WO2012173316A1 - Flexible display substrate - Google Patents

Flexible display substrate Download PDF

Info

Publication number
WO2012173316A1
WO2012173316A1 PCT/KR2011/009563 KR2011009563W WO2012173316A1 WO 2012173316 A1 WO2012173316 A1 WO 2012173316A1 KR 2011009563 W KR2011009563 W KR 2011009563W WO 2012173316 A1 WO2012173316 A1 WO 2012173316A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
ene
monomer
fluorene
hepta
Prior art date
Application number
PCT/KR2011/009563
Other languages
French (fr)
Korean (ko)
Inventor
양필례
송민경
최진식
이동희
채헌승
Original Assignee
코오롱인더스트리 주식회사
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
Priority claimed from KR1020110131012A external-priority patent/KR101450952B1/en
Application filed by 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Priority to JP2014515704A priority Critical patent/JP5827400B2/en
Priority to CN201180071685.3A priority patent/CN103619581B/en
Publication of WO2012173316A1 publication Critical patent/WO2012173316A1/en

Links

Images

Classifications

    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20—Constructional details
    • H01J2211/34—Vessels, containers or parts thereof, e.g. substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2329/00—Electron emission display panels, e.g. field emission display panels
    • H01J2329/86—Vessels
    • H01J2329/8605—Front or back plates
    • H01J2329/8615—Front or back plates characterised by the material

Definitions

  • the present invention relates to a flexible display substrate.
  • the display method is a plasma display panel (PDP), a liquid crystal display (LCD), an organic EL (Organic Light Emitting Diodes (OLED), etc.), which is a flat panel display in a conventional CRT (Cathode Ray Tube) method.
  • PDP plasma display panel
  • LCD liquid crystal display
  • OLED Organic Light Emitting Diodes
  • CTR Cathode Ray Tube
  • the substrate is basically used as a glass material.
  • a high temperature heat treatment is required as a condition for forming a TFT (thin film transistor).
  • glass substrates are basically too hard, and thus have a problem in that they are not suitable as flexible substrates due to their poor flexibility.
  • a flexible display substrate As a flexible display substrate, it is excellent in weight, formability, non-destructiveness, design, etc. compared to glass substrate, and in particular, it can be produced by a roll-to-roll production method to reduce manufacturing cost. Research into a technology using a plastic material is being actively conducted, but a flexible display substrate of a plastic material suitable for commercialization has not been developed.
  • Such plastic substrates basically require excellent light transmittance and complex thermal stability, chemical resistance, surface flatness, and the like, in order to be a substrate of a flexible display.
  • the thermal expansion coefficient Excellent thermal stability, represented by Coefficient of Thermal Expansion (CTE) is required.
  • the present invention is to provide a flexible display substrate having excellent thermal stability while maintaining excellent optical properties.
  • the flexible display substrate of the present invention includes a glass fiber layer and a resin layer formed on both surfaces of the glass island layer, wherein the resin layer includes a unit structure from an acrylic monomer and a unit structure from a cyclic olefin monomer, and includes a weight average molecular weight.
  • This compound includes 500 to 1,000,000.
  • the compound in the resin layer more preferably comprises 100 parts by weight of the unit structure from the acrylic monomer and 25 to 400 parts by weight of the unit structure from the cyclic olefin monomer.
  • the cyclic olefin monomer that forms the unit structure from the cyclic olefin monomer in the resin layer is bicyclo [2.2.1] hepta-2-ene (bicyclo [2.2.1] hepta-2-ene).
  • cyclic olefin monomer that forms the unit structure from the cyclic olefin monomer in the resin layer is preferably one or more selected from formula (1).
  • R 1 to R 6 are each the same or different hydrocarbon groups having 1 to 10 carbon atoms, unsubstituted or substituted with a linking group containing hydrogen or oxygen, nitrogen, sulfur or silicon, or a polar group, a single bond or a divalent linking group
  • the branch is selected from an aromatic group, a silane group and a halogen atom, and n is an integer of 1 to 10.
  • n is preferably 4 to 10 in the unit structure from the monomer of Chemical Formula 1.
  • the resin layer may include a unit structure from an acrylic monomer, a unit structure from a monomer of Formula 1, and a unit structure from a monomer of Formula 2, wherein the compound in the resin layer is an acrylic monomer. It is more preferable to include 50-200 parts by weight of the unit structure from the monomer of Formula 1 and 20 to 200 parts by weight of the unit structure from the monomer of Formula 2 based on 100 parts by weight of the unit structure from.
  • R 7 to R 10 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms having a linking group containing hydrogen or oxygen, nitrogen, sulfur or silicon, an aromatic group having a polar group, a single bond or a divalent linking group, A silane group, a halogen atom, and at least one of R 7 to R 10 includes a divalent linking group such as acrylate or methacrylate.
  • the acrylic monomer forming the unit structure from the acrylic monomer in the resin layer is preferably a bifunctional or more functional acrylic or methacryl compound, wherein the acrylic monomer is bisphenol-A diacrylate (bisphenol-A- diacrylate), bisphenol-S diacrylate, dicyclopentadienyl diacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocy Anurate triacrylate (tris (2-hydroxyethyl) isocyanurate triacrylate), pentaerythritol tetraacrylate, bisphenol-A dimethacrylate, bisphenol-S-dimethacrylate ( bisphenol-S dimethacrylate), dicyclopentadienyl dimethacrylate, pentaery With pentaerythritol trimethacrylate, tris (2-hydroxyethyl) isocyanurate trimethacrylate, and pentaerythritol tetrameth,
  • the fluorene-based monomer forming the unit structure from the monomer of Formula 1 in the resin layer is not particularly limited to the fluorene skeleton-containing acrylate may be any fluorene skeleton-containing acrylate having two or more functional groups.
  • fluorene skeleton structure examples include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy- 3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy- It may be at least one selected from the group consisting of 3,5-dichlorophenyl) fluorene and 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene.
  • the glass fiber layer is a glass fiber layer of 4 ⁇ 20um diameter is aligned in one direction, it is preferable to form a glass fiber layer with a thickness of 20 ⁇ 200um in the form of weaving cross warp and weft yarns crosswise and longitudinally crosswise one by one. Do.
  • the present invention provides a flexible display substrate having excellent thermal stability while maintaining excellent optical properties.
  • the flexible display substrate of the present invention is formed of a photosensitive resin composition layer on both sides of the glass fiber layer by impregnating the photosensitive resin composition with a glass fiber layer made of glass fiber in order to maintain excellent optical properties as well as excellent thermal stability as a plastic substrate, After adjusting the thickness suitably, it can be obtained by UV-curing and forming a resin layer.
  • the glass fiber layer is a glass fiber of 4 ⁇ 15um diameter aligned in one direction, can be formed with a thickness of 20 ⁇ 200um, such a glass fiber layer is excellent in thermal properties, absorptivity, less hygroscopic. Because of its chemical durability, it does not corrode, has a strong tensile strength, a small elongation rate, and electrical insulation.
  • the compound contained in the resin layer includes a unit structure from an acrylic monomer and a unit structure from a cyclic olefin monomer.
  • the acrylic monomer may be variously selected according to the hydrophilic and hydrophobic physical properties of the composition before curing, and serves to improve the compatibility of the composition before curing. Since there are many commercial products with a viscosity ranging from 100 cPs to 50000 cPs, a wide range of choices are made, and since photocuring proceeds by radical formation of a photoinitiator, a polymer is formed by photopolymerization and plays a role of forming a network as a basic support for film forming. .
  • the cyclic olefin monomer as a low viscosity and high refractive compound, it has a stable aromatic molecular structure, has a high glass transition temperature, thereby improving thermal stability.
  • the wear resistance is excellent, reducing the frequency of scratches, and the chemical resistance is excellent, which helps to prevent the change of physical properties during the post-process and device fabrication.
  • the weight average molecular weight of the compound photopolymerized by UV-cure of an acryl-type monomer and a cyclic olefin type monomer is 500-1,000,000. If the weight average molecular weight is less than 500, there is a high possibility that a large amount of fume generation and weight loss occurs in the post-processing step after curing, and if it exceeds 1,000,000, the film becomes hard and the flexibility decreases.
  • the resin layer more preferably comprises 100 parts by weight of the unit structure from the acrylic monomer and 25 to 400 parts by weight of the unit structure from the cyclic olefin monomer, the refractive index of the glass fiber within this content range is It can go well and become a more transparent substrate.
  • the cyclic olefin monomer which forms a unit structure from the cyclic olefin monomer in the resin layer is bicyclo [2.2.1] hepta-2-ene, 5 5-methyl-bicyclo [2.2.1] hepta-2-ene (5-methyl-bicyclo [2.2.1] hepta-2-ene), 5-ethyl-bicyclo [2.2.1] hepta-2-ene ( 5-ethyl-bicyclo [2.2.1] hepta-2-ene), 5-propyl-bicyclo [2.2.1] hepta-2-ene (5-propyl-bicyclo [2.2.1] hepta-2-ene) , 5-hexyl-bicyclo [2.2.1] hepta-2-ene (5-hexyl-bicyclo [2.2.1] hepta-2-ene), 5-decyl-bicyclo [2.2.1] hepta-2- En (5-decyl-bicyclo [2.2.1
  • the cyclic olefin monomer forming a unit structure from the cyclic olefin monomer in the resin layer may be represented by the following formula (1): Is preferably.
  • a monomer is a low viscosity high refractive compound, which greatly improves the refractive index of the resin layer to minimize the refractive index with the glass fiber layer, thereby reducing the reflectance at the interface between the glass fiber layer and the resin layer, thereby improving the overall light transmittance of the substrate. It can be.
  • it has a stable aromatic molecular structure, has a high glass transition temperature, and thermal stability is greatly improved.
  • the wear resistance is excellent, reducing the frequency of scratches, and the chemical resistance is excellent, which helps to prevent the change of physical properties during the post-process and device fabrication.
  • R 1 to R 6 are each the same or different hydrocarbon groups having 1 to 10 carbon atoms, unsubstituted or substituted with a linking group containing hydrogen or oxygen, nitrogen, sulfur or silicon, or a polar group, a single bond or a divalent linking group
  • the branch is selected from an aromatic group, a silane group and a halogen atom, n is an integer of 1 to 10.
  • the hydrocarbon group having 1 to 10 carbon atoms may be any one alkyl group selected from the group consisting of methyl group, ethyl group, propyl group, and combinations thereof; Any one cycloalkyl group selected from the group consisting of a cyclopentyl group, a cyclohexyl group, and a combination thereof; Any one alkenyl group selected from the group consisting of a vinyl group, an aryl group, a propenyl group, and a combination thereof; It is preferable to include any one or more selected from.
  • the substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure as shown in Formula 1, or may be bonded to the ring structure through a linking group.
  • linking group examples include a linking group containing a divalent hydrocarbon group having 1 to 10 carbon atoms, oxygen, nitrogen, sulfur or silicon, for example, carbonyl group, oxycarbonyl group, sulfone group, ether bond, thioether bond, imino group, and amide. A bond, a siloxane bond, etc. are mentioned, The linking group containing these multiple may be sufficient.
  • the polar group examples include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alcohol cicarbonyl group, a cyano group, an amide group, an imide group, an amino group, an acyl group, a sulfonyl group, and a carboxyl group. More specifically, the alkoxy group includes a methoxy group, an ethoxy group, and the like, and the carbonyloxy group includes an alkylcarbonyloxy group such as an acetoxy group and propionyloxy group, an ethoxycarbonyl group, and the like.
  • the primary amino group is mentioned.
  • the divalent linking group is an alkylene group, particularly 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, for example, methylene group, ethylene group, trimethylene group, arylene group, oxy And alkylene groups, oxyarylene groups, oxycarbonyl groups, iminocarbonyl groups, carbonyl groups, acetylene groups, ureylene groups, hetero atoms such as sulfur and oxygen, and amino groups. Moreover, you may combine 2 or more of these coupling groups.
  • an aromatic group should be included, which includes one hydrogen leaving body of the aromatic compound.
  • the 1 hydrogen leaving body examples include benzene, pentarene, naphthalene, azulene, heptarene, biphenylene, indacene, acenaphthalene, phenanthrene, anthracene, fluoranthene, acefenanthrene, prephenylene, pyrene , Chrysene, naphthacene, flyaden, pisene, perylene, penpafen, pentacene, tetraphenylene, hexaphene, pensasene, rubisen, coronene, trinaphthylene, heptaphene, heptacene, pyracene, Any one monocyclic compound selected from the group consisting of ovaren and combinations thereof, thiophene, thianthrene, furan, pyran, isobenzofuran, chromen, xanthene, phenoxathiine,
  • the silane group is any one selected from the group consisting of any one alkoxysilyl group or trimethylsilyl group, triethylsiligo group and combinations thereof selected from the group consisting of trimethoxysilyl group, triethoxysilyl group and combinations thereof. It is preferable that it is a triorgano siloxy group.
  • n is preferably 4 to 10 in the unit structure from the monomer of Chemical Formula 1.
  • the fluorene-based monomer forming a unit structure from the monomer of Formula 1 may be any fluorene skeleton-containing acrylate having a fluorene skeleton-containing acrylate is not particularly limited and two or more functional groups.
  • fluorene skeleton structure examples include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy- 3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy- At least one selected from the group consisting of 3,5-dichlorophenyl) fluorene and 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene.
  • the flexible display substrate of the present invention it is preferable to further include a unit structure from the monomer of the formula (2) in the resin layer.
  • R 7 to R 10 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms having a linking group containing hydrogen or oxygen, nitrogen, sulfur or silicon, an aromatic group having a polar group, a single bond or a divalent linking group, A silane group, a halogen atom, and at least one of R 7 to R 10 includes a divalent linking group such as acrylate or methacrylate.
  • the unit structure from the monomer of Formula 2 greatly improves the refractive index of the resin layer to minimize the refractive index with the glass fiber layer, thereby reducing the reflectance at the interface between the glass fiber layer and the resin layer, thereby improving the overall light transmittance of the substrate.
  • the monomer of the formula (2) is a compound having a high refractive index of 1.58 or more, and has a high glass transition temperature, crosslinking degree and heat resistance at the same time.
  • the compound of the resin layer has 50 to 200 parts by weight of the unit structure from the monomer of Formula 1 and the monomer of Formula 2 based on 100 parts by weight of the unit structure from the acrylic monomer.
  • the unit structure from 20 to 200 parts by weight, and within this content range is well matched with the refractive index of the glass fiber can be a more transparent substrate.
  • the hardness of the substrate is too high to increase the hardness of the substrate, The problem of inferior flexible performance may occur.
  • the hydrocarbon group having 1 to 10 carbon atoms includes any one alkyl group selected from the group consisting of methyl group, ethyl group, propyl group, and combinations thereof; Any one cycloalkyl group selected from the group consisting of a cyclopentyl group, a cyclohexyl group, and a combination thereof; Any one alkenyl group selected from the group consisting of a vinyl group, an aryl group, a propenyl group, and a combination thereof; It is preferable to include any one or more selected from.
  • the substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure as shown in Formula 1, or may be bonded to the ring structure through a linking group.
  • linking group examples include a linking group containing a divalent hydrocarbon group having 1 to 10 carbon atoms, oxygen, nitrogen, sulfur or silicon, for example carbonyl group, oxycarbonyl group, sulfone group, ether bond, thioether bond, imino group, and amide. A bond, a siloxane bond, etc. are mentioned, The linking group containing these multiple may be sufficient.
  • the polar group examples include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alcohol cicarbonyl group, a cyano group, an amide group, an imide group, an amino group, an acyl group, a sulfonyl group, and a carboxyl group. More specifically, the alkoxy group includes a methoxy group, an ethoxy group, and the like, and the carbonyloxy group includes an alkylcarbonyloxy group such as an acetoxy group and propionyloxy group, an ethoxycarbonyl group, and the like.
  • the primary amino group is mentioned.
  • the divalent linking group is an alkylene group, particularly 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, for example, methylene group, ethylene group, trimethylene group, arylene group, oxyalkyl
  • a hetero group such as a ethylene group, an oxy arylene group, an oxy carbonyl group, an iminocarbonyl group, a carbonyl group, an acetylene group, a ureylene group, sulfur, oxygen, an amino group, etc. are mentioned. Moreover, you may combine 2 or more of these coupling groups.
  • the aromatic group should include an aromatic group through the linking group, and the aromatic group may include one hydrogen leaving body of the aromatic compound.
  • the 1 hydrogen leaving body examples include benzene, pentarene, naphthalene, azulene, heptarene, biphenylene, indacene, acenaphthalene, phenanthrene, anthracene, fluoranthene, acefenanthrene, prephenylene, pyrene , Chrysene, naphthacene, flyaden, pisene, perylene, penpafen, pentacene, tetraphenylene, hexaphene, pensasene, rubisen, coronene, trinaphthylene, heptaphene, heptacene, pyracene, Any one monocyclic compound selected from the group consisting of ovaren and combinations thereof, thiophene, thianthrene, furan, pyran, isobenzofuran, chromen, xanthene, phenoxathiine,
  • the silane group is any one selected from the group consisting of any one alkoxysilyl group or trimethylsilyl group, triethylsiligo group and combinations thereof selected from the group consisting of trimethoxysilyl group, triethoxysilyl group and combinations thereof It is preferable that it is a triorgano siloxy group.
  • the acrylic monomer forming the unit structure from the acrylic monomer in the resin layer is preferably a bifunctional or more functional acrylic or methacryl compound, wherein the acrylic monomer is bisphenol-A diacrylate (bisphenol-A-diacrylate ), Bisphenol-S diacrylate, dicyclopentadienyl diacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanu Tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate, bisphenol-A dimethacrylate, bisphenol-S-dimethacrylate (bisphenol -S dimethacrylate), dicyclopentadienyl dimethacrylate, pentaerythritol Consisting of pentaerythritol trimethacrylate, tris (2-hydroxyethyl) isocyanurate trimethacrylate, and pentaerythritol
  • the photosensitive resin composition for forming the resin layer of the present invention further includes a photoinitiator as a main composition in addition to the above-mentioned monomers in order to photocure them.
  • the photopolymerization initiator in the present invention means a compound which causes decomposition or bonding by exposure and generates active species capable of initiating polymerization of the acrylic monomers such as radicals, anions and cations and the cyclic olefin monomers.
  • the photoinitiator may select a conventional photoinitiator capable of photocuring the acrylic monomer and the cyclic olefin monomer.
  • photopolymerization initiator examples include Irgacure 907, Irgacure 369, Irgacure OX01, Irgacure 242, Thioxanthone, 2,4-Diethyl Thioxanthone, Thioxanthone-4-Sulfonic Acid, Benzophenone, and 4,4'-bis (di Ethylamino) benzophenone, acetophenone, p-dimethylaminoacetophenone, ⁇ , ⁇ '-dimethoxyacetoxy benzophenone, 2,2'-dimethoxy-2-petylacetophenone, p-methoxyacetophenone, 2 -Methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
  • the content of the photopolymerization initiator may have a range of 0.5 to 20% by weight based on 100% by weight of the composition.
  • the content of the photopolymerization initiator is less than 0.5% by weight, the sensitivity is not sufficient, the acrylic polymerization conversion rate is 80% or less, the tackiness of the sticky monomer may remain, and it is difficult to have the basic optical properties of the film to be formed.
  • the content of the photopolymerization initiator exceeds 20% by weight, the light transmittance, haze, yellow index, etc. of the formed film tends to be lowered.
  • a diluent is included, and the content of the diluent is preferably 20 to 80% by weight.
  • ethers such as alcohol, such as methanol and ethanol, tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol Propylene glycol alkyl ether acetates, such as butyl ether acetate, etc. are mentioned.
  • diethylene glycol dimethyl ether diethylene glycol diethyl ether, propylene glycol methyl ether acetates methyl ethyl ketone, cyclohexanone, and 4-hydride from the viewpoint of solubility, reactivity with each component, and convenience of coating film formation.
  • Methyl ester of ketone acetic acid such as oxy-4-methyl-2-pentanane, ethyl ester, propyl ester, butyl ester ethyl ester of 2-hydroxypropionic acid, ethyl ester of methyl ester 2-hydroxy-2-methylpropionic acid
  • Methyl ester of oxyacetic acid ethyl ester, butyl ester ethyl lactate, propyl lactate, butyl lactate methyl ester, ethyl ester, propyl ester, butyl ester methyl ester of propoxy acetic acid, ethyl ester, propyl ester, butyl ester Methyl ester of oxyacetic acid, ethyl ester, propyl ester, butyl ester Methyl ester Methyl ester of oxyacetic acid, ethyl ester, Lofil ester, butyl ester
  • the diluent may also be used with high boiling diluents.
  • high boiling whitening agent that can be used, for example, N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, benzyl ethyl Ethers.
  • the diluent is included in the range of 20 to 80% by weight based on 100% by weight of the composition, if the content of the whitening agent is in the above range can be obtained an effect that can form a desired film.
  • additives such as surfactants, curing accelerators, antioxidants for the expression of special functions.
  • the additives may include a surfactant for improving the surface coating properties
  • the surfactant is a fluorine and silicone-based surfactant, such as 3M's FC-129, FC-170C, FC-430, DIC's F- 172, F-173, F-183, F-470, F-475, and Shin-Etsu Silicone KP322, KP323, KP340, and KP341.
  • Such surfactants may be included in an amount of 5 parts by weight or less, preferably 2 parts by weight or less, based on 100 parts by weight of the composition. If the content of the surfactant exceeds 5 parts by weight, there is a problem that foaming occurs during the application, this problem affects the glass fiber impregnation and film formation is undesirable.
  • the resin composition of this invention may contain a small amount of antioxidant, an ultraviolet absorber, a dye pigment, etc. in the range which does not impair the characteristics, such as transparency, solvent resistance, and heat resistance, as needed.
  • a photosensitive resin composition by mixing the components and contents (wt%) as shown in Table 1, and stirred for 3 hours, and then impregnated with a glass fiber layer having a thickness of 40 ⁇ 150 ⁇ m ultrasonic wave for about 5-30 minutes After treatment (SONICATION), and placed between the glass substrate and the release film, using a doctor blade to adjust the thickness of the resin layer on one side of the glass fiber layer to 40 ⁇ 130um after the UV curing to obtain a substrate.
  • the transmittance and haze of the film were measured using a D65 light source using Method3. At this time, the wavelength is 550 nm.
  • the Yellow Index of the film was measured using an ASTM E313 measurement method using a UV-vis spectrometer (Varian, CARY-100 model).
  • the film was placed between the machines using an Abbe refractor and measured at 25 ° C.
  • the FT-IR spectrophotometer (Avatar 360 FT-IR, manufactured by Thermo Nicolet) is used to measure the transmittance in the 500 ⁇ 4000cm-1 area in the reflection mode (with Smart Miracle accessory).
  • Comparative Example 1 the light transmittance did not reach 90%, the Haze exceeded 40%, and the YI value exceeded 6.5, but Examples 1 to 5 all showed superior optical characteristics than Comparative Example 1. have.
  • thermogravimetric analysis for thermal stability evaluation is the same as FIG. 1 (in FIG. 1, the Y-axis shows the residual rate (%) having thermal stability up to 600 degrees), and the resultant ring
  • the residue is about 40% by weight when heated up to 600 ° C, but Examples 1 to 5 remain in excess of about 50% by weight, indicating excellent thermal stability.
  • Trimethylolpropane acetalization product diacrylate (R-604, manufactured by Nippon Kayaku) and Tetrakis (glycidyloxyphenyl) ethane-GAC 25 corresponding to the monomer of formula (2) based on 100 parts by weight of trimethylolpropane acetalization product diacrylate.
  • Two release films are placed in two glass substrates, and a glass fiber layer is spread therein, and the thickness of the resin layer is adjusted to 100 ⁇ m using a doctor blade, and irradiated with UV light of about 10 J / cm 2 on both sides.
  • the glass substrate and the release film were removed to obtain a substrate.
  • Example 6 except that 50 parts by weight of Tetrakis (glycidyloxyphenyl) ethane-GAC corresponding to the monomer of Formula 2 based on 100 parts by weight of trimethylolpropane acetalization product diacrylate was the same as in Example 6 The substrate was prepared.
  • Example 6 except that 100 parts by weight of Tetrakis (glycidyloxyphenyl) ethane-GAC corresponding to the monomer of Formula 2 based on 100 parts by weight of trimethylolpropane acetalization product diacrylate was the same as in Example 6
  • the substrate was prepared.
  • Example 6 the monomer corresponding to the monomer of Formula 2 was 1,1,2,2-Tetrakis [4- (acryloxy polyethoxy) phenyl] ethane, and the content thereof was 100 parts by weight of trimethylolpropane acetalization product diacrylate.
  • a substrate was manufactured in the same manner as in Example 6, except that 50 parts by weight was included as a standard.
  • Example 9 100 parts by weight of the monomer 1,1,2,2-Tetrakis [4- (acryloxy polyethoxy) phenyl] ethane corresponding to the monomer of Formula 2 was based on 100 parts by weight of trimethylolpropane acetalization product diacrylate.
  • a substrate was manufactured in the same manner as in Example 4 except for the inclusion.
  • a substrate was prepared in the same manner as in Example 6 except that the monomer of Formula 2 was not included in Example 6.
  • the transmittance and haze of the film were measured using a D65 light source using Method3.
  • the wavelength is based on 550nm.
  • the temperature was raised at a rate of 10 ° C. for 1 minute under a nitrogen atmosphere, and a load was applied at a weight of 1 g.
  • a load was applied at a weight of 1 g.
  • the heat history of a film after heating up 10 degreeC / min from room temperature to 200 degreeC, it heated up again to 300 degreeC at a speed of 10 degreeC / min from room temperature, and computed the coefficient of thermal expansion in 50-250 temperature range.
  • Examples 6 to 10 of the present invention shows a high light transmittance as in Comparative Example 2 even when using a glass fiber. And by including the unit structure from the monomer of Formula 2, it can be seen that Examples 6 to 10 can obtain excellent Tg of 230 ° C. or higher and a thermal expansion coefficient of 15 ppm or less.

Abstract

A flexible display substrate of the present invention comprises a glass fiber layer and resin layers which are formed on both sides of the glass fiber layer, and the resin layer comprises a unit structure from an acryl monomer and a unit structure from a monomer having a fluorine backbone structure.

Description

플렉서블 디스플레이 기판Flexible display board
본 발명은 플렉서블 디스플레이 기판에 관한 것이다. The present invention relates to a flexible display substrate.
최근에는 디스플레이 방식이 종래의 CRT(Cathode Ray Tube) 방식에서 평판 디스플레이인 플라즈마 디스플레이(Plasma display pannel ; PDP), 액정표시장치(Liquid crystal display ; LCD), 유기EL(Organic Light Emitting Diodes ; OLED) 등으로 전환되었고, 특히, 향후에는 이러한 평판 디스플레이를 플렉서블 디스플레이로 실현할 수 있도록 전세계적으로 연구가 활발하게 진행되고 있는 중이다. Recently, the display method is a plasma display panel (PDP), a liquid crystal display (LCD), an organic EL (Organic Light Emitting Diodes (OLED), etc.), which is a flat panel display in a conventional CRT (Cathode Ray Tube) method. In particular, research is being actively conducted around the world to realize such a flat panel display as a flexible display in the future.
위와 같은 평판 디스플레이에서는 기본적으로 기판을 유리소재로 사용하는데, 일반적인 평판 디스플레이에서는 TFT(박막 트랜지스터)를 형성시키기 위한 조건으로 고온 열처리가 필요하므로 이에 가장 적합한 소재로 유리기판이 이용되었다.In the flat panel display as described above, the substrate is basically used as a glass material. In the general flat panel display, a high temperature heat treatment is required as a condition for forming a TFT (thin film transistor).
그러나, 유리기판은 기본적으로 너무 딱딱한 특성을 가지므로, 가요성이 떨어져 플렉서블 디스플레이의 기판으로는 적합하지 않다는 문제점이 있는 것이다. However, glass substrates are basically too hard, and thus have a problem in that they are not suitable as flexible substrates due to their poor flexibility.
이에 플렉서블 디스플레이 기판으로 유리기판에 대비하여 무게, 성형성, 비파괴성, 디자인 등이 우수하고, 특히, 롤-투-롤(Roll-To-Roll) 생산 방식으로 생산할 수 있어 제조단가를 절감할 수 있는 플라스틱 소재를 이용하는 기술에 대한 연구가 활발하게 이루어지고 있으나, 아직 상용화에 이를 정도로 적합한 플라스틱 소재의 플렉서블 디스플레이 기판이 개발되지 않은 실정이다. As a flexible display substrate, it is excellent in weight, formability, non-destructiveness, design, etc. compared to glass substrate, and in particular, it can be produced by a roll-to-roll production method to reduce manufacturing cost. Research into a technology using a plastic material is being actively conducted, but a flexible display substrate of a plastic material suitable for commercialization has not been developed.
이와 같은 플라스틱 기판이 플렉서블 디스플레이의 기판이 되기 위해서는 기본적으로 우수한 광투과도가 요구됨과 동시에 열적 안정성, 내화학성, 표면 평탄성 등의 특성들이 복합적으로 요구되고, 특히, 우수한 광학 특성을 유지함과 동시에 열팽창계수(Coefficient of Thermal Expansion ; CTE)로 대표되는 우수한 열적 안정성이 요구된다. Such plastic substrates basically require excellent light transmittance and complex thermal stability, chemical resistance, surface flatness, and the like, in order to be a substrate of a flexible display. In particular, the thermal expansion coefficient ( Excellent thermal stability, represented by Coefficient of Thermal Expansion (CTE), is required.
본 발명은 우수한 광학특성을 유지함과 동시에 우수한 열적 안정성을 가지는 플렉서블 디스플레이 기판을 제공하려는 것이다. The present invention is to provide a flexible display substrate having excellent thermal stability while maintaining excellent optical properties.
본 발명의 플렉서블 디스플레이 기판은 유리섬유층과 상기 유리섬층의 양면에 형성된 수지층을 포함하고, 상기 수지층은 아크릴계 단량체로부터의 단위구조와 고리형 올레핀계 단량체로부터의 단위구조를 포함하고, 중량평균분자량이 500~1,000,000인 화합물을 포함한다. 이 때, 상기 수지층에서 상기 화합물은 아크릴계 단량체로부터의 단위구조 100중량부와 고리형 올레핀계 단량체로부터의 단위구조 25~400중량부를 포함하는 것이 더욱 바람직하다. The flexible display substrate of the present invention includes a glass fiber layer and a resin layer formed on both surfaces of the glass island layer, wherein the resin layer includes a unit structure from an acrylic monomer and a unit structure from a cyclic olefin monomer, and includes a weight average molecular weight. This compound includes 500 to 1,000,000. At this time, the compound in the resin layer more preferably comprises 100 parts by weight of the unit structure from the acrylic monomer and 25 to 400 parts by weight of the unit structure from the cyclic olefin monomer.
또, 상기 수지층에서 상기 고리형 올레핀계 단량체로부터의 단위구조를 형성하는 고리형 올레핀계 단량체는 비시클로[2.2.1]헵타-2-엔 (bicyclo[2.2.1]hepta-2-ene), 5-메틸-비시클로[2.2.1]헵타-2-엔 (5-methyl-bicyclo[2.2.1]hepta-2-ene), 5-에틸-비시클로[2.2.1]헵타-2-엔 (5-ethyl-bicyclo[2.2.1]hepta-2-ene), 5-프로필-비시클로[2.2.1]헵타-2-엔(5-propyl-bicyclo[2.2.1]hepta-2-ene), 5-헥실-비시클로[2.2.1]헵타-2-엔 (5-hexyl-bicyclo[2.2.1]hepta-2-ene), 5-데실-비시클로[2.2.1]헵타-2-엔 (5-decyl-bicyclo[2.2.1]hepta-2-ene), 5,6-디메틸-비시클로[2.2.1]헵타-2-엔 (5,6-dimethyl-bicyclo[2.2.1]hepta-2-ene), 5-메틸-5-에틸-비시클로[2.2.1]헵타-2-엔 (5-methyl-5-ethyl-bicyclo[2.2.1]hepta-2-ene), 5-페닐-비시클로[2.2.1]헵타-2-엔 (5-phenyl-bicyclo[2.2.1]hepta-2-ene), 5-시클로헥실-비시클로[2.2.1]헵타-2-엔 (5-cyclohexyl-bicyclo[2.2.1]hepta-2-ene), 트리시클로[4.3.0.12,5]데카-3-엔(tricyclo[4.3.0.12,5]deca-3-ene), 테트라시클로[4.4.0.12,5.17,10]도데카-3-엔 (tetracyclo[4.4.0.12,5.17,10]dodeca-3-ene), 3-메틸-테트라시클로[4.4.0.12,5.17,10]도데카-8-엔 (3-methyl-tetracyclo[4.4.0.12,5.17,10]dodeca-8-ene), 3-에틸-테트라시클로[4.4.0.12,5.17,10]도데카-8-엔 (3-ethyl-tetracyclo[4.4.0.12,5.17,10]dodeca-8-ene), 메틸 2-메틸-비시클로[2.2.1]헵타-5-엔-2-카르복실레이트 (methyl 2-methyl-bicyclo[2.2.1]hepta-5-ene-2-carboxylate), 2-메틸-비시클로[2.2.1]헵타-5-엔 아크릴레이트 (2-methyl-bicyclo[2.2.1]hepta-5-ene acrylate), 2-메틸-비시클로[2.2.1]헵타-5-엔 메타크릴레이트 (2-methyl-bicyclo[2.2.1]hepta-5-ene methacrylate), 디메틸 비시클로[2.2.1]헵타-5-엔-2,3-디카르복실레이트 (dimethyl bicyclo[2.2.1]hepta-5-ene-2,3-dicarboxylate), 디에틸 비시클로[2.2.1]헵타-5-엔-2,3-디카르복실레이트 (diethyl bicyclo[2.2.1]hepta-5-ene-2,3-dicarboxylate), 3-메틸-3-메톡시카르보닐-테트라시클로[4.4.0.12,5.17,10]도데카-8-엔 (3-methyl-3-methoxycarbonyl-tetracyclo[4.4.0.12,5.17,10]dodeca-8-ene), 비시클로[2.2.1]헵타-5-엔-N-시클로헥실-2,3-말레이미드 (bicyclo[2.2.1]hepta-5-ene-N-cyclohexyl-2,3-maleimide), 비시클로[2.2.1]헵타-5-엔-2-스피로-3'-N-페닐석신이미드 (bicyclo[2.2.1]hepta-5-ene-2-spiro-3'-N-phenylsuccinmide), 비시클로[2.2.1]헵타-5-엔-2-스피로-3'-N-시클로헥실석신이미드(bicyclo[2.2.1]hepta-5-ene-2-spiro-3'-N-cyclohexylsuccinmide), 2-[(3-에틸-3-옥세타닐)메톡시]비시클로[2.2.1]헵타-2-엔 (2-[(3-ethyl-3-oxetanyl)methoxy]bicyclo[2.2.1]hepta-2-ene), 2-[(3-에틸-3-옥세타닐)메톡시메틸]비시클로[2.2.1]헵타-2-엔 (2-[(3-ethyl-3-oxetanyl)methoxymethyl]bicyclo[2.2.1]hepta-2-ene), (3-에틸-3-옥세타닐)메틸 비시클로[2.2.1]헵타-5-엔-2-카르복실레이트 (3-ethyl-3-oxetanyl)methylbicyclo[2.2.1]hepta-5-ene-2-carboxylate), 5-트리에톡시실릴-비시클로[2.2.1]헵타-2-엔 (5-triethoxysilyl-bicyclo[2.2.1]-hepta-2-ene), 5-메틸디메톡시실릴-비시클로[2.2.1]헵타-2-엔 (5-methyldimethoxysilyl-bicyclo[2.2.1]hepta-2-ene), 5-[1'-메틸-2',5'-디옥사-1'-실라시클로펜틸]-비시클로[2.2.1]헵타-2-엔 (5-[1'-methyl-2',5'-dioxa-1'-silacyclopentyl]-bicyclo[2.2.1]hepta-2-ene), 5-[1'-메틸-3',3',4',4'-테트라페닐-2',5'-디옥사-1'-실라시클로펜틸]-비시클로[2.2.1]헵타-2-엔 (5-[1'-methyl-3',3',4',4'-tetraphenyl-2',5'-dioxa-1'-silacyclopentyl]-bicyclo[2.2.1]hepta-2-ene), 5-[1',4',4'-트리메틸-2' 및 6'-디옥사-1'-실라시클로헥실]-비시클로[2.2.1]헵타-2-엔 (5-[1',4',4'-trimethyl-2' and 6'-dioxa-1'-silacyclohexyl]-bicyclo[2.2.1]hepta-2-ene) 으로 구성되는 군에서 선택된 1 이상일 수 있다. In addition, the cyclic olefin monomer that forms the unit structure from the cyclic olefin monomer in the resin layer is bicyclo [2.2.1] hepta-2-ene (bicyclo [2.2.1] hepta-2-ene). , 5-methyl-bicyclo [2.2.1] hepta-2-ene (5-methyl-bicyclo [2.2.1] hepta-2-ene), 5-ethyl-bicyclo [2.2.1] hepta-2- 5-ethyl-bicyclo [2.2.1] hepta-2-ene, 5-propyl-bicyclo [2.2.1] hepta-2-ene (5-propyl-bicyclo [2.2.1] hepta-2-ene ene), 5-hexyl-bicyclo [2.2.1] hepta-2-ene, 5-decyl-bicyclo [2.2.1] hepta- 2-ene (5-decyl-bicyclo [2.2.1] hepta-2-ene), 5,6-dimethyl-bicyclo [2.2.1] hepta-2-ene (5,6-dimethyl-bicyclo [2.2. 1] hepta-2-ene), 5-methyl-5-ethyl-bicyclo [2.2.1] hepta-2-ene (5-methyl-5-ethyl-bicyclo [2.2.1] hepta-2-ene) , 5-phenyl-bicyclo [2.2.1] hepta-2-ene (5-phenyl-bicyclo [2.2.1] hepta-2-ene), 5-cyclohexyl-bicyclo [2.2.1] hepta-2 -Ene (5-cyclohexyl-bicyclo [2.2.1] hepta-2-ene), tricyclo [4.3.0.12,5] deca-3-ene (tricy clo [4.3.0.12,5] deca-3-ene), tetracyclo [4.4.0.12,5.17,10] dodeca-3-ene (tetracyclo [4.4.0.12,5.17,10] dodeca-3-ene), 3-methyl-tetracyclo [4.4.0.12,5.17,10] dodeca-8-ene (3-methyl-tetracyclo [4.4.0.12,5.17,10] dodeca-8-ene), 3-ethyl-tetracyclo [ 4.4.0.12,5.17,10] dodeca-8-ene (3-ethyl-tetracyclo [4.4.0.12,5.17,10] dodeca-8-ene), methyl 2-methyl-bicyclo [2.2.1] hepta- 5-ene-2-carboxylate (methyl 2-methyl-bicyclo [2.2.1] hepta-5-ene-2-carboxylate), 2-methyl-bicyclo [2.2.1] hepta-5-ene acrylate (2-methyl-bicyclo [2.2.1] hepta-5-ene acrylate), 2-methyl-bicyclo [2.2.1] hepta-5-ene methacrylate (2-methyl-bicyclo [2.2.1] hepta -5-ene methacrylate), dimethyl bicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylate (dimethyl bicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylate), Diethyl bicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylate, 3-methyl-3- Methoxycarbonyl-tetra Chloro [4.4.0.12,5.17,10] dodeca-8-ene (3-methyl-3-methoxycarbonyl-tetracyclo [4.4.0.12,5.17,10] dodeca-8-ene), bicyclo [2.2.1] hepta -5-ene-N-cyclohexyl-2,3-maleimide (bicyclo [2.2.1] hepta-5-ene-N-cyclohexyl-2,3-maleimide), bicyclo [2.2.1] hepta-5 -En-2-spiro-3'-N-phenylsuccinimide (bicyclo [2.2.1] hepta-5-ene-2-spiro-3'-N-phenylsuccinmide), bicyclo [2.2.1] hepta- 5-en-2-spiro-3'-N-cyclohexylsuccinimide (bicyclo [2.2.1] hepta-5-ene-2-spiro-3'-N-cyclohexylsuccinmide), 2-[(3-ethyl -3-oxetanyl) methoxy] bicyclo [2.2.1] hepta-2-ene (2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hepta-2-ene), 2-[(3-ethyl-3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hepta-2-ene (2-[(3-ethyl-3-oxetanyl) methoxymethyl] bicyclo [2.2.1 ] hepta-2-ene), (3-ethyl-3-oxetanyl) methyl bicyclo [2.2.1] hepta-5-ene-2-carboxylate (3-ethyl-3-oxetanyl) methylbicyclo [2.2 .1] hepta-5-ene-2-carboxylate), 5-triethoxysilyl-bicyclo [2.2.1] hepta-2-ene (5-tri ethoxysilyl-bicyclo [2.2.1] -hepta-2-ene), 5-methyldimethoxysilyl-bicyclo [2.2.1] hepta-2-ene (5-methyldimethoxysilyl-bicyclo [2.2.1] hepta-2- ene), 5- [1'-methyl-2 ', 5'-dioxa-1'-silacyclopentyl] -bicyclo [2.2.1] hepta-2-ene (5- [1'-methyl-2 ', 5'-dioxa-1'-silacyclopentyl] -bicyclo [2.2.1] hepta-2-ene), 5- [1'-methyl-3', 3 ', 4', 4'-tetraphenyl-2 ', 5'-dioxa-1'-silacyclopentyl] -bicyclo [2.2.1] hepta-2-ene (5- [1'-methyl-3', 3 ', 4', 4'-tetraphenyl -2 ', 5'-dioxa-1'-silacyclopentyl] -bicyclo [2.2.1] hepta-2-ene), 5- [1', 4 ', 4'-trimethyl-2' and 6'-dioxa -1'-Silacyclohexyl] -bicyclo [2.2.1] hepta-2-ene (5- [1 ', 4', 4'-trimethyl-2 'and 6'-dioxa-1'-silacyclohexyl]- bicyclo [2.2.1] hepta-2-ene) may be one or more selected from the group consisting of.
그리고, 상기 수지층에서 상기 고리형 올레핀계 단량체로부터의 단위구조를 형성하는 고리형 올레핀계 단량체는 화학식 1로부터 선택된 1 이상인 것이 바람직하다. In addition, the cyclic olefin monomer that forms the unit structure from the cyclic olefin monomer in the resin layer is preferably one or more selected from formula (1).
<화학식 1><Formula 1>
Figure PCTKR2011009563-appb-I000001
Figure PCTKR2011009563-appb-I000001
여기에서, R1 내지 R6는 각각 같거나 다르게 수소 또는 산소, 질소, 황 또는 규소를 포함하는 연결기로 치환되거나 치환되지 않은 탄소수 1 내지 10의 탄화수소기이거나, 극성기, 단일결합 또는 2가의 연결기를 가지는 방향족기, 실란기, 할로겐 원자 중에서 선택되는 것이고, n은 1 내지 10의 정수이다.Wherein R 1 to R 6 are each the same or different hydrocarbon groups having 1 to 10 carbon atoms, unsubstituted or substituted with a linking group containing hydrogen or oxygen, nitrogen, sulfur or silicon, or a polar group, a single bond or a divalent linking group The branch is selected from an aromatic group, a silane group and a halogen atom, and n is an integer of 1 to 10.
광투과성 및 열적안정성을 고려할 때 좋기로는 상기 화학식 1의 단량체로부터의 단위구조에서 n은 4~10인 것이 바람직하다.In consideration of light transmittance and thermal stability, n is preferably 4 to 10 in the unit structure from the monomer of Chemical Formula 1.
또한, 상기 수지층은 아크릴계 단량체로부터의 단위구조와 화학식 1의 단량체로부터의 단위구조 및 다음 화학식 2의 단량체로부터의 단위구조를 포함하는 것일 수 있고, 이 때, 상기 수지층에서 상기 화합물은 아크릴계 단량체로부터의 단위구조 100중량부를 기준으로 화학식 1의 단량체로부터의 단위구조를 50~200중량부 및 화학식 2의 단량체로부터의 단위구조를 20~200중량부를 포함하는 것이 더욱 바람직하다.The resin layer may include a unit structure from an acrylic monomer, a unit structure from a monomer of Formula 1, and a unit structure from a monomer of Formula 2, wherein the compound in the resin layer is an acrylic monomer. It is more preferable to include 50-200 parts by weight of the unit structure from the monomer of Formula 1 and 20 to 200 parts by weight of the unit structure from the monomer of Formula 2 based on 100 parts by weight of the unit structure from.
<화학식 2><Formula 2>
Figure PCTKR2011009563-appb-I000002
Figure PCTKR2011009563-appb-I000002
여기서, R7 내지 R10은 수소 또는 산소, 질소, 황 또는 규소를 포함하는 연결기를 가지는 치환되거나 치환되지 않은 탄소수 1 내지 10의 탄화수소기이거나, 극성기, 단일결합 또는 2가의 연결기를 가지는 방향족기, 실란기, 할로겐 원자 중에서 선택되고, R7 내지 R10 중에서 적어도 하나는 아크릴레이트나 메타아크릴레이트 같은 2가의 연결기를 포함한다. Here, R 7 to R 10 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms having a linking group containing hydrogen or oxygen, nitrogen, sulfur or silicon, an aromatic group having a polar group, a single bond or a divalent linking group, A silane group, a halogen atom, and at least one of R 7 to R 10 includes a divalent linking group such as acrylate or methacrylate.
그리고, 상기 수지층에서 상기 아크릴계 단량체로부터의 단위구조를 형성하는 아크릴계 단량체는 2관능 이상의 아크릴 또는 메타크릴 화합물인 것이 바람직하고, 이 때, 상기 아크릴계 단량체는 비스페놀-A 디아크릴레이트 (bisphenol-A-diacrylate), 비스페놀-S 디아크릴레이트 (bisphenol-S diacrylate), 디시클로펜타디에닐 디아크릴레이트(dicyclopentadienyl diacrylate), 펜타에리트리톨 트리아크릴레이트 (pentaerythritol triacrylate), 트리스(2-히드록시에틸)이소시아누레이트 트리아크릴레이트 (tris(2-hydroxyethyl)isocyanurate triacrylate), 펜타에리트리톨 테트라아크릴레이트 (pentaerythritol tetraacrylate), 비스페놀-A 디메타크릴레이트 (bisphenol-A dimethacrylate), 비스페놀-S-디메타크릴레이트 (bisphenol-S dimethacrylate), 디시클로펜타디에닐 디메타크릴레이트 (dicyclopentadienyl dimethacrylate), 펜타에리트리톨 트리메타크릴레이트 (pentaerythritol trimethacrylate), 트리스(2-히드록시에틸)이소시아누레이트 트리메타크릴레이트 (tris(2-hydroxyethyl)isocyanurate trimethacrylate), 및 펜타에리트리톨 테트라메타크릴레이트 (pentaerythritol tetramethacrylate)로 이루어지는 군에서 선택된 1 이상일 수 있다. In addition, the acrylic monomer forming the unit structure from the acrylic monomer in the resin layer is preferably a bifunctional or more functional acrylic or methacryl compound, wherein the acrylic monomer is bisphenol-A diacrylate (bisphenol-A- diacrylate), bisphenol-S diacrylate, dicyclopentadienyl diacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocy Anurate triacrylate (tris (2-hydroxyethyl) isocyanurate triacrylate), pentaerythritol tetraacrylate, bisphenol-A dimethacrylate, bisphenol-S-dimethacrylate ( bisphenol-S dimethacrylate), dicyclopentadienyl dimethacrylate, pentaery With pentaerythritol trimethacrylate, tris (2-hydroxyethyl) isocyanurate trimethacrylate, and pentaerythritol tetramethacrylate It may be one or more selected from the group consisting of.
그리고, 상기 수지층에서 상기 화학식 1의 단량체로부터의 단위구조를 형성하는 플루오렌계 단량체는 플루오렌 골격 함유 아크릴레이트가 특히 제한되지 않고 2이상의 작용기를 갖는 임의 플루오렌 골격 함유 아크릴레이트 일 수 있다. 플루오렌 골격 구조로는 9,9-비스(4-히드록시페닐)플루오렌, 9,9-비스(4-히드록시-3-메틸페닐)플루오렌, 9,9-비스(4-히드록시-3-클로로페닐)플루오렌, 9,9-비스(4-히드록시-3-브로모페닐)플루오렌, 9,9-비스(4-히드록시-3-플루오로페닐)플루오렌, 9,9-비스(4-히드록시-3-메톡시페닐)플루오렌, 9,9-비스(4-히드록시-3,5-디메틸페닐)플루오렌, 9,9-비스(4-히드록시-3,5-디클로로페닐)플루오렌 및 9,9-비스(4-히드록시-3,5-디브로모페닐)플루오렌으로 이루어지는 군에서 선택된 1 이상일 수 있다.In addition, the fluorene-based monomer forming the unit structure from the monomer of Formula 1 in the resin layer is not particularly limited to the fluorene skeleton-containing acrylate may be any fluorene skeleton-containing acrylate having two or more functional groups. Examples of the fluorene skeleton structure include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy- 3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy- It may be at least one selected from the group consisting of 3,5-dichlorophenyl) fluorene and 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene.
그리고, 상기 유리 섬유층은 직경 4~20um의 유리섬유가 일방향으로 배향 정렬되고, 가로와 세로 방향의 날실과 씨실이 한올씩 교차로 Cross된 직조 형태로 20~200um의 두께로 유리 섬유층을 형성하는 것이 바람직하다. And, the glass fiber layer is a glass fiber layer of 4 ~ 20um diameter is aligned in one direction, it is preferable to form a glass fiber layer with a thickness of 20 ~ 200um in the form of weaving cross warp and weft yarns crosswise and longitudinally crosswise one by one. Do.
본 발명은 우수한 광학특성을 유지함과 동시에 우수한 열적 안정성을 가지는 플렉서블 디스플레이 기판을 제공하였다.The present invention provides a flexible display substrate having excellent thermal stability while maintaining excellent optical properties.
도 1은 실시예 1 내지 5 및 비교예 1의 TGA분석 결과 그래프.1 is a graph of the results of TGA analysis of Examples 1 to 5 and Comparative Example 1.
본 발명의 플렉서블 디스플레이 기판은 플라스틱 기판으로서 우수한 광학특성을 유지함과 동시에 우수한 열적 안정성을 가지기 위하여, 유리섬유로 이루어진 유리섬유층을 감광성 수지 조성물에 함침하여 유리섬유층의 양면에 감광성 수지 조성물층을 형성시키고, 이의 두께를 적절히 조절한 뒤에 UV 경화시켜 수지층을 형성시킴으로써 얻을 수 있다. The flexible display substrate of the present invention is formed of a photosensitive resin composition layer on both sides of the glass fiber layer by impregnating the photosensitive resin composition with a glass fiber layer made of glass fiber in order to maintain excellent optical properties as well as excellent thermal stability as a plastic substrate, After adjusting the thickness suitably, it can be obtained by UV-curing and forming a resin layer.
이 때, 유리섬유층은 지름 4~15um의 유리섬유가 일방향으로 배향 정렬되고, 20~200um의 두께로 형성될 수 있고, 이와 같은 유리섬유층은 열적특성이 우수하며, 흡수성이 없고, 흡습성이 적다. 화학적 내구성이 있기 때문에 부식하지 않으며, 인장강도가 강하고, 신장률이 적고 전기 절연성이 큰 장점이 있다. At this time, the glass fiber layer is a glass fiber of 4 ~ 15um diameter aligned in one direction, can be formed with a thickness of 20 ~ 200um, such a glass fiber layer is excellent in thermal properties, absorptivity, less hygroscopic. Because of its chemical durability, it does not corrode, has a strong tensile strength, a small elongation rate, and electrical insulation.
그리고, 상기 수지층에 포함되는 화합물은 아크릴계 단량체로부터의 단위구조와 고리형 올레핀계 단량체로부터의 단위구조를 포함한다. The compound contained in the resin layer includes a unit structure from an acrylic monomer and a unit structure from a cyclic olefin monomer.
이 화합물에서 아크릴계 단량체는 경화전 조성물의 하이드로필릭, 하이드로포빅 물성에 따라 다양하게 선택할 수 있으며, 경화전 조성물의 상용성을 향상시키는 역할을 한다. 점도가 100cPs~50000cPs 까지 다양한 상용 제품이 많으므로 선택의 폭이 넓고, 광개시제의 라디칼 형성에 의해 광경화가 진행되므로, 광중합에 의해 중합체가 형성되고, 필름 제막의 기본 지지체로써 네트워크를 형성하는 역할을 한다. In this compound, the acrylic monomer may be variously selected according to the hydrophilic and hydrophobic physical properties of the composition before curing, and serves to improve the compatibility of the composition before curing. Since there are many commercial products with a viscosity ranging from 100 cPs to 50000 cPs, a wide range of choices are made, and since photocuring proceeds by radical formation of a photoinitiator, a polymer is formed by photopolymerization and plays a role of forming a network as a basic support for film forming. .
고리형 올레핀계 단량체의 경우, 저점도, 고굴절 화합물로서, 안정한 아로마틱 분자 구조를 가지고 있어서, 높은 유리전이 온도를 가지고, 이에 따라 열적 안정성이 향상된다. 이외에도 내마모성이 우수하여 스크래치 발생 빈도를 줄이고, 내약품성이 우수하여 후공정 및 소자 제작 시에도 물성 변화를 발생시키지 않는데 큰 도움을 준다. In the case of the cyclic olefin monomer, as a low viscosity and high refractive compound, it has a stable aromatic molecular structure, has a high glass transition temperature, thereby improving thermal stability. In addition, the wear resistance is excellent, reducing the frequency of scratches, and the chemical resistance is excellent, which helps to prevent the change of physical properties during the post-process and device fabrication.
이와 같이 아크릴계 단량체와 고리형 올레핀계 단량체의 UV경화에 의하여 광중합된 화합물은 그 중량평균분자량이 500~1,000,000인 것이 바람직하다. 중량평균분자량이 500미만인 경우에는 경화 후 후공정 단계에서 Fume 발생 및 Weight Loss가 크게 발생할 가능성이 크고, 1,000,000를 초과하는 경우에는 필름이 딱딱해지고 플렉시블리티가 감소하는 단점이 있다.Thus, it is preferable that the weight average molecular weight of the compound photopolymerized by UV-cure of an acryl-type monomer and a cyclic olefin type monomer is 500-1,000,000. If the weight average molecular weight is less than 500, there is a high possibility that a large amount of fume generation and weight loss occurs in the post-processing step after curing, and if it exceeds 1,000,000, the film becomes hard and the flexibility decreases.
이 때, 상기 수지층은 아크릴계 단량체로부터의 단위구조 100중량부와 고리형 올레핀계 단량체로부터의 단위구조 25~400중량부를 포함하는 것이 더욱 바람직하고, 이 함량 범위 내에서 유리섬유와의 굴절율 조화가 잘 되어 더욱 투명한 기판이 될 수 있다. At this time, the resin layer more preferably comprises 100 parts by weight of the unit structure from the acrylic monomer and 25 to 400 parts by weight of the unit structure from the cyclic olefin monomer, the refractive index of the glass fiber within this content range is It can go well and become a more transparent substrate.
상기 수지층에서 상기 고리형 올레핀계 단량체로부터의 단위구조를 형성하는 고리형 올레핀계 단량체는 비시클로[2.2.1]헵타-2-엔 (bicyclo[2.2.1]hepta-2-ene), 5-메틸-비시클로[2.2.1]헵타-2-엔 (5-methyl-bicyclo[2.2.1]hepta-2-ene), 5-에틸-비시클로[2.2.1]헵타-2-엔 (5-ethyl-bicyclo[2.2.1]hepta-2-ene), 5-프로필-비시클로[2.2.1]헵타-2-엔(5-propyl-bicyclo[2.2.1]hepta-2-ene), 5-헥실-비시클로[2.2.1]헵타-2-엔 (5-hexyl-bicyclo[2.2.1]hepta-2-ene), 5-데실-비시클로[2.2.1]헵타-2-엔 (5-decyl-bicyclo[2.2.1]hepta-2-ene), 5,6-디메틸-비시클로[2.2.1]헵타-2-엔 (5,6-dimethyl-bicyclo[2.2.1]hepta-2-ene), 5-메틸-5-에틸-비시클로[2.2.1]헵타-2-엔 (5-methyl-5-ethyl-bicyclo[2.2.1]hepta-2-ene), 5-페닐-비시클로[2.2.1]헵타-2-엔 (5-phenyl-bicyclo[2.2.1]hepta-2-ene), 5-시클로헥실-비시클로[2.2.1]헵타-2-엔 (5-cyclohexyl-bicyclo[2.2.1]hepta-2-ene), 트리시클로[4.3.0.12,5]데카-3-엔(tricyclo[4.3.0.12,5]deca-3-ene), 테트라시클로[4.4.0.12,5.1 7,10]도데카-3-엔 (tetracyclo[4.4.0.12,5.17,10]dodeca-3-ene), 3-메틸-테트라시클로[4.4.0.12,5.17,10]도데카-8-엔 (3-methyl-tetracyclo[4.4.0.12,5.17,10]dodeca-8-ene),3-에틸-테트라시클로[4.4.0.12,5.17,10]도데카-8-엔 (3-ethyl-tetracyclo[4.4.0.12,5.17,10]dodeca-8-ene), 메틸 2-메틸-비시클로[2.2.1]헵타-5-엔-2-카르복실레이트 (methyl 2-methyl-bicyclo[2.2.1]hepta-5-ene-2-carboxylate), 2-메틸-비시클로[2.2.1]헵타-5-엔 아크릴레이트 (2-methyl-bicyclo[2.2.1]hepta-5-ene acrylate), 2-메틸-비시클로[2.2.1]헵타-5-엔 메타크릴레이트 (2-methyl-bicyclo[2.2.1]hepta-5-ene methacrylate), 디메틸 비시클로[2.2.1]헵타-5-엔-2,3-디카르복실레이트 (dimethyl bicyclo[2.2.1]hepta-5-ene-2,3-dicarboxylate), 디에틸 비시클로[2.2.1]헵타-5-엔-2,3-디카르복실레이트 (diethyl bicyclo[2.2.1]hepta-5-ene-2,3-dicarboxylate), 3-메틸-3-메톡시카르보닐-테트라시클로[4.4.0.12,5.17,10]도데카-8-엔 (3-methyl-3-methoxycarbonyl-tetracyclo[4.4.0.12,5.1 7,10]dodeca-8-ene), 비시클로[2.2.1]헵타-5-엔-N-시클로헥실-2,3-말레이미드 (bicyclo[2.2.1]hepta-5-ene-N-cyclohexyl-2,3-maleimide), 비시클로[2.2.1]헵타-5-엔-2-스피로-3'-N-페닐석신이미드 (bicyclo[2.2.1]hepta-5-ene-2-spiro-3'-N-phenylsuccinmide), 비시클로[2.2.1]헵타-5-엔-2-스피로-3'-N-시클로헥실석신이미드(bicyclo[2.2.1]hepta-5-ene-2-spiro-3'-N-cyclohexylsuccinmide), 2-[(3-에틸-3-옥세타닐)메톡시]비시클로[2.2.1]헵타-2-엔 (2-[(3-ethyl-3-oxetanyl)methoxy]bicyclo[2.2.1]hepta-2-ene), 2-[(3-에틸-3-옥세타닐)메톡시메틸]비시클로[2.2.1]헵타-2-엔 (2-[(3-ethyl-3-oxetanyl)methoxymethyl]bicyclo[2.2.1]hepta-2-ene), (3-에틸-3-옥세타닐)메틸 비시클로[2.2.1]헵타-5-엔-2-카르복실레이트 (3-ethyl-3-oxetanyl)methylbicyclo[2.2.1]hepta-5-ene-2-carboxylate), 5-트리에톡시실릴-비시클로[2.2.1]헵타-2-엔 (5-triethoxysilyl-bicyclo[2.2.1]-hepta-2-ene), 5-메틸디메톡시실릴-비시클로[2.2.1]헵타-2-엔 (5-methyldimethoxysilyl-bicyclo[2.2.1]hepta-2-ene), 5-[1'-메틸-2',5'-디옥사-1'-실라시클로펜틸]-비시클로[2.2.1]헵타-2-엔 (5-[1'-methyl-2',5'-dioxa-1'-silacyclopentyl]-bicyclo[2.2.1]hepta-2-ene), 5-[1'-메틸-3',3',4',4'-테트라페닐-2',5'-디옥사-1'-실라시클로펜틸]-비시클로[2.2.1]헵타-2-엔 (5-[1'-methyl-3',3',4',4'-tetraphenyl-2',5'-dioxa-1'-silacyclopentyl]-bicyclo[2.2.1]hepta-2-ene), 5-[1',4',4'-트리메틸-2' 및 6'-디옥사-1'-실라시클로헥실]-비시클로[2.2.1]헵타-2-엔 (5-[1',4',4'-trimethyl-2' and 6'-dioxa-1'-silacyclohexyl]-bicyclo[2.2.1]hepta-2-ene) 으로 구성되는 군에서 선택된 1 이상일 수 있다. The cyclic olefin monomer which forms a unit structure from the cyclic olefin monomer in the resin layer is bicyclo [2.2.1] hepta-2-ene, 5 5-methyl-bicyclo [2.2.1] hepta-2-ene (5-methyl-bicyclo [2.2.1] hepta-2-ene), 5-ethyl-bicyclo [2.2.1] hepta-2-ene ( 5-ethyl-bicyclo [2.2.1] hepta-2-ene), 5-propyl-bicyclo [2.2.1] hepta-2-ene (5-propyl-bicyclo [2.2.1] hepta-2-ene) , 5-hexyl-bicyclo [2.2.1] hepta-2-ene (5-hexyl-bicyclo [2.2.1] hepta-2-ene), 5-decyl-bicyclo [2.2.1] hepta-2- En (5-decyl-bicyclo [2.2.1] hepta-2-ene), 5,6-dimethyl-bicyclo [2.2.1] hepta-2-ene (5,6-dimethyl-bicyclo [2.2.1] hepta-2-ene), 5-methyl-5-ethyl-bicyclo [2.2.1] hepta-2-ene (5-methyl-5-ethyl-bicyclo [2.2.1] hepta-2-ene), 5 -Phenyl-bicyclo [2.2.1] hepta-2-ene (5-phenyl-bicyclo [2.2.1] hepta-2-ene), 5-cyclohexyl-bicyclo [2.2.1] hepta-2-ene (5-cyclohexyl-bicyclo [2.2.1] hepta-2-ene), tricyclo [4.3.0.12,5] deca-3-ene (tricyclo [4] .3.0.12,5] deca-3-ene), tetracyclo [4.4.0.12,5.1 7,10] tedecyclo-3-ene (tetracyclo [4.4.0.12,5.17,10] dodeca-3-ene), 3-methyl-tetracyclo [4.4.0.12,5.17,10] dodeca-8-ene (3-methyl-tetracyclo [4.4.0.12,5.17,10] dodeca-8-ene), 3-ethyl-tetracyclo [ 4.4.0.12,5.17,10] dodeca-8-ene (3-ethyl-tetracyclo [4.4.0.12,5.17,10] dodeca-8-ene), methyl 2-methyl-bicyclo [2.2.1] hepta- 5-ene-2-carboxylate (methyl 2-methyl-bicyclo [2.2.1] hepta-5-ene-2-carboxylate), 2-methyl-bicyclo [2.2.1] hepta-5-ene acrylate (2-methyl-bicyclo [2.2.1] hepta-5-ene acrylate), 2-methyl-bicyclo [2.2.1] hepta-5-ene methacrylate (2-methyl-bicyclo [2.2.1] hepta -5-ene methacrylate), dimethyl bicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylate (dimethyl bicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylate), Diethyl bicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylate, 3-methyl-3- Methoxycarbonyl-Tetracycle [4.4.0.12,5.17,10] dodeca-8-ene (3-methyl-3-methoxycarbonyl-tetracyclo [4.4.0.12,5.1 7,10] dodeca-8-ene), bicyclo [2.2.1] hepta -5-ene-N-cyclohexyl-2,3-maleimide (bicyclo [2.2.1] hepta-5-ene-N-cyclohexyl-2,3-maleimide), bicyclo [2.2.1] hepta-5 -En-2-spiro-3'-N-phenylsuccinimide (bicyclo [2.2.1] hepta-5-ene-2-spiro-3'-N-phenylsuccinmide), bicyclo [2.2.1] hepta- 5-en-2-spiro-3'-N-cyclohexylsuccinimide (bicyclo [2.2.1] hepta-5-ene-2-spiro-3'-N-cyclohexylsuccinmide), 2-[(3-ethyl -3-oxetanyl) methoxy] bicyclo [2.2.1] hepta-2-ene (2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hepta-2-ene), 2-[(3-ethyl-3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hepta-2-ene (2-[(3-ethyl-3-oxetanyl) methoxymethyl] bicyclo [2.2.1 ] hepta-2-ene), (3-ethyl-3-oxetanyl) methyl bicyclo [2.2.1] hepta-5-ene-2-carboxylate (3-ethyl-3-oxetanyl) methylbicyclo [2.2 .1] hepta-5-ene-2-carboxylate), 5-triethoxysilyl-bicyclo [2.2.1] hepta-2-ene (5-trietho xysilyl-bicyclo [2.2.1] -hepta-2-ene), 5-methyldimethoxysilyl-bicyclo [2.2.1] hepta-2-ene (5-methyldimethoxysilyl-bicyclo [2.2.1] hepta-2- ene), 5- [1'-methyl-2 ', 5'-dioxa-1'-silacyclopentyl] -bicyclo [2.2.1] hepta-2-ene (5- [1'-methyl-2 ', 5'-dioxa-1'-silacyclopentyl] -bicyclo [2.2.1] hepta-2-ene), 5- [1'-methyl-3', 3 ', 4', 4'-tetraphenyl-2 ', 5'-dioxa-1'-silacyclopentyl] -bicyclo [2.2.1] hepta-2-ene (5- [1'-methyl-3', 3 ', 4', 4'-tetraphenyl -2 ', 5'-dioxa-1'-silacyclopentyl] -bicyclo [2.2.1] hepta-2-ene), 5- [1', 4 ', 4'-trimethyl-2' and 6'-dioxa -1'-Silacyclohexyl] -bicyclo [2.2.1] hepta-2-ene (5- [1 ', 4', 4'-trimethyl-2 'and 6'-dioxa-1'-silacyclohexyl]- bicyclo [2.2.1] hepta-2-ene) may be one or more selected from the group consisting of.
특히, 본 발명의 플렉서블 디스플레이 기판의 광투과도와 열적 안정성을 동시에 크게 향상시키기 위해서는 상기 수지층에서 상기 고리형 올레핀계 단량체로부터의 단위구조를 형성하는 고리형 올레핀계 단량체는 다음 화학식 1로 표시되는 화합물인 것이 바람직하다. 이와 같은 단량체는 저점도 고굴절 화합물로서, 수지층의 굴절율을 크게 향상시켜 유리섬유층과의 굴절율을 최소화시키고, 이에 따라 유리섬유층과 수지층 사이의 계면에서 반사율을 저하시켜 기판의 전체 광투과율을 향상시킬 수 있는 것이다. 또, 안정한 아로마틱 분자 구조를 가지고 있어서, 높은 유리전이 온도를 가지며, 열적 안정성이 크게 향상된다. 이외에도 내마모성이 우수하여 스크래치 발생 빈도를 줄이고, 내약품성이 우수하여 후공정 및 소자 제작 시에도 물성 변화를 발생시키지 않는데 큰 도움을 준다. In particular, in order to greatly improve light transmittance and thermal stability of the flexible display substrate of the present invention, the cyclic olefin monomer forming a unit structure from the cyclic olefin monomer in the resin layer may be represented by the following formula (1): Is preferably. Such a monomer is a low viscosity high refractive compound, which greatly improves the refractive index of the resin layer to minimize the refractive index with the glass fiber layer, thereby reducing the reflectance at the interface between the glass fiber layer and the resin layer, thereby improving the overall light transmittance of the substrate. It can be. In addition, it has a stable aromatic molecular structure, has a high glass transition temperature, and thermal stability is greatly improved. In addition, the wear resistance is excellent, reducing the frequency of scratches, and the chemical resistance is excellent, which helps to prevent the change of physical properties during the post-process and device fabrication.
<화학식 1><Formula 1>
Figure PCTKR2011009563-appb-I000003
Figure PCTKR2011009563-appb-I000003
여기에서, R1 내지 R6는 각각 같거나 다르게 수소 또는 산소, 질소, 황 또는 규소를 포함하는 연결기로 치환되거나 치환되지 않은 탄소수 1 내지 10의 탄화수소기이거나, 극성기, 단일결합 또는 2가의 연결기를 가지는 방향족기, 실란기, 할로겐 원자 중에서 선택되고, n은 1 내지 10의 정수이다.Wherein R 1 to R 6 are each the same or different hydrocarbon groups having 1 to 10 carbon atoms, unsubstituted or substituted with a linking group containing hydrogen or oxygen, nitrogen, sulfur or silicon, or a polar group, a single bond or a divalent linking group The branch is selected from an aromatic group, a silane group and a halogen atom, n is an integer of 1 to 10.
또, 상기 탄소수 1 내지 10의 탄화수소기는 메틸기, 에틸기, 프로필기 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나의 알킬기; 시클로펜틸기, 시클로헥실기 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나의 시클로알킬기; 비닐기, 아릴기, 프로페닐기 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나의 알케닐기; 중에서 선택되는 어느 하나 이상을 포함하는 것이 바람직하다.  The hydrocarbon group having 1 to 10 carbon atoms may be any one alkyl group selected from the group consisting of methyl group, ethyl group, propyl group, and combinations thereof; Any one cycloalkyl group selected from the group consisting of a cyclopentyl group, a cyclohexyl group, and a combination thereof; Any one alkenyl group selected from the group consisting of a vinyl group, an aryl group, a propenyl group, and a combination thereof; It is preferable to include any one or more selected from.
상기 치환 또는 비치환된 탄화수소기는 화학식 1과 같이 직접 환 구조에 결합될 수도 있지만, 연결기를 통하여 환 구조에 결합될 수도 있다. The substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure as shown in Formula 1, or may be bonded to the ring structure through a linking group.
상기 연결기로는 탄소 원자수 1 내지 10의 2가의 탄화수소기, 산소, 질소, 황 또는 규소를 포함하는 연결기, 예를 들면 카르보닐기, 옥시카르보닐기, 슬폰기, 에테르 결합, 티오에테르 결합, 이미노기, 아미드 결합, 실록산 결합 등을 들 수 있고, 이들의 복수를 포함하는 연결기일 수도 있다. Examples of the linking group include a linking group containing a divalent hydrocarbon group having 1 to 10 carbon atoms, oxygen, nitrogen, sulfur or silicon, for example, carbonyl group, oxycarbonyl group, sulfone group, ether bond, thioether bond, imino group, and amide. A bond, a siloxane bond, etc. are mentioned, The linking group containing these multiple may be sufficient.
상기 극성기는 수산기, 탄소수 1 내지 10의 알콕시기, 카르보닐옥시기, 알콜시카르보닐기, 시아노기, 아미드기, 이미드기, 아미노기, 아실기, 술포닐기 및 카르복실기 등을 들 수 있다. 더욱 구체적으로는 상기 알콕시기로는 메톡시기, 에톡시기 등을 들 수 있고, 카르보닐옥시기로는 아세톡시기, 프로피오닐옥시기 등의 알킬카르보닐옥시기, 에톡시카르보닐기 등을 들 수 있고 아미노기로는 제1급 아미노기를 들 수 있다.Examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alcohol cicarbonyl group, a cyano group, an amide group, an imide group, an amino group, an acyl group, a sulfonyl group, and a carboxyl group. More specifically, the alkoxy group includes a methoxy group, an ethoxy group, and the like, and the carbonyloxy group includes an alkylcarbonyloxy group such as an acetoxy group and propionyloxy group, an ethoxycarbonyl group, and the like. The primary amino group is mentioned.
상기 단일결합 또는 2가의 연결기를 가지는 방향족기에서 2가의 연결기로는 알킬렌기 특히 탄소수 1 내지 10, 바람직하게는 1 내지 5이며, 예를 들어 메틸렌기, 에틸렌기, 트리메틸렌기, 아릴렌기, 옥시알킬렌기, 옥시아릴렌기, 옥시 카르보닐기, 이미노카르보닐기, 카르보닐기, 아세틸렌기, 우레일렌기, 황이나 산소 등 헤테로 원자, 아미노기 등을 들 수 있다. 또한 이들의 연결기를 2개 이상 조합하여도 된다. In the aromatic group having a single bond or a divalent linking group, the divalent linking group is an alkylene group, particularly 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, for example, methylene group, ethylene group, trimethylene group, arylene group, oxy And alkylene groups, oxyarylene groups, oxycarbonyl groups, iminocarbonyl groups, carbonyl groups, acetylene groups, ureylene groups, hetero atoms such as sulfur and oxygen, and amino groups. Moreover, you may combine 2 or more of these coupling groups.
이러한 연결기를 통하여 방향족기를 포함하여야 하는데 상기 방향족기는 방향족 화합물의 1 수소 이탈체를 포함한다. Through such a linking group, an aromatic group should be included, which includes one hydrogen leaving body of the aromatic compound.
상기 1 수소 이탈체로 구체적인 예로는 벤젠, 펜타렌, 나프탈렌, 아줄렌, 헵타렌, 비페닐렌, 인다센, 아세나프탈렌, 페난트렌, 안트라센, 플루오란센, 아세페난트릴렌, 프리페닐렌, 피렌, 크리센, 나프타센, 플라이아덴, 피센, 페릴렌, 펜파펜, 펜타센, 테트라페닐렌, 헥사펜, 펜사센, 루비센, 코로넨, 트리나프틸렌, 헵타펜, 헵타센, 피라센, 오바렌 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나의 단고리 화합물, 티오펜, 티안트렌, 푸란, 피란, 이소벤조푸란, 크로멘, 크산텐, 페노크사티인, 피롤, 이미다졸, 피라졸, 이소티아졸, 이소옥사졸, 피리딘, 피라딘, 피리미딘, 피리디진, 인돌리딘, 이소인돌, 인돌, 인다졸, 푸린, 퀴놀리딘, 이소퀴논, 퀴놀린, 프탈라진, 나프틸리딘, 키노키살린, 시노린, 프테리딘, 카르바졸, 베타카르보린, 페난틸리딘, 아크리딘, 페리미딘, 페난트롤린, 페나딘, 페나르사진, 페노티아딘, 프라잔, 페노키사진 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나의 헤테로고리 화합물 및 이들의 치환기를 가지는 것이 바람직하다. Specific examples of the 1 hydrogen leaving body include benzene, pentarene, naphthalene, azulene, heptarene, biphenylene, indacene, acenaphthalene, phenanthrene, anthracene, fluoranthene, acefenanthrene, prephenylene, pyrene , Chrysene, naphthacene, flyaden, pisene, perylene, penpafen, pentacene, tetraphenylene, hexaphene, pensasene, rubisen, coronene, trinaphthylene, heptaphene, heptacene, pyracene, Any one monocyclic compound selected from the group consisting of ovaren and combinations thereof, thiophene, thianthrene, furan, pyran, isobenzofuran, chromen, xanthene, phenoxathiine, pyrrole, imidazole, pyrazole, Isothiazole, Isoxazole, Pyridine, Pyridine, Pyrimidine, Pyridinine, Indolidine, Isoindole, Indole, Indazole, Purine, Quinolidine, Isoquinone, Quinoline, Phthazine, Naphthyridine, Keno Chisarin, cynoline, pteridine, carbazole, betacarboline, phenanthilidine, acri It is preferred to have any one heterocyclic compound selected from the group consisting of dine, perimidine, phenanthroline, phenadine, phenarzin, phenothiadine, prazan, phenocyazine, and combinations thereof and substituents thereof. .
상기 실란기는 트리메톡시실릴기, 트릴에톡시실릴기 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나의 알콕시실릴기 또는 트리메틸실릭시기, 트리에틸실리고시기 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나의 트리오르가노실록시기인 것이 바람직하다. The silane group is any one selected from the group consisting of any one alkoxysilyl group or trimethylsilyl group, triethylsiligo group and combinations thereof selected from the group consisting of trimethoxysilyl group, triethoxysilyl group and combinations thereof. It is preferable that it is a triorgano siloxy group.
상기 할로겐 원자로는 불소, 염소, 브롬 등을 들 수 있다. Fluorine, chlorine, bromine, etc. are mentioned as said halogen atom.
상기 화학식 1의 단량체에 있어서 알킬렌 옥사이드의 반복단위 수인 n의 증가에 따라 광투과성은 향상되나 반면에 열적 안정성이 떨어질 수 있다. 이러한 측면에서 광투과성 및 열적안정성을 고려할 때 좋기로는 상기 화학식 1의 단량체로부터의 단위구조에서 n은 4~10인 것이 바람직하다.In the monomer of Chemical Formula 1, light transmittance may be improved with increasing number of repeating units of alkylene oxide, but thermal stability may be deteriorated. In consideration of light transmittance and thermal stability in this aspect, n is preferably 4 to 10 in the unit structure from the monomer of Chemical Formula 1.
구체적인 일예로, 상기 화학식 1의 단량체로부터의 단위구조를 형성하는 플루오렌계 단량체는 플루오렌 골격 함유 아크릴레이트가 특히 제한되지 않고 2이상의 작용기를 갖는 임의 플루오렌 골격 함유 아크릴레이트 일 수 있다. 플루오렌 골격 구조로는 9,9-비스(4-히드록시페닐)플루오렌, 9,9-비스(4-히드록시-3-메틸페닐)플루오렌, 9,9-비스(4-히드록시-3-클로로페닐)플루오렌, 9,9-비스(4-히드록시-3-브로모페닐)플루오렌, 9,9-비스(4-히드록시-3-플루오로페닐)플루오렌, 9,9-비스(4-히드록시-3-메톡시페닐)플루오렌, 9,9-비스(4-히드록시-3,5-디메틸페닐)플루오렌, 9,9-비스(4-히드록시-3,5-디클로로페닐)플루오렌 및 9,9-비스(4-히드록시-3,5-디브로모페닐)플루오렌으로 구성되는 군에서 선택된 1 이상일 수 있다. As a specific example, the fluorene-based monomer forming a unit structure from the monomer of Formula 1 may be any fluorene skeleton-containing acrylate having a fluorene skeleton-containing acrylate is not particularly limited and two or more functional groups. Examples of the fluorene skeleton structure include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy- 3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy- At least one selected from the group consisting of 3,5-dichlorophenyl) fluorene and 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene.
특히, 본 발명의 플렉서블 디스플레이 기판의 광투과도와 열적 안정성을 동시에 크게 향상시키기 위하여서는 상기 수지층에서 화학식 2의 단량체로부터의 단위구조를 더 포함하는 것이 바람직하다. In particular, in order to greatly improve the light transmittance and thermal stability of the flexible display substrate of the present invention, it is preferable to further include a unit structure from the monomer of the formula (2) in the resin layer.
<화학식 2><Formula 2>
Figure PCTKR2011009563-appb-I000004
Figure PCTKR2011009563-appb-I000004
여기서, R7 내지 R10은 수소 또는 산소, 질소, 황 또는 규소를 포함하는 연결기를 가지는 치환되거나 치환되지 않은 탄소수 1 내지 10의 탄화수소기이거나, 극성기, 단일결합 또는 2가의 연결기를 가지는 방향족기, 실란기, 할로겐 원자 중에서 선택되고, R7 내지 R10 중에서 적어도 하나는 아크릴레이트나 메타아크릴레이트 같은 2가의 연결기를 포함한다. Here, R 7 to R 10 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms having a linking group containing hydrogen or oxygen, nitrogen, sulfur or silicon, an aromatic group having a polar group, a single bond or a divalent linking group, A silane group, a halogen atom, and at least one of R 7 to R 10 includes a divalent linking group such as acrylate or methacrylate.
화학식 2의 단량체로부터의 단위구조는 수지층의 굴절율을 크게 향상시켜 유리섬유층과의 굴절율을 최소화시키고, 이에 따라 유리섬유층과 수지층 사이의 계면에서 반사율을 저하시켜 기판의 전체 광투과율을 향상시킬 수 있는 것이다. 즉, 또, 화학식 2의 단량체는, 1.58이상의 높은 굴절율을 가진 화합물로서, 높은 유리 전이 온도 및 가교도 및 내열성을 동시에 가진다. 이와 같이 화학식 2의 단량체로부터의 단위구조를 포함하는 경우 상기 수지층의 화합물은 아크릴계 단량체로부터의 단위구조 100중량부를 기준으로 화학식 1의 단량체로부터의 단위구조를 50~200중량부 및 화학식 2의 단량체로부터의 단위구조를 20~200중량부를 포함하는 것이 더욱 바람직하고, 이 함량 범위 내에서 유리섬유와의 굴절율 조화가 잘 되어 더욱 투명한 기판이 될 수 있다. 그리고, 아크릴계 단량체로부터의 단위구조 100중량부 대비 화학식 1의 단량체 및/또는 화학식 2의 단량체로부터의 단위구조를 200중량부를 초과하여 포함하는 경우에는 경화도가 너무 높아져서 기판의 경도가 지나치게 증가하게 되어, 가요성능이 떨어지는 문제점이 발생할 수 있다.The unit structure from the monomer of Formula 2 greatly improves the refractive index of the resin layer to minimize the refractive index with the glass fiber layer, thereby reducing the reflectance at the interface between the glass fiber layer and the resin layer, thereby improving the overall light transmittance of the substrate. It is. That is, the monomer of the formula (2) is a compound having a high refractive index of 1.58 or more, and has a high glass transition temperature, crosslinking degree and heat resistance at the same time. As such, when the unit structure from the monomer of Formula 2 is included, the compound of the resin layer has 50 to 200 parts by weight of the unit structure from the monomer of Formula 1 and the monomer of Formula 2 based on 100 parts by weight of the unit structure from the acrylic monomer. It is more preferable that the unit structure from 20 to 200 parts by weight, and within this content range is well matched with the refractive index of the glass fiber can be a more transparent substrate. In addition, when including more than 200 parts by weight of the unit structure from the monomer of formula (1) and / or the monomer of formula (2) relative to 100 parts by weight of the unit structure from the acrylic monomer, the hardness of the substrate is too high to increase the hardness of the substrate, The problem of inferior flexible performance may occur.
상기 화학식 2에 있어서, 상기 탄소수 1 내지 10의 탄화수소기는 메틸기, 에틸기, 프로필기 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나의 알킬기; 시클로펜틸기, 시클로헥실기 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나의 시클로알킬기; 비닐기, 아릴기, 프로페닐기 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나의 알케닐기; 중에서 선택되는 어느 하나 이상을 포함하는 것이 바람직하다. In Chemical Formula 2, the hydrocarbon group having 1 to 10 carbon atoms includes any one alkyl group selected from the group consisting of methyl group, ethyl group, propyl group, and combinations thereof; Any one cycloalkyl group selected from the group consisting of a cyclopentyl group, a cyclohexyl group, and a combination thereof; Any one alkenyl group selected from the group consisting of a vinyl group, an aryl group, a propenyl group, and a combination thereof; It is preferable to include any one or more selected from.
상기 치환 또는 비치환된 탄화수소기는 화학식 1과 같이 직접 환 구조에 결합될 수도 있지만, 연결기를 통하여 환 구조에 결합될 수도 있다. The substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure as shown in Formula 1, or may be bonded to the ring structure through a linking group.
상기 연결기로는 탄소 원자수 1 내지 10의 2가의 탄화수소기, 산소, 질소, 황 또는 규소를 포함하는 연결기, 예를 들면 카르보닐기, 옥시카르보닐기, 슬폰기, 에테르 결합, 티오에테르 결합, 이미노기, 아미드 결합, 실록산 결합 등을 들 수 있고, 이들의 복수를 포함하는 연결기일 수도 있다. Examples of the linking group include a linking group containing a divalent hydrocarbon group having 1 to 10 carbon atoms, oxygen, nitrogen, sulfur or silicon, for example carbonyl group, oxycarbonyl group, sulfone group, ether bond, thioether bond, imino group, and amide. A bond, a siloxane bond, etc. are mentioned, The linking group containing these multiple may be sufficient.
상기 극성기는 수산기, 탄소수 1 내지 10의 알콕시기, 카르보닐옥시기, 알콜시카르보닐기, 시아노기, 아미드기, 이미드기, 아미노기, 아실기, 술포닐기 및 카르복실기 등을 들 수 있다. 더욱 구체적으로는 상기 알콕시기로는 메톡시기, 에톡시기 등을 들 수 있고, 카르보닐옥시기로는 아세톡시기, 프로피오닐옥시기 등의 알킬카르보닐옥시기, 에톡시카르보닐기 등을 들 수 있고 아미노기로는 제1급 아미노기를 들 수 있다.Examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alcohol cicarbonyl group, a cyano group, an amide group, an imide group, an amino group, an acyl group, a sulfonyl group, and a carboxyl group. More specifically, the alkoxy group includes a methoxy group, an ethoxy group, and the like, and the carbonyloxy group includes an alkylcarbonyloxy group such as an acetoxy group and propionyloxy group, an ethoxycarbonyl group, and the like. The primary amino group is mentioned.
상기 단일결합 또는 2가의 연결기를 가지는 방향족기에서 2가의 연결기로는 알킬렌기 특히 탄소수 1 내지 10, 바람직하게는 1 내지 5이며 예를 들어 메틸렌기, 에틸렌기, 트리메틸렌기, 아릴렌기, 옥시알킬렌기, 옥시아릴렌기, 옥시 카르보닐기, 이미노카르보닐기, 카르보닐기, 아세틸렌기, 우레일렌기, 황이나 산소 등 헤테로 원자, 아미노기 등을 들 수 있다. 또한 이들의 연결기를 2개 이상 조합하여도 된다. In the aromatic group having a single bond or a divalent linking group, the divalent linking group is an alkylene group, particularly 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, for example, methylene group, ethylene group, trimethylene group, arylene group, oxyalkyl A hetero group, such as a ethylene group, an oxy arylene group, an oxy carbonyl group, an iminocarbonyl group, a carbonyl group, an acetylene group, a ureylene group, sulfur, oxygen, an amino group, etc. are mentioned. Moreover, you may combine 2 or more of these coupling groups.
이러한 연결기를 통하여 방향족기를 포함하여야 하는데 상기 방향족기는 방향족 화합물의 1 수소 이탈체를 포함할 수 있다.The aromatic group should include an aromatic group through the linking group, and the aromatic group may include one hydrogen leaving body of the aromatic compound.
상기 1 수소 이탈체로 구체적인 예로는 벤젠, 펜타렌, 나프탈렌, 아줄렌, 헵타렌, 비페닐렌, 인다센, 아세나프탈렌, 페난트렌, 안트라센, 플루오란센, 아세페난트릴렌, 프리페닐렌, 피렌, 크리센, 나프타센, 플라이아덴, 피센, 페릴렌, 펜파펜, 펜타센, 테트라페닐렌, 헥사펜, 펜사센, 루비센, 코로넨, 트리나프틸렌, 헵타펜, 헵타센, 피라센, 오바렌 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나의 단고리 화합물, 티오펜, 티안트렌, 푸란, 피란, 이소벤조푸란, 크로멘, 크산텐, 페노크사티인, 피롤, 이미다졸, 피라졸, 이소티아졸, 이소옥사졸, 피리딘, 피라딘, 피리미딘, 피리디진, 인돌리딘, 이소인돌, 인돌, 인다졸, 푸린, 퀴놀리딘, 이소퀴논, 퀴놀린, 프탈라진, 나프틸리딘, 키노키살린, 시노린, 프테리딘, 카르바졸, 베타카르보린, 페난틸리딘, 아크리딘, 페리미딘, 페난트롤린, 페나딘, 페나르사진, 페노티아딘, 프라잔, 페노키사진 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나의 헤테로고리 화합물 및 이들의 치환기를 가지는 것이 바람직하다. Specific examples of the 1 hydrogen leaving body include benzene, pentarene, naphthalene, azulene, heptarene, biphenylene, indacene, acenaphthalene, phenanthrene, anthracene, fluoranthene, acefenanthrene, prephenylene, pyrene , Chrysene, naphthacene, flyaden, pisene, perylene, penpafen, pentacene, tetraphenylene, hexaphene, pensasene, rubisen, coronene, trinaphthylene, heptaphene, heptacene, pyracene, Any one monocyclic compound selected from the group consisting of ovaren and combinations thereof, thiophene, thianthrene, furan, pyran, isobenzofuran, chromen, xanthene, phenoxathiine, pyrrole, imidazole, pyrazole, Isothiazole, Isoxazole, Pyridine, Pyridine, Pyrimidine, Pyridinine, Indolidine, Isoindole, Indole, Indazole, Purine, Quinolidine, Isoquinone, Quinoline, Phthazine, Naphthyridine, Keno Chisarin, cynoline, pteridine, carbazole, betacarboline, phenanthilidine, acri It is preferred to have any one heterocyclic compound selected from the group consisting of dine, perimidine, phenanthroline, phenadine, phenarzin, phenothiadine, prazan, phenocyazine, and combinations thereof and substituents thereof. .
상기 실란기는 트리메톡시실릴기, 트릴에톡시실릴기 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나의 알콕시실릴기 또는 트리메틸실릭시기, 트리에틸실리고시기 및 이들의 조합으로 이루어진 군에서 선택된어느 하나의 트리오르가노실록시기인 것이 바람직하다. The silane group is any one selected from the group consisting of any one alkoxysilyl group or trimethylsilyl group, triethylsiligo group and combinations thereof selected from the group consisting of trimethoxysilyl group, triethoxysilyl group and combinations thereof It is preferable that it is a triorgano siloxy group.
상기 할로겐 원자로는 불소, 염소, 브롬 등을 들 수 있다. Fluorine, chlorine, bromine, etc. are mentioned as said halogen atom.
한편, 수지층에서 상기 아크릴계 단량체로부터의 단위구조를 형성하는 아크릴계 단량체는 2관능 이상의 아크릴 또는 메타크릴 화합물인 것이 바람직하고, 이 때, 상기 아크릴계 단량체는 비스페놀-A 디아크릴레이트 (bisphenol-A-diacrylate), 비스페놀-S 디아크릴레이트 (bisphenol-S diacrylate), 디시클로펜타디에닐 디아크릴레이트(dicyclopentadienyl diacrylate), 펜타에리트리톨 트리아크릴레이트 (pentaerythritol triacrylate), 트리스(2-히드록시에틸)이소시아누레이트 트리아크릴레이트 (tris(2-hydroxyethyl)isocyanurate triacrylate), 펜타에리트리톨 테트라아크릴레이트 (pentaerythritol tetraacrylate), 비스페놀-A 디메타크릴레이트 (bisphenol-A dimethacrylate), 비스페놀-S-디메타크릴레이트 (bisphenol-S dimethacrylate), 디시클로펜타디에닐 디메타크릴레이트 (dicyclopentadienyl dimethacrylate), 펜타에리트리톨 트리메타크릴레이트 (pentaerythritol trimethacrylate), 트리스(2-히드록시에틸)이소시아누레이트 트리메타크릴레이트 (tris(2-hydroxyethyl)isocyanurate trimethacrylate), 및 펜타에리트리톨 테트라메타크릴레이트 (pentaerythritol tetramethacrylate)로 이루어지는 군에서 선택된 1 이상일 수 있다. On the other hand, the acrylic monomer forming the unit structure from the acrylic monomer in the resin layer is preferably a bifunctional or more functional acrylic or methacryl compound, wherein the acrylic monomer is bisphenol-A diacrylate (bisphenol-A-diacrylate ), Bisphenol-S diacrylate, dicyclopentadienyl diacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanu Tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate, bisphenol-A dimethacrylate, bisphenol-S-dimethacrylate (bisphenol -S dimethacrylate), dicyclopentadienyl dimethacrylate, pentaerythritol Consisting of pentaerythritol trimethacrylate, tris (2-hydroxyethyl) isocyanurate trimethacrylate, and pentaerythritol tetramethacrylate It may be one or more selected from the group.
본 발명의 수지층을 형성하기 위한 감광성 수지 조성물은 메인 조성으로는 상술한 단량체들 이외에, 이들을 광경화시키기 위하여 광개시제를 더 포함한다. 본 발명에서의 광중합 개시제란 노광에 의해 분해 또는 결합을 일으키며 라디칼, 음이온, 양이온 등의 상기 아크릴계 단량체 및 고리형 올레핀계 단량체의 중합을 개시할 수 있는 활성종을 발생시키는 화합물을 의미한다. 여기서 광개시제는 아크릴계 단량체 및 고리형 올레핀계 단량체를 광경화시킬 수 있는 통상의 광개시제를 선택할 수 있다. The photosensitive resin composition for forming the resin layer of the present invention further includes a photoinitiator as a main composition in addition to the above-mentioned monomers in order to photocure them. The photopolymerization initiator in the present invention means a compound which causes decomposition or bonding by exposure and generates active species capable of initiating polymerization of the acrylic monomers such as radicals, anions and cations and the cyclic olefin monomers. Here, the photoinitiator may select a conventional photoinitiator capable of photocuring the acrylic monomer and the cyclic olefin monomer.
상기 광중합 개시제로는 Irgacure 907, Irgacure 369, Irgacure OX01, Irgacure 242, 티옥산톤, 2,4-디에틸 티옥산톤, 티옥산톤-4-술폰산, 벤조페논, 4,4'-비스(디에틸아미노)벤조페논, 아세토페논, p-디메틸아미노아세토페논, α,α'-디메톡시아세톡시 벤조페논, 2,2'-디메톡시-2-페틸아세토페논, p-메톡시아세토페논, 2-메틸[4-(메틸티오)페닐]-2-모르폴리노-1-프로파논, 2-벤질-2-디에틸아미노-1-(4-모르폴리노페닐)-부탄-1-온, 2-히드록시-2-메틸-1-페닐프로판-1-온, 4-(2-히드록시에톡시)페닐-(2-히드록시-2-프로필)케톤, 1-히드록시시클로헥실 페닐케톤 등의 케톤류; 안트라퀴논, 1,4-나프토퀴논 등의 퀴논류; 1,3,5-트리스(트리클로로메틸)-s-트리아진, 1,3-비스(트리클로로메틸)-5-(2-클로로페닐)-s-트리아진, 1,3-비스(트리클로로페닐)-s-트리아진, 페나실클로라이드, 트리브로모메틸페닐술폰, 트리스(트리클로로메틸)-s-트리아진 등의 할로겐 화합물; 디-t-부틸 퍼옥사이드 등의 과산화물; 2,4,6-트리메틸 벤조일 디페닐 포스핀 옥사이드 등의 아실 포스핀 옥사이드류;가 사용될 수 있다. 본 발명에서 상기 광중합 개시제는 단독 또는 조합하여 사용될 수 있다. Examples of the photopolymerization initiator include Irgacure 907, Irgacure 369, Irgacure OX01, Irgacure 242, Thioxanthone, 2,4-Diethyl Thioxanthone, Thioxanthone-4-Sulfonic Acid, Benzophenone, and 4,4'-bis (di Ethylamino) benzophenone, acetophenone, p-dimethylaminoacetophenone, α, α'-dimethoxyacetoxy benzophenone, 2,2'-dimethoxy-2-petylacetophenone, p-methoxyacetophenone, 2 -Methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone Ketones such as these; Quinones such as anthraquinone and 1,4-naphthoquinone; 1,3,5-tris (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2-chlorophenyl) -s-triazine, 1,3-bis (trichloro Halogen compounds such as rophenyl) -s-triazine, phenacyl chloride, tribromomethylphenyl sulfone and tris (trichloromethyl) -s-triazine; Peroxides such as di-t-butyl peroxide; Acyl phosphine oxides such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; can be used. In the present invention, the photopolymerization initiator may be used alone or in combination.
상기 광중합 개시제의 함량은 조성물 100중량%를 기준으로 하여 0.5 내지 20중량%의 범위를 가질 수 있다. 상기 광중합 개시제의 함량이 0.5중량% 미만이면 감도가 충분하지 않아 아크릴계 중합 전환율이 80%이하로, 끈적끈적한 단량체의 택성이 남을 수 있고, 형성하고자 하는 필름의 기본 광학 물성을 가지기 어렵다. 또한, 상기 광중합 개시제의 함량이 20중량% 초과하면 형성된 필름의 광투과성, 헤이즈, 옐로우 인덱스 등이 저하되기 쉽다. The content of the photopolymerization initiator may have a range of 0.5 to 20% by weight based on 100% by weight of the composition. When the content of the photopolymerization initiator is less than 0.5% by weight, the sensitivity is not sufficient, the acrylic polymerization conversion rate is 80% or less, the tackiness of the sticky monomer may remain, and it is difficult to have the basic optical properties of the film to be formed. In addition, when the content of the photopolymerization initiator exceeds 20% by weight, the light transmittance, haze, yellow index, etc. of the formed film tends to be lowered.
그리고, 감광성 수지 조성물의 점도를 조절하기 위하여 희석제를 포함하며, 희석제의 함량은 중량 20~80% 인 것이 바람직하다. And, in order to adjust the viscosity of the photosensitive resin composition, a diluent is included, and the content of the diluent is preferably 20 to 80% by weight.
상기 희석제로는 상기 조성물의 제조 또는 점도 유지를 위한 것으로써 다음과 같은 물질을 사용할 수 있다. 예컨대, 메탄올, 에탄올 등의 알코올류 테트라하이드로퓨란, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르 등의 에테르류 프로필렌 글리콜 메틸 에테르 아세테이트, 프로필렌 글리콜 에틸 에테르 아세테이트, 프로펠렌 글리콜 프로필 에테르 아세테이트, 프로필렌 글리콜 부틸 에테르 아세테이트 등의 프로필렌 글리콜 알킬 에테르 아세테이트류 등을 들 수 있다. 이러한 희석제 가운데에서 용해성, 각 성분과의 반응성 및 도막 형성의 편리성의 관점에서 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 프로펠렌 글리콜 메틸 에테르 아세테이트류 메틸에틸케톤, 시클로헥사논, 4-히드록시-4-메틸-2-펜타난 등의 케톤류 아세트산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르 2-히드록시프로피온산의 에틸에스테르, 메틸에스테르 2-히드록시-2-메틸프로피온산의에틸에스테르 히드록시아세트산의 메틸에스테르, 에틸에스테르, 부틸 에스테르 젖산에틸, 젖산프로필, 젖산부틸 메톡시아세트산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르 프로폭시아세트산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르 부톡시아세트산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르 2-메톡시프로피온산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르 2-에톡시프로피온산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르 2-부톡시프로피온산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르 3-메톡시프로판의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르 3-에톡시프로피온산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르 3-부톡시프로피온산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르 등의 에스테르류의 사용이 바람직하다. As the diluent, the following materials may be used for preparing the composition or maintaining the viscosity. For example, ethers, such as alcohol, such as methanol and ethanol, tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol Propylene glycol alkyl ether acetates, such as butyl ether acetate, etc. are mentioned. Among these diluents, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetates methyl ethyl ketone, cyclohexanone, and 4-hydride from the viewpoint of solubility, reactivity with each component, and convenience of coating film formation. Methyl ester of ketone acetic acid such as oxy-4-methyl-2-pentanane, ethyl ester, propyl ester, butyl ester ethyl ester of 2-hydroxypropionic acid, ethyl ester of methyl ester 2-hydroxy-2-methylpropionic acid Methyl ester of oxyacetic acid, ethyl ester, butyl ester ethyl lactate, propyl lactate, butyl lactate methyl ester, ethyl ester, propyl ester, butyl ester methyl ester of propoxy acetic acid, ethyl ester, propyl ester, butyl ester Methyl ester of oxyacetic acid, ethyl ester, Lofil ester, butyl ester Methyl ester of 2-methoxypropionic acid, ethyl ester, propyl ester, butyl ester methyl ester of 2-ethoxypropionic acid, ethyl ester, propyl ester, butyl ester methyl ester of 2-butoxypropionic acid, ethyl ester , Propyl ester, butyl ester methyl ester of 3-methoxy propane, ethyl ester, propyl ester, butyl ester methyl ester of 3-ethoxypropionic acid, ethyl ester, propyl ester, butyl ester methyl ester of 3-butoxypropionic acid, ethyl Use of esters, such as ester, propyl ester, and butyl ester, is preferable.
또한 상기 희석제는 고비등점 희석제와 함께 사용될 수 있다. 사용 가능한 고비등점 희서제로서, 예컨대 N-메틸 포름아미드, N,N-디메틸 포름아미드, N-메틸 아세트아미드, N,N-디메틸 아세트아미드, N-메틸 피롤리돈, 디메틸 설폭시드, 벤질 에틸 에테르를 들 수 있다. The diluent may also be used with high boiling diluents. As the high boiling whitening agent that can be used, for example, N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, benzyl ethyl Ethers.
상기 희석제는 조성물 100중량%를 기준으로 하여 20 내지 80중량%의 범위로 포함하는데, 상기 희서제의 함량이 상기 범위 내에 있는 경우 원할한 필름을 제막할 수 있는 효과를 얻을 수 있다. The diluent is included in the range of 20 to 80% by weight based on 100% by weight of the composition, if the content of the whitening agent is in the above range can be obtained an effect that can form a desired film.
이 외에도 특별한 기능의 발현을 위하여 계면활성제, 경화촉진제, 산화방지제 등 첨가제를 더 포함할 수도 있다.In addition, it may further include additives such as surfactants, curing accelerators, antioxidants for the expression of special functions.
상기 첨가제 중 특히 표면 도포성을 향상하기 위한 계면활성제를 포함할 수 있는데, 계면활성제로는 불소 및 실리콘계 계면활성제, 예를 들면 3M사의 FC-129, FC-170C, FC-430, DIC사의 F-172, F-173, F-183, F-470, F-475, 신에츠실리콘사의 KP322, KP323, KP340, KP341 등이 있다. 이러한 계면활성제는 조성물 100 중량부를 기준으로 하여 5 중량부 이하, 바람직하게는 2 중량부 이하로 포함될 수 있다. 계면활성제의 함량이 5 중량부를 초과하는 경우 도포시 거품이 발생하는 문제가 있고, 이러한 문제는 유리섬유 함침 및 필름 제막 시에 영향을 주어 바람직하지 않다. Among the additives, in particular, it may include a surfactant for improving the surface coating properties, the surfactant is a fluorine and silicone-based surfactant, such as 3M's FC-129, FC-170C, FC-430, DIC's F- 172, F-173, F-183, F-470, F-475, and Shin-Etsu Silicone KP322, KP323, KP340, and KP341. Such surfactants may be included in an amount of 5 parts by weight or less, preferably 2 parts by weight or less, based on 100 parts by weight of the composition. If the content of the surfactant exceeds 5 parts by weight, there is a problem that foaming occurs during the application, this problem affects the glass fiber impregnation and film formation is undesirable.
그리고, 본 발명의 수지 조성물 중에는 필요에 따라 투명성, 내용제성, 내열성 등의 특성을 손상시키지 않은 범위에서 소량의 산화 방지제, 자외선 흡수제 , 염색 안료 등을 포함해도 좋다. And the resin composition of this invention may contain a small amount of antioxidant, an ultraviolet absorber, a dye pigment, etc. in the range which does not impair the characteristics, such as transparency, solvent resistance, and heat resistance, as needed.
이하, 본 발명의 실시예를 설명한다. Hereinafter, embodiments of the present invention will be described.
<실시예 1 내지 5 및 비교예 1><Examples 1 to 5 and Comparative Example 1>
하기 표 1과 같은 성분 및 함량(중량%)을 혼합하고, 이를 3시간 동안 교반하여 감광성 수지 조성물을 제조한 후, 여기에 두께 40~150㎛를 가지는 유리섬유층을 함침하여 약 5~30분간 초음파 처리(SONICATION)하고, 이를 유리기판과 이형필름 사이에 놓고 닥터블레이드를 이용하여 유리섬유층 일면의 수지층의 두께가 40~130um가 되도록 두께를 조절한 후에 UV경화를 진행시켜 기판을 얻었다.To prepare a photosensitive resin composition by mixing the components and contents (wt%) as shown in Table 1, and stirred for 3 hours, and then impregnated with a glass fiber layer having a thickness of 40 ~ 150㎛ ultrasonic wave for about 5-30 minutes After treatment (SONICATION), and placed between the glass substrate and the release film, using a doctor blade to adjust the thickness of the resin layer on one side of the glass fiber layer to 40 ~ 130um after the UV curing to obtain a substrate.
표 1
수지층 화합물 단량체 희석제 광개시제
화학식 1 단량체 아크릴계 단량체
E60 E90
비교예 1 - 58 20 20 2
실시예 1 38 20 20 20 2
실시예 2 38 20 20 20 2
실시예 3 38 20 20 20 2
실시예 4 38 20 20 20 2
실시예 5 38 20 20 20 2
Table 1
Resin Layer Compound Monomer diluent Photoinitiator
Formula 1 Monomer Acrylic monomer
E60 E90
Comparative Example 1 - 58 20 20 2
Example 1 38 20 20 20 2
Example 2 38 20 20 20 2
Example 3 38 20 20 20 2
Example 4 38 20 20 20 2
Example 5 38 20 20 20 2
여기에서, 실시예 1 내지 5에서 고리형 올레핀계 단량체는 화학식 1의 화합물(R1 내지 R6 모두 수소)로서, 실시예 1은 n=2, 실시예 2는 n=4, 실시예 3은 n=6, 실시예 4은 n=8, 실시예 5는 n=10인 경우이고, 아크릴계 단량체로 사용된 E60와 E90은 SK CYTEC에서 제조된, 상품명 EBECRYL 9260, EBECRYL 9390 제품이며, 희석제는 프로필렌 글리콜 에틸 에테르 아세테이트를 사용하였고, 광개시제는 Irgacure 907, Irgacure 369 1:1 혼합 사용하였다.Here, in Examples 1 to 5, the cyclic olefin monomer is a compound of Formula 1 (all of R 1 to R 6 are hydrogen), Example 1 is n = 2, Example 2 is n = 4, and Example 3 is n = 6, Example 4 is n = 8, Example 5 is n = 10, E60 and E90 used as an acrylic monomer are the products of EBECRYL 9260, EBECRYL 9390, manufactured by SK CYTEC, Diluent is propylene Glycol ethyl ether acetate was used, and photoinitiator Irgacure 907, Irgacure 369 1: 1 mixed.
이와 같이 얻은 실시예 1 내지 5 및 비교예 1의 성능을 평가한 결과는 다음 표 2 및 도 1과 같으며, 각 평가항목에 대한 측정방법은 다음과 같다.The results of evaluating the performance of Examples 1 to 5 and Comparative Example 1 thus obtained are as shown in Table 2 and Figure 1, the measurement method for each evaluation item is as follows.
<Transmittance & Haze측정방법><Measurement of Transmittance & Haze>
헤이즈 측정기 (Nippon Denshoku사 제품, NDH2000모델)을 이용하여 Method3으로 D65 광원으로 필름의 투과도 및 헤이즈를 측정한다. 이때 파장은 550nm 기분이다.Using a haze meter (Nippon Denshoku Co., NDH2000 model), the transmittance and haze of the film were measured using a D65 light source using Method3. At this time, the wavelength is 550 nm.
<Y.I 측정방법><Y.I measurement method>
UV-vis spectrometer(Varian사 제품, CARY-100모델)을 이용하여 ASTM E313측정법을 이용하여, 필름의 Yellow Index를 측정하였다.The Yellow Index of the film was measured using an ASTM E313 measurement method using a UV-vis spectrometer (Varian, CARY-100 model).
<굴절율><Refractive index>
Abbe 굴절기를 이용하여 필름을 기계 사이에 넣고 25℃에서 측정하였다.The film was placed between the machines using an Abbe refractor and measured at 25 ° C.
<열중량분석기 분석방법>Thermogravimetric analysis method
N2 조건 하에서 600℃에서 10℃/min 승온하면서 발생하는 weight loss(%)가 되는 부분을 중점으로 관찰하였다.The weight loss (%) that occurred while raising the temperature at 600 ° C to 10 ° C / min under N2 conditions was observed with emphasis.
<IR><IR>
FT-적외선 분광광도계(FT-IR spectrophotometer; Thermo Nicolet사 Avatar 360 FT-IR제품)를 이용하여 반사모드(Smart Miracle 악세사리 장착)로 500~4000cm-1영역의 Transmittance값을 측정한다.The FT-IR spectrophotometer (Avatar 360 FT-IR, manufactured by Thermo Nicolet) is used to measure the transmittance in the 500 ~ 4000cm-1 area in the reflection mode (with Smart Miracle accessory).
표 2
Transmittance(%) Haze(%) YI
비교예1 89.06 42.57 6.7413
실시예1 90.15 13.7 6.2885
실시예2 90.25 7.2 6.3455
실시예3 90.87 29.03 6.4135
실시예4 90.50 12.3 6.1225
실시예5 91.71 17.31 6.0961
TABLE 2
Transmittance (%) Haze (%) YI
Comparative Example 1 89.06 42.57 6.7413
Example 1 90.15 13.7 6.2885
Example 2 90.25 7.2 6.3455
Example 3 90.87 29.03 6.4135
Example 4 90.50 12.3 6.1225
Example 5 91.71 17.31 6.0961
이와 같이, 비교예1은 광투과도가 90%에 이르지 못하고, Haze가 40%를 상회하고, Y.I치가 6.5를 상회하지만, 실시예 1 내지 5는 모두 비교예1보다 우수한 광학특성을 보임을 알 수 있다.As described above, in Comparative Example 1, the light transmittance did not reach 90%, the Haze exceeded 40%, and the YI value exceeded 6.5, but Examples 1 to 5 all showed superior optical characteristics than Comparative Example 1. have.
그리고, 열안정성 평가를 위하여 열중량분석기(THERMOGRAVIMETRIC ANALYZER ; TGA)로 분석한 결과는 도 1(도 1에서 Y축은 600도까지 열적안정성을 가지는 잔류율(%)를 나타낸다)과 같고, 그 결과 고리형 올레핀계 단량체를 포함하지 않은 비교예 1은 600도까지 승온하였을 때 잔류물이 약 40 중량%이나, 실시예 1 내지 5는 약 50중량%를 초과 잔류하여 열안정성이 우수함을 알 수 있다.The thermogravimetric analysis (THERMOGRAVIMETRIC ANALYZER; TGA) for thermal stability evaluation is the same as FIG. 1 (in FIG. 1, the Y-axis shows the residual rate (%) having thermal stability up to 600 degrees), and the resultant ring In Comparative Example 1, which does not include the type olefinic monomer, the residue is about 40% by weight when heated up to 600 ° C, but Examples 1 to 5 remain in excess of about 50% by weight, indicating excellent thermal stability.
<실시예 6><Example 6>
트리메틸롤프로판 아세탈화 생성물 디아크릴레이트(R-604, Nippon Kayaku 제품)와, 이 트리메틸롤프로판 아세탈화 생성물 디아크릴레이트 100중량부 기준으로 화학식 2의 단량체에 해당하는 Tetrakis(glycidyloxyphenyl)ethane-GAC 25중량부, 2가의 작용기를 갖는 플루오렌 아크릴레이트 (HR-6060, 미원스페셜티케미칼 제품, 화학식 1에 있어서 R1 내지 R6는 모두 H이고, n은 3인 화합물) 100중량부를 먼저 혼합하고, 이 단량체 혼합물 100중량부를 기준으로, 1-히드록시시클로헥실 페닐 케톤 (Irgacure184, Basf사 제품) 2중량부와, 프로필렌 글리콜 에틸 에테르 아세테이트 30중량부를 더 혼합하여 경화전 수지층 조성물을 제조하였다. 이 경화전 수지층 조성물에 100㎛ 두께의 유리섬유를 함침시키고, 30분간 초음파 처리(SONICATION)하였다. 이를 유리기판 2장 안에 이형필름 2장을 위치시키고, 그 가운데에 유리섬유층을 펼쳐 넣고 닥터블레이드를 이용하여 수지층의 두께가 100㎛가 되도록 조절하여, 양쪽으로 약 10J/cm2의 UV광으로 조사시키고, 유리기판과 이형필름은 제거하여 기판을 얻었다. Trimethylolpropane acetalization product diacrylate (R-604, manufactured by Nippon Kayaku) and Tetrakis (glycidyloxyphenyl) ethane-GAC 25 corresponding to the monomer of formula (2) based on 100 parts by weight of trimethylolpropane acetalization product diacrylate. Parts by weight, 100 parts by weight of fluorene acrylate having a divalent functional group (HR-6060, manufactured by Miwon Specialty Chemical, R 1 to R 6 in Formula 1 are all H and n is 3) Based on 100 parts by weight of the monomer mixture, 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone (Irgacure184, manufactured by Basf) and 30 parts by weight of propylene glycol ethyl ether acetate were further mixed to prepare a resin layer composition before curing. This resin layer composition before hardening was impregnated with glass fiber of 100 micrometers thickness, and it sonicated for 30 minutes. Two release films are placed in two glass substrates, and a glass fiber layer is spread therein, and the thickness of the resin layer is adjusted to 100 μm using a doctor blade, and irradiated with UV light of about 10 J / cm 2 on both sides. The glass substrate and the release film were removed to obtain a substrate.
<실시예 7><Example 7>
실시예 6에서 화학식 2의 단량체에 해당하는 Tetrakis(glycidyloxyphenyl)ethane-GAC의 함량을 트리메틸롤프로판 아세탈화 생성물 디아크릴레이트 100중량부 기준으로 50중량부 포함한 것을 제외하고는 실시예 6과 동일하게 하여 기판을 제조하였다.In Example 6, except that 50 parts by weight of Tetrakis (glycidyloxyphenyl) ethane-GAC corresponding to the monomer of Formula 2 based on 100 parts by weight of trimethylolpropane acetalization product diacrylate was the same as in Example 6 The substrate was prepared.
<실시예 8><Example 8>
실시예 6에서 화학식 2의 단량체에 해당하는 Tetrakis(glycidyloxyphenyl)ethane-GAC의 함량을 트리메틸롤프로판 아세탈화 생성물 디아크릴레이트 100중량부 기준으로 100중량부 포함한 것을 제외하고는 실시예 6과 동일하게 하여 기판을 제조하였다.In Example 6, except that 100 parts by weight of Tetrakis (glycidyloxyphenyl) ethane-GAC corresponding to the monomer of Formula 2 based on 100 parts by weight of trimethylolpropane acetalization product diacrylate was the same as in Example 6 The substrate was prepared.
<실시예 9>Example 9
실시예 6에서 화학식 2의 단량체에 해당하는 단량체를 1,1,2,2-Tetrakis[4-(acryloxy polyethoxy)phenyl]ethane로 하고, 이의 함량을 트리메틸롤프로판 아세탈화 생성물 디아크릴레이트 100중량부 기준으로 50중량부 포함한 것을 제외하고는 실시예 6과 동일하게 하여 기판을 제조하였다.In Example 6, the monomer corresponding to the monomer of Formula 2 was 1,1,2,2-Tetrakis [4- (acryloxy polyethoxy) phenyl] ethane, and the content thereof was 100 parts by weight of trimethylolpropane acetalization product diacrylate. A substrate was manufactured in the same manner as in Example 6, except that 50 parts by weight was included as a standard.
<실시예 10><Example 10>
실시예 9에서 화학식 2의 단량체에 해당하는 단량체 1,1,2,2-Tetrakis[4-(acryloxy polyethoxy)phenyl]ethane의 함량을 트리메틸롤프로판 아세탈화 생성물 디아크릴레이트 100중량부 기준으로 100중량부 포함한 것을 제외하고는 실시예 4와 동일하게 하여 기판을 제조하였다.In Example 9, 100 parts by weight of the monomer 1,1,2,2-Tetrakis [4- (acryloxy polyethoxy) phenyl] ethane corresponding to the monomer of Formula 2 was based on 100 parts by weight of trimethylolpropane acetalization product diacrylate. A substrate was manufactured in the same manner as in Example 4 except for the inclusion.
<비교예 2>Comparative Example 2
실시예 6에서 화학식 2의 단량체를 포함하지 않는 것을 제외하고는 실시예 6과 동일하게 하여 기판을 제조하였다. A substrate was prepared in the same manner as in Example 6 except that the monomer of Formula 2 was not included in Example 6.
이와 같이 얻은 실시예 6 내지 10 및 비교예 2의 성능을 평가한 결과는 다음 표 3과 같으며, 각 평가항목의 측정방법은 다음과 같다. The results of evaluating the performance of Examples 6 to 10 and Comparative Example 2 obtained as described above are shown in Table 3 below, and the measurement method of each evaluation item is as follows.
<Transmittance & Haze측정방법><Measurement of Transmittance & Haze>
헤이즈 측정기 (Nippon Denshoku사 제품, NDH2000모델)을 이용하여 Method3으로 D65 광원으로 필름의 투과도 및 헤이즈를 측정한다. 이때 파장은 550nm 기준이다.Using a haze meter (Nippon Denshoku Co., NDH2000 model), the transmittance and haze of the film were measured using a D65 light source using Method3. The wavelength is based on 550nm.
<Tg 측정><Tg measurement>
Perkin Elmer사의 모델 TGA -TGA7 을 사용하여 승온 속도 10℃/분으로 측정하였다. Using a model TGA-TGA7 from Perkin Elmer, the temperature was measured at a rate of 10 ° C./min.
<열팽창계수> <Coefficient of thermal expansion>
Perkin Elmer사의 모델 TMA-Diamond를 사용하여, 질소 분위기 하에서 1분간 10℃ 비율로 승온 시키고, 1g중량으로 하중을 가하였다. 필름의 열 이력을 제거하기 위해 실온에서부터 200℃까지 10℃/min 승온한 후, 다시 실온에서부터 10℃/min의 속도로 300℃까지 승온하고, 50내지 250 온도 범위에서의 열팽창계수를 산출하였다. Using Perkin Elmer's model TMA-Diamond, the temperature was raised at a rate of 10 ° C. for 1 minute under a nitrogen atmosphere, and a load was applied at a weight of 1 g. In order to remove the heat history of a film, after heating up 10 degreeC / min from room temperature to 200 degreeC, it heated up again to 300 degreeC at a speed of 10 degreeC / min from room temperature, and computed the coefficient of thermal expansion in 50-250 temperature range.
표 3
Transmittance(%) Haze(%) Tg() 열팽창계수(ppm)
비교예2 91 3.6 211 18
실시예6 90 3.7 >230 15
실시예7 90 6.2 >230 14
실시예8 88 17.2 >230 11
실시예9 90 3.3 >230 14
실시예10 88 15.3 >230 12
TABLE 3
Transmittance (%) Haze (%) Tg () Coefficient of thermal expansion (ppm)
Comparative Example 2 91 3.6 211 18
Example 6 90 3.7 > 230 15
Example 7 90 6.2 > 230 14
Example 8 88 17.2 > 230 11
Example 9 90 3.3 > 230 14
Example 10 88 15.3 > 230 12
본 발명의 실시예 6 내지 10은 유리섬유를 사용하는 경우에도 비교예2와 같이 높은 광투과율을 보여준다. 그리고, 화학식 2의 단량체로부터의 단위구조를 포함함으로써 실시예 6 내지 10은 230℃ 이상의 우수한 Tg와 15ppm이하의 열팽창계수를 얻을 수 있는 것을 알 수 있다.Examples 6 to 10 of the present invention shows a high light transmittance as in Comparative Example 2 even when using a glass fiber. And by including the unit structure from the monomer of Formula 2, it can be seen that Examples 6 to 10 can obtain excellent Tg of 230 ° C. or higher and a thermal expansion coefficient of 15 ppm or less.

Claims (7)

  1. 유리섬유층과 상기 유리섬유층의 양면에 형성된 수지층을 포함하고, It includes a glass fiber layer and a resin layer formed on both sides of the glass fiber layer,
    상기 수지층은 아크릴계 단량체로부터의 단위구조 100중량부와 다음 화학식 1의 단량체로부터의 단위구조 25~400중량부를 포함하고, 중량평균분자량이 500~1,000,000인 화합물을 포함하는 것인 플렉서블 디스플레이 기판. The resin layer is a flexible display substrate comprising 100 parts by weight of the unit structure from the acrylic monomer and 25 to 400 parts by weight of the unit structure from the monomer of the formula (1), and comprises a compound having a weight average molecular weight of 500 ~ 1,000,000.
    화학식 1Formula 1
    Figure PCTKR2011009563-appb-I000005
    Figure PCTKR2011009563-appb-I000005
    여기에서, R1 내지 R6는 각각 같거나 다르게 수소 또는 산소, 질소, 황 또는 규소를 포함하는 연결기로 치환되거나 치환되지 않은 탄소수 1 내지 10의 탄화수소기이거나, 극성기, 단일결합 또는 2가의 연결기를 가지는 방향족기, 실란기, 할로겐 원자 중에서 선택되고; n은 1 내지 10의 정수이다.Wherein R 1 to R 6 are each the same or different hydrocarbon groups having 1 to 10 carbon atoms, unsubstituted or substituted with a linking group containing hydrogen or oxygen, nitrogen, sulfur or silicon, or a polar group, a single bond or a divalent linking group Branch is selected from an aromatic group, a silane group and a halogen atom; n is an integer from 1 to 10.
  2. 제1항에 있어서, 상기 유리섬유층은 지름 4~15um의 유리섬유가 일방향으로 배향 정렬되고, 20~200um의 두께로 형성된 것을 특징으로 하는 플렉서블 디스플레이 기판.The flexible display substrate of claim 1, wherein the glass fiber layer has a diameter of about 4 μm to about 15 μm and is formed in a thickness of about 20 μm to about 200 μm.
  3. 제1항에 있어서, 상기 수지층에서 상기 화합물은 아크릴계 단량체로부터의 단위구조 100중량부, 화학식 1의 단량체로부터의 단위구조 50~200중량부 및 화학식 2의 단량체로부터의 단위구조 20~200중량부를 포함하는 것인 플렉서블 디스플레이 기판.According to claim 1, wherein the compound in the resin layer is 100 parts by weight of the unit structure from the acrylic monomer, 50 to 200 parts by weight of the unit structure from the monomer of Formula 1 and 20 to 200 parts by weight of the unit structure from the monomer of Formula 2 Flexible display substrate comprising.
    화학식 2Formula 2
    Figure PCTKR2011009563-appb-I000006
    Figure PCTKR2011009563-appb-I000006
    여기서, R7 내지 R10은 수소 또는 산소, 질소, 황 또는 규소를 포함하는 연결기를 가지는 치환되거나 치환되지 않은 탄소수 1 내지 10의 탄화수소기이거나, 극성기, 단일결합 또는 2가의 연결기를 가지는 방향족기, 실란기, 할로겐 원자 중에서 선택되고, R7 내지 R10 중에서 적어도 하나는 아크릴레이트나 메타아크릴레이트 같은 2가의 연결기를 포함한다. Here, R 7 to R 10 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms having a linking group containing hydrogen or oxygen, nitrogen, sulfur or silicon, an aromatic group having a polar group, a single bond or a divalent linking group, A silane group, a halogen atom, and at least one of R 7 to R 10 includes a divalent linking group such as acrylate or methacrylate.
  4. 제3항에 있어서, 상기 수지층에서 상기 아크릴계 단량체로부터의 단위구조는 2관능 이상의 아크릴계 또는 메타크릴계 화합물로부터 선택된 아크릴계 단량체로부터 형성된 것을 특징으로 하는 플렉서블 디스플레이 기판.The flexible display substrate of claim 3, wherein the unit structure from the acrylic monomer in the resin layer is formed from an acrylic monomer selected from an acrylic or methacrylic compound having two or more functional groups.
  5. 제4항에 있어서, 상기 아크릴계 단량체는 비스페놀-A 디아크릴레이트 (bisphenol-A-diacrylate), 비스페놀-S 디아크릴레이트 (bisphenol-S diacrylate), 디시클로펜타디에닐 디아크릴레이트(dicyclopentadienyl diacrylate), 펜타에리트리톨 트리아크릴레이트 (pentaerythritol triacrylate), 트리스(2-히드록시에틸)이소시아누레이트 트리아크릴레이트 (tris(2-hydroxyethyl)isocyanurate triacrylate), 펜타에리트리톨 테트라아크릴레이트 (pentaerythritol tetraacrylate), 비스페놀-A 디메타크릴레이트 (bisphenol-A dimethacrylate), 비스페놀-S-디메타크릴레이트 (bisphenol-S dimethacrylate), 디시클로펜타디에닐 디메타크릴레이트 (dicyclopentadienyl dimethacrylate), 펜타에리트리톨 트리메타크릴레이트 (pentaerythritol trimethacrylate), 트리스(2-히드록시에틸)이소시아누레이트 트리메타크릴레이트 (tris(2-hydroxyethyl)isocyanurate trimethacrylate), 및 펜타에리트리톨 테트라메타크릴레이트 (pentaerythritol tetramethacrylate)로 이루어지는 군에서 선택된 1 이상인 것을 특징으로 하는 플렉서블 디스플레이 기판.The method of claim 4, wherein the acrylic monomer is bisphenol-A diacrylate (bisphenol-A-diacrylate), bisphenol-S diacrylate (bisphenol-S diacrylate), dicyclopentadienyl diacrylate (dicyclopentadienyl diacrylate), Pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate, bisphenol- Bisphenol-A dimethacrylate, bisphenol-S dimethacrylate, dicyclopentadienyl dimethacrylate, pentaerythritol trimethacrylate (pentaerythritol trimethacrylate), tris (2-hydroxyethyl) isocyanurate trimethacrylate (tris (2-hydroxyethyl) isocyanurate trimethacrylat e), and at least one selected from the group consisting of pentaerythritol tetramethacrylate.
  6. 제 1 항에 있어서, 상기 수지층에서 화학식 1의 단량체로부터의 단위구조는 플루오렌 골격 구조가 9,9-비스(4-히드록시페닐)플루오렌, 9,9-비스(4-히드록시-3-메틸페닐)플루오렌, 9,9-비스(4-히드록시-3-클로로페닐)플루오렌, 9,9-비스(4-히드록시-3-브로모페닐)플루오렌, 9,9-비스(4-히드록시-3-플루오로페닐)플루오렌, 9,9-비스(4-히드록시-3-메톡시페닐)플루오렌, 9,9-비스(4-히드록시-3,5-디메틸페닐)플루오렌, 9,9-비스(4-히드록시-3,5-디클로로페닐)플루오렌 및 9,9-비스(4-히드록시-3,5-디브로모페닐)플루오렌으로 구성되는 군에서 선택된 1 이상인 것을 특징으로 하는 플렉서블 디스플레이 기판.The unit structure of the monomer of Formula 1 in the resin layer is fluorene skeleton structure of 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-) 3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9- Bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5 -Dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene and 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene Flexible display substrate, characterized in that at least one selected from the group consisting of.
  7. 제 1 항에 있어서, 상기 수지층에서 화학식 1의 단량체로부터의 단위구조에 있어서 n은 4~10인 것을 특징으로 하는 플렉서블 디스플레이 기판.The flexible display substrate of claim 1, wherein n is 4 to 10 in a unit structure of the monomer of Formula 1 in the resin layer.
PCT/KR2011/009563 2011-06-15 2011-12-13 Flexible display substrate WO2012173316A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2014515704A JP5827400B2 (en) 2011-06-15 2011-12-13 Flexible display board
CN201180071685.3A CN103619581B (en) 2011-06-15 2011-12-13 Flexible display substrate

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR20110058071 2011-06-15
KR10-2011-0058072 2011-06-15
KR20110058072 2011-06-15
KR10-2011-0058071 2011-06-15
KR1020110131012A KR101450952B1 (en) 2011-06-15 2011-12-08 The flexible display substrate
KR10-2011-0131012 2011-12-08

Publications (1)

Publication Number Publication Date
WO2012173316A1 true WO2012173316A1 (en) 2012-12-20

Family

ID=47357284

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2011/009563 WO2012173316A1 (en) 2011-06-15 2011-12-13 Flexible display substrate

Country Status (1)

Country Link
WO (1) WO2012173316A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010033128A (en) * 1998-10-14 2001-04-25 호소이 쇼지로 Antireflection material and polarizing film using the same
JP2002302539A (en) * 2001-04-04 2002-10-18 Sumitomo Bakelite Co Ltd Resin substrate for liquid crystal display element
JP2002303854A (en) * 2001-04-04 2002-10-18 Sumitomo Bakelite Co Ltd Resin substrate for liquid crystal display element
JP2002303853A (en) * 2001-04-04 2002-10-18 Sumitomo Bakelite Co Ltd Resin substrate for liquid crystal display element
JP4285242B2 (en) * 2002-01-25 2009-06-24 住友ベークライト株式会社 Transparent composite composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010033128A (en) * 1998-10-14 2001-04-25 호소이 쇼지로 Antireflection material and polarizing film using the same
JP2002302539A (en) * 2001-04-04 2002-10-18 Sumitomo Bakelite Co Ltd Resin substrate for liquid crystal display element
JP2002303854A (en) * 2001-04-04 2002-10-18 Sumitomo Bakelite Co Ltd Resin substrate for liquid crystal display element
JP2002303853A (en) * 2001-04-04 2002-10-18 Sumitomo Bakelite Co Ltd Resin substrate for liquid crystal display element
JP4285242B2 (en) * 2002-01-25 2009-06-24 住友ベークライト株式会社 Transparent composite composition

Similar Documents

Publication Publication Date Title
WO2014163352A1 (en) Polyimide cover substrate
KR101966736B1 (en) Modified Polyimide and Curable Resin Composition Comprising Same
WO2017111289A1 (en) Polyamic acid composition to which alicyclic monomers are applied and transparent polyimide film using same
WO2017039159A1 (en) Low temperature curing composition, cured film formed therefrom, and electronic device having cured film
WO2016140559A1 (en) Composition for polyimide film for flexible substrate of optoelectronic device
TWI722787B (en) Polyimide precursor composition and polyimide film, substrate for display device, and optical device prepared by using same
WO2020159193A1 (en) Polyimide precursor composition and polyimide film, substrate for display device, and optical device, each manufactured therefrom
WO2012173316A1 (en) Flexible display substrate
KR101450952B1 (en) The flexible display substrate
WO2011028075A2 (en) Hard coating composition and a production method for the same and a hard coating film formed using the hard coating composition
KR20190029565A (en) Modified Polyimide and Curable Resin Composition Comprising Same
WO2021177648A1 (en) Flexible window film and display device comprising same
KR20140026660A (en) The flexible display substrate
WO2022065886A1 (en) Low-refractive-index thermosetting composition, optical member formed therefrom, and display apparatus
WO2010140804A2 (en) Norbornene resins for encapsulating optical device
WO2020145674A1 (en) Poly(amide-imide) block copolymer, and composition and polymer film each comprising same
WO2012086959A2 (en) Photo-curable resin composition for printing process
WO2014193177A2 (en) Open-structure polyhedral oligomeric silsesquioxane and composition comprising same
KR20140119938A (en) Flexible display substrate and method for manufacturing the same
WO2022098183A1 (en) Adhesive film, optical member comprising same, and optical display device comprising same
KR20150033839A (en) A glass fiber sheet and flexible display substrate comprising the same
WO2020116980A1 (en) Resin composition for anti-glare coating and anti-glare coating film prepared thereby
KR102465430B1 (en) Polyimide precursor composition and polyimide film substrate for display device, and optical device prepared by using same
WO2010021476A2 (en) Photopolymerizable oligomer, photopolymerizable resin composition containing the same, and optical fiber
WO2022019609A1 (en) Anti-glare film, polarizing plate and display apparatus

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: 11867762

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014515704

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11867762

Country of ref document: EP

Kind code of ref document: A1