메타크릴레이트를 모노머로 사용한 것 외에는 제조예 1과 동일하게 해서 하기 화학식 1-8-1의 중합체 A-16을 얻었다. 겔 여과 크로마토그래피에 의해 A-16 중합체의 평균 분자량(MW)을 측정한 바, 27,700이었다.Except for using 4- (4-methoxyphenylpropenyl) oxy-3-hydroxycyclohexylmethyl methacrylate of the following Chemical Formula 1-8 as the monomer, the same procedure as in Preparation Example 1 was given to the following Chemical Formula 1-8-1 Polymer A-16 was obtained. It was 27,700 when the average molecular weight (MW) of the A-16 polymer was measured by gel filtration chromatography.
[화학식 1-8][Formula 1-8]
Figure PCTKR2019001826-appb-I000035
Figure PCTKR2019001826-appb-I000035
[화학식 1-8-1][Formula 1-8-1]
Figure PCTKR2019001826-appb-I000036
Figure PCTKR2019001826-appb-I000036
[제조예 17] 중합체 A-17의 제조Preparation Example 17 Preparation of Polymer A-17
하기 화학식 1-9의 4-아다만탄카르복시옥시-3-히드록시시클로헥실메틸메타크릴레이트를 모노머로 사용한 것 외에는 제조예 1과 동일하게 해서 화학식 1-9-1의 중합체 A-17을 얻었다. 겔 여과 크로마토그래피에 의해 A-17 중합체의 평균 분자량(MW)을 측정한 바, 31,700이었다.Polymer A-17 of Chemical Formula 1-9-1 was obtained in the same manner as in Production Example 1 except that 4-adamantanecarboxyoxy-3-hydroxycyclohexylmethyl methacrylate of Chemical Formula 1-9 was used as a monomer. . It was 31,700 when the average molecular weight (MW) of the A-17 polymer was measured by the gel filtration chromatography.
[화학식 1-9][Formula 1-9]
Figure PCTKR2019001826-appb-I000037
Figure PCTKR2019001826-appb-I000037
[화학식 1-9-1][Formula 1-9-1]
Figure PCTKR2019001826-appb-I000038
Figure PCTKR2019001826-appb-I000038
[제조예 18] 중합체 A-18의 제조Preparation Example 18 Preparation of Polymer A-18
화학식 1-5의 2-히드록시시클로헥실메타크릴레이트를 모노머로 사용한 것 외에는 제조예 8과 동일하게 해서 하기 화학식의 중합체 A-18을 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 25,500이었다.Polymer A-18 of the following formula was obtained in the same manner as in Production Example 8 except that 2-hydroxycyclohexyl methacrylate of the formula (1-5) was used as the monomer. It was 25,500 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
Figure PCTKR2019001826-appb-I000039
Figure PCTKR2019001826-appb-I000039
[제조예 19] 중합체 A-19의 제조Preparation Example 19 Preparation of Polymer A-19
하기 화학식 1-10의 3-히드록시아다만틸 메틸-2-메타크릴레이트를 모노머로 사용한 것 외에는 제조예 1과 동일하게 해서 하기 화학식 1-10-1의 중합체 A-19를 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 35,700이었다.Polymer A-19 of formula 1-10-1 was obtained in the same manner as in Preparation Example 1 except that 3-hydroxyadamantyl methyl-2-methacrylate of formula 1-10 was used as a monomer. It was 35,700 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[화학식 1-10][Formula 1-10]
Figure PCTKR2019001826-appb-I000040
Figure PCTKR2019001826-appb-I000040
[화학식 1-10-1][Formula 1-10-1]
Figure PCTKR2019001826-appb-I000041
Figure PCTKR2019001826-appb-I000041
[제조예 20] 중합체 A-20의 제조Preparation Example 20 Preparation of Polymer A-20
하기 화학식 1-11의 2-히드록시-4-메타크릴옥시메틸-시클로헥실-3-시클로헥센-1-카르복실레이트를 모노머로 사용한 것 외에는 제조예 1과 동일하게 해서 하기 화학식 1-11-1의 중합체 A-20를 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 26,700이었다.The same procedure as in Preparation Example 1 was repeated except for using 2-hydroxy-4-methacryloxymethyl-cyclohexyl-3-cyclohexene-1-carboxylate of Chemical Formula 1-11 as a monomer. Polymer A-20 of 1 was obtained. It was 26,700 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[화학식 1-11][Formula 1-11]
Figure PCTKR2019001826-appb-I000042
Figure PCTKR2019001826-appb-I000042
[화학식 1-11-1][Formula 1-11-1]
Figure PCTKR2019001826-appb-I000043
Figure PCTKR2019001826-appb-I000043
[제조예 21] 중합체 A-21의 제조 Preparation Example 21 Preparation of Polymer A-21
하기 화학식 1-12의 4-(2-시클로헥실아세틸)옥시-3-히드록시시클로헥산메틸 2-메타크릴레이트를 모노머로 사용한 것 외에는 제조예 1과 동일하게 해서 화학식 1-12-1의 중합체 A-21를 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 30,700이었다.The polymer of Formula 1-12-1 in the same manner as in Production Example 1 except that 4- (2-cyclohexylacetyl) oxy-3-hydroxycyclohexanemethyl 2-methacrylate of Formula 1-12 was used as a monomer. A-21 was obtained. It was 30,700 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[화학식 1-12][Formula 1-12]
Figure PCTKR2019001826-appb-I000044
Figure PCTKR2019001826-appb-I000044
[화학식 1-12-1][Formula 1-12-1]
Figure PCTKR2019001826-appb-I000045
Figure PCTKR2019001826-appb-I000045
[제조예 22] 중합체 A-22의 제조Preparation Example 22 Preparation of Polymer A-22
화학식 1-5의 2-히드록시시클로헥실메타크릴레이트 및 벤질메타크릴레이트를 모노머로 사용한 것 외에는 제조예 8과 동일하게 해서 하기 화학식의 중합체 A-22를 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 32,700이었다.Polymer A-22 of the following formula was obtained in the same manner as in Production Example 8 except that 2-hydroxycyclohexyl methacrylate and benzyl methacrylate of the formula (1-5) were used as the monomers. It was 32,700 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
Figure PCTKR2019001826-appb-I000046
Figure PCTKR2019001826-appb-I000046
[제조예 23] 중합체 A-23의 제조 Preparation Example 23 Preparation of Polymer A-23
화학식 1-8의 4-(4-메톡시페닐프로펜오일)옥시-3-히드록시시클로헥실메틸메타크릴레이트 및 화학식 1-13의 3,4-에폭시시클로헥실메틸메타크릴레이트를 모노머로 이용하고, 그 100질량부를 프로필렌글리콜모노메틸에테르(PGME)에 20질량%가 되도록 용해시켰다. 얻어진 용액에 질소 가스를 불어넣으면서 80℃까지 승온하고 2,2'-아조비스이소부티로니트릴(AIBN)을 모노머 총량에 대해 4몰% 첨가한 뒤, 80℃에서 8시간 반응을 실시하여 중합체를 얻었다. 그 후, 4-메톡시시아나믹산과 메타크릴산을 각각 99중량부 및 1질량부, 또 테트라에틸암모늄브로마이드 3몰% 첨가한 뒤 100℃까지 승온하고, 38시간 반응을 실시하여 중합체 하기 화학식 1-13-1의 A-23을 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 42,900이었다.4- (4-methoxyphenylpropenyl) oxy-3-hydroxycyclohexylmethyl methacrylate of formula 1-8 and 3,4-epoxycyclohexylmethyl methacrylate of formula 1-13 as monomers And 100 mass parts of it was melt | dissolved so that it may become 20 mass% in propylene glycol monomethyl ether (PGME). The mixture was heated to 80 ° C while blowing nitrogen gas into the solution, and 4 mol% of 2,2'-azobisisobutyronitrile (AIBN) was added to the total amount of the monomers, followed by reaction at 80 ° C for 8 hours. Got it. Thereafter, 99 parts by weight and 1 part by mass of 4-methoxycyanamic acid and methacrylic acid were added, and 3 mol% of tetraethylammonium bromide was added thereto, the temperature was raised to 100 ° C, and the reaction was carried out for 38 hours to give a polymer. A-23 of 1-13-1 was obtained. It was 42,900 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
[화학식 1-13][Formula 1-13]
Figure PCTKR2019001826-appb-I000047
Figure PCTKR2019001826-appb-I000047
[화학식 1-13-1][Formula 1-13-1]
Figure PCTKR2019001826-appb-I000048
Figure PCTKR2019001826-appb-I000048
[제조예 24] 중합체 A-24의 제조Preparation Example 24 Preparation of Polymer A-24
메틸 메타크릴레이트, 글리시딜 메타크릴레이트 및 디시클로펜타디에닐 메타크릴레이트를 모노머로 사용한 것 외에는 제조예 8과 동일하게 해서 하기 화학식의 중합체 A-24를 얻었다. 겔 여과 크로마토그래피에 의해 이 중합체의 평균 분자량(MW)을 측정한 바, 35,700이었다.Polymer A-24 of the following formula was obtained in the same manner as in Production Example 8 except that methyl methacrylate, glycidyl methacrylate and dicyclopentadienyl methacrylate were used as monomers. It was 35,700 when the average molecular weight (MW) of this polymer was measured by the gel filtration chromatography.
Figure PCTKR2019001826-appb-I000049
Figure PCTKR2019001826-appb-I000049
2. 분리층의 형성2. Formation of Separation Layer
본 발명의 각종 경화성 수지 조성물을 이하와 같이 제조하여 2종의 유리 기판상에 도포하여 가열 경화시켜서 성막하였다.Various curable resin compositions of this invention were manufactured as follows, apply | coated on two types of glass substrates, and heat-hardened and formed into a film.
[합성예 1]Synthesis Example 1
중합체 A-1의 4.4질량부, 가교제로 하기 화학식 B-1의 헥사메톡시메틸멜라민(니카랏쿠MW-30, ㈜삼화케미컬) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 0.7mm 두께의 소다 유리 및 0.5mm 두께의 무알칼리 유리(EAGLE-XG, 코닝사) 위에 각각 스핀 코팅에 의해 도포하고, 150℃ 이상에서 30분간 가열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-1, 0.4 parts by mass of hexamethoxymethylmelamine (NicarakkMW-30, Samwha Chemical Co., Ltd.) as a crosslinking agent and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst And 95 parts by mass of propylene glycol monomethyl ether (PGME). This solution was applied onto a 0.7 mm thick soda glass and a 0.5 mm alkali free glass (EAGLE-XG, Corning) by spin coating, and heated at 150 DEG C or higher for 30 minutes to form a film thickness of about 300 nm. .
[화학식 B-1][Formula B-1]
Figure PCTKR2019001826-appb-I000050
Figure PCTKR2019001826-appb-I000050
[합성예 2]Synthesis Example 2
중합체 A-1의 3.2질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.8질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.3.2 parts by mass of polymer A-1, 0.8 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 3]Synthesis Example 3
중합체 A-1의 2.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 2.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.2.4 parts by mass of polymer A-1, 2.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 4]Synthesis Example 4
중합체 A-2의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-2, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as the polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 5]Synthesis Example 5
중합체 A-3의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-3, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as the polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 6]Synthesis Example 6
중합체 A-4의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-4, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as the polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 7]Synthesis Example 7
중합체 A-5의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다. 4.4 parts by mass of polymer A-5, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as the polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 8]Synthesis Example 8
중합체 A-8의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-8, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as the polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 9]Synthesis Example 9
중합체 A-9의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-9, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 10]Synthesis Example 10
중합체 A-10의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산의 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.95 mass parts of propylene glycol monomethyl ether (PGME) as 4.4 mass parts of polymer A-10, 0.4 mass part of crosslinking agent hexamethoxymethyl melamine (formula B-1), and 0.2 mass part of pyridinium-p-toluenesulfonic acid as a polymerization catalyst. Dissolved in parts. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 11]Synthesis Example 11
중합체 A-11의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-11, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 12]Synthesis Example 12
중합체 A-12의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-12, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as the polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 13]Synthesis Example 13
중합체 A-1의 4.4질량부, 가교제로 하기 화학식 B-2의 1,3,4,6-테트라키스(메톡시메틸)글리코루릴(니카랏쿠MW-270, ㈜삼화케미컬) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-1, 0.4 parts by mass of 1,3,4,6-tetrakis (methoxymethyl) glycoluril (Nikarakku MW-270, Samwha Chemical Co., Ltd.) and polymerization as the crosslinking agent As a catalyst, 0.2 mass part of pyridinium-p-toluenesulfonic acid was melt | dissolved in 95 mass parts of propylene glycol monomethyl ether (PGME). Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[화학식 B-2][Formula B-2]
Figure PCTKR2019001826-appb-I000051
Figure PCTKR2019001826-appb-I000051
[합성예 14]Synthesis Example 14
중합체 A-1의 4.4질량부, 가교제로 하기 화학식 B-3의 테트라메톡시메틸벤조구아나민 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-1, 0.4 parts by mass of tetramethoxymethylbenzoguanamine of the formula (B-3) as a crosslinking agent, and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, propylene glycol monomethyl ether (PGME) It melt | dissolved in 95 mass parts. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[화학식 B-3][Formula B-3]
Figure PCTKR2019001826-appb-I000052
Figure PCTKR2019001826-appb-I000052
[합성예 15]Synthesis Example 15
중합체 A-1의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 라우릴벤젠술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-1, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1) and 0.2 parts by mass of laurylbenzenesulfonic acid were dissolved in 95 parts by mass of propylene glycol monomethyl ether (PGME) as a polymerization catalyst. . Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 16]Synthesis Example 16
중합체 A-1의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 열산 발생제 산에이드 SI-100L(삼신화학공업(주))0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-1, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1), and 0.2 parts by mass of thermal acid generator acid aid SI-100L (Samshin Chemical Co., Ltd.) as propylene glycol It melt | dissolved in 95 mass parts of monomethyl ether (PGME). Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[비교합성예 1]Comparative Example 1
중합체 A-6의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-6, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as the polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[비교합성예 2]Comparative Example 2
중합체 A-7의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-7, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as the polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[비교합성예 3]Comparative Example 3
중합체 A-13의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-13, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as the polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[비교합성예 4]Comparative Example 4
중합체 A-14의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-14, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as the polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[비교합성예 5]Comparative Example 5
중합체 A-15의 4.4질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-15, 0.4 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as the polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[비교합성예 6]Comparative Example 6
중합체 A-1의 4.4질량부, 이소시아누레이트계 가교제로 듀라네이트 TPA-100(旭化成 ㈜) 0.4질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.4.4 parts by mass of polymer A-1, 0.4 parts by mass of duranate TPA-100 (isomer), and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, and propylene glycol monomethyl ether (PGME ) Was dissolved in 95 parts by mass. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 17]Synthesis Example 17
중합체 A-16의 3.2질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.8질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.3.2 parts by mass of polymer A-16, 0.8 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 18]Synthesis Example 18
중합체 A-17의 3.2질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.8질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.3.2 parts by mass of polymer A-17, 0.8 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 19]Synthesis Example 19
중합체 A-18의 3.2질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.8질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다. 3.2 parts by mass of polymer A-18, 0.8 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 20]Synthesis Example 20
중합체 A-19의 3.2질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.8질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.3.2 parts by mass of polymer A-19, 0.8 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 21]Synthesis Example 21
중합체 A-20의 3.2질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.8질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.3.2 parts by mass of polymer A-20, 0.8 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 22]Synthesis Example 22
중합체 A-21의 3.2질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.8질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.3.2 parts by mass of polymer A-21, 0.8 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 23]Synthesis Example 23
중합체 A-22의 3.2질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.8질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.3.2 parts by mass of polymer A-22, 0.8 parts by mass of crosslinking agent hexamethoxymethylmelamine (formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[합성예 24]Synthesis Example 24
중합체 A-23의 3.2질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.8질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.3.2 parts by mass of polymer A-23, 0.8 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
[비교합성예 7]Comparative Example 7
중합체 A-24의 3.2질량부, 가교제 헥사메톡시메틸멜라민(화학식 B-1) 0.8질량부 및 중합 촉매로서 피리디늄-p-톨루엔술폰산 0.2질량부를, 프로필렌글리콜모노메틸에테르(PGME) 95질량부에 용해시켰다. 이 용액을 이용해서, 합성예 1과 마찬가지로 소다 유리 및 무알칼리 유리 위에 각각 도포, 열처리하여 약 300nm의 막두께를 성막했다.3.2 parts by mass of polymer A-24, 0.8 parts by mass of crosslinking agent hexamethoxymethylmelamine (Formula B-1) and 0.2 parts by mass of pyridinium-p-toluenesulfonic acid as a polymerization catalyst, 95 parts by mass of propylene glycol monomethyl ether (PGME) Dissolved in. Using this solution, a film thickness of about 300 nm was formed by coating and heat-treating on soda glass and an alkali free glass similarly to the synthesis example 1, respectively.
실시예 및 비교예Examples and Comparative Examples
상기 합성예 1 내지 23 및 비교합성예 1 내지 7에서 형성한 분리층상에 보호층으로서 유기절연막을 도포 및 경화한 후, ITO를 증착하고 포토레지스트를 이용하여 전극 패턴층을 형성하였다. 이후, 상기의 포토레지스트를 재차 도포 및 경화하고, 통상의 포토리소공정을 통하여 패드전극 부분의 일부분을 노출시킨 후, 점착제가 접합되어 있는 폴리에틸렌테레프탈레이트(PET)를 롤라미네이터를 사용하여 접합하여, 실시예 1 내지 23 및 비교예 1 내지 7의 필름 터치 센서를 제조하였다.After coating and curing an organic insulating film as a protective layer on the separation layers formed in Synthesis Examples 1 to 23 and Comparative Synthesis Examples 1 to 7, ITO was deposited and an electrode pattern layer was formed using a photoresist. Thereafter, the photoresist is applied and cured again, and a part of the pad electrode part is exposed through a normal photolithography process, and then the polyethylene terephthalate (PET) to which the pressure-sensitive adhesive is bonded is bonded using a roll laminator. Film touch sensors of Examples 1 to 23 and Comparative Examples 1 to 7 were prepared.
시험예: 실시예 1 내지 19 및 비교예 1 내지 6의 분리층의 물성 평가Test Example: Evaluation of physical properties of the separation layers of Examples 1 to 19 and Comparative Examples 1 to 6
1. 박리력 측정1. Peel force measurement
상기 실험예 및 비교예의 필름 터치 센서를 글래스로부터 박리시키는데 필요한 힘의 크기(박리력)를 다음과 같은 방법을 통해 정량적으로 측정하였다. 측정 장비로 TENSILON RTG-1310(㈜ A&데이), 로드셀로 UR-100N-D형을 이용한 측정은 유리 기판 상에 형성된 필름 터치 센서에 니치 반 테이프(24mm폭)를 붙여, 박리 각도 90°로 박리속도는 300mm/분의 일정한 속도로 당겨 박리력을 측정하여 그 값을 하기 표 1에 나타내었다. 실시예 1 내지 16의 박리력은 소수점 이하 3자리로 표현하였으며, 나머지는 소수점 이하 2자리까지 표시하였다.The magnitude of the force (peel force) required to peel the film touch sensors of the Experimental and Comparative Examples from the glass was measured quantitatively by the following method. For measurement using TENSILON RTG-1310 (A & Day Co., Ltd.) and load cell type UR-100N-D as measuring equipment, attach a niche half tape (24 mm width) to a film touch sensor formed on a glass substrate, and peel at 90 ° peeling angle. The speed is measured by peeling force at a constant speed of 300 mm / min and the values are shown in Table 1 below. Peel force of Examples 1 to 16 was expressed by three decimal places, and the rest was displayed to two decimal places.
구분division 기판: 소다 유리 박리력(N/mm2)Substrate: Soda Glass Peeling Force (N / mm 2 ) 기판:EAGLE-XG박리력(N/mm2)Substrate: EAGLE-XG Peeling Force (N / mm 2 )
실시예 1Example 1 0.0210.021 0.0310.031
실시예 2Example 2 0.0310.031 0.0350.035
실시예 3Example 3 0.0410.041 0.0420.042
실시예 4Example 4 0.0320.032 0.0350.035
실시예 5Example 5 0.0130.013 0.0380.038
실시예 6Example 6 0.0780.078 0.0850.085
실시예 7Example 7 0.0190.019 0.0360.036
실시예 8Example 8 0.0620.062 0.0840.084
실시예 9Example 9 0.0480.048 0.0640.064
실시예 10Example 10 0.0350.035 0.0450.045
실시예 11Example 11 0.0240.024 0.0390.039
실시예 12Example 12 0.0180.018 0.0280.028
실시예 13Example 13 0.0250.025 0.0420.042
실시예 14Example 14 0.0310.031 0.0510.051
실시예 15Example 15 0.0360.036 0.0380.038
실시예 16Example 16 0.0580.058 0.0740.074
비교예 1Comparative Example 1 3.03.0 4.24.2
비교예 2Comparative Example 2 3.83.8 5.25.2
비교예 3Comparative Example 3 4.24.2 4.64.6
비교예 4Comparative Example 4 2.82.8 3.73.7
비교예 5Comparative Example 5 2.22.2 3.23.2
비교예 6Comparative Example 6 8.78.7 9.29.2
표 1에 나타난 바와 같이, 비교예 1 내지 6의 박리력이 2.2 내지 8.7N/mm2(소다 유리 기판) 및 3.2 내지 9.2N/mm2(EAGLE-XG 기판)이었던 반면, 실시예 1 내지 16의 박리력은 0.013 내지 0.078N/mm2(소다 유리 기판) 및 0.028 내지 0.085N/mm2(EAGLE-XG 기판)으로, 비교예에 비해 2자릿수나 작은 것으로 나타났다. 실제로, 비교예의 필름 터치 센서는 높은 박리력으로 인해 필름 터치 센서나 기판이 파괴되었음에 반해, 실시예의 각 필름 터치 센서는 모두, 무리 없이 용이하게 박리할 수 있었다.As shown in Table 1, the peeling forces of Comparative Examples 1 to 6 were 2.2 to 8.7 N / mm 2 (soda glass substrate) and 3.2 to 9.2 N / mm 2 (EAGLE-XG substrate), while Examples 1 to 16 were used. The peel force of was 0.013 to 0.078 N / mm 2 (soda glass substrate) and 0.028 to 0.085 N / mm 2 (EAGLE-XG substrate), which was two orders of magnitude smaller than the comparative example. In fact, while the film touch sensor of the comparative example was damaged due to the high peel force, the film touch sensor or the substrate was broken, and each film touch sensor of the example could be easily peeled off without difficulty.
2. 소성 후 경화 수지 박막에 대한 박리력 평가2. Evaluation of Peeling Force on Cured Resin Thin Films after Firing
경화 수지 박막 상에 포토리소그라피법이나 인쇄법을 이용한 패터닝으로 회로 제작할 때의 소성 공정을 상정하여, 경화 수지 박막을 소성했을 경우의 박리력을 계측했다. 즉, 실시예 1 및 7, 비교예 1 및 2에 대해, 소다 유리 기판상에 형성된 경화 수지 박막을 230℃에서 1시간 또는 3시간 소성하고, 상기 1에 기재한 장치 및 방법으로 각각의 박리력을 계측했다. 결과를, 그 실시예 및 비교예에서의 소성 전 박리력(초기 박리력)값과 함께 표 2에 나타내었다.The baking process at the time of circuit preparation by patterning using the photolithography method or the printing method on the cured resin thin film was assumed, and the peeling force at the time of baking a cured resin thin film was measured. That is, for Examples 1 and 7, Comparative Examples 1 and 2, the cured resin thin film formed on the soda glass substrate was calcined at 230 ° C. for 1 hour or 3 hours, and the peeling force of each of the above-described apparatuses and methods was used. Was measured. The result is shown in Table 2 with the peeling force (initial peeling force) value before baking in the Example and the comparative example.
구분division 초기 박리력(N/mm2)Initial Peel Force (N / mm 2 ) 230℃가열 1시간 후 박리력 (N/mm2)Peeling force after 1 hour of heating at 230 ℃ (N / mm 2 ) 230℃가열 3시간 후 박리력 (N/mm2)Peeling force after 3 hours of heating at 230 ℃ (N / mm 2 )
실시예 1Example 1 0.0210.021 0.0210.021 0.0310.031
실시예 7Example 7 0.0190.019 0.0370.037 0.0420.042
비교예 1Comparative Example 1 3.03.0 4.54.5 5.75.7
비교예 2Comparative Example 2 3.83.8 4.64.6 7.27.2
표 2에서 나타난 바와 같이, 실시예 1 및 7의 경우, 230℃에서 1시간 또는 3시간 소성한 후에도, 소성 전의 비교예 1 및 2의 박리력과 비교할 때 2자릿수나 낮은 박리력을 나타냈으며, 기판에서 무리없이 용이하게 박리할 수 있었다. 반면, 비교예 1 및 2의 경우에는 소성 전보다 한층 더 강하게 유리 기판에 접착되어 있었다.As shown in Table 2, in Examples 1 and 7, even after firing at 230 ° C. for 1 hour or 3 hours, the peeling force was two orders of magnitude lower than that of Comparative Examples 1 and 2 before firing. The substrate could be easily peeled off without difficulty. On the other hand, in Comparative Examples 1 and 2, the adhesive was more strongly adhered to the glass substrate than before firing.
상기 2와 동일한 방법으로 경화 수지 박막 상에 포토리소그라피법이나 인쇄법을 이용한 패터닝으로 회로 제작할 때의 소성 공정을 상정하여, 경화 수지 박막을 소성했을 경우의 박리력을 계측했다. 즉, 실시예 12, 17 내지 24 및 비교예 7에 대해, 소다 유리 기판상에 형성된 경화 수지 박막을 230℃에서 20분 소성하고, 상기 1에 기재한 장치 및 방법으로 각각의 박리력을 계측했다. 결과를, 그 실시예 및 비교예에서의 소성 전 박리력(초기 박리력)값과 함께 표 3에 나타내었다.The peeling force at the time of baking a cured resin thin film was measured by assuming the baking process at the time of circuit preparation by the patterning using the photolithography method or the printing method on the cured resin thin film in the same way as said 2 above. That is, about Example 12, 17-24, and the comparative example 7, the cured resin thin film formed on the soda glass board | substrate was baked at 230 degreeC for 20 minutes, and each peeling force was measured with the apparatus and method of the said 1st. . The result is shown in Table 3 with the peeling force (initial peeling force) value before baking in the Example and the comparative example.
구분division 초기 박리력(N/mm2)Initial Peel Force (N / mm 2 ) 230℃에서 20분 소성 후 박리력(N/mm2)Peeling force after firing at 230 ℃ for 20 minutes (N / mm 2 )
실시예 12Example 12 0.030.03 0.030.03
실시예 17Example 17 0.040.04 0.040.04
실시예 18Example 18 0.040.04 0.040.04
실시예 19Example 19 0.040.04 0.040.04
실시예 20Example 20 0.040.04 0.040.04
실시예 21Example 21 0.050.05 0.050.05
실시예 22Example 22 0.070.07 0.070.07
실시예 23Example 23 0.080.08 0.080.08
실시예 24Example 24 0.050.05 0.050.05
비교예 7Comparative Example 7 3.83.8 3.83.8
표 3에 나타난 바와 같이, 실시예 12, 17 내지 24는 230℃에서 20분 소성한 후에도, 소성 전과 마찬가지로 소성 전의 비교예 7에 비해 2자릿수나 낮은 박리력을 나타냈으며, 기판에서 무리없이 용이하게 박리할 수 있었다. 반면, 비교예 7은 소성 전과 마찬가지로 박리력이 높았으며, 유리 기판에서 쉽게 떼어낼 수 없었다.As shown in Table 3, Examples 12, 17 to 24, after firing at 230 ° C. for 20 minutes, exhibited two orders of magnitude lower peeling force as compared to Comparative Example 7 before firing, and was easily removed without difficulty on the substrate. It could peel off. On the other hand, Comparative Example 7 had a high peel force as before firing, and could not be easily removed from the glass substrate.
3. 가교제 및 혼합 비율을 변화시킨 경우의 소성 후 박리력 평가3. Evaluation of Peeling Force After Firing When Crosslinking Agent And Mixing Ratio Are Changed
가교제의 종류와 고분자/가교제의 혼합비율을 다음 표 5와 같이 변화시킨 경우, 실시예 25 내지 27 및 비교예 8 내지 10 의 박리력 측정을 실시하였다. When the type of crosslinking agent and the mixing ratio of the polymer / crosslinking agent were changed as shown in Table 5 below, the peeling force of Examples 25 to 27 and Comparative Examples 8 to 10 was measured.
<평가 기준><Evaluation Criteria>
기판: 소다 유리 (주석 처리면에 코팅)Substrate: Soda glass (coated on the tinned surface)
제막: 스핀 코트 >150℃ 또는 230℃에서 30 분간 베이킹Production: 30 minutes baking at spin coat> 150 ° C or 230 ° C
※ 마감 막 두께 50 ~ 200nm※ finish film thickness 50-200nm
박리 시험 조건: 니치 반 테이프(24mm 폭)로 박리 시험 실시.Peel test conditions: Peel test was carried out with niche half tape (24 mm width).
사용된 폴리머는 중합체 A-3였다.The polymer used was polymer A-3.
사용된 가교제는 표 4와 같다. 표 4 중, MW-30은 상기 식 (B-1)의 헥사메톡시메틸멜라민(니카랏쿠 MW-30, (주)삼화케미컬)이며, MW-30LF는 헥사메톡시메틸멜라민(낮은 유리 포름알데히드 제품) (니카랏쿠 MW-30LF, (주)삼화케미컬)이며, MX-270은 상기 식 (B-2)의 1,3,4,6-테트라키스(메톡시메틸)글리코루릴 (니카랏쿠 MW-270, (주)삼화케미컬)이다.The crosslinking agents used are shown in Table 4. In Table 4, MW-30 is hexamethoxymethylmelamine of the formula (B-1) (Nikarakku MW-30, Samwha Chemical Co., Ltd.), MW-30LF is hexamethoxymethylmelamine (low glass formaldehyde) Product) (Nikarakku MW-30LF, Samwha Chemical Co., Ltd.), MX-270 is 1,3,4,6-tetrakis (methoxymethyl) glycoluril of the formula (B-2) (Nikarakku MW) -270, Samhwa Chemical Co., Ltd.
MW-30MW-30 MW-30LFMW-30LF MX-270MX-270
구조rescue
Figure PCTKR2019001826-appb-I000053
Figure PCTKR2019001826-appb-I000053
Figure PCTKR2019001826-appb-I000054
Figure PCTKR2019001826-appb-I000054
Figure PCTKR2019001826-appb-I000055
Figure PCTKR2019001826-appb-I000055
중앙골격Central skeleton 트리아진Triazine 글리코루릴Glycoril
MW-30를 기준화합물로 하여, 다른 화합물의 혼합 비율을 변경하며 박리력 및 박리 특성을 검토 하였다(실시예 25 내지 27 및 비교예 8 내지 10). 실험 결과를 표 5에 나타내었다. 표 5 중, 박리시험 항목에서 "○"는 형성된 필름 터치 센서가 무리없이 쉽게 벗겨져 이박리성을 나타냈다는 것이고, "Х"는 쉽게 떼어낼 수 없고, 이박리성을 갖지 않았다는 것을 의미한다.Using MW-30 as a reference compound, the peeling force and the peeling characteristics were examined while changing the mixing ratio of other compounds (Examples 25 to 27 and Comparative Examples 8 to 10). The experimental results are shown in Table 5. In Table 5, "○" in the peel test item means that the formed film touch sensor peeled easily without difficulty and exhibited peeling property, and "Х" means that it was not easily detachable and did not have peeling property.
폴리머Polymer 가교제Crosslinking agent 혼합비율(폴리머/가교제)Mixing ratio (polymer / crosslinking agent) 박리특성Peeling Characteristics
박리력(N/mm2)Peel force (N / mm 2 ) 박리시험Peel Test
실시예 25Example 25 중합체A-3Polymer A-3 MW-30MW-30 45/5045/50 0.020.02
비교예 8Comparative Example 8 90/1090/10 7.57.5 ХХ
비교예 9Comparative Example 9 MW-30LFMW-30LF 45/5045/50 8.18.1 ХХ
비교예 10Comparative Example 10 91/1091/10 7.27.2 ХХ
실시예 26Example 26 MX-270MX-270 45/5045/50 0.020.02
실시예 27Example 27 90/1090/10 0.020.02
표 5에서 볼 수 있듯이, MW-30을 사용한 경우, 폴리머/가교제의 혼합 비율이 45/50일 경우 박리력은 0.02로 낮았으며, 이박리성을 나타냈다. 혼합 비율이 90/10일 경우 박리력은 7.5로 크고, 이박리성을 나타내지 않았다. MX-270을 사용하는 경우 혼합 비율이 45/50인 경우 및 90/10인 경우 모두에서 낮은 박리력 및 이박리성을 나타냈다. 한편 MW-30LF은 혼합비율이 45/50인 경우 및 90/10인 경우 모두에서 박리력이 높았으며, 이박리성을 나타내지 않았다. 이는 MW-30LF는 포름 알데히드가 적어 MW-30에 비해 메틸올 부분(열 가교 반응 점)이 부족하기 때문으로 추정된다.As can be seen in Table 5, when MW-30 was used, the peel force was as low as 0.02 when the polymer / crosslinking agent mixture ratio was 45/50. When the mixing ratio was 90/10, the peeling force was large as 7.5, and no peeling property was shown. When the MX-270 was used, the peeling force and the peeling property were low in both the mixing ratio of 45/50 and 90/10. On the other hand, MW-30LF had a high peeling force in both the mixing ratio of 45/50 and 90/10, and showed no peeling property. It is assumed that MW-30LF has less formaldehyde and lacks a methylol moiety (thermal crosslinking reaction point) compared to MW-30.
4. 분리층의 박리력의 역치 측정4. Measurement of threshold value of peeling force of separation layer
폴리머, 가교제 및 산 촉매의 중량비(wt%)를 변화시키며, 제작된 분리층의 박리력 측정을 실시했다. 즉, 실시예 28 내지 38 및 비교예 11 내지 15에 대해 다음 표 6에 기재된 중량비로 고분자, 가교제 및 산 촉매를 사용하여 제조한 용액을 소다 유리 기판 상에 도포하고, 230℃ 에서 20 분간 소성 한 것 이외에는 실시 예 1과 동일하게하여 분리층을 성막한 뒤, 위 1에 기재한 장치 및 방법에 따라 각각의 박리력을 측정하여 비교하였다. 결과를 표 6에 나타낸다. The weight ratio (wt%) of the polymer, the crosslinking agent and the acid catalyst was changed, and the peel force of the prepared separation layer was measured. That is, for Examples 28 to 38 and Comparative Examples 11 to 15, a solution prepared using a polymer, a crosslinking agent, and an acid catalyst at a weight ratio shown in Table 6 was applied onto a soda glass substrate, and baked at 230 ° C. for 20 minutes. Except for the formation of the separation layer in the same manner as in Example 1, and then by measuring the peel force of each according to the apparatus and method described in the above 1 was compared. The results are shown in Table 6.
폴리머Polymer 가교제Crosslinking agent 산촉매함량(wt%)Acid catalyst content (wt%) 박리력(N/mm2)Peel force (N / mm 2 )
성분ingredient 함량(wt%)Content (wt%) 성분ingredient 함량(wt%)Content (wt%)
비교예 11Comparative Example 11 A-3A-3 9090 B-1B-1 55 55 5.235.23
비교예 12Comparative Example 12 A-3A-3 8787 B-1B-1 88 55 2.122.12
실시예 28Example 28 A-3A-3 8585 B-1B-1 1010 55 0.020.02
실시예 29Example 29 A-3A-3 6363 B-1B-1 3232 55 0.030.03
실시예 30Example 30 A-3A-3 4545 B-1B-1 5050 55 0.020.02
비교예 13Comparative Example 13 A-3A-3 9090 B-2B-2 55 55 5.205.20
비교예 14Comparative Example 14 A-3A-3 9494 B-2B-2 1One 55 7.907.90
실시예 31Example 31 A-3A-3 8787 B-2B-2 88 55 0.020.02
실시예 32Example 32 A-3A-3 8585 B-2B-2 1010 55 0.030.03
비교예 15Comparative Example 15 A-5A-5 9494 B-2B-2 1One 55 8.398.39
실시예 33Example 33 A-5A-5 9292 B-2B-2 33 55 0.060.06
실시예 34Example 34 A-5A-5 9090 B-2B-2 55 55 0.020.02
실시예 35Example 35 A-5A-5 8787 B-2B-2 88 55 0.030.03
실시예 36Example 36 A-5A-5 8585 B-2B-2 1010 55 0.020.02
실시예 37Example 37 A-16A-16 7070 B-1B-1 2525 55 0.020.02
실시예 38Example 38 A-17A-17 7070 B-1B-1 2525 55 0.020.02
표 6에 나타난 바와 같이, 가교제 B-1은 고분자, 가교제 및 산 촉매의 총량을 기준으로 함량이 10중량% 이상일 때 이박리성이 발현되었으며(실시예 28 내지 30), 가교제 B-2은 고분자, 가교제 및 산 촉매의 총량을 기준으로 3중량% 이상의 함량일 때 이박리성이 발현되었다 (실시예 33 내지 38).As shown in Table 6, the crosslinking agent B-1 exhibited dissociation property when the content was 10% by weight or more based on the total amount of the polymer, the crosslinking agent and the acid catalyst (Examples 28 to 30), and the crosslinking agent B-2 was a polymer. When the content was 3% by weight or more based on the total amount of the crosslinking agent and the acid catalyst, the peeling property was expressed (Examples 33 to 38).
또한, 표 5의 비교예 8에서는 고분자/가교제의 혼합 비율이 90/10인 경우 이박리성이 나타나지 않았지만, 산 촉매를 사용한 거의 같은 혼합 비율(85/10)의 표 6의 실시예 28에서는 이박리성이 발현하였다. 따라서 산 촉매 첨가시 이박리성이 용이하게 나타난다고 할 수 있다.In Comparative Example 8 of Table 5, when the polymer / crosslinking agent mixture ratio was 90/10, no dissociation property was observed. In Example 28 of Table 6 of Table 6, which was about the same mixing ratio (85/10) using an acid catalyst, Peelability was expressed. Therefore, it can be said that the peeling property easily appears when the acid catalyst is added.
 이상과 같이, 본 발명의 바람직한 실시예를 이용하여 본 발명을 예시하였지만, 본 발명은 특허청구 범위에 의해서만 그 범위가 해석되어야 할 것이며, 상기 예시로 든 바람직한 실시예에 한정되어서는 안될 것으로 이해된다.As mentioned above, although this invention was illustrated using the preferable Example of this invention, it is understood that the scope should be interpreted only by the claim, and should not be limited to the above-mentioned preferred embodiment. .

Claims (55)

  1. 분리층;Separation layer;
    상기 분리층 상에 형성되되, 센싱 전극 및 상기 센싱 전극의 일단에 형성되는 패드 전극을 포함하는 전극 패턴층; 및An electrode pattern layer formed on the separation layer, the electrode pattern layer including a sensing electrode and a pad electrode formed at one end of the sensing electrode; And
    상기 전극 패턴층 상부에 형성되며 상기 전극 패턴층의 일부 또는 전부를 덮도록 형성되는 절연층;을 포함하며,And an insulating layer formed on the electrode pattern layer and covering a part or all of the electrode pattern layer.
    상기 분리층은,The separation layer,
    알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH기 함유기를 가진 측쇄를 구비한 쇄상 폴리머 및 가교제를 포함하고,A chain polymer having a side chain having an alcoholic secondary or tertiary OH containing group or a phenolic OH group containing group and a crosslinking agent,
    상기 쇄상 폴리머는 하기 화학식 1로 표시되는 모노머 및 하기 화학식 2로 표시되는 모노머 중에서 선택되는 적어도 하나의 모노머로부터 유래된 단위를 포함하는 것인 경화성 수지 조성물로 형성되며,The chain polymer is formed of a curable resin composition comprising a unit derived from at least one monomer selected from a monomer represented by Formula 1 and a monomer represented by Formula 2 below,
    상기 가교제는, 트리아진계 화합물, 그 축합체 및 이들의 혼합물; 글리콜우릴계 화합물, 그 축합체 및 이들의 혼합물; 및 이미다졸리디논계 화합물, 그 축합체 및 이들의 혼합물로 이루어진 군에서 선택되는 것인, 필름 터치 센서:The crosslinking agent may include a triazine compound, a condensate thereof, and a mixture thereof; Glycoluril compounds, their condensates, and mixtures thereof; And an imidazolidinone-based compound, a condensate thereof, and a mixture thereof.
    [화학식 1][Formula 1]
    Figure PCTKR2019001826-appb-I000056
    Figure PCTKR2019001826-appb-I000056
    (화학식 1 중, R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고, (Formula 1, R 1a is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl group and substituted or unsubstituted alkenyl group,
    L1은 단일결합, 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고,L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
    L2는 O 또는 NH이고,L 2 is O or NH,
    R2a, R3a 및 R4a는 서로 독립적으로 수소, 및 치환 또는 비치환 탄화수소기로 이루어진 군에서 선택되고, R 2a , R 3a and R 4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon group,
    단 R2a, R3a 및 R4a 중 적어도 1개는 치환 또는 비치환의 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기거나,Provided that at least one of R 2a , R 3a and R 4a is a substituted or unsubstituted alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group,
    혹은 R2a, R3a 및 R4a 중 적어도 2개가 하나가 되어, 알코올성 제2급 또는 제3급 OH 또는 페놀성 OH를 포함하는, 치환 또는 비치환 시클로알킬기, 치환 또는 비치환 시클로알케닐기, 치환 또는 비치환 방향족기, 치환 또는 비치환 헤테로 방향족기, 및 이들을 포함하는 다환임)Or a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, substituted with at least two of R 2a , R 3a and R 4a and containing an alcoholic secondary or tertiary OH or phenolic OH Or an unsubstituted aromatic group, a substituted or unsubstituted hetero aromatic group, and a polycyclic including them)
    [화학식 2][Formula 2]
    Figure PCTKR2019001826-appb-I000057
    Figure PCTKR2019001826-appb-I000057
    (화학식 2 중, R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고,(Formula 2, R 1a is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl group and substituted or unsubstituted alkenyl group,
    L1은 단일결합, 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고,L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
    R5a 내지 R14a는 서로 독립적으로 수소, 히드록시기 및 하기 화학식 3으로 표시되는 작용기로 이루어진 군 중에서 선택되거나, 또는 하나가 되어 환을 형성하되, 단 R5a 내지 R14a 또는 상기 환의 치환기 중 적어도 하나는 히드록시기임)R 5a to R 14a are each independently selected from the group consisting of hydrogen, a hydroxy group, and a functional group represented by the following formula (3), or one to form a ring, provided that at least one of R 5a to R 14a or a substituent of the ring is Hydroxy group)
    [화학식 3][Formula 3]
    Figure PCTKR2019001826-appb-I000058
    Figure PCTKR2019001826-appb-I000058
    (화학식 3 중, R15a는 치환 또는 비치환 알킬기, 치환 또는 비치환 알케닐기, 치환 또는 비치환 시클로알킬기, 치환 또는 비치환 시클로알케닐기, 치환 또는 비치환 방향족기, 및 치환 또는 비치환 헤테로 방향족기로 이루어진 군에서 선택됨)In Formula 3, R 15a is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic. Selected from the group consisting of flags)
  2. 청구항 1에 있어서, 상기 L1은 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되는, 필름 터치 센서.The film touch sensor according to claim 1, wherein L 1 is selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkenylene group.
  3. 청구항 1에 있어서, 상기 L1은 치환 또는 비치환 알킬렌기인, 필름 터치 센서.The film touch sensor according to claim 1, wherein L 1 is a substituted or unsubstituted alkylene group.
  4. 청구항 1에 있어서, 상기 L1은 메틸렌기인, 필름 터치 센서.The film touch sensor according to claim 1, wherein L 1 is a methylene group.
  5. 청구항 1에 있어서, 상기 쇄상 폴리머는 하기 화학식 6으로 표시되는 모노머 단위를 포함하는, 필름 터치 센서:The method according to claim 1, wherein the chain polymer comprises a monomer unit represented by the following formula (6), the film touch sensor:
    [화학식 6][Formula 6]
    Figure PCTKR2019001826-appb-I000059
    Figure PCTKR2019001826-appb-I000059
    (화학식 6 중,(In formula 6,
    R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고,R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkenyl group,
    L1은 단일결합, 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고,L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
    R19a는 치환 또는 비치환 시클로알킬기, 치환 또는 비치환 시클로알케닐기, 치환 또는 비치환 방향족기, 및 치환 또는 비치환 헤테로 방향족기로 이루어진 군에서 선택됨)R 19a is selected from the group consisting of a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic group)
  6. 청구항 5에 있어서, 상기 L1은 치환 또는 비치환 알킬렌기인, 필름 터치 센서.The film touch sensor according to claim 5, wherein L 1 is a substituted or unsubstituted alkylene group.
  7. 청구항 5에 있어서, 상기 L1은 메틸렌기인, 필름 터치 센서.The film touch sensor of claim 5, wherein L 1 is a methylene group.
  8. 청구항 5에 있어서, 상기 R19a는 페닐기인, 필름 터치 센서.The film touch sensor of claim 5, wherein R 19a is a phenyl group.
  9. 청구항 1에 있어서, 상기 가교제는 트리아진계 화합물, 트리아진계 화합물의 축합체 및 이들의 혼합물로 이루어진 군에서 선택되는, 필름 터치 센서.The film touch sensor of claim 1, wherein the crosslinking agent is selected from the group consisting of triazine-based compounds, condensates of triazine-based compounds, and mixtures thereof.
  10. 청구항 1에 있어서, 상기 가교제는 하기 화학식 B-1으로 표시되는 화합물인, 필름 터치 센서:The method according to claim 1, wherein the crosslinking agent is a compound represented by the formula B-1, the touch sensor film:
    [화학식 B-1][Formula B-1]
    Figure PCTKR2019001826-appb-I000060
    Figure PCTKR2019001826-appb-I000060
  11. 청구항 1에 있어서, 상기 L1은 단일 결합인, 필름 터치 센서.The film touch sensor of claim 1, wherein L 1 is a single bond.
  12. 청구항 1에 있어서, 상기 R5a 내지 R14a 중 어느 2개 이상이 히드록시기이고, 나머지는 수소인, 필름 터치 센서.2. The film touch sensor according to claim 1, wherein any two or more of R 5a to R 14a are hydroxyl groups, and others are hydrogen.
  13. 청구항 1에 있어서, 상기 R5a 내지 R14a 중 어느 하나가 히드록시기이고, 나머지는 수소인, 필름 터치 센서.The film touch sensor according to claim 1, wherein any one of R 5a to R 14a is a hydroxy group, and the other is hydrogen.
  14. 청구항 1에 있어서, 상기 R5a 내지 R13a는 수소이고, R14a는 히드록시기인, 필름 터치 센서.The film touch sensor of claim 1, wherein R 5a to R 13a are hydrogen and R 14a is a hydroxy group.
  15. 청구항 1에 있어서, 상기 가교제는 글리코우릴계 화합물, 글리코우릴계 화합물의 축합체 및 이들의 혼합물로 이루어진 군에서 선택되는, 필름 터치 센서.The film touch sensor of claim 1, wherein the crosslinking agent is selected from the group consisting of glycouril compounds, condensates of glycouril compounds, and mixtures thereof.
  16. 청구항 1에 있어서, 상기 가교제는 하기 화학식 B-2로 표시되는 화합물인, 필름 터치 센서:The method according to claim 1, wherein the crosslinking agent is a film touch sensor, which is a compound represented by the formula B-2:
    [화학식 B-2][Formula B-2]
    Figure PCTKR2019001826-appb-I000061
    Figure PCTKR2019001826-appb-I000061
  17. 청구항 1에 있어서, 상기 가교제는 하기 화학식 B-3으로 표시되는 화합물인, 필름 터치 센서:The film touch sensor of claim 1, wherein the crosslinking agent is a compound represented by Chemical Formula B-3:
    [화학식 B-3][Formula B-3]
    Figure PCTKR2019001826-appb-I000062
    Figure PCTKR2019001826-appb-I000062
  18. 청구항 1에 있어서, 상기 경화성 수지 조성물은 용액으로 제공되는, 필름 터치 센서.The film touch sensor of claim 1, wherein the curable resin composition is provided in a solution.
  19. 청구항 18에 있어서, 상기 용액의 용매는 알코올을 포함하는, 필름 터치 센서.The film touch sensor of claim 18, wherein the solvent of the solution comprises an alcohol.
  20. 청구항 19에 있어서, 상기 알코올은 1급 알코올을 포함하는, 필름 터치 센서.The film touch sensor of claim 19, wherein the alcohol comprises a primary alcohol.
  21. 청구항 19에 있어서, 상기 알코올은 에탄올을 포함하는, 필름 터치 센서.The film touch sensor of claim 19, wherein the alcohol comprises ethanol.
  22. 청구항 19에 있어서, 상기 알코올의 함량은 상기 용매 중량 중 10 중량% 이상으로 존재하는, 필름 터치 센서.The film touch sensor of claim 19, wherein the content of alcohol is present in at least 10% by weight of the weight of the solvent.
  23. 청구항 1에 있어서, 상기 가교제는, 완전 또는 부분 알콕시메틸화 멜라민, 그 축합체 및 이들의 혼합물; 완전 또는 부분 알콕시메틸화 구아나민, 그 축합체 및 이들의 혼합물; 완전 또는 부분 알콕시메틸화 아세토구아나민, 그 축합체 및 이들의 혼합물; 완전 또는 부분 알콕시메틸화 벤조구아나민, 그 축합체 및 이들의 혼합물; 완전 또는 부분 알콕시메틸화 글리콜우릴, 그 축합체 및 이들의 혼합물; 및 완전 또는 부분 알콕시메틸화 이미다졸리디논, 그 축합체 및 이들의 혼합물;로 이루어진 군에서 선택된 것을 포함하는, 필름 터치 센서.The method of claim 1, wherein the crosslinking agent is selected from the group consisting of fully or partially alkoxymethylated melamine, condensates thereof and mixtures thereof; Fully or partially alkoxymethylated guanamines, their condensates and mixtures thereof; Fully or partially alkoxymethylated acetoguanamine, its condensates and mixtures thereof; Fully or partially alkoxymethylated benzoguanamine, condensates thereof and mixtures thereof; Fully or partially alkoxymethylated glycolurils, their condensates and mixtures thereof; And fully or partially alkoxymethylated imidazolidinone, condensates thereof, and mixtures thereof.
  24. 청구항 1에 있어서, 상기 가교제는 하기 화학식 7, 9 및 10으로 표시되는 화합물 및 이들의 각 축합체로 이루어진 군에서 선택된 것을 포함하는, 필름 터치 센서:The method according to claim 1, wherein the crosslinking agent comprises a compound represented by the following formula 7, 9 and 10 and selected from the group consisting of each condensate thereof, the film touch sensor:
    [화학식 7][Formula 7]
    Figure PCTKR2019001826-appb-I000063
    Figure PCTKR2019001826-appb-I000063
    (화학식 7 중, R1b는 탄소수 1 내지 25의 치환 또는 비치환 알킬기, 탄소수 2 내지 25의 치환 또는 비치환 알케닐기, 탄소수 6 내지 25의 치환 또는 비치환 방향족기, 탄소수 4 내지 25의 치환 또는 비치환 헤테로 방향족기, 및 하기 화학식 8로 표시되는 2치환 아민으로 이루어진 군에서 선택되고, In Formula 7, R 1b is a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 25 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 25 carbon atoms, substituted with 4 to 25 carbon atoms, or It is selected from the group consisting of an unsubstituted hetero aromatic group, and a disubstituted amine represented by the formula (8),
    R2b, R3b, R4b 및 R5b 는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기, 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택됨)R 2b , R 3b , R 4b and R 5b are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms)
    [화학식 8][Formula 8]
    Figure PCTKR2019001826-appb-I000064
    Figure PCTKR2019001826-appb-I000064
    (화학식 8 중, R6b 및 R7b 는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기, 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택됨)(In Formula 8, R 6b and R 7b are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.)
    [화학식 9][Formula 9]
    Figure PCTKR2019001826-appb-I000065
    Figure PCTKR2019001826-appb-I000065
    (화학식 9 중, R8b, R9b, R10b 및 R11b는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기, 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택됨)(In Formula 9, R 8b , R 9b , R 10b and R 11b are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.)
    [화학식 10][Formula 10]
    Figure PCTKR2019001826-appb-I000066
    Figure PCTKR2019001826-appb-I000066
    (화학식 10 중, R12b 및 R13b는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬기, 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고,In Formula 10, R 12b and R 13b are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms,
    R14b 및 R15b는 서로 독립적으로 수소, 탄소수 1 내지 10의 치환 또는 비치환 알킬기, 및 탄소수 2 내지 10의 치환 또는 비치환 알케닐기로 이루어진 군에서 선택됨)R 14b and R 15b are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms)
  25. 청구항 24에 있어서, 상기 가교제 중 축합체는 상기 화학식 7, 화학식 9 또는 화학식 10으로 표시되는 화합물의 중합체를 포함하는, 필름 터치 센서.The film touch sensor of claim 24, wherein the condensate in the crosslinking agent comprises a polymer of a compound represented by Formula 7, Formula 9, or Formula 10.
  26. 청구항 24에 있어서, 상기 가교제 중 축합체는 상기 화학식 7, 화학식 9 또는 화학식 10로 표시되는 화합물의 2량체, 3량체 및 4차 이상의 고차 중합체 중 적어도 1개를 포함하는, 필름 터치 센서.25. The film touch sensor of claim 24, wherein the condensate in the crosslinker comprises at least one of dimers, trimers, and quaternary or higher order polymers of the compounds represented by Formula 7, Formula 9 or Formula 10.
  27. 청구항 24에 있어서, 상기 가교제는 상기 화학식 7, 화학식 9 또는 화학식 10으로 표시되는 화합물에 대해 1.3 내지 1.8의 중량평균 중합도를 각각 가지는 것인, 필름 터치 센서.The film touch sensor according to claim 24, wherein the crosslinking agent has a weight average polymerization degree of 1.3 to 1.8 with respect to the compound represented by Chemical Formula 7, Chemical Formula 9 or Chemical Formula 10, respectively.
  28. 청구항 24에 있어서, The method of claim 24,
    R1b는 탄소수 6 내지 25의 치환 또는 비치환 방향족기 및 하기 화학식 11로 표시되는 2치환 아민으로 이루어진 군에서 선택되고,R 1b is selected from the group consisting of a substituted or unsubstituted aromatic group having 6 to 25 carbon atoms and a disubstituted amine represented by the following formula (11),
    R2b 내지 R13b 는 서로 독립적으로 탄소수 1 내지 10의 치환 또는 비치환 알킬이고,R 2b to R 13b are each independently a substituted or unsubstituted alkyl having 1 to 10 carbon atoms,
    R14b 및 R15b는 서로 독립적으로 수소인, 터치 필름 센서:Touch film sensors wherein R 14b and R 15b are independently of each other hydrogen:
    [화학식 11][Formula 11]
    Figure PCTKR2019001826-appb-I000067
    Figure PCTKR2019001826-appb-I000067
  29. 청구항 1에 있어서, 상기 쇄상 폴리머와 상기 가교제의 질량비는 1: 0.05 내지 1:2인, 필름 터치 센서.The film touch sensor of claim 1, wherein a mass ratio of the chain polymer and the crosslinking agent is 1: 0.05 to 1: 2.
  30. 청구항 1에 있어서, 상기 경화성 수지 조성물은 산 촉매를 더 포함하는, 필름 터치 센서.The film touch sensor of claim 1, wherein the curable resin composition further comprises an acid catalyst.
  31. 청구항 30에 있어서, 상기 산 촉매는 브뢴스테드산, 루이스산, 이들의 혼합물, 이들의 염 및 이들의 용매화물로 이루어진 군에서 선택되는, 필름 터치 센서.31. The film touch sensor of claim 30, wherein the acid catalyst is selected from the group consisting of Bronsted acid, Lewis acid, mixtures thereof, salts thereof, and solvates thereof.
  32. 청구항 1에 있어서, 상기 경화성 수지 조성물은 계면 활성제, 필러, 첨가제 및 발포제로 이루어진 군에서 선택된 적어도 하나를 더 포함하는, 필름 터치 센서.The film touch sensor of claim 1, wherein the curable resin composition further comprises at least one selected from the group consisting of a surfactant, a filler, an additive, and a blowing agent.
  33. 청구항 1에 있어서, 상기 경화성 수지 조성물은 계면 활성제를 더 포함하는, 필름 터치 센서.The film touch sensor of claim 1, wherein the curable resin composition further comprises a surfactant.
  34. 청구항 1에 있어서, 상기 경화성 수지 조성물은 발포제를 더 포함하는, 필름 터치 센서.The film touch sensor of claim 1, wherein the curable resin composition further comprises a blowing agent.
  35. 청구항 1에 있어서, 상기 경화성 수지 조성물은 150℃에서 1분의 가열에 의해 경화되는 경화성을 가지는, 필름 터치 센서.The film touch sensor according to claim 1, wherein the curable resin composition has curability that is cured by heating at 150 ° C. for 1 minute.
  36. 청구항 1에 있어서, 분리층은 400nm에서 99%의 이상의 투과율(%T) 및 0.1 이하의 b*을 가지는, 필름 터치 센서.The film touch sensor of claim 1, wherein the separation layer has a transmittance (% T) of at least 99% and a b * of at most 0.1 at 400 nm.
  37. 청구항 1에 있어서, 상기 분리층은 230℃ 내지 300℃의 내열성을 가지는, 필름 터치 센서.The film touch sensor of claim 1, wherein the separation layer has heat resistance of 230 ° C. to 300 ° C. 3.
  38. 청구항 1에 있어서, 상기 분리층은 230℃ 내지 260℃의 1 내지 2시간, 내열성을 가지는, 필름 터치 센서.The film touch sensor according to claim 1, wherein the separation layer has heat resistance of 1 to 2 hours at 230 ° C to 260 ° C.
  39. 청구항 1에 있어서, 상기 분리층은 230℃에서 8시간 이상, 내열성을 가지는, 필름 터치 센서.The film touch sensor according to claim 1, wherein the separation layer has heat resistance at 230 ° C. for at least 8 hours.
  40. 청구항 1에 있어서, 상기 분리층은 230℃에서 1 내지 2시간, 내열성을 가지는, 필름 터치 센서.The film touch sensor of claim 1, wherein the separation layer has heat resistance at 230 ° C. for 1 to 2 hours.
  41. 청구항 1에 있어서, 상기 분리층은 소다 유리제 기판 또는 무알칼리 유리제 기판에서 0.5N/mm2 이하의 박리력을 가지는, 필름 터치 센서.The film touch sensor according to claim 1, wherein the separation layer has a peel force of 0.5 N / mm 2 or less on a soda glass substrate or an alkali free glass substrate.
  42. 청구항 1에 있어서, 상기 분리층은 소다 유리제 기판 또는 무알칼리 유리제 기판에서 0.1N/mm2 이하의 박리력을 가지는, 필름 터치 센서.The film touch sensor according to claim 1, wherein the separation layer has a peel force of 0.1 N / mm 2 or less on a soda glass substrate or an alkali free glass substrate.
  43. 청구항 1에 있어서, 상기 필름 터치 센서는 상기 분리층과 상기 전극 패턴층 사이에 형성되는 보호층을 더 포함하는, 필름 터치 센서.The film touch sensor of claim 1, wherein the film touch sensor further comprises a protective layer formed between the separation layer and the electrode pattern layer.
  44. 청구항 1에 있어서, 상기 절연층의 상부에 배치되는 광학필름을 더 포함하는, 필름 터치 센서.The film touch sensor of claim 1, further comprising an optical film disposed on the insulating layer.
  45. 청구항 1에 있어서, 상기 전극 패턴층은 금속, 금속나노와이어, 금속산화물, 탄소나노튜브, 그래 핀, 전도성 고분자 및 도전성 잉크로 이루어진 군에서 선택된 적어도 하나로 형성된, 필름 터치 센서.The film touch sensor of claim 1, wherein the electrode pattern layer is formed of at least one selected from the group consisting of metal, metal nanowires, metal oxides, carbon nanotubes, graphene, conductive polymers, and conductive inks.
  46. 청구항 1에 있어서, 상기 분리층의 상기 전극 패턴층이 형성되는 반대 면에 점착제 또는 접착제를 매개로 형성되는 기능성 필름층을 더 포함하는, 필름 터치 센서.The film touch sensor of claim 1, further comprising a functional film layer formed on the opposite side of the separation layer on which the electrode pattern layer is formed by using an adhesive or an adhesive.
  47. 청구항 46에 있어서, 상기 기능성 필름층은 투명 필름, 위상차 필름, 등방성 필름, 보호 필름, 편광판, 편광자, 배리어 필름으로 이루어진 군에서 선택된 적어도 하나의 기능성 필름인, 필름 터치 센서.The film touch sensor of claim 46, wherein the functional film layer is at least one functional film selected from the group consisting of a transparent film, a retardation film, an isotropic film, a protective film, a polarizing plate, a polarizer, and a barrier film.
  48. 청구항 46에 있어서, 상기 기능성 필름층은 기재 필름 상에 기능성 코팅층이 형성된 필름이고,The method according to claim 46, wherein the functional film layer is a film having a functional coating layer formed on a base film,
    상기 기능성 코팅층은 코팅형 유기막층, 코팅형 위상차층, 코팅형 편광자층 또는 코팅형 배향막층을 포함하는, 필름 터치 센서.The functional coating layer is a film touch sensor comprising a coating organic film layer, a coating type retardation layer, a coating polarizer layer or a coating alignment film layer.
  49. (i) 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 갖는 측쇄를 포함하는 쇄상 폴리머와 가교제를 준비하는 단계;(i) preparing a chain polymer and a crosslinking agent comprising a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group;
    (ii) 상기 쇄상 폴리머와 상기 가교제를 포함하는 경화성 수지 조성물을 기판 상에 도포하여 경화성 수지 조성물 도막을 형성하는 단계; 및(ii) applying a curable resin composition comprising the chain polymer and the crosslinking agent onto a substrate to form a curable resin composition coating film; And
    (iii) 상기 경화성 수지 조성물 도막에서 중합 반응을 시켜 경화시킴으로써 분리층을 형성하는 단계;를 포함하는, 필름 터치 센서의 제조방법.(iii) forming a separation layer by performing a polymerization reaction on the curable resin composition coating film to cure the film.
  50. 청구항 49에 있어서, 상기 제조방법은The method of claim 49, wherein the manufacturing method
    (iv) 상기 기판 상에 형성되어 있는 상기 분리층을 상기 기판에서 박리하는 단계를 더 포함하는 필름 터치 센서의 제조방법.(iv) peeling the separation layer formed on the substrate from the substrate.
  51. 청구항 49에 있어서, 상기 쇄상 폴리머를 구성하는 모노머 단위에서 알코올성 제2급 또는 제3급 OH함유기 또는 페놀성 OH함유기를 포함하는 모노머 단위가 차지하는 비율은 30 내지 100몰%인, 필름 터치 센서의 제조방법.The film touch sensor as set forth in claim 49, wherein a monomer unit comprising an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group is 30 to 100 mol% in the monomer unit constituting the chain polymer. Manufacturing method.
  52. 청구항 49에 있어서, 상기 가교제는 완전 또는 부분 알콕시메틸화 멜라민, 완전 또는 부분 알콕시메틸화 구아나민, 완전 또는 부분 알콕시메틸화 아세토구아나민, 또는 완전 또는 부분 알콕시메틸화 벤조구아나민, 및 완전 또는 부분 알콕시메틸화 글리콜우릴로 이루어진 군에서 선택되는 것인, 필름 터치 센서의 제조방법.The method of claim 49, wherein the crosslinker is fully or partially alkoxymethylated melamine, fully or partially alkoxymethylated guanamine, fully or partially alkoxymethylated acetoguanamine, or fully or partially alkoxymethylated benzoguanamine, and fully or partially alkoxymethylated glycoluril Will be selected from the group consisting of, the manufacturing method of the film touch sensor.
  53. 청구항 49에 있어서, 상기 쇄상 폴리머와 상기 가교제의 질량비는 1: 0.05 내지 1:2인, 필름 터치 센서 제조방법.The method of claim 49, wherein the mass ratio of the chain polymer and the crosslinking agent is from 1: 0.05 to 1: 2.
  54. 캐리어 기판;A carrier substrate;
    상기 캐리어 기판 상에 형성되는 분리층;A separation layer formed on the carrier substrate;
    상기 분리층 상에 형성되되, 센싱 전극 및 상기 센싱 전극의 일단에 형성되는 패드 전극을 포함하는 전극 패턴층;An electrode pattern layer formed on the separation layer, the electrode pattern layer including a sensing electrode and a pad electrode formed at one end of the sensing electrode;
    상기 전극 패턴층 상부에 형성되며 상기 전극 패턴층의 일부 또는 전부를 덮도록 형성되는 절연층;을 포함하며,And an insulating layer formed on the electrode pattern layer and covering a part or all of the electrode pattern layer.
    알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기를 가진 측쇄를 구비한 쇄상 폴리머 및 가교제를 포함하고,A chain polymer having a side chain having an alcoholic secondary or tertiary OH-containing group or a phenolic OH-containing group and a crosslinking agent,
    상기 쇄상 폴리머는 하기 화학식 1로 표시되는 모노머 및 하기 화학식 2로 표시되는 모노머 중에서 선택되는 적어도 하나의 모노머로부터 유래된 단위를 포함하는 것인 경화성 수지 조성물로 형성되며,The chain polymer is formed of a curable resin composition comprising a unit derived from at least one monomer selected from a monomer represented by Formula 1 and a monomer represented by Formula 2 below,
    상기 가교제는, 트리아진계 화합물, 그 축합체 및 이들의 혼합물; 글리콜우릴계 화합물, 그 축합체 및 이들의 혼합물; 및 이미다졸리디논계 화합물, 그 축합체 및 이들의 혼합물로 이루어진 군에서 선택되는 것인, 필름 터치 센서용 구조체:The crosslinking agent may include a triazine compound, a condensate thereof, and a mixture thereof; Glycoluril compounds, their condensates, and mixtures thereof; And an imidazolidinone-based compound, a condensate thereof, and a mixture thereof.
    [화학식 A][Formula A]
    Figure PCTKR2019001826-appb-I000068
    Figure PCTKR2019001826-appb-I000068
    (화학식 A 중, R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고,In Formula A, R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group,
    L1은 단일결합, 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고,L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
    L2는 O 또는 NH이고,L 2 is O or NH,
    R2a, R3a 및 R4a는 서로 독립적으로 수소, 및 치환 또는 비치환 탄화수소기로 이루어진 군에서 선택되고, R 2a , R 3a and R 4a are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon group,
    단 R2a, R3a 및 R4a 중 적어도 1개는 치환 또는 비치환의 알코올성 제2급 또는 제3급 OH 함유기 또는 페놀성 OH 함유기거나,Provided that at least one of R 2a , R 3a and R 4a is a substituted or unsubstituted alcoholic secondary or tertiary OH-containing group or phenolic OH-containing group,
    혹은 R2a, R3a 및 R4a 중 적어도 2개가 하나가 되어, 알코올성 제2급 또는 제3급 OH 또는 패놀성 OH를 포함하는, 치환 또는 비치환 시클로알킬기, 치환 또는 비치환 시클로알케닐기, 치환 또는 비치환 방향족기, 치환 또는 비치환 헤테로 방향족기, 및 이들을 포함하는 다환임)Or a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, substituted with at least two of R 2a , R 3a and R 4a and containing an alcoholic secondary or tertiary OH or phenolic OH Or an unsubstituted aromatic group, a substituted or unsubstituted hetero aromatic group, and a polycyclic including them)
    [화학식 B][Formula B]
    Figure PCTKR2019001826-appb-I000069
    Figure PCTKR2019001826-appb-I000069
    (화학식 11 중, R1a는 수소, 치환 또는 비치환 알킬기 및 치환 또는 비치환 알케닐기로 이루어진 군에서 선택되고,In Formula 11, R 1a is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group,
    L1은 단일결합, 치환 또는 비치환 알킬렌기 및 치환 또는 비치환 알케닐렌기로 이루어진 군에서 선택되고,L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkenylene group,
    R5a 내지 R14a는 서로 독립적으로 수소, 히드록시기 및 하기 화학식 C로 표시되는 작용기로 이루어진 군 중에서 선택되거나, 또는 하나가 되어 환을 형성하되, 단 R5a 내지 R14a 또는 상기 환의 치환기 중 적어도 하나는 히드록시기임)R 5a to R 14a are each independently selected from the group consisting of hydrogen, a hydroxy group, and a functional group represented by the following general formula (C), or one to form a ring, provided that at least one of R 5a to R 14a or a substituent of the ring is Hydroxy group)
    [화학식 C][Formula C]
    Figure PCTKR2019001826-appb-I000070
    Figure PCTKR2019001826-appb-I000070
    (화학식 C 중, R15a는 치환 또는 비치환 알킬기, 치환 또는 비치환 알케닐기, 치환 또는 비치환 시클로알킬기, 치환 또는 비치환 시클로알케닐기, 치환 또는 비치환 방향족기, 및 치환 또는 비치환 헤테로 방향족기로 이루어진 군에서 선택됨)In Formula C, R 15a is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heteroaromatic Selected from the group consisting of flags)
  55. 청구항 54에 있어서, 상기 필름 터치 센서용 구조체는 상기 분리층과 상기 전극 패턴층 사이에 형성되는 보호층을 더 포함하는, 필름 터치 센서용 구조체.55. The structure of claim 54, wherein the structure for film touch sensors further comprises a protective layer formed between the separation layer and the electrode pattern layer.
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