WO2015102149A1 - Composition for forming resin layer and flexible display substrate using the same - Google Patents

Composition for forming resin layer and flexible display substrate using the same Download PDF

Info

Publication number
WO2015102149A1
WO2015102149A1 PCT/KR2014/001131 KR2014001131W WO2015102149A1 WO 2015102149 A1 WO2015102149 A1 WO 2015102149A1 KR 2014001131 W KR2014001131 W KR 2014001131W WO 2015102149 A1 WO2015102149 A1 WO 2015102149A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
glass fiber
fiber sheet
bisphenol
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2014/001131
Other languages
French (fr)
Inventor
Byung-Joon AN
Bo-Mi Lee
Dong-Hee Lee
Heon-Seung Chae
Pil-Rye Yang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kolon Industries Inc
Original Assignee
Kolon Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kolon Industries Inc filed Critical Kolon Industries Inc
Publication of WO2015102149A1 publication Critical patent/WO2015102149A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes

Definitions

  • the present invention relates to a composition for forming a resin layer, a flexible display substrate using the same, and a manufacturing method thereof.
  • CTR cathode ray tube
  • LCD liquid crystal displays
  • OLED organic light emitting diodes
  • a plastic substrate is an essential material necessary for realizing plastic flat panel displays or next-generation displays, and a demand for a plastic substrate is created in accordance with the development of the flexible display industry. Comparing the physical properties of a plastic substrate for realizing flexible displays with those of a conventional glass substrate, a plastic substrate is excellent in terms of weight, formability, non-breakability, design, roll-to-roll processability and the like, which are essential characteristics of flexible displays. However, in order for an optical plastic film to be used as a plastic substrate, it is required to improve the plastic substrate's physical properties, such as chemical resistance, thermal characteristics, air barrier properties and the like, which are poorer than those of a glass substrate.
  • an object of the present invention is to provide a composition for forming a resin layer, which includes a silicon-based binder and an acrylic monomer or an epoxy resin, a flexible display substrate having improved heat resistance, which is manufactured using the composition, and a method of manufacturing the flexible display substrate.
  • an aspect of the present invention provides a composition for forming a resin layer, including: a silicon-based binder having a structure of Formula 1 below; at least one compound selected from the group consisting of an acrylic monomer and an epoxy resin; and an initiator:
  • R 1 to R 4 are the same as or different from one another, and are each independently an alkyl group of C 1 to C 12 , an allyl group of C 2 to C 12 , an aralkyl group of C 2 to C 12 or an alkenyl group of C 2 to C 12 ;
  • R 5 and R 6 are the same as or different from each other, and are each independently hydrogen or a vinyl group; and S is an integer of 2 to 1000.
  • the mixing ratio of the silicon-based binder and the compound may be 7: 3 to 1: 9 by weight.
  • composition may further include: 9.5 to 70 wt% of the silicon-based binder; 30 to 90 wt% of the at least one compound selected from the group consisting of an acrylic monomer and an epoxy resin; and 0.5 to 20 wt% of the initiator.
  • the acrylic monomer may be at least one selected from the group consisting of bisphenol-A ethylene oxide diacrylate, bisphenol-A ethylene oxide dimethacrylate, bisphenol-A ethoxylate diacrylate, bisphenol-A ethoxylate dimethacrylate, bisphenol-A polyethoxylate diacrylate, bisphenol-A diacrylate, bisphenol-S diacrylate, dicyclopentadienyl diacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol tetracrylate, bisphenol-A dimethacrylate, bisphenol-S dimethacrylate, dicyclopentadienyl dimethacrylate, pentaerythritol trimethacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate, and pentaerythritol tetramethacrylate.
  • the epoxy resin may be at least one selected from the group consisting of a glycidyl epoxy resin and an alicyclic epoxy resin.
  • composition may further include a surfactant.
  • composition may further include a solvent.
  • Another aspect of the present invention provides flexible display substrate, including a glass fiber sheet impregnated with the composition.
  • Still another aspect of the present invention provides a method of manufacturing a flexible display substrate including a glass fiber sheet and a resin layer formed on both sides of the glass fiber sheet, including the steps of: impregnating a glass fiber sheet with the composition for a resin layer of claim 1; and UV-irradiating the glass fiber sheet impregnated with the composition to UV-cure the glass fiber sheet.
  • the method may include the steps of: impregnating a glass fiber sheet with the composition for a resin layer of; laminating a release film on both sides of the glass fiber sheet impregnated with the composition; UV-irradiating the glass fiber sheet laminated with the release film to UV-cure the glass fiber sheet; and separating the release film from the UV-cured glass fiber sheet.
  • the method may further include the step of heating the UV-cured glass fiber sheet to 200 to 300°C to thermally cure the glass fiber sheet, after the step of UV-curing the glass fiber sheet.
  • this flexible display substrate When a flexible display substrate is manufactured using the composition for forming a resin layer according to the present invention, this flexible display substrate has excellent formability, is transparent and flexible, and has excellent thermal expansibility, excellent heat resistance and excellent flame retardance. Therefore, this flexible display substrate can replace a conventional glass substrate.
  • the present invention provides a composition for forming a resin layer, including: a silicon-based binder having a structure of Formula 1 below; at least one compound selected from the group consisting of an acrylic monomer and an epoxy resin; and an initiator:
  • R 1 to R 4 are the same as or different from one another, and are each independently an alkyl group of C 1 to C 12 , an allyl group of C 2 to C 12 , an aralkyl group of C 2 to C 12 or an alkenyl group of C 2 to C 12 ;
  • R 5 and R 6 are the same as or different from each other, and are each independently hydrogen or a vinyl group; and S is an integer of 2 to 1000.
  • the acrylic monomer may be a 2-functional or more acrylic or methacrylic compound.
  • the acrylic monomer may be at least one selected from the group consisting of bisphenol-A ethylene oxide diacrylate, bisphenol-A ethylene oxide dimethacrylate, bisphenol-A ethoxylate diacrylate, bisphenol-A ethoxylate dimethacrylate, bisphenol-A polyethoxylate diacrylate, bisphenol-A diacrylate, bisphenol-S diacrylate, dicyclopentadienyl diacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol tetracrylate, bisphenol-A dimethacrylate, bisphenol-S dimethacrylate, dicyclopentadienyl dimethacrylate, pentaerythritol trimethacrylate, tris(2-hydroxyethyl)iso
  • the epoxy resin is referred to as a resin having at least one epoxy group.
  • the epoxy group may be a glycidyl epoxy resin or an alicyclic epoxy resin.
  • the glycidyl epoxy resin may be a bisphenol-A epoxy resin, a bisphenol-F epoxy resin, a bisphenol-S epoxy resin, a naphthalene-type epoxy resin or a hydrogenated compound thereof; an epoxy resin having a dicyclopentadiene backbone; an epoxy resin having a triglycidyl isocyanurate backbone; an epoxy resin having a cardo backbone; or an epoxy resin having a polysiloxane backbone.
  • the alicyclic epoxy resin may be 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 1,2,8,9-diepoxylimonene, ⁇ -caprolactone whose both ends are respectively ester-bonded with 3,4-epoycyclohexylmethanol and 3,4-epoxycyclohexane carboxylic acid, or an epoxy resin having a hydrogenated bisphenol-A backbone.
  • the mixing ratio of the silicon-based binder and the compound may be 7: 3 to 1: 9 by weight. It is preferred that the silicon-based binder having high flexibility and heat resistance be used alone. However, the composition including only the silicon-based resin cannot be applied to a roll-to-roll process for attaching a release film unable to resist a temperature of 150°C or higher to both sides of a glass fiber sheet impregnated with the composition and curing the glass fiber sheet coated with the release film, because the thermal cure temperature thereof is 150°C or higher.
  • the silicon-based binder when the silicon-based binder is mixed with an acrylic monomer or an epoxy resin and then used, a release film is attached to both sides of a glass fiber sheet impregnated with the composition, the glass fiber sheet is photocured, the release film is removed from the glass fiber sheet, and then the glass fiber sheet is thermally photocured.
  • the release film can smoothly move along a roll without being sticky when this release film is removed before thermal curing after photocuring during a roll-to-roll process.
  • the mixing ratio of the silicon-based binder and the compound exceeds 7:3, the release film cannot smoothly move along a roll without being sticky when this release film is removed before thermal curing after photocuring during a roll-to-roll process.
  • the mixing ratio of the compound and the silicon-based binder does not reach 1:9, the content of the silicon-based binder in the composition is extremely low and thus the effects of improvement of flexibility and heat resistance cannot be expected.
  • composition for forming a resin layer according to the present invention may further include an initiator for curing the above-mentioned silicon-based binder and compound.
  • the initiator may be a photopolymerization initiator or thermopolymerization initiator.
  • the photopolymerization initiator is referred to as a compound causing decomposition or bonding using lithographic exposure and creating active species capable of initiating the polymerization of the silicon-based binder with the acylic monomer or epoxy resin such as radical, anion, cation or the like.
  • Examples of the photopolymerization initiator may include: acetophenone compounds, such as 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinopropane-1; benzoin ether compounds, such as benzoin ethyl ether, benzoin isopropyl ether, and anisyl methy ether; ⁇ -ketol compounds, such as 2-methyl-2-hydroxypropiophenone; ketal compounds, such as benzyl dimethyl ketal; aromatic sulfonyl chloride compounds, such as 2-naphthalenesulfonyl chloride; photoactive oxime
  • thermopolymerization initiator may include: organic peroxides, such as benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide; and azo compounds, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile
  • the composition for forming a resin layer may include 9.5 to 70 wt% of the silicon-based binder; 30 to 90 wt% of the at least one compound selected from the group consisting of an acrylic monomer and an epoxy resin; and 0.5 to 20 wt% of the initiator.
  • the contents of the silicon-based binder, compound and initiator in the composition deviate from the above ranges, respectively, the heat resistance, thermal expansibility and flame retardance of the composition may be deteriorated.
  • the composition for forming a resin layer may further include a surfactant and a solvent for the purpose of realizing specific functions.
  • the surfactant is effective in modifying the surface of a resin layer, and, preferably, may be a silicon-based surfactant or a fluorine-based surfactant.
  • the silicon-based surfactant may include a silicon group and an ionic group.
  • the ionic group may be an anionic group. Specific examples of the anionic group may include carboxylate, sulfonate, phosphonate and the like.
  • the surfactant In order for the surfactant to be converted into fumes during UV-curing or thermal curing in the process of manufacturing a flexible display substrate, it is preferred that the surfactant have a solid content of 80 to 100 wt% based 100 wt% of the total amount thereof and have a flash point of 100°C or higher.
  • the surfactant be included in an amount of 0.005 to 5 parts by weight, preferably 0.01 to 1 parts by weight, based on 100 parts by weight of the solid content of the composition for forming a resin layer.
  • the surfactant is included in an amount of less than 0.005 parts by weight, the effect of modifying the surface of a resin layer may be insufficient, and, when the surfactant is included in an amount of more than 5 parts by weight, the heat resistance of a resin layer may be deteriorated.
  • the solvent may be selected from among ketones, ethers, esters, alcohols, hydrocarbons, acetonitrile, nitromethane, water, and mixtures thereof.
  • the solvent may include: ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like; ethers, such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like; esters, such as ethyl acetate, ethoxyethyl acetate and the like; alcohols, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-butoxyethanol and the like; hydrocarbons, such as n-hexane,
  • the method of manufacturing a flexible display substrate may include the steps of: impregnating a glass fiber sheet with the composition for a resin layer; and UV-irradiating the glass fiber sheet impregnated with the composition to UV-cure the glass fiber sheet.
  • the intensity of UV-irradiation may be changed depending on the kind of components included in the composition for forming a resin layer and the amount of the photopolymerization initiator. Further, it is preferred that a release film be laminated on both sides of the glass fiber sheet impregnated with the composition before the step of UV-curing the glass fiber sheet, and that the release film be separated from the both side of the glass fiber sheet after the step of UV-curing the glass fiber sheet.
  • the temperature and pressure of a laminating machine may be adjusted according to the purpose of the present invention. As such, when the glass fiber sheet is laminated with the release film and then UV-cured, it is easy to uniformly control the final thickness of a resin layer formed after UV-irradiation.
  • the method may further include the step of heating the UV-cured glass fiber sheet to thermally cure the glass fiber sheet, after the step of UV-curing the glass fiber sheet, depending on the kind of the composition applied to the glass fiber sheet.
  • the thermal curing temperature may be 200 to 300°C
  • the thermal curing time may be properly adjusted in consideration of the kind of the composition and the thermal curing temperature.
  • the flexible substrate may include a glass fiber sheet impregnated with the composition for forming a resin layer.
  • the flexible display substrate is manufactured by the above method, and may have a thickness of 10 to 200 um.
  • the flexible display substrate is characterized in that it has excellent flexibility and heat resistance.
  • this flexible display substrate may have a thermal expansion coefficient of 10 ppm/°C or less.
  • a glass fiber sheet having a thickness of 40 to 60 um was impregnated with the composition for forming a resin layer at room temperature for 1 hour. Thereafter, a release film was laminated on both sides of the glass fiber sheet impregnated with the composition using a laminating machine, and then the glass fiber sheet laminated with the release film was UV-cured using a UV-exposing machine. Subsequently, the release film was removed from the both sides of the UV-cured glass fiber sheet, and then this glass fiber sheet was thermally cured, thereby finally obtaining a substrate.
  • a glass fiber sheet having a thickness of 40 to 60 um was impregnated with the composition for forming a resin layer at room temperature for 1 hour. Thereafter, a release film was laminated on both sides of the glass fiber sheet impregnated with the composition using a laminating machine, and then the glass fiber sheet laminated with the release film was UV-cured using a UV-exposing machine. Subsequently, the release film was removed from the both sides of the UV-cured glass fiber sheet, and then this glass fiber sheet was thermally cured, thereby finally obtaining a substrate.
  • compositions for forming a resin layer of Examples 1 and 2 25 wt% of bisphenol-A ethoxylate diacrylate, 15 wt% of ethoxylated bisphenol fluorene diacrylate (manufacturer: Hannong Chemical Co., Ltd., product name: BPF-022), 50 wt% of ethoxylated pentaerythritol tetracrylate (manufacturer: Hannong Chemical Co., Ltd., product name: PE-044) and 10 wt% of fluorene acrylate having a bivalent functional group (manufacturer: Miwon Chemical Co., Ltd., product name: HR-6082) were first mixed to obtain a mixture.
  • the substrates of Examples 1 and 2 and Comparative Example 1 were first heated from room temperature to 330°C at a heating rate of 10 °C/min under an N 2 atmosphere of a thermo-mechanical analyzer (TMA), were cooled from 330°C to room temperature at a cooling rate of 5 °C/min, and were then second heated from room temperature to 330°C at a heating rate of 10 °C/min.
  • TMA thermo-mechanical analyzer
  • the CTEs of these substrates were measured at 50°C intervals from room temperature to 330°C, and then the average value thereof was calculated.
  • each of the substrates of Examples 1 and 2 and Comparative Example 1 was heated from room temperature to 150°C at a heating rate of 10 °C/min under an N 2 atmosphere of a thermo-gravimetric analyzer (TGA), and then maintained at 150°C for 10 minutes. Then, each of the substrates was heated cooled from 150°C to 300°C at a heating rate of 10 °C/min, and was then maintained at 300°C for 1 hour and 10 minutes. The weight loss (%) thereof, which had been generated for 1 hour from 2 minutes to 62 minutes after it reached 300°C, was measured.
  • TGA thermo-gravimetric analyzer
  • the ⁇ Ra (roughness) of each of the substrates of Examples 1 and 2 and Comparative Example 1 was evaluated by measuring the surface roughness of each substrate having an area of 1mm x 1mm before and after heat treatment (250°C/10min) using a 10x magnification lens as a 3D profiler.
  • the CTE of the substrate of Comparative Example 1 is 14 ppm/°C or less, whereas that of the Example 1 is 7 ppm/°C or less and that of Example 2 is 9 ppm/°C or less, and that the weight loss of the substrate of Comparative Example 1 is 1.5% or less, whereas that of Example 1 is 1.0% or less and that of Example 2 is 1.2% or less.
  • the ⁇ Ra of the substrate of Comparative Example 1 is 600 nm or less, whereas that of Example 1 is 100 nm or less and that of Example 2 is 200 nm or less.
  • this flexible display substrate When a flexible display substrate is manufactured using the composition for forming a resin layer according to the present invention, this flexible display substrate has excellent formability, is transparent and flexible, and has excellent thermal expansibility, excellent heat resistance and excellent flame retardance. Therefore, this flexible display substrate can replace a conventional glass substrate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)

Abstract

Disclosed herein is a composition for forming a resin layer, including: a silicon-based binder; at least one compound selected from the group consisting of an acrylic monomer and an epoxy resin; and an initiator. When a flexible display substrate is manufactured using the composition for forming a resin layer, this flexible display substrate has excellent formability, is transparent and flexible, and has excellent thermal expansibility, excellent heat resistance and excellent flame retardance. Therefore, this flexible display substrate can replace a conventional glass substrate.

Description

COMPOSITION FOR FORMING RESIN LAYER AND FLEXIBLE DISPLAY SUBSTRATE USING THE SAME
The present invention relates to a composition for forming a resin layer, a flexible display substrate using the same, and a manufacturing method thereof.
Recently, in display methods, the use of conventional cathode ray tube (CRT) displays has switched to flat panel displays, such as plasma display panels (PDPs), liquid crystal displays (LCDs), organic light emitting diodes (OLEDs) and the like. Particularly, research into flat panel displays has been actively conducted such that they can be realized into flexible displays in the future.
Meanwhile, a plastic substrate is an essential material necessary for realizing plastic flat panel displays or next-generation displays, and a demand for a plastic substrate is created in accordance with the development of the flexible display industry. Comparing the physical properties of a plastic substrate for realizing flexible displays with those of a conventional glass substrate, a plastic substrate is excellent in terms of weight, formability, non-breakability, design, roll-to-roll processability and the like, which are essential characteristics of flexible displays. However, in order for an optical plastic film to be used as a plastic substrate, it is required to improve the plastic substrate's physical properties, such as chemical resistance, thermal characteristics, air barrier properties and the like, which are poorer than those of a glass substrate.
For this purpose, there was proposed a method of impregnating a glass fiber sheet with resin. However, when a conventional film impregnated with only acrylic resin or epoxy resin is used, there are problems in that it is difficult to apply this film to a high-temperature process because it has poor heat resistance and in that it is difficult to apply this film to a substrate for flexible displays because it is brittle.
Accordingly, the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a composition for forming a resin layer, which includes a silicon-based binder and an acrylic monomer or an epoxy resin, a flexible display substrate having improved heat resistance, which is manufactured using the composition, and a method of manufacturing the flexible display substrate.
In order to accomplish the above object, an aspect of the present invention provides a composition for forming a resin layer, including: a silicon-based binder having a structure of Formula 1 below; at least one compound selected from the group consisting of an acrylic monomer and an epoxy resin; and an initiator:
[Formula 1]
Figure PCTKR2014001131-appb-I000001
wherein R1 to R4 are the same as or different from one another, and are each independently an alkyl group of C1 to C12, an allyl group of C2 to C12, an aralkyl group of C2 to C12 or an alkenyl group of C2 to C12; R5 and R6 are the same as or different from each other, and are each independently hydrogen or a vinyl group; and S is an integer of 2 to 1000.
Here, the mixing ratio of the silicon-based binder and the compound may be 7: 3 to 1: 9 by weight.
Further, the composition may further include: 9.5 to 70 wt% of the silicon-based binder; 30 to 90 wt% of the at least one compound selected from the group consisting of an acrylic monomer and an epoxy resin; and 0.5 to 20 wt% of the initiator.
Further, the acrylic monomer may be at least one selected from the group consisting of bisphenol-A ethylene oxide diacrylate, bisphenol-A ethylene oxide dimethacrylate, bisphenol-A ethoxylate diacrylate, bisphenol-A ethoxylate dimethacrylate, bisphenol-A polyethoxylate diacrylate, bisphenol-A diacrylate, bisphenol-S diacrylate, dicyclopentadienyl diacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol tetracrylate, bisphenol-A dimethacrylate, bisphenol-S dimethacrylate, dicyclopentadienyl dimethacrylate, pentaerythritol trimethacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate, and pentaerythritol tetramethacrylate.
Further, the epoxy resin may be at least one selected from the group consisting of a glycidyl epoxy resin and an alicyclic epoxy resin.
Further, the composition may further include a surfactant.
Further, the composition may further include a solvent.
Another aspect of the present invention provides flexible display substrate, including a glass fiber sheet impregnated with the composition.
Still another aspect of the present invention provides a method of manufacturing a flexible display substrate including a glass fiber sheet and a resin layer formed on both sides of the glass fiber sheet, including the steps of: impregnating a glass fiber sheet with the composition for a resin layer of claim 1; and UV-irradiating the glass fiber sheet impregnated with the composition to UV-cure the glass fiber sheet.
The method may include the steps of: impregnating a glass fiber sheet with the composition for a resin layer of; laminating a release film on both sides of the glass fiber sheet impregnated with the composition; UV-irradiating the glass fiber sheet laminated with the release film to UV-cure the glass fiber sheet; and separating the release film from the UV-cured glass fiber sheet.
The method may further include the step of heating the UV-cured glass fiber sheet to 200 to 300℃ to thermally cure the glass fiber sheet, after the step of UV-curing the glass fiber sheet.
When a flexible display substrate is manufactured using the composition for forming a resin layer according to the present invention, this flexible display substrate has excellent formability, is transparent and flexible, and has excellent thermal expansibility, excellent heat resistance and excellent flame retardance. Therefore, this flexible display substrate can replace a conventional glass substrate.
Hereinafter, the present invention will be described in detail.
The present invention provides a composition for forming a resin layer, including: a silicon-based binder having a structure of Formula 1 below; at least one compound selected from the group consisting of an acrylic monomer and an epoxy resin; and an initiator:
[Formula 1]
Figure PCTKR2014001131-appb-I000002
wherein R1 to R4 are the same as or different from one another, and are each independently an alkyl group of C1 to C12, an allyl group of C2 to C12, an aralkyl group of C2 to C12 or an alkenyl group of C2 to C12; R5 and R6 are the same as or different from each other, and are each independently hydrogen or a vinyl group; and S is an integer of 2 to 1000.
In the composition for forming a resin layer, the acrylic monomer may be a 2-functional or more acrylic or methacrylic compound. In this case, the acrylic monomer may be at least one selected from the group consisting of bisphenol-A ethylene oxide diacrylate, bisphenol-A ethylene oxide dimethacrylate, bisphenol-A ethoxylate diacrylate, bisphenol-A ethoxylate dimethacrylate, bisphenol-A polyethoxylate diacrylate, bisphenol-A diacrylate, bisphenol-S diacrylate, dicyclopentadienyl diacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol tetracrylate, bisphenol-A dimethacrylate, bisphenol-S dimethacrylate, dicyclopentadienyl dimethacrylate, pentaerythritol trimethacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate, and pentaerythritol tetramethacrylate.
In the composition for forming a resin layer, the epoxy resin is referred to as a resin having at least one epoxy group. For example, the epoxy group may be a glycidyl epoxy resin or an alicyclic epoxy resin.
The glycidyl epoxy resin may be a bisphenol-A epoxy resin, a bisphenol-F epoxy resin, a bisphenol-S epoxy resin, a naphthalene-type epoxy resin or a hydrogenated compound thereof; an epoxy resin having a dicyclopentadiene backbone; an epoxy resin having a triglycidyl isocyanurate backbone; an epoxy resin having a cardo backbone; or an epoxy resin having a polysiloxane backbone.
The alicyclic epoxy resin may be 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 1,2,8,9-diepoxylimonene, ε-caprolactone whose both ends are respectively ester-bonded with 3,4-epoycyclohexylmethanol and 3,4-epoxycyclohexane carboxylic acid, or an epoxy resin having a hydrogenated bisphenol-A backbone.
In the composition for forming a resin layer, the mixing ratio of the silicon-based binder and the compound may be 7: 3 to 1: 9 by weight. It is preferred that the silicon-based binder having high flexibility and heat resistance be used alone. However, the composition including only the silicon-based resin cannot be applied to a roll-to-roll process for attaching a release film unable to resist a temperature of 150℃ or higher to both sides of a glass fiber sheet impregnated with the composition and curing the glass fiber sheet coated with the release film, because the thermal cure temperature thereof is 150℃ or higher. Therefore, when the silicon-based binder is mixed with an acrylic monomer or an epoxy resin and then used, a release film is attached to both sides of a glass fiber sheet impregnated with the composition, the glass fiber sheet is photocured, the release film is removed from the glass fiber sheet, and then the glass fiber sheet is thermally photocured. In the case where the composition ratio of the silicon-based binder and the acrylic monomer or the epoxy resin is appropriately adjusted, the release film can smoothly move along a roll without being sticky when this release film is removed before thermal curing after photocuring during a roll-to-roll process. Therefore, when the mixing ratio of the silicon-based binder and the compound exceeds 7:3, the release film cannot smoothly move along a roll without being sticky when this release film is removed before thermal curing after photocuring during a roll-to-roll process. In contrast, when the mixing ratio of the compound and the silicon-based binder does not reach 1:9, the content of the silicon-based binder in the composition is extremely low and thus the effects of improvement of flexibility and heat resistance cannot be expected.
The composition for forming a resin layer according to the present invention may further include an initiator for curing the above-mentioned silicon-based binder and compound. The initiator may be a photopolymerization initiator or thermopolymerization initiator.
In the present invention, the photopolymerization initiator is referred to as a compound causing decomposition or bonding using lithographic exposure and creating active species capable of initiating the polymerization of the silicon-based binder with the acylic monomer or epoxy resin such as radical, anion, cation or the like. Examples of the photopolymerization initiator may include: acetophenone compounds, such as 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α-hydroxy-α,α'-dimethylacetophenone, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinopropane-1; benzoin ether compounds, such as benzoin ethyl ether, benzoin isopropyl ether, and anisyl methy ether; α-ketol compounds, such as 2-methyl-2-hydroxypropiophenone; ketal compounds, such as benzyl dimethyl ketal; aromatic sulfonyl chloride compounds, such as 2-naphthalenesulfonyl chloride; photoactive oxime compounds, such as 1-phenone-1,1-propandione-2-(o-ethoxycarbonyl)oxime; benzophenone compounds, such as benzophenone, benzoyl benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; diphenyl(2,4,6-trimethylbenzoyl phosphine oxide; and methylbenzoyl formate.
Examples of the thermopolymerization initiator may include: organic peroxides, such as benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide; and azo compounds, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovalerate), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazoline-2-yl)propane].
The composition for forming a resin layer may include 9.5 to 70 wt% of the silicon-based binder; 30 to 90 wt% of the at least one compound selected from the group consisting of an acrylic monomer and an epoxy resin; and 0.5 to 20 wt% of the initiator. When the contents of the silicon-based binder, compound and initiator in the composition deviate from the above ranges, respectively, the heat resistance, thermal expansibility and flame retardance of the composition may be deteriorated.
In the present invention, if necessary, the composition for forming a resin layer may further include a surfactant and a solvent for the purpose of realizing specific functions.
The surfactant is effective in modifying the surface of a resin layer, and, preferably, may be a silicon-based surfactant or a fluorine-based surfactant. The silicon-based surfactant may include a silicon group and an ionic group. The ionic group may be an anionic group. Specific examples of the anionic group may include carboxylate, sulfonate, phosphonate and the like.
In order for the surfactant to be converted into fumes during UV-curing or thermal curing in the process of manufacturing a flexible display substrate, it is preferred that the surfactant have a solid content of 80 to 100 wt% based 100 wt% of the total amount thereof and have a flash point of 100℃ or higher.
Further, it is preferred that the surfactant be included in an amount of 0.005 to 5 parts by weight, preferably 0.01 to 1 parts by weight, based on 100 parts by weight of the solid content of the composition for forming a resin layer. When the surfactant is included in an amount of less than 0.005 parts by weight, the effect of modifying the surface of a resin layer may be insufficient, and, when the surfactant is included in an amount of more than 5 parts by weight, the heat resistance of a resin layer may be deteriorated.
The solvent may be selected from among ketones, ethers, esters, alcohols, hydrocarbons, acetonitrile, nitromethane, water, and mixtures thereof. Examples of the solvent may include: ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like; ethers, such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like; esters, such as ethyl acetate, ethoxyethyl acetate and the like; alcohols, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-butoxyethanol and the like; hydrocarbons, such as n-hexane, n-heptane, iso-octane, benzene, toluene, xylene, gasoline, diesel, kerosene and the like; acetonitrile; nitromethane; and water. These solvents may be used independently or in a mixture of two or more.
The method of manufacturing a flexible display substrate may include the steps of: impregnating a glass fiber sheet with the composition for a resin layer; and UV-irradiating the glass fiber sheet impregnated with the composition to UV-cure the glass fiber sheet.
In the step of UV-curing the glass fiber sheet, the intensity of UV-irradiation may be changed depending on the kind of components included in the composition for forming a resin layer and the amount of the photopolymerization initiator. Further, it is preferred that a release film be laminated on both sides of the glass fiber sheet impregnated with the composition before the step of UV-curing the glass fiber sheet, and that the release film be separated from the both side of the glass fiber sheet after the step of UV-curing the glass fiber sheet. At the time of laminating the release film, the temperature and pressure of a laminating machine may be adjusted according to the purpose of the present invention. As such, when the glass fiber sheet is laminated with the release film and then UV-cured, it is easy to uniformly control the final thickness of a resin layer formed after UV-irradiation.
Further, the method may further include the step of heating the UV-cured glass fiber sheet to thermally cure the glass fiber sheet, after the step of UV-curing the glass fiber sheet, depending on the kind of the composition applied to the glass fiber sheet. In this case, the thermal curing temperature may be 200 to 300℃, and the thermal curing time may be properly adjusted in consideration of the kind of the composition and the thermal curing temperature. As such, in the step of thermal curing, the insufficiently UV-cured glass fiber sheet formed in the step of UV-curing is further thermally cured to sufficiently cure the glass fiber sheet, thus improving the heat resistance of a substrate as a final product.
The flexible substrate may include a glass fiber sheet impregnated with the composition for forming a resin layer.
The flexible display substrate is manufactured by the above method, and may have a thickness of 10 to 200 um.
The flexible display substrate is characterized in that it has excellent flexibility and heat resistance. For example, this flexible display substrate may have a thermal expansion coefficient of 10 ppm/℃ or less.
Hereinafter, the present invention will be described in more detail with reference to the following Examples, Comparative Example and Experimental Example. However, these Examples are set forth to illustrate the present invention, and the scope of the invention is not limited thereto.
Example 1
20 wt% of bisphenol-A ethylene oxide diacrylate (manufacturer: Miwon Chemical Co., Ltd., product name: Miramer M240), 30 wt% of bisphenol-A ethylene oxide dimethacrylate (manufacturer: KYOEISHA Corp., product name: BP-4EM) and 50 wt% of a silicon-based binder having a structure of Formula 1 above (R1 to R3: methyl group, R4: phenyl group, R5 to R6: vinyl group, S: 10) were mixed to obtain a first mixture. Then, 2 wt% of 1-hydroxycylclohexyl phenyl ketone (Irgacure 184, manufactured by BASF Corporation) and 2 wt% of benzoyl peroxide, based on the amount of the first mixture, were respectively added to the first mixture to obtain a second mixture. Then, the second mixture was stirred for 1 hour to prepare a composition for forming a resin layer.
A glass fiber sheet having a thickness of 40 to 60 um was impregnated with the composition for forming a resin layer at room temperature for 1 hour. Thereafter, a release film was laminated on both sides of the glass fiber sheet impregnated with the composition using a laminating machine, and then the glass fiber sheet laminated with the release film was UV-cured using a UV-exposing machine. Subsequently, the release film was removed from the both sides of the UV-cured glass fiber sheet, and then this glass fiber sheet was thermally cured, thereby finally obtaining a substrate.
Example 2
50 wt% of 3,4-epoxycyclohexylmethyl-3, 10 wt% of bisphenol-A ethylene oxide dimethacrylate and 40 wt% of a silicon-based binder having a structure of Formula 1 above (R1 to R3: methyl group, R4: phenyl group, R5 to R6: vinyl group, S: 10) were mixed to obtain a first mixture. Then, 2 wt% of benzoyl peroxide, based on the amount of the first mixture, were added to the first mixture to obtain a second mixture. Then, the second mixture was stirred for 1 hour to prepare a composition for forming a resin layer.
A glass fiber sheet having a thickness of 40 to 60 um was impregnated with the composition for forming a resin layer at room temperature for 1 hour. Thereafter, a release film was laminated on both sides of the glass fiber sheet impregnated with the composition using a laminating machine, and then the glass fiber sheet laminated with the release film was UV-cured using a UV-exposing machine. Subsequently, the release film was removed from the both sides of the UV-cured glass fiber sheet, and then this glass fiber sheet was thermally cured, thereby finally obtaining a substrate.
Comparative Example 1
Unlike the compositions for forming a resin layer of Examples 1 and 2, 25 wt% of bisphenol-A ethoxylate diacrylate, 15 wt% of ethoxylated bisphenol fluorene diacrylate (manufacturer: Hannong Chemical Co., Ltd., product name: BPF-022), 50 wt% of ethoxylated pentaerythritol tetracrylate (manufacturer: Hannong Chemical Co., Ltd., product name: PE-044) and 10 wt% of fluorene acrylate having a bivalent functional group (manufacturer: Miwon Chemical Co., Ltd., product name: HR-6082) were first mixed to obtain a mixture. Then, 2 wt% of 1-hydroxycylclohexyl phenyl ketone, based on the amount of the mixture, was added to the mixture, and stirred for 1 hour to prepare an impregnation solution. Thereafter, the impregnation solution was processed in the same manner as in Example 1, thereby finally obtaining a substrate.
Experimental Example
Regarding the substrates of Examples 1 and 2 and Comparative Example 1, the CTE (coefficient of thermal expansion), TGA (thermogravimetric analysis) and surface characteristics after heat treatment were evaluated, and the results thereof are given in Table 1 below.
<CTE measuring method>
The substrates of Examples 1 and 2 and Comparative Example 1 were first heated from room temperature to 330℃ at a heating rate of 10 ℃/min under an N2 atmosphere of a thermo-mechanical analyzer (TMA), were cooled from 330℃ to room temperature at a cooling rate of 5 ℃/min, and were then second heated from room temperature to 330℃ at a heating rate of 10 ℃/min. At the time of second heating the substrates, the CTEs of these substrates were measured at 50℃ intervals from room temperature to 330℃, and then the average value thereof was calculated.
<TGA analysis method>
Each of the substrates of Examples 1 and 2 and Comparative Example 1 was heated from room temperature to 150℃ at a heating rate of 10 ℃/min under an N2 atmosphere of a thermo-gravimetric analyzer (TGA), and then maintained at 150℃ for 10 minutes. Then, each of the substrates was heated cooled from 150℃ to 300℃ at a heating rate of 10 ℃/min, and was then maintained at 300℃ for 1 hour and 10 minutes. The weight loss (%) thereof, which had been generated for 1 hour from 2 minutes to 62 minutes after it reached 300℃, was measured.
<Surface characteristics evaluation method>
The ΔRa (roughness) of each of the substrates of Examples 1 and 2 and Comparative Example 1 was evaluated by measuring the surface roughness of each substrate having an area of 1mm x 1mm before and after heat treatment (250℃/10min) using a 10x magnification lens as a 3D profiler.
Table 1
Class. Ex. 1 Ex. 2 Comp. Ex. 1
CTE < 7 ppm/℃ < 9 ppm/℃ < 14 ppm/℃
Weight loss (300℃ for 1hr) < 1% < 1.2% < 1.5%
ΔRa (Roughness) < 100nm < 200nm < 600nm
As given in Table 1 above, it can be ascertained that the CTE of the substrate of Comparative Example 1 is 14 ppm/℃ or less, whereas that of the Example 1 is 7 ppm/℃ or less and that of Example 2 is 9 ppm/℃ or less, and that the weight loss of the substrate of Comparative Example 1 is 1.5% or less, whereas that of Example 1 is 1.0% or less and that of Example 2 is 1.2% or less. Further, it can be ascertained that the ΔRa of the substrate of Comparative Example 1 is 600 nm or less, whereas that of Example 1 is 100 nm or less and that of Example 2 is 200 nm or less.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
When a flexible display substrate is manufactured using the composition for forming a resin layer according to the present invention, this flexible display substrate has excellent formability, is transparent and flexible, and has excellent thermal expansibility, excellent heat resistance and excellent flame retardance. Therefore, this flexible display substrate can replace a conventional glass substrate.

Claims (11)

  1. A composition for forming a resin layer, comprising:
    a silicon-based binder having a structure of Formula 1 below;
    at least one compound selected from the group consisting of an acrylic monomer and an epoxy resin; and
    an initiator:
    [Formula 1]
    Figure PCTKR2014001131-appb-I000003
    wherein R1 to R4 are the same as or different from one another, and are each independently an alkyl group of C1 to C12, an allyl group of C2 to C12, an aralkyl group of C2 to C12 or an alkenyl group of C2 to C12,
    R5 and R6 are the same as or different from each other, and are each independently hydrogen or a vinyl group, and
    S is an integer of 2 to 1000.
  2. The composition of claim 1, wherein a mixing ratio of the silicon-based binder and the compound is 7: 3 to 1: 9 by weight.
  3. The composition of claim 1, comprising: 9.5 to 70 wt% of the silicon-based binder; 30 to 90 wt% of the at least one compound selected from the group consisting of an acrylic monomer and an epoxy resin; and 0.5 to 20 wt% of the initiator.
  4. The composition of claim 1, wherein the acrylic monomer is at least one selected from the group consisting of bisphenol-A ethylene oxide diacrylate, bisphenol-A ethylene oxide dimethacrylate, bisphenol-A ethoxylate diacrylate, bisphenol-A ethoxylate dimethacrylate, bisphenol-A polyethoxylate diacrylate, bisphenol-A diacrylate, bisphenol-S diacrylate, dicyclopentadienyl diacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol tetracrylate, bisphenol-A dimethacrylate, bisphenol-S dimethacrylate, dicyclopentadienyl dimethacrylate, pentaerythritol trimethacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate, and pentaerythritol tetramethacrylate.
  5. The composition of claim 1, wherein the epoxy resin is at least one selected from the group consisting of a glycidyl epoxy resin and an alicyclic epoxy resin.
  6. The composition of claim 1, further comprising a surfactant.
  7. The composition of claim 1, further comprising a solvent, wherein the solvent is selected from the group consisting of ketones, ethers, esters, alcohols, hydrocarbons, acetonitrile, nitromethane, water, and mixtures thereof.
  8. A flexible display substrate, comprising a glass fiber sheet impregnated with the composition of claim 1.
  9. A method of manufacturing a flexible display substrate including a glass fiber sheet and a resin layer formed on both sides of the glass fiber sheet, comprising the steps of:
    impregnating a glass fiber sheet with the composition for a resin layer of claim 1; and
    UV-irradiating the glass fiber sheet impregnated with the composition to UV-cure the glass fiber sheet.
  10. The method of claim 9, comprising the steps of:
    impregnating a glass fiber sheet with the composition for a resin layer of claim 1;
    laminating a release film on both sides of the glass fiber sheet impregnated with the composition;
    UV-irradiating the glass fiber sheet laminated with the release film to UV-cure the glass fiber sheet; and
    separating the release film from the UV-cured glass fiber sheet.
  11. The method of claim 9, further comprising the step of heating the UV-cured glass fiber sheet to 200 to 300℃ to thermally cure the glass fiber sheet, after the step of UV-curing the glass fiber sheet.
PCT/KR2014/001131 2013-12-30 2014-02-12 Composition for forming resin layer and flexible display substrate using the same Ceased WO2015102149A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020130167131A KR101575440B1 (en) 2013-12-30 2013-12-30 Composition for forming resin layer and flexible display substrate using the same
KR10-2013-0167131 2013-12-30

Publications (1)

Publication Number Publication Date
WO2015102149A1 true WO2015102149A1 (en) 2015-07-09

Family

ID=53493486

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/001131 Ceased WO2015102149A1 (en) 2013-12-30 2014-02-12 Composition for forming resin layer and flexible display substrate using the same

Country Status (3)

Country Link
KR (1) KR101575440B1 (en)
TW (1) TWI515280B (en)
WO (1) WO2015102149A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018217682A1 (en) * 2017-05-23 2018-11-29 Alpha Assembly Solutions Inc. Graphene enhanced and engineered materials for membrane touch switch and other flexible electronic structures
US20220153918A1 (en) * 2020-11-17 2022-05-19 Divergent Technologies, Inc. Isocyanurate resin compositions

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102590498B1 (en) * 2016-02-19 2023-10-19 삼성디스플레이 주식회사 Flexible display device, method for fabricating window member of the same, hard coating composition
KR102169052B1 (en) * 2019-01-15 2020-10-22 경상대학교산학협력단 Photocurable composition for 3D printer
WO2021199838A1 (en) * 2020-03-30 2021-10-07 宇部マテリアルズ株式会社 Polypropylene resin composition, method for producing polypropylene resin composition, and molded object

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090065220A (en) * 2007-12-17 2009-06-22 제일모직주식회사 Photosensitive resin composition and light shielding layer manufactured using the same
KR20090075525A (en) * 2008-01-04 2009-07-08 주식회사 엘지화학 Photosensitive silicone resin composition and cured film manufactured therefrom
KR20110125851A (en) * 2010-05-14 2011-11-22 (주)스마트이노베이션 Resin composition for display card manufacturing and display card manufacturing method using the same
KR20120138610A (en) * 2011-06-15 2012-12-26 코오롱인더스트리 주식회사 The flexible display substrate
KR20130139133A (en) * 2012-06-12 2013-12-20 제일모직주식회사 Composite sheet, method for preparing thereof and display substrate comprising the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090065220A (en) * 2007-12-17 2009-06-22 제일모직주식회사 Photosensitive resin composition and light shielding layer manufactured using the same
KR20090075525A (en) * 2008-01-04 2009-07-08 주식회사 엘지화학 Photosensitive silicone resin composition and cured film manufactured therefrom
KR20110125851A (en) * 2010-05-14 2011-11-22 (주)스마트이노베이션 Resin composition for display card manufacturing and display card manufacturing method using the same
KR20120138610A (en) * 2011-06-15 2012-12-26 코오롱인더스트리 주식회사 The flexible display substrate
KR20130139133A (en) * 2012-06-12 2013-12-20 제일모직주식회사 Composite sheet, method for preparing thereof and display substrate comprising the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018217682A1 (en) * 2017-05-23 2018-11-29 Alpha Assembly Solutions Inc. Graphene enhanced and engineered materials for membrane touch switch and other flexible electronic structures
US11624000B2 (en) 2017-05-23 2023-04-11 Alpha Assembly Solutions Inc. Graphene enhanced and engineered materials for membrane touch switch and other flexible electronic structures
US12497532B2 (en) 2017-05-23 2025-12-16 Alpha Assembly Solutions Inc. Graphene enhanced and engineered materials for membrane touch switch and other flexible electronic structures
US20220153918A1 (en) * 2020-11-17 2022-05-19 Divergent Technologies, Inc. Isocyanurate resin compositions

Also Published As

Publication number Publication date
KR20150078060A (en) 2015-07-08
TWI515280B (en) 2016-01-01
KR101575440B1 (en) 2015-12-07
TW201525093A (en) 2015-07-01

Similar Documents

Publication Publication Date Title
CN112126372B (en) Method for manufacturing antistatic surface protective film, antistatic surface protective film
WO2015102149A1 (en) Composition for forming resin layer and flexible display substrate using the same
WO2013137621A1 (en) Adhesive composition
CN107108782A (en) Terminal-modified soluble polyfunctional vinyl aromatic co-polymer, curable resin composition and use its light guide wave duct
WO2009131321A2 (en) Pressure-sensitive adhesive compositions, polarizers and liquid crystal displays comprising the same
CN109852280B (en) Adhesive composition and surface protective film
US20140242384A1 (en) Removable water-dispersible acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet
TWI741081B (en) Adhesive composition and surface-protective film
CN104204010B (en) Resin composition, transparent film for touch panel sensor using the same, and touch panel
KR102607576B1 (en) Adhesive composition
WO2013094585A1 (en) Glass fiber composite resin substrate
JP7775684B2 (en) Curable resin compositions, cured products and articles
JP2014088483A (en) Gelatinous curable resin composition, device for image display and manufacturing method of device for image display
JP7587367B2 (en) Polarizing film with pressure-sensitive adhesive layer, image display panel, method for producing image display panel, and pressure-sensitive adhesive layer
CN111471144B (en) Acrylic acid modified low-dielectric fluorine-containing polyphenyl ether mixed glue and 5G copper-clad plate prepared from same
WO2014119425A1 (en) Active-energy-ray-curable composition for optical members, cured article, and optical lens and sheet or film for optical lenses each produced using said cured article
KR102376111B1 (en) Curable organic/inorganic hybrimer resin composition with high refractive index and the method of manufacturing the same
WO2018097660A1 (en) Curable composition
CN108795348A (en) Adhesion agent composition and surface protection film
WO2012141453A2 (en) Method of preparing resin composition for optical film by using continuous bulk polymerization and methods of preparing optical film and polarizing plate using the resin composition
WO2020045358A1 (en) Composition, adhesive including same, cured object obtained therefrom, and production method therefor
WO2013019040A2 (en) Photo-curable organic-inorganic hybrid resin composition
CN110951420B (en) Adhesive composition
TWI682003B (en) Coloring resin composition, and color filter and display device using the same
JP2015146000A (en) Resin composition for optical waveguide formation, resin film for optical waveguide formation, and optical waveguide using the resin composition and the resin film

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14876714

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14876714

Country of ref document: EP

Kind code of ref document: A1