WO2017217609A1 - Composition pour film de fenêtre, film de fenêtre formé à partir de celle-ci, et dispositif d'affichage souple comprenant la composition - Google Patents

Composition pour film de fenêtre, film de fenêtre formé à partir de celle-ci, et dispositif d'affichage souple comprenant la composition Download PDF

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WO2017217609A1
WO2017217609A1 PCT/KR2016/012362 KR2016012362W WO2017217609A1 WO 2017217609 A1 WO2017217609 A1 WO 2017217609A1 KR 2016012362 W KR2016012362 W KR 2016012362W WO 2017217609 A1 WO2017217609 A1 WO 2017217609A1
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window film
group
formula
sio
siloxane resin
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PCT/KR2016/012362
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English (en)
Korean (ko)
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이은수
최진희
김민혜
강경구
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삼성에스디아이 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the present invention relates to a composition for a window film, a window film formed therefrom, and a flexible display device including the same.
  • Flexible display devices are thin, light, impact resistant, and can be folded and unfolded to produce a variety of forms.
  • Patent Document 1 discloses an optical film produced by curing a hard coat resin composition containing a siloxane resin containing an alicyclic epoxy group.
  • the optical film prepared according to Patent Document 1 has a high surface hardness, but has a brittle characteristic after curing, so that flexibility is poor, cracks are easily formed, and curl characteristics are large, resulting in post processability. There was a problem that a problem occurred.
  • An object of the present invention is to provide a composition for a window film that can implement a window film having a high surface hardness and a low curl.
  • Another object of the present invention is to provide a window film formed by the composition for a window film as described above and a flexible display device including the same.
  • the present invention is a first siloxane resin represented by the following formula (1) or (2); And it provides a composition for a window film comprising a second siloxane resin represented by the formula (3).
  • R 1 is a functional group containing an alicyclic epoxy group or an alicyclic epoxy group
  • R 4 is a functional group containing an alicyclic epoxy group or an alicyclic epoxy group
  • the present invention includes a base layer, a coating layer formed on one surface of the base layer, wherein the coating layer is a first siloxane resin represented by Formula 1 or Formula 2, and a second siloxane resin represented by Formula 3 It provides a window film formed by a composition comprising a.
  • the present invention provides a flexible display device including the window film.
  • composition for a window film of the present invention may include a hard-type siloxane resin and a soft-type siloxane resin having a specific structure, thereby realizing a window film having high surface hardness and less curling.
  • the window film manufactured using the composition of the present invention has a high surface hardness and can be usefully used as an alternative to a high hardness window glass substrate, and has a low curl after curing, thereby providing excellent processability.
  • FIG. 1 is a cross-sectional view of a window film according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a window film according to another embodiment of the present invention.
  • FIG 3 is a cross-sectional view of a flexible display device according to an embodiment of the present invention.
  • FIG. 4 is a cross-sectional view according to an exemplary embodiment of the display unit of FIG. 3.
  • FIG. 5 is a cross-sectional view of a flexible display device according to another exemplary embodiment of the present invention.
  • FIG. 6 is a cross-sectional view of a flexible display device according to still another embodiment of the present invention.
  • FIG. 7 is a schematic diagram of a curl measurement in the present specification.
  • pencil hardness is to cut the window film to a size of about 50mm in width, about 50mm in length to prepare a specimen, and attach the edge of the specimen using 3M tape on a 2T-thick soda-lime glass substrate, and then The hardness of the coating layer on the center without 3M tape was measured using the SHINTO Scientfic company's HEIDON-14EW instrument.
  • a pencil of 6B to 9H manufactured by Mitsubishi Co., Ltd. was used.
  • the load of the pencil on the coating layer was about 1 kg
  • the angle at which the pencil was drawn was about 45 °
  • the speed at which the pencil was drawn was about 60 mm / min. If the scratch occurs more than one time to evaluate five times, the pencil hardness is measured using the pencil of the step below, and the five times the five times the maximum pencil hardness value when there is no scratch.
  • “Curl” refers to FIG. 7, when the window film 1 is cut to a predetermined size and then placed on the table bottom surface 2 and left at about 25 ° C. and about 50% relative humidity. , It is a value obtained by measuring the highest height H from the bottom surface 2 to the corner portion of the window film 1.
  • substituted means, unless specifically stated, that at least one hydrogen atom of the functional group is a hydroxyl group, an unsubstituted C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C3 to C10 cycloalkyl group, an unsubstituted C6 to Substituted with C1 to C10 alkyl group substituted with C20 aryl group, C7 to C20 arylalkyl group, benzophenone group, C1 to C10 alkyl group substituted with C6 to C20 aryl group, or C1 to C10 alkoxy group do.
  • alicyclic epoxy group means an epoxidized C5 to C20 cycloalkyl group.
  • cycloaliphatic epoxy group-containing functional group means an alkyl group of C1 to C12 or a cycloalkyl group of C5 to C20, having at least one epoxidized C5 to C20 cycloalkyl group.
  • glycidyl group-containing functional group means a glycidoxy group, or a C1 to C12 alkyl group or a C5 to C20 cycloalkyl group having a glycidyl group or glycidoxy group.
  • halogen means fluorine, chlorine, bromine or iodine.
  • Ec is a (3,4-epoxycyclohexyl) ethyl group
  • Gp is a 3-glycidoxypropyl group
  • composition for window films which concerns on this invention contains the 2 types of siloxane resin from which a structure differs, and specifically contains the hard 1st siloxane resin and the soft 2nd siloxane resin.
  • the first siloxane resin may be represented by the following Chemical Formula 1 or Chemical Formula 2.
  • R 1 is a functional group containing an alicyclic epoxy group or an alicyclic epoxy group, specifically, may be an epoxycyclohexyl group, an epoxycyclohexylalkyl group, and more specifically, an epoxycyclohexyl group, (3 , 4-epoxycyclohexyl) methyl ((3,4-epoxycyclohexyl) methyl) group, (3,4-epoxycyclohexyl) ethyl ((3,4-epoxycyclohexyl) ethyl) group, (3,4-epoxycyclohexyl) ) (3,4-epoxycyclohexyl) propyl) group, and the like.
  • R 2 is a glycidyl group or a glycidyl group-containing functional group, specifically, may be a glycidyl group, a glycidoxyalkyl group, or the like, and more specifically, may be a glycidyl group or a glycidoxypropyl group.
  • R 3 is a functional group containing an alicyclic epoxy group or an alicyclic epoxy group, and specifically, may be an epoxycyclohexyl group, an epoxycyclohexylalkyl group, and more specifically, an epoxycyclohexyl group, (3 , 4-epoxycyclohexyl) methyl ((3,4-epoxycyclohexyl) methyl) group, (3,4-epoxycyclohexyl) ethyl ((3,4-epoxycyclohexyl) ethyl) group, (3,4-epoxycyclohexyl) ) (3,4-epoxycyclohexyl) propyl) group, and the like.
  • the first siloxane resin comprises the [SiO 4/2] of a repeating unit having a solid properties after curing, it is possible to improve the hardness of the window film.
  • the second siloxane resin may be represented by the following formula (3).
  • R 4 is a functional group containing an alicyclic epoxy group or an alicyclic epoxy group, specifically, may be an epoxycyclohexyl group, an epoxycyclohexylalkyl group, and more specifically, an epoxycyclohexyl group, (3 , 4-epoxycyclohexyl) methyl ((3,4-epoxycyclohexyl) methyl) group, (3,4-epoxycyclohexyl) ethyl ((3,4-epoxycyclohexyl) ethyl) group, (3,4-epoxycyclohexyl) ) (3,4-epoxycyclohexyl) propyl) group, and the like.
  • R 5 is a glycidyl group or a glycidyl group-containing functional group, specifically, may be a glycidyl group, a glycidoxyalkyl group, or the like, and more specifically, may be a glycidyl group or a glycidoxypropyl group.
  • the second siloxane resin serves as a soft type siloxane resin to improve flexibility and reduce curl.
  • soft siloxane resins have excellent flexibility but low surface hardness. Therefore, when using a soft type siloxane mixed, it is common that surface hardness falls.
  • the soft type siloxane resin represented by the formula (3) is used in combination with the hard type siloxane resin represented by the formula (1) or (2), the surface hardness is rather improved. In addition, the curling phenomenon after curing was also significantly improved.
  • the composition of the present invention may simultaneously realize high surface hardness and low curling property when the window film is manufactured by using the first and second siloxane resins having a specific structure.
  • the composition of the present invention is a weight ratio of about 2: 8, 3: 7, 4: 6, 5: 5, 6: 4, 7: 3, or 8: 2 of the first siloxane resin to the second siloxane resin. It can be included as.
  • the composition of the present invention may comprise the first siloxane resin to the second siloxane resin in the range of at least one of the above weight ratio and at most one of the above weight ratio.
  • the compositions of the present invention may comprise the first siloxane resin to the second siloxane resin in a weight ratio of about 2: 8 to about 8: 2, specifically about 4: 6 to about 6: 4 Can be . When the compounding ratio is satisfied, both surface hardness and curl characteristics are excellent.
  • composition of the present invention may further include a crosslinking agent and a curing agent in addition to the first siloxane resin and the second siloxane resin.
  • the crosslinking agent may be cured with the first siloxane resin and the second siloxane resin by containing a crosslinkable functional group such as an epoxy group or an oxetane group to increase the hardness of the window film.
  • the crosslinking agent may further increase the flexibility of the coating layer by further comprising at least one of a chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and a hydrogenated aromatic hydrocarbon group.
  • the crosslinking agent may include at least one of a chain aliphatic epoxy monomer, a cyclic aliphatic epoxy monomer, a hydrogenated aromatic hydrocarbon epoxy monomer, and an oxetane monomer.
  • Chain aliphatic epoxy monomers include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,7-octadiene diepoxide, trimethylolpropane Triglycidyl ether, polyethylene glycol diglycidyl ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ether; Polyglycidyl ethers of polyether polyols obtained by adding one or two or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; Diglycidyl esters of aliphatic long-chain dibasic acids; Monoglycidyl ethers of aliphatic higher alcohols; Glycidyl ethers of higher fatty acids; Epoxidized soybean oil; Butyl epoxy
  • the cyclic aliphatic epoxy monomer is a compound having one or more epoxy groups in the alicyclic group, and may specifically include an alicyclic epoxy carboxylate, an alicyclic epoxy (meth) acrylate, and the like. More specifically, (3,4-epoxycyclohexyl) methyl-3 ', 4'-epoxycyclohexanecarboxylate (3,4-epoxycyclohexyl) methyl 3', 4'-epoxycyclohexanecarboxylate), diglycidyl 1, 2-cyclohexanedicarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meth-dioxane (2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metha-dioxane), bis (3,4-
  • Hydrogenated aromatic hydrocarbon epoxy monomer means a compound obtained by selectively hydrogenating an aromatic epoxy monomer under pressure in the presence of a catalyst.
  • aromatic epoxy monomers include bisphenol type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S; Novolac type epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, hydroxybenzaldehyde phenol novolac epoxy resins; And polyfunctional epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyvinyl phenol, and the like, but are not limited thereto.
  • Oxetane monomers include 3-methyloxetane, 2-methyloxetane, 2-ethylhexyl oxetane, 3-oxetanol, 2-methyleneoxetane, 3,3-oxetane dimethanethiol, 4- (3-methyl Oxetan-3-yl) benzonitrile, N- (2,2-dimethylpropyl) -3-methyl-3-oxetanemethaneamine, N- (1,2-dimethylbutyl) -3-methyl-3- Oxetanemethaneamine, (3-ethyloxetan-3-yl) methyl (meth) acrylate, 4-[(3-ethyloxetan-3-yl) methoxy] butan-1-ol, 3-ethyl- May comprise one or more of 3-hydroxymethyloxetane, xylenebisoxetane, 3- [ethyl-3 [[(3-e
  • the crosslinking agent is about 0.1 part by weight to about 50 parts by weight, specifically about 3 parts by weight to about 30 parts by weight, and more specifically about 5 parts by weight based on 100 parts by weight of the total amount of siloxane resin in which the first and second siloxane resins are combined. To about 30 parts by weight. In the above range, the flexibility and hardness of the coating layer of the window film can be increased.
  • the initiator is for curing the siloxane resin and the crosslinking agent, one or more of a photocationic initiator, an optical radical initiator may be used.
  • Photocationic initiators can be used those commonly known to those skilled in the art. Specifically, onium salts containing cations and anions can be used.
  • diphenyl iodonium 4-methoxy diphenyl iodonium, bis (4-methylphenyl) iodonium, bis (4-tert- butylphenyl) iodonium, bis (dodecylphenyl) iodonium, (4- Triaryl sulfoniums, such as diaryl iodonium, such as methylphenyl) [4- (2-methylpropyl) phenyl] iodonium, triphenylsulfonium, and diphenyl-4-thiophenoxy phenylsulfonium, bis [4- (Diphenyl sulfonio) phenyl] sulfide etc.
  • the anion include hexafluorophosphate, tetrafluoroborate, hexafluoroantimonate, hexafluoroarsenate, hexachloroantimonate, and the like.
  • the initiator may be included in an amount of about 0.1 parts by weight to about 20 parts by weight, specifically about 0.5 parts by weight to about 10 parts by weight, based on 100 parts by weight of the total amount of the siloxane resin in which the first and second siloxane resins are combined. In the above range, the siloxane resin can be sufficiently cured and the transparency of the window film can be prevented from decreasing with the remaining amount of initiator.
  • composition for a window film according to the present invention may further comprise nanoparticles, if necessary.
  • the nanoparticles are for further improving the hardness of the window film, and may include, for example, one or more of silica, aluminum oxide, zirconium oxide, and titanium oxide, but are not limited thereto.
  • the nanoparticles may be surface treated with at least a portion of a surface of a silicon compound for mixing with the siloxane resin.
  • the nanoparticles may have a shape of spherical, plate-like, amorphous, etc., the average particle diameter may be about 1nm to about 200nm, specifically about 10nm to about 50nm, but is not limited thereto.
  • the nanoparticles may be included in an amount of about 0.1 parts by weight to about 60 parts by weight, specifically about 10 parts by weight to about 50 parts by weight, based on 100 parts by weight of the siloxane resin in which the first and second siloxane resins are combined. It is possible to increase the hardness of the window film without affecting the surface roughness and transparency of the window film in the average particle diameter and content range.
  • the composition for a window film according to the present invention may further include an additive.
  • the additive may provide additional functionality to the window film.
  • the additives may include additives that are typically added to the window film.
  • the additive may include one or more of a UV absorber, a reaction inhibitor, an adhesion enhancer, a thixotropic imparting agent, a conductivity imparting agent, a color regulator, a stabilizer, an antistatic agent, an antioxidant, and a leveling agent, but is not limited thereto.
  • the reaction inhibitor may include ethynylcyclohexane.
  • An adhesion promoter may include a silane compound having an epoxy or alkoxysilyl group.
  • the thixotropic agent may include fumed silica and the like.
  • the conductivity providing agent may include metal powder such as silver and copper aluminum.
  • Dye control agents may include pigments, dyes and the like.
  • the UV absorber can increase the light resistance of the window film. UV absorbers can be used conventional absorbents known to those skilled in the art.
  • the additive may be included in an amount of about 0.01 part by weight to about 5 parts by weight, specifically about 0.1 part by weight to about 2.5 parts by weight, based on 100 parts by weight of the total amount of the siloxane resin in which the first and second siloxane resins are combined. In the above range can improve the hardness and flexibility of the window film and implement the additive effect.
  • composition for a window film according to the present invention may further include a solvent in order to facilitate coatability, coatability or processability.
  • the solvent may include one or more of methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, but is not limited thereto.
  • FIG. 1 is a cross-sectional view of a window film according to an embodiment of the present invention.
  • the window film 100 includes a base layer 110 and a coating layer 120, the coating layer 120 is formed of the composition for the window film of the present invention described above Can be.
  • the base layer 110 supports the coating layer 120 and increases the mechanical strength of the window film 100, and may be formed of an optically transparent and flexible resin.
  • the resin may be a polyester resin including polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, and the like, polycarbonate resin, polyimide resin, polystyrene resin, polymethyl methacrylate, and the like. It may include one or more of a poly (meth) acrylate resin containing.
  • the substrate layer 110 may have a thickness of about 10 ⁇ m to about 200 ⁇ m, specifically about 30 ⁇ m to about 150 ⁇ m, and more specifically about 30 ⁇ m to about 100 ⁇ m. It can be used for the window film in the above range.
  • the base layer 110 may be attached on the display unit, the touch screen panel, or the polarizer by an adhesive layer.
  • the coating layer 120 is formed on the base layer 110 to protect the base layer 110 and the display unit, the touch screen panel or the polarizing plate, and cures the composition for a window film according to the present invention. It is formed by. Since the composition for window films is the same as what was demonstrated above, the detailed description is abbreviate
  • the coating layer 120 has a thickness of about 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, Or 100 ⁇ m.
  • the coating layer 120 may have a thickness in a range of at least one of the above values and at most one of the above values.
  • the coating layer 120 may have a thickness of about 30 ⁇ m to about 100 ⁇ m, specifically about 30 ⁇ m to about 80 ⁇ m, and more specifically about 30 ⁇ m to about 60 ⁇ m.
  • another surface of the coating layer 120 may further include a functional surface layer such as an anti-reflection layer, an anti-glare layer, a hard coating layer, an antistatic layer, and the like.
  • a functional surface layer such as an anti-reflection layer, an anti-glare layer, a hard coating layer, an antistatic layer, and the like.
  • Figure 2 is a cross-sectional view of the window film according to another embodiment of the present invention.
  • a window film according to another embodiment of the present invention will be described with reference to FIG. 2.
  • the window film 200 includes a base layer 110, a coating layer 120 formed on one surface of the base layer 110, and an adhesive layer formed on the other surface of the base layer 110.
  • the coating layer 120 may be formed of a composition for a window film according to embodiments of the present invention.
  • the adhesive layer 130 is for attaching the window film 200 to a polarizing plate, a touch screen panel, or a display unit.
  • the pressure-sensitive adhesive layer 130 may be formed of, for example, a pressure-sensitive adhesive layer containing a pressure-sensitive resin such as (meth) acrylic resin, urethane resin, silicone resin, and / or epoxy resin, a curing agent, a photoinitiator, and a silane coupling agent. have.
  • the (meth) acrylic resin may be a (meth) acrylic copolymer having an alkyl group, a hydroxyl group, an aromatic group, a carboxylic acid group, an alicyclic group, a heteroalicyclic group, or the like, and may include a conventional (meth) acrylic copolymer.
  • the (meth) acrylic copolymer is a (meth) acrylic monomer having a C1 to C10 unsubstituted alkyl group, a (meth) acrylic monomer having a C1 to C10 alkyl group having at least one hydroxyl group, C6 to C20 At least one of a (meth) acrylic monomer having an aromatic group, a (meth) acrylic monomer having a carboxylic acid group, a (meth) acrylic monomer having a C3 to C20 alicyclic group, and a (meth) acrylic monomer having a C3 to C10 heteroalicyclic group It may be formed by polymerizing a monomer mixture comprising.
  • Bifunctional (meth) acrylates such as hexanediol diacrylate, as polyfunctional (meth) acrylate; Trifunctional (meth) acrylate of trimethylolpropane tri (meth) acrylate; Tetrafunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate; 5-functional (meth) acrylates such as dipentaerythritol penta (meth) acrylate; Six-functional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate may be used, but is not limited thereto.
  • the photoinitiator may include the photoradical initiator described above as a conventional photoinitiator.
  • the silane coupling agent may include a silane coupling agent having an epoxy group such as 3-glycidoxypropyltrimethoxysilane and the like.
  • the pressure-sensitive adhesive layer composition is 100 parts by weight of the (meth) acrylic resin, about 0.1 parts by weight to about 30 parts by weight of the curing agent, about 0.1 parts by weight to about 10 parts by weight of the photoinitiator, about 0.1 parts by weight to about 20 parts by weight of the silane coupling agent. It may include parts by weight.
  • the window film may be attached well on the display unit, the touch screen panel or the polarizing plate.
  • the adhesive layer 130 may have a thickness of about 10 ⁇ m to about 100 ⁇ m. In the above range, optical elements such as window films and polarizing plates may be adhered with sufficient adhesive force.
  • the window film according to the present invention as described above may be prepared by coating and curing the composition for a window film according to the present invention on the base layer 110.
  • the method of coating the composition for the window film on the base layer 110 is not particularly limited, and coating methods well known in the art, for example, bar coating, spin coating, dip coating, roll coating, flow coating, die Coating and the like can be used.
  • the curing of the composition for a window film may be performed by one or more methods of photo curing and thermal curing.
  • the light curing may be performed, for example, by irradiating the coated window film with light having a wavelength of about 400 nm or less with a light amount of about 10 mJ / cm 2 to about 1000 mJ / cm 2 .
  • the thermal curing may be performed by, for example, treating the coated window film composition at about 40 ° C. to about 200 ° C. for about 1 hour to about 30 hours, but is not limited thereto.
  • the composition for the window film is coated on the base layer 110 and then cured, the composition for the window film is dried and cured to prevent the surface roughness of the coating layer from being increased due to photocuring and thermal curing for a long time.
  • the drying may be performed at about 40 ° C. to about 200 ° C. for about 1 minute to about 30 hours, but is not limited thereto.
  • the window film 100 of the present invention as described above is optically transparent and can be used in a transparent display device.
  • the window film 100 may have a light transmittance of about 88% or more, specifically about 88% to about 100%, in a visible light region, specifically, about 400 nm to about 800 nm.
  • the window film 100 has an excellent surface hardness of the pencil hardness of about 7H or more, specifically about 7H to about 9H.
  • the window film 100 has a curl of about -10, -9, -8, -7, -6, -5, -4, -3, -2, -1, 0, +1, It can be +2, +3, +4, +5, +6, +7, +8, +9, +10 mm.
  • the window film 100 may have a curl in a range of at least one of the above values and at most one of the above values.
  • the window film 100 may have a curl of about ⁇ 10 mm to about +10 mm, specifically about ⁇ 8 mm to about +8 mm, and more specifically about ⁇ 6 mm to about +6 mm.
  • + and-indicate the direction in which the curl occurs + means that the convex form of the convex form occurs when the substrate layer is placed on the bottom surface,--may have the coating layer facing the bottom surface.
  • FIG. 3 is a cross-sectional view of a flexible display device according to an embodiment of the present invention
  • FIG. 4 is a cross-sectional view of an embodiment of the display unit of FIG. 3.
  • the flexible display device 300 may include a display unit 350a, an adhesive layer 360, a polarizer 370, a touch screen panel 380, and a window film 390.
  • the window film 390 may be a window film according to embodiments of the present invention.
  • the display unit 350a is for driving the flexible display device 300 and may include a substrate and an optical element formed on the substrate.
  • the optical device may be an OLED, an LED, or an LCD device, but is not limited thereto.
  • the display unit 350a may include a lower substrate 310, a thin film transistor 316, an organic light emitting diode 315, a planarization layer 314, a protective film 318, and an insulating film 317. Can be.
  • the lower substrate 310 supports the display unit 350a, and the thin film transistor 316 and the organic light emitting diode 315 may be formed on the lower substrate 310.
  • a flexible printed circuit board (FPCB) for driving the touch screen panel 380 may be formed on the lower substrate 310.
  • the flexible printed circuit board may further include a timing controller, a power supply, and the like for driving the organic light emitting diode array.
  • the lower substrate 310 may include a substrate formed of a flexible resin.
  • the lower substrate 310 may include a flexible substrate such as a silicon substrate, a polyimide substrate, a polycarbonate substrate, a polyacrylate substrate, but is not limited thereto. .
  • a plurality of pixel areas are defined by crossing a plurality of driving wires (not shown) and sensor wires (not shown), and the thin film transistor 316 and the thin film transistor 316 are defined for each pixel area.
  • the organic light emitting diode array including the organic light emitting diode 315 connected to the) may be formed.
  • a gate driver for applying an electrical signal to the driving line may be formed in the form of a gate in panel.
  • the gate-in panel circuit unit may be formed on one side or both sides of the display area.
  • the thin film transistor 316 controls the current flowing through the semiconductor by applying an electric field perpendicular to the current, and may be formed on the lower substrate 310.
  • the thin film transistor 316 may include a gate electrode 310a, a gate insulating layer 311, a semiconductor layer 312, a source electrode 313a, and a drain electrode 313b.
  • the thin film transistor 316 is an oxide thin film transistor using an oxide of indium gallium zinc oxide (IGZO), ZnO, or TiO as the semiconductor layer 312, an organic thin film transistor using an organic material as the semiconductor layer, and amorphous silicon as the semiconductor layer. It may be an amorphous silicon thin film transistor to be used, or a polycrystalline silicon thin film transistor to use polycrystalline silicon as a semiconductor layer.
  • the planarization layer 314 may cover the thin film transistor 316 and the circuit portion 310b to planarize the top surfaces of the thin film transistor 316 and the circuit portion 310b so that the organic light emitting diode 315 may be formed.
  • the planarization layer 314 may be formed of a spin-on-glass (SOG) film, a polyimide polymer, a polyacrylic polymer, or the like, but is not limited thereto.
  • the organic light emitting diode 315 implements a display by emitting light by itself, and may include a first electrode 315a, an organic light emitting layer 315b, and a second electrode 315c which are sequentially stacked. Adjacent organic light emitting diodes may be distinguished through the insulating layer 317.
  • the organic light emitting diode 315 may include a bottom light emitting structure in which light generated in the organic light emitting layer 315b is emitted through the lower substrate, or a top light emitting structure in which light generated in the organic light emitting layer 315b is emitted upward.
  • the passivation layer 318 may cover the organic light emitting diode 315 to protect the organic light emitting diode 315.
  • the passivation layer 318 may be formed of an inorganic material such as SiOx, SiNx, SiC, SiON, SiONC, and amorphous carbon (aC). It may be formed of an organic material such as meth) acrylate, epoxy polymer, imide polymer and the like.
  • the passivation layer 318 may include an encapsulation layer in which a layer formed of an inorganic material and a layer formed of an organic material are sequentially stacked one or more times.
  • the adhesive layer 360 adheres the display unit 350a and the polarizing plate 370, and is formed of an adhesive composition including a (meth) acrylate-based resin, a curing agent, an initiator, and a silane coupling agent. Can be.
  • the polarizer 370 may implement polarization of internal light or prevent reflection of external light to implement a display or increase a contrast ratio of the display.
  • the polarizing plate may be composed of a polarizer alone.
  • the polarizer may include a polarizer and a protective film formed on one or both sides of the polarizer.
  • the polarizing plate may include a polarizer and a protective coating layer formed on one or both surfaces of the polarizer.
  • the polarizer, the protective film, and the protective coating layer may use a conventional one known to those skilled in the art.
  • the touch screen panel 380 detects a change in capacitance generated when a human body or a conductor such as a stylus touches to generate an electrical signal.
  • the display unit 350a may be driven by the signal.
  • the touch screen panel 380 is formed by patterning a flexible and conductive conductor, and may include a second sensor electrode formed between the first sensor electrode and the first sensor electrode to cross the first sensor electrode. have.
  • the conductor for the touch screen panel 380 may include, but is not limited to, metal nanowires, conductive polymers, carbon nanotubes, and the like.
  • the window film 390 may be formed on the outermost side of the flexible display device 300 to protect the display device.
  • an adhesive layer is further formed between the polarizing plate 370 and the touch screen panel 380 and / or between the touch screen panel 380 and the window film 390 to form a polarizing plate, a touch screen panel, and a window film. It can strengthen the bond between them.
  • the adhesive layer may be formed of an adhesive composition including a (meth) acrylate resin, a curing agent, an initiator, and a silane coupling agent.
  • a polarizer may be further formed below the display unit 350a to implement polarization of the internal light.
  • FIG. 5 is a cross-sectional view of a flexible display device according to another exemplary embodiment of the present invention.
  • the touch screen panel 380 is not directly formed on the window film 390.
  • 380 is substantially the same as a flexible display device according to an embodiment of the present invention except that it is formed.
  • the touch screen panel 380 may be formed together with the display 350a.
  • the display panel 350a may be thinner and brighter than the flexible display device according to the exemplary embodiment of the present invention, and thus may have good visibility.
  • the touch screen panel 380 may be formed by deposition, but is not limited thereto.
  • the adhesive layer is further formed to increase the mechanical strength of the display device.
  • a polarizing plate is further formed below the display unit 350a to induce polarization of internal light to improve a display image.
  • FIG. 6 is a cross-sectional view of a flexible display device according to still another embodiment of the present invention.
  • the flexible display apparatus 500 includes the display unit 350b, except that the polarizer 370 and the touch screen panel 380 are not included. Is substantially the same as a flexible display device according to an embodiment of the present invention.
  • the display unit 350b may include a substrate and an optical element including an LCD, an OLED, or an LED element formed on the substrate, and the display unit 350b may have a touch screen panel therein.
  • the flexible display window film of the present embodiments can be used in a non-flexible display device.
  • siloxane resin A prepared in Preparation Example 1 as siloxane resin and siloxane resin C prepared in Preparation Example 3 were mixed at a weight ratio of 5: 5.
  • a window film was prepared.
  • siloxane resin A prepared in Preparation Example 1 and siloxane resin C prepared in Preparation Example 3 were mixed with a siloxane resin in a weight ratio of 8: 2.
  • a window film was prepared.
  • siloxane resin B prepared in Preparation Example 2 and siloxane resin C prepared in Preparation Example 3 were mixed with a siloxane resin in a weight ratio of 5: 5.
  • a window film was prepared.
  • a window film was manufactured in the same manner as in Example 1 except that the siloxane resin C prepared in Preparation Example 3 was used alone as the siloxane resin.
  • a window film was manufactured in the same manner as in Example 1, except that siloxane resin A prepared in Preparation Example 1 was used alone as the siloxane resin.
  • a window film was manufactured in the same manner as in Example 1 except for using the siloxane resin B prepared in Preparation Example 2 alone as the siloxane resin.
  • compositions of the window films used in Examples 1 to 4 and Comparative Examples 1 to 3 are shown in Table 1 below.
  • Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Siloxane resin A 20 50 80 - - 100 - B - - - 50 - - 100 C 80 50 20 50 100 - - Crosslinking agent 10 10 10 10 10 10 10 Initiator 3 3 3 3 3 3 3 3 3
  • Pencil hardness and curling properties of the window film prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were measured according to the following physical property measurement method. The measurement results are shown in the following [Table 2].
  • Pencil hardness to prepare a specimen by cutting the window film prepared in the above Examples and Comparative Examples in a size of 50mm horizontal, 50mm vertical, and paste the edge of the specimen using 3M tape on a 2T thick soda-lime glass substrate give. Then, the coating layer hardness at the center side without the 3M tape of the specimen was measured using a SHINTO Scientfic company's HEIDON-14EW instrument. In measuring the pencil hardness, a pencil of 6B to 9H manufactured by Mitsubishi Corporation was used. The load of the pencil on the coating layer was 1 kg, the angle at which the pencil was drawn was 45 °, and the speed at which the pencil was drawn was 60 mm / min. If the scratch occurs more than one time to evaluate five times, the pencil hardness is measured using the pencil of the step below, the five times the five times the maximum pencil hardness value when there is no scratch.
  • the window films of Examples 1 to 4 using the hard type siloxane resin and the soft type siloxane resin mixed were excellent in pencil hardness of 7H or more and low in curling of 10mm or less. have.
  • the window films of Examples 1 to 4 have better pencil hardness than the window films of Comparative Examples 2 and 3 using the hard type siloxane resin alone.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)

Abstract

L'invention concerne une composition pour film de fenêtre, qui comprend une première résine de siloxane représentée par la formule chimique 1 ou la formule chimique 2, et une seconde résine de siloxane représentée par la formule chimique 3. Elle concerne un film de fenêtre formé à partir de la composition; et un dispositif d'affichage souple comprenant la composition.
PCT/KR2016/012362 2016-06-15 2016-10-31 Composition pour film de fenêtre, film de fenêtre formé à partir de celle-ci, et dispositif d'affichage souple comprenant la composition WO2017217609A1 (fr)

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KR1020160074779A KR101908186B1 (ko) 2016-06-15 2016-06-15 윈도우 필름용 조성물, 이로부터 형성된 윈도우 필름 및 이를 포함하는 플렉시블 디스플레이 장치
KR10-2016-0074779 2016-06-15

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CN116234885A (zh) * 2020-11-19 2023-06-06 株式会社Lg化学 用于柔性显示装置的覆盖窗和柔性显示装置

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KR102133772B1 (ko) * 2018-11-30 2020-07-14 한국생산기술연구원 수지 조성물 및 이를 이용해 제조된 필름

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JP2012214753A (ja) * 2011-03-30 2012-11-08 Daikin Industries Ltd 硬化性樹脂組成物、及び、硬化物
JP2014069554A (ja) * 2012-10-02 2014-04-21 Fujifilm Corp 積層フィルム、光学積層フィルム、および表示装置
JP2014091256A (ja) * 2012-11-02 2014-05-19 Sharp Corp 保護板及び表示装置
JP2014176988A (ja) * 2013-03-14 2014-09-25 Fujifilm Corp 積層フィルムおよび表示装置
KR20160066679A (ko) * 2014-12-02 2016-06-13 삼성에스디아이 주식회사 윈도우 필름용 조성물, 이로부터 형성된 플렉시블 윈도우 필름 및 이를 포함하는 플렉시블 디스플레이 장치

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JP2012214753A (ja) * 2011-03-30 2012-11-08 Daikin Industries Ltd 硬化性樹脂組成物、及び、硬化物
JP2014069554A (ja) * 2012-10-02 2014-04-21 Fujifilm Corp 積層フィルム、光学積層フィルム、および表示装置
JP2014091256A (ja) * 2012-11-02 2014-05-19 Sharp Corp 保護板及び表示装置
JP2014176988A (ja) * 2013-03-14 2014-09-25 Fujifilm Corp 積層フィルムおよび表示装置
KR20160066679A (ko) * 2014-12-02 2016-06-13 삼성에스디아이 주식회사 윈도우 필름용 조성물, 이로부터 형성된 플렉시블 윈도우 필름 및 이를 포함하는 플렉시블 디스플레이 장치

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Publication number Priority date Publication date Assignee Title
CN116234885A (zh) * 2020-11-19 2023-06-06 株式会社Lg化学 用于柔性显示装置的覆盖窗和柔性显示装置
CN116234885B (zh) * 2020-11-19 2024-03-12 株式会社Lg化学 用于柔性显示装置的覆盖窗和柔性显示装置

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