KR102404134B1 - Cover window plate - Google Patents

Abstract

The present invention relates to a cover window substrate, and more particularly, to a polymer base film; and an organic layer and an inorganic layer laminated on one side of the polymer base film, and since the organic layer is thicker than the inorganic layer, excellent hardness can be implemented even with a thin film, and thus, it can be applied to a thin film lightweight image display device It relates to a cover window substrate capable of simultaneously exhibiting high hardness and excellent flexibility.

Description

Cover window board {COVER WINDOW PLATE}

The present invention relates to a cover window substrate.

Recently, various display devices have a window cover for display protection on the display panel to protect the display panel from scratches or external impact, and in most cases, tempered glass for display is used as the window cover. Tempered glass for display is thinner than general glass, but it has high strength and is strong against scratches.

However, tempered glass has a disadvantage that it is not suitable for reducing the weight of portable devices due to its heavy weight, and it is difficult to implement an unbreakable property because it is vulnerable to external shocks, and it is not bent over a certain level and is bendable. It is not suitable as a flexible display material having a foldable function.

In recent years, various studies have been conducted on optical plastic covers having strength or scratch resistance corresponding to tempered glass while securing flexibility and impact resistance. In general, there are polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), etc. as a transparent plastic cover material for optical use, which is more flexible than tempered glass. However, in the case of these polymer plastic substrates, compared to tempered glass used as a window cover for display protection, not only exhibit insufficient physical properties in terms of hardness and scratch resistance, but also insufficient impact resistance. Therefore, various attempts are being made to supplement the physical properties required by coating the composite resin composition on these plastic substrates.

In the case of a general hard coating, a composition consisting of a resin containing a photocurable functional group such as (metha)acrylate or epoxy, a curing agent or a curing catalyst and other additives is used, and in particular, In the case of the composite resin, it can be used as a display protection window with improved hardness and scratch resistance by coating it on an optical plastic base film.

However, in the case of general (meth)acrylate or epoxy high-functional group photocurable composite resin, it is difficult to realize high hardness corresponding to tempered glass, and curling phenomenon due to shrinkage occurs greatly during curing, and flexibility is also There is a disadvantage in that it is not sufficient as a protective window substrate for application to a flexible display.

Korean Patent Application Laid-Open No. 2013-74167 discloses a plastic substrate.

Korea Patent Publication No. 2013-74167

An object of the present invention is to provide a cover window substrate capable of simultaneously implementing high hardness and excellent flexibility.

An object of the present invention is to provide a thin and lightweight cover window substrate.

An object of the present invention is to provide an image display device including the cover window substrate.

1. Polymer base film; and an organic layer and an inorganic layer laminated on one side of the polymer base film;

wherein the organic layer is thicker than the inorganic layer.

2. The cover window substrate according to 1 above, wherein a thickness ratio of the organic layer and the inorganic layer is 1: 0.05 to 0.5.

3. The cover window substrate according to the above 1, wherein the organic layer is formed of a composition for forming an organic layer including an acrylic polymerizable compound, a photoinitiator, and a solvent.

4. The cover window substrate according to the above 1, wherein the organic layer is formed of a composition for forming an organic layer comprising a polyfunctional (meth)acryl alkoxy silane oligomer represented by the following formula (1):

[Formula 1]

(Wherein, R ₁ and R ₂ are the same as or different from each other, and each independently represents a C1 to C10 aliphatic or aromatic hydrocarbon, R ₃ is a C1 to C15 aliphatic or aromatic hydrocarbon, and R ₄ is a C3 to C50 aliphatic or aromatic hydrocarbon. Hydrocarbon or a functional group derived from a polyol having at least one molecular structure selected from the group consisting of polyether, polyester, polyolefin, polyacrylate and polycarbonate, Y is an acrylate group or a methacrylate group, and m is an integer from 1 to 3, and n is an integer from 3 to 21).

5. In the above 1, the organic layer is a composition for forming an organic layer comprising a polyfunctional (meth)acrylate (A) having an ethylene glycol group and a polyfunctional urethane (meth)acrylate (B) having a cyclohexyl group. formed, the cover window substrate.

6. The cover window substrate according to the above 1, wherein the inorganic layer is formed of an inorganic material including silicon, silicon oxide and silicon carbide.

7. The cover window substrate according to the above 6, wherein the inorganic material has a ratio of silicon carbide bonds to 30 to 60% of the total bonds.

8. The cover window substrate according to 1 above, further comprising a primer layer comprising a compound represented by the following formula (8) between the organic layer and the inorganic layer:

[Formula 8]

(Wherein, R ₁ and R ₃ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms,

R ₂ is a functional group represented by the following Chemical Formula 9 or 10)

[Formula 9]

(Wherein, R ₄ is an alkylene group having 1 to 6 carbon atoms, and R ₅ is hydrogen or an alkyl group having 1 to 6 carbon atoms)

[Formula 10]

(Wherein, R ₆ is an alkylene group having 1 to 6 carbon atoms).

9. The cover window substrate according to 1 above, which is laminated in this order of the polymer base film, the inorganic layer, and the organic layer, and further comprises a primer layer comprising a compound represented by the following formula (8) between the polymer base film and the inorganic layer:

[Formula 8]

(Wherein, R ₁ and R ₃ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms,

R ₂ is a functional group represented by the following Chemical Formula 9 or 10)

[Formula 9]

(Wherein, R ₄ is an alkylene group having 1 to 6 carbon atoms, and R ₅ is hydrogen or an alkyl group having 1 to 6 carbon atoms)

[Formula 10]

(Wherein, R ₆ is an alkylene group having 1 to 6 carbon atoms).

10. The cover window substrate according to 1 above, comprising a plurality of organic layers and inorganic layers alternately stacked on one side of the polymer base film.

11. The cover window substrate according to 1 above, further comprising at least one of an organic layer and an inorganic layer on the other side of the polymer base film.

12. The cover window substrate according to the above 1, further comprising an anti-fingerprint layer on the outermost side of the one side of the polymer base film.

13. Polymer based film; and a plurality of organic and inorganic layers alternately stacked on one side of the polymer substrate film;

The thickness ratio of the organic layer and the inorganic layer is 1: 0.05 to 0.5, the cover window substrate.

14. In the above 13, the organic layer is formed of a composition for forming an organic layer comprising a polyfunctional (meth)acryl alkoxy silane oligomer represented by the following formula (1),

The inorganic layer includes silicon, silicon oxide and silicon carbide, and the ratio of silicon carbide bonds is 30 to 60% of the total bonds.

[Formula 1]

(Wherein, R ₁ and R ₂ are the same as or different from each other, and each independently represents a C1 to C10 aliphatic or aromatic hydrocarbon, R ₃ is a C1 to C15 aliphatic or aromatic hydrocarbon, and R ₄ is a C3 to C50 aliphatic or aromatic hydrocarbon. Hydrocarbon or a functional group derived from a polyol having at least one molecular structure selected from the group consisting of polyether, polyester, polyolefin, polyacrylate and polycarbonate, Y is an acrylate group or a methacrylate group, and m is an integer from 1 to 3, and n is an integer from 3 to 21).

15. In the above 13, the organic layer is formed of a composition for forming an organic layer comprising a polyfunctional (meth)acrylate (A) having an ethylene glycol group and a polyfunctional urethane (meth)acrylate (B) having a cyclohexyl group will,

The inorganic layer includes silicon, silicon oxide and silicon carbide, and the ratio of silicon carbide bonds is 30 to 60% of the total bonds.

The cover window substrate of the present invention can realize high hardness and excellent flexibility at the same time. Accordingly, it can be preferably applied to a flexible display device.

The present invention is a polymer base film; and an organic layer and an inorganic layer laminated on one side of the polymer substrate film, wherein the organic layer is thicker than the inorganic layer, thereby realizing high hardness and excellent flexibility at the same time, a cover window that can be preferably applied to a flexible display device It's about the board.

Hereinafter, the present invention will be described in detail.

The cover window substrate of the present invention includes a polymer-based film; and an organic layer and an inorganic layer laminated on one side of the polymer base film.

The polymer substrate film serves as a substrate in the cover window substrate of the present invention.

The material of the polymer base film is not particularly limited as long as it has transparency and appropriate strength, for example, a cycloolefin-based derivative having a unit of a monomer containing a cycloolefin such as norbornene or a polycyclic norbornene-based monomer; Cellulose selected from acetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, isobutyl ester cellulose, propionyl cellulose, butyryl cellulose or acetyl propionyl cellulose, ethylene-vinyl acetate copolymer, polyester, polystyrene, polyamide, poly Etherimide, polyacrylic, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone , polyether sulfone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, and epoxy.

The thickness of the polymer base film is not particularly limited, and may be, for example, 1 to 100 µm, preferably 10 to 80 µm. If the thickness of the polymer base film is less than 1 μm, it may be difficult to realize sufficient hardness and impact resistance of the cover window substrate. If it exceeds 100 μm, the film is excessively thick and an anvil effect may occur during pressurization, and Reducing weight can be difficult.

The cover window substrate of the present invention includes an organic layer and an inorganic layer laminated on one side of the polymer base film.

A typical cover window substrate includes a thick organic/inorganic hybrid layer on a polymer base film to realize high hardness. However, in the case of the organic/inorganic hybrid layer, when it is formed as a thick film to realize hardness, a crystalline structure is usually generated, and cracks may occur when repetitive bending fatigue is applied. Therefore, the cover window substrate including the same has a problem in that it is difficult to be applied to a flexible display device.

However, the cover window substrate of the present invention includes an organic layer and an inorganic layer without using an organic/inorganic hybrid layer.

When the organic layer and the inorganic layer are laminated on one side of the polymer base film as in the present invention, since two different layers are laminated, the crystal growth directions of each layer are different, so that the propagation of cracks is reduced. In addition, since both compressive stress and tensile stress exist, the stress may be offset. Accordingly, it has excellent flexibility and can be preferably applied to a flexible display device.

The stacking order of the organic layer and the inorganic layer is not particularly limited, and may be stacked in the order of the polymer base film, the organic layer, and the inorganic layer, or may be stacked in the order of the polymer base film, the inorganic layer, and the inorganic layer.

The organic layer may be formed by coating and curing a composition for forming an organic layer on a polymer base film or an inorganic layer.

As the composition for forming the organic layer, any composition known in the art may be used without limitation, and may include, for example, an acrylic polymerizable compound, a photoinitiator, a solvent, and the like.

As the acrylic polymerizable compound, (meth)acrylate-based monomers, oligomers, and the like known in the art may be used without limitation.

The (meth)acrylate-based monomer can be polymerized by ultraviolet light, and serves to impart durability to the film, maintain viscoelasticity, and improve the coatability of the composition by controlling the viscosity.

As the (meth)acrylate-based monomer, 1 to 6-functional acrylic monomer may be used, and specific examples thereof include ethyl acrylate, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, butyl acrylate, iso Butyl acrylate, allyl methacrylate, 2-ethoxyethyl (meth) acrylate, isodecyl (meth) acrylate, 2-dodecyl thioethyl methacrylate, octyl acrylate, isooctyl acrylate, 2-meth Toxyethyl acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth)

Acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, isodexyl (meth) acrylate, stearyl (meth) acrylate, tetrafurfuryl (meth) acrylate, phenoxyethyl (meth) ) Monofunctional monomers, such as acrylate, octadecyl methacrylate, isobornyl (meth)acrylate, tetrahydrofuryl acrylate, and acryloylmorpholine; 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, bisphenol A-ethylene Glycol diacrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) Acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphoric acid Di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, di(acryloxyethyl)isocyanurate, allylated cyclohexyldi(meth)acrylate, dimethyloldi bifunctional monomers such as cyclopentane diacrylate, ethylene oxide-modified hexahydrophthalic acid diacrylate, tricyclodecane dimethanol acrylate, neopentyl glycol-modified trimethylolpropane diacrylate, and adamantane diacrylate; Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane Trifunctional monomers such as tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, and glycerol tri(meth)acrylate ; tetrafunctional monomers such as diglycerin tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate; 5-functional monomers, such as dipentaerythritol penta (meth)acrylate; 6 functional monomers, such as dipentaerythritol hexa (meth)acrylate; and the like may be used, and preferably 3 to 6 functional monomers may be used. These can be used individually or in mixture of 2 or more types.

The (meth)acrylate-based monomer is used in an amount of 5 to 40% by weight, preferably 15 to 30% by weight within 100% by weight of the total photocurable coating composition. If the content is less than the above range, there is a risk that the curing rate is low or the storage elastic modulus is too low to cause cohesive failure. Adjust it appropriately and use it.

A (meth)acrylate-based oligomer is a material that can be cured by ultraviolet light. It is preferred that three or more (meth)acrylic functional groups are used, but an ultraviolet curable type containing monofunctional or bifunctional (meth)acrylic functional groups depending on the characteristics after curing. It is an oligomer.

The oligomer has a weight average molecular weight (Mw) of 1,000 to 40,000, preferably 1,000 to 35,000.

These polyfunctional (meth)acrylate oligomers are commercially available epoxy (meth)acrylate oligomers, urethane (meth)acrylate oligomers, polyester (meth)acrylates, melamine (meth)acrylate oligomers, and combinations thereof. One selected from the group consisting of is possible, and preferably selected from the urethane (meth) acrylate group is advantageous in imparting mechanical properties and flexibility.

The polyfunctional (meth)acrylate oligomer is used in an amount of 10 to 50% by weight, preferably 15 to 40% by weight, in 100% by weight of the total photocurable coating composition as a solid content. If the content is less than the above range, it is difficult to sufficiently implement mechanical properties by UV curing. On the contrary, if the content exceeds the above range, the viscosity of the composition is high and there is a high possibility that an appearance defect occurs. do.

The acrylic polymerizable compound according to the present invention may further include a polyfunctional (meth)acrylic alkoxy silane oligomer.

The polyfunctional (meth)acryl alkoxy silane oligomer according to the present invention may be represented by the following Chemical Formula 1:

[Formula 1]

(Wherein, R ₁ and R ₂ are the same as or different from each other, and each independently represents a C1 to C10 aliphatic or aromatic hydrocarbon, R ₃ is a C1 to C15 aliphatic or aromatic hydrocarbon, and R ₄ is a C3 to C50 aliphatic or aromatic hydrocarbon. Hydrocarbon or a functional group derived from a polyol having at least one molecular structure selected from the group consisting of polyether, polyester, polyolefin, polyacrylate and polycarbonate, Y is an acrylate group or a methacrylate group, and m is an integer from 1 to 3, and n is an integer from 3 to 21).

Preferably, R ₁ and R ₂ are the same as or different from each other, and each independently represents a C1 to C6 alkyl group, a C3 to C10 cycloalkyl group, a C6 to C10 aryl group, or a C3 to C8 N, O or S a heteroaryl group including, more preferably a C1 to C6 alkyl group, and most preferably a C1 to C4 alkyl group.

In addition, R ₃ is a C1 to C6 alkylene group, a C3 to C10 cycloalkylene group, a C6 to C10 arylene group, or a C3 to C8 heteroarylene group including N, O or S, more preferably C1 to C6 alkylene group, most preferably C1 to C4 alkylene group.

, 또는 폴리에테르, 폴리에스테르, 폴리올레핀, 폴리아크릴레이트 및 폴리카보네이트로 이루어진 군에서 선택된 1종 이상의 분자구조를 갖는 폴리올로부터 유래되고, 이때 q 및 r은 0 이상의 정수이고, X는 O, N 또는 S이다.R ₄ is represented by -R ₅ -R ₆ , wherein R ₅ is a C1 to C6 alkylene group, a C3 to C10 cycloalkylene group, a C6 to C10 arylene group, or C3 to C8 N, O or S It is a heteroarylene group including, R ₆ is

, or from a polyol having at least one molecular structure selected from the group consisting of polyether, polyester, polyolefin, polyacrylate and polycarbonate, wherein q and r are integers of 0 or more, and X is O, N or S to be.

The * mark of R ₆ means that Y is connected, and when q is 0, it means an oligomer having three (meth)acrylate functional groups.

이며, 이때 0≤q≤10이고, r은 0 또는 1이고, X는 O이다.Preferably, R ₅ is a C1 to C6 alkylene group, and R ₆ is

, where 0≤q≤10, r is 0 or 1, and X is O.

Y is an acrylate group or a methacrylate group.

The polyfunctional (meth)acryl alkoxysilane oligomer of Chemical Formula 1 is used in a urethane reaction between the alkoxysilane isocyanate compound represented by Chemical Formula 2 and the hydroxyl group-containing polyfunctional (meth)acrylate monomer represented by Chemical Formula 3 as shown in Scheme 1 below. can be manufactured by

[Scheme 1]

In the above formula, descriptions of R ₁ to R ₄ , Y, m, and n are the same as in the case of Formula 5.

In Scheme 1, an isocyanate group (NCO) present in the alkoxysilane isocyanate compound of Formula 2 and a hydroxyl group (OH) present in the polyfunctional (meth)acrylate monomer of Formula 3 react with a urethane bond (-NHC (=O) O-) is formed.

Any alkoxysilane isocyanate compound of Formula 2 may be used as long as it satisfies the above Formula, and is not particularly limited in the present invention. For example, it is possible to directly manufacture or purchase a commercially available one. Commercially available products include Shin-Etsu's KBE-9007 (3-isocyanatopropyl triethoxy silane), Momentive's A-link 25 (3-isocyanatopropyl triethoxy silane) A-link35 (3 -isocyanatopropyl trimethoxy silane) and the like can be used.

In addition, the hydroxyl group-containing polyfunctional (meth)acrylate monomer of Formula 3 may be used as long as it satisfies the above formula, and is not particularly limited in the present invention.

For example, the trifunctional monomer is pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, tris(2- There are hydroxyethyl) isocyanurate tri (meth) acrylate, and the tetrafunctional monomer can include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and the like, and a pentafunctional monomer As the dipentaerythritol penta (meth) acrylate is possible, the 6-functional monomer can be used dipentaerythritol hexa (meth) acrylate.

Commercially available products include M340, M600, PS4040, PS420, PS4500, PS460, PS4610, PS610, PS6300, PS643, SP1013, SP1106, SP1107, SP1114 (Miwon Specialty Chemicals), DPHA (Nippon Explosives), EBECRYL®- 436, EBECRYL®-450, EBECRYL®-586, EBECRYL®-657, EBECRYL®-810, EBECRYL®-830, EBECRYL®-811, EBECRYL®-812, EBECRYL®-870, EBECRYL®-871, EBECRYL®- Commercially introduced products such as 890, EBECRYL®-1657, and EBECRYL®-2870 (Cytec) can be used, but any compound containing a hydroxyl group and having 3 or more (meth)acrylates can be applied regardless.

In addition, the hydroxyl group-containing polyfunctional (meth)acrylate monomer of Formula 3 is a polyol in which Y is bonded to a polyol having at least one molecular structure selected from the group consisting of polyether, polyester, polyolefin, polyacrylate and polycarbonate. It may be an oligomer. Preferably, it may be a polyether polyol of polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol and polytetramethylene ether glycol. As the oligomer, those having a number average molecular weight of 500 to 2000 are used.

Such polyol oligomer can be prepared by a known method, for example, polyester polyol is prepared by reaction of a dicarboxylic acid with a polyhydric alcohol.

At this time, the dicarboxylic acid is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azeralic acid, sebric acid, dodecanedioric acid, phthalic acid, isophthalic acid, terephthalic acid , hydroginate phthalic acid and the like are possible.

Polyhydric alcohols having two or more hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, vicinaldiol, propanediol, butanediol, hexanediol, caprolactone-modified diol, glycerin, trimethylol Propane, pentaerythritol, dipentaerythritol, xylitol, sorbitol, mannitol and sucrose, polyethylene glycol, hyperbranched polyhydric alcohols, and the like are possible.

At this time, the hyper-branched polyhydric alcohol reacts with a polyhydric alcohol and a substance containing two or more alcohols and a carboxyl group in one molecule, for example, a monomer such as dimethylol propinoic acid, and depending on the number of alcohols, 1 to 2 It means that it is prepared by a tea reaction.

Scheme 1 can be prepared through a condensation reaction by dissolving it in a solvent in the presence of a catalyst.

The catalyst is not particularly limited in the present invention, and may be any catalyst known to effectively promote urethane formation. Representatively, examples of catalysts include tertiary amines, tin octoate (= tin 2-ethylhexanoate), copper naphthenate, cobalt naphthenate, zinc naphthenate, potassium acetate and lead 2-ethylhexanoate. is possible, and preferably a tertiary amine or tin octoate is used. The catalyst may be a mixture of two or more of the above compounds.

Tertiary amines are triethylenediamine, pentamethyldipropylenetriamine, tris(3-dimethylaminopropyl)amine, dimethylcyclohexylamine, methyldicyclohexylamine, N,N-dimethylethanolamine, dimethylaminopropylamine, N ,N,N",N"-tetramethyldipropylenetriamine, N,N-bis-(3-dimethylaminopropyl)-N-isopropanolamine, N-(3-dimethylaminopropyl)-N,N-di Isopropanolamine, 2-(2-dimethylaminoethoxy)ethanol, 2-[N-(dimethylaminoethyl)-N-methylamino]ethanol, trimethylamine, triethylamine, tributylamine, trioctylamine, diethyl cyclohexylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine (N-cocomorpholine), N-methyldiethanolamine; N,N-dimethylethanolamine, N,N'-bis(2-hydroxypropyl)piperazine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetra Methyl-1,3-propanediamine, 1,4-bis(2-hydroxypropyl)-2-methylpiperazine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, N-ethylhexamethylene Amine, N-ethylpiperidine, alpha-methylbenzyldimethylamine, dimethylhexadecylamine, dimethylcetylamine, bisdimethylaminoethyl ether, pentamethyldiethylenetriamine, permethylated polyamine, branched polyamine, 2-[N -(dimethylaminoethoxyethyl)-N-methylamino]ethanol, alkoxylated polyamine, imidazole-boron, aminopropyl-bis(aminoethyl)ether, 2-dimethylaminoethyl urea, N,N'-bis(2 -Dimethylaminoethyl)urea, N,N-bis(2-dimethylaminoethyl)urea, 3-dimethylaminopropyl urea, N,N'-bis(3-dimethylaminopropyl)urea, N,N'-bis( 3-Dimethylaminopropyl)urea, 1-(N-methyl-3-pyrrolidino)methyl urea, 1,3-bis(N-methyl-3-pyrrolidino)methyl urea, 3-piperidinopropyl urea , N,N'-bis(3-piperidinopropyl)urea, 2-piperidinoethyl urea, N,N'-bis(2-piperidinoethyl)urea, and the like.

The catalyst may be used in an amount of 10 to 500 ppm by weight in the total composition (based on 100 g).

The oligomer of formula 1 contains a polymerization inhibitor upon storage to avoid premature polymerization. Such polymerization inhibitors include, but are not limited to, phenothiazine, hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, p-benzoquinone, t-butyl hydroquinone, triphenyl stibine and o-nitrotoluene. does not The polymerization inhibitor may be a mixture of two or more of the above compounds. The polymerization inhibitor may preferably be used in an amount within 50 to 5,000 ppm by weight, preferably within 100 to 800 ppm by weight, based on the total weight of the corresponding reaction product.

In the case of the oligomer of Formula 1, there are up to three alkoxysilane groups, so it shows excellent adhesion regardless of the substrate such as glass or polymer film. In addition, it is possible to secure optical properties by forming a transparent coating film due to the polyfunctional (meth)acrylate group, and to secure excellent mechanical properties. Compared to the conventional photocurable resin including an acrylic oligomer using a silane coupling agent to improve adhesiveness, it is possible to obtain an adhesive improvement effect without using a silane coupling agent that causes deterioration of mechanical properties.

When the oligomer of Formula 1 is used in the photocurable coating composition, the content is limited in consideration of the above-mentioned adhesiveness, optical properties, and mechanical strength, and preferably 20 to 75% by weight of the total weight of the composition for forming an organic layer as a solid content, Preferably, it may be included in an amount of 30 to 60% by weight. If the content is less than 20% by weight, the physical properties, particularly adhesion, are insufficient, and the use of additives such as an additional adhesion enhancer is required. .

In another embodiment of the present invention, the composition for forming an organic layer according to the present invention is a polyfunctional (meth)acrylate (A) having an ethylene glycol group as an acrylic polymerizable compound and a polyfunctional urethane (meth) having a cyclohexyl group It may include an acrylate (B).

The polyfunctional (meth)acrylate (A) having an ethylene glycol group is a component that can control the crack characteristics and curl of the coated film by giving flexibility in the composition and controlling the curing density, and adding ethylene oxide to the polyhydric alcohol to obtain a polyfunctional alcohol having an ethylene glycol group, and it can be prepared by condensation reaction of (meth)acrylic acid with the polyfunctional alcohol.

The polyhydric alcohol may be specifically glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like, but is not limited thereto.

Specific examples of the polyfunctional (meth)acrylate (A) having an ethylene glycol group include trimethylolpropane (EO) ₃ tri (meth) acrylate, trimethylolpropane (EO) ₆ tri (meth) acrylate, trimethylol Propane (EO) ₉ tri (meth) acrylate, glycerin (EO) ₃ tri (meth) acrylate, glycerin (EO) ₆ tri (meth) acrylate, glycerin (EO) ₉ tri (meth) acrylate, pentaerythritol (EO) ₄ tetra (meth) acrylate, pentaerythritol (EO) ₈ tetra (meth) acrylate, pentaerythritol (EO) ₁₂ tetra (meth) acrylate, dipentaerythritol (EO) ₆ hexa (meth) acrylate , dipentaerythritol (EO) ₁₂ hexa (meth) acrylate, dipentaerythritol (EO) ₁₈ hexa (meth) acrylate, and the like.

The polyfunctional (meth)acrylate (A) having an ethylene glycol group may include at least one selected from the group consisting of compounds of Chemical Formulas 4 and 5 below.

[Formula 4]

[Formula 5]

The polyfunctional urethane (meth)acrylate (B) having a cyclohexyl group is a component for improving the mechanical properties of the film to be coated. Diisocyanate having a cyclohexyl group and polyfunctional (meth)acrylate having a hydroxyl group are condensed It can be prepared by reaction.

The diisocyanate having a cyclohexyl group may be specifically 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, etc., but is not limited thereto.

The polyfunctional (meth)acrylate having a hydroxyl group may be specifically trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc., but is not limited thereto. .

The polyfunctional urethane (meth)acrylate (B) having a cyclohexyl group may include at least one selected from the group consisting of compounds of Chemical Formulas 6 and 7 below.

[Formula 6]

[Formula 7]

The polyfunctional (meth)acrylate (A) having an ethylene glycol group and the polyfunctional urethane (meth)acrylate (B) having a cyclohexyl group may be included to satisfy Equation 1 below.

[Equation 1]

n < Y < 2 n

(wherein, Y is (number of (meth)acryl functional groups in A x weight ratio of A) + ((meth)arc in B

The number of reel functional groups x the weight ratio of B), n is the number of ethylene glycols in A x the weight ratio of A, and the weight ratio of A + B is 1).

When Equation 1 is satisfied, hardness and flexibility are excellent.

The polyfunctional (meth)acrylate (A) having an ethylene glycol group and the polyfunctional urethane (meth)acrylate (B) having a cyclohexyl group are 5 to 50% by weight of the total weight of the composition for forming an organic layer, preferably 10 to It may be included in 50% by weight. If the content is less than 5% by weight, the hardness may decrease, and if it is more than 50% by weight, the shrinkage of the organic layer may increase and curl or cracks may occur.

The photoinitiator may be used without limitation as long as it is used in the art. There are Type 1 photoinitiators, which generate radicals due to the decomposition of molecules due to differences in chemical structure or molecular bonding energy, and Type 2 photoinitiators, which coexist with tertiary amines, which are hydrogen recovery types. Specific examples of Type 1 photoinitiators include 4-phenoxydichloroacetphenone, 4-t-butyldichloroacetphenone, 4-t-butyltrichloroacetphenone, diethoxyacetphenone, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl Acetphenones, such as propan-1-one, 4-(2-hydroxyethoxy)-phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, benzoin, benzoinmethyl Benzoins, such as ether, benzoin ethyl ether, and benzyl dimethyl ketal, acylphosphine oxides, a titanocene compound, etc. are mentioned. Specific examples of Type 2 photoinitiators include benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl ether, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzol-4'-methyldiphenylsulfide, 3,3' -benzophenones such as methyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, and thioxanthone such as isopropylthioxanthone Oxanthone etc. are mentioned. Each of these may be used alone or in combination of two or more. In addition, the Type 1 photoinitiator and the Type 2 photoinitiator may be used alone or in combination.

The photoinitiator may be included in an amount of 0.1 to 20 wt%, preferably 1 to 10 wt%, based on the total weight of the composition for forming an organic layer. If it is less than 0.1% by weight, curing does not proceed sufficiently, making it difficult to implement mechanical properties or adhesion of the finally obtained coating film.

The solvent may be used without limitation as long as it is used in the art. Specifically, alcohol-based (methanol, ethanol, isopropanol, butanol, propylene glycol methoxy alcohol, etc.), ketone-based (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, etc.), acetate-based (methyl acetate, ethyl acetate, butyl acetate, propylene glycol methoxyacetate, etc.), cellosolve (methyl cellosolve, ethyl cellosolve, propyl cellosolve, etc.), hydrocarbon-based (normal hexane, normal heptane, benzene, toluene, xyl Ren et al.) and the like. Each of the above solvents may be used alone or in combination of two or more.

The solvent may be included in an amount of 10 to 80% by weight, preferably 30 to 60% by weight, based on the total weight of the composition for forming an organic layer. If it is less than 10% by weight, the viscosity is high and workability is poor, and if it is more than 80% by weight, it is difficult to adjust the thickness of the coating film, and there is a disadvantage in that the appearance is poor due to the occurrence of dry stains.

If necessary, the composition for forming an organic layer according to the present invention may further include inorganic nanoparticles to further improve mechanical properties.

The inorganic nanoparticles may have an average particle diameter of 1 to 100 nm, preferably 5 to 50 nm. These inorganic nanoparticles are uniformly formed in the coating film to improve mechanical properties such as abrasion resistance, scratch resistance, and pencil hardness. If the particle size is less than the above range, aggregation occurs in the composition and a uniform coating film cannot be formed and the above effect cannot be expected. Rather, a problem occurs in that mechanical properties are deteriorated.

The material of the inorganic nanoparticles may be a metal oxide, for example, Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, One selected from the group consisting of ZnO-Al, Nb ₂ O ₃ , SnO, MgO, and combinations thereof may be used, and preferably Al ₂ O ₃ , SiO ₂ , ZrO ₂ and the like may be used. The inorganic nanoparticles may be prepared directly or purchased commercially. Commercially available products may be used dispersed in an organic solvent at a concentration of 20 to 60% by weight.

The inorganic nanoparticles may be included in an amount of 10 to 60% by weight based on the total weight of the composition for forming an organic layer. If it is less than 10% by weight, mechanical properties such as abrasion resistance, scratch resistance, pencil hardness, etc. may not be sufficient, and if it is more than 60% by weight, it interferes with curability and, on the contrary, mechanical properties are deteriorated, and the appearance may be poor.

The composition for forming an organic layer includes, in addition to the above components, components commonly used in the art, for example, a leveling agent, a UV stabilizer, a heat stabilizer, an antioxidant, a UV absorber, a surfactant, a lubricant, an antifouling agent, and the like. may include

The inorganic layer may be formed of an inorganic material including silicon, silicon oxide (SiO _x (0<x≤4)) and silicon carbide. Preferably, the ratio of silicon carbide bonds may be 30 to 60% of the total bonds (Si, SiC, SiO _x , SiO ₂ ). If the bonding ratio of silicon carbide is less than 30% by weight, the effect of improving hardness may be reduced, and if it is more than 60% by weight, transmittance may be lowered, so that it may be difficult to use as a cover window substrate. The silicon carbide bonding ratio can be measured by X-ray photoelectron spectroscopy (XPS), which can be controlled by changing the vaporization amount of the precursor Si(CH ₃ ) ₄ and the ratio of O ₂ gas.

The inorganic layer may be a deposition layer formed by a chemical vapor deposition method or a physical vapor deposition method known in the art.

In the cover window substrate of the present invention, the organic layer is thicker than the inorganic layer.

The cover window substrate of the present invention includes an organic layer and an inorganic layer laminated on one side of the polymer base film. When the inorganic layer is thick, crystal grains may grow, which may decrease strength and flexibility. Therefore, since the organic layer is thicker than the inorganic layer, it is possible to suppress grain growth of the inorganic layer to improve strength and flexibility. In addition, when the inorganic layer becomes thick, the transmittance may decrease.

The thickness ratio is not particularly limited, and for example, the thickness ratio of the organic layer and the inorganic layer may be 1: 0.05 to 0.5. When the thickness of the inorganic layer is too thin and less than the above range, hardness may be reduced, and if too thick and exceeding the above range, crystal grains may grow and flexibility may be reduced.

The thickness of the organic layer and the inorganic layer is not particularly limited as long as the thickness ratio is satisfied. For example, the thickness of the organic layer may be 0.5 to 10 μm. The thickness of the inorganic layer may be, for example, 0.05 to 3 μm, preferably 0.05 to 1.5 μm, and more preferably 0.3 to 1.0 μm.

The cover window substrate of the present invention may further include a primer layer between the organic layer and the inorganic layer or between the polymer base film and the inorganic layer.

The primer layer enhances the adhesion between the organic layer and the inorganic layer, and between the polymer base film and the inorganic layer, thereby improving hardness and flexibility.

The primer layer may be formed by applying and curing a composition for forming a primer layer.

The composition for forming a primer layer may include a compound of Formula 8 below.

[Formula 8]

(Wherein, R ₁ and R ₃ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms,

R ₂ is a functional group represented by the following Chemical Formula 9 or 10)

[Formula 9]

(Wherein, R ₄ is an alkylene group having 1 to 6 carbon atoms, and R ₅ is hydrogen or an alkyl group having 1 to 6 carbon atoms)

[Formula 10]

(Wherein, R ₆ is an alkylene group having 1 to 6 carbon atoms).

In Chemical Formula 8, the hydroxyl group bonded to the silicon atom interacts with the functional group on the surface of the transparent inorganic layer, and the R ₂ group including the (meth)acrylate group or the epoxy group interacts with the organic functional group of the polymer base film or the organic layer. It improves the adhesion between the polymer base film and the inorganic layer, and the organic layer and the inorganic layer.

In the present invention, "(meth)acryl-" refers to "methacryl-", "acryl-", or both.

The composition for forming a primer layer may further include a solvent commonly used in the art.

Examples of the solvent include alcohols such as ethanol, n-propyl alcohol, isopropyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; and the like. These solvents can be used individually or in mixture of 2 or more types, respectively.

For the purpose of improving adhesion, an adhesive layer may be included in addition to the primer layer.

The adhesive layer may be formed by applying and curing an adhesive composition.

As the adhesive composition, photocurable adhesive compositions known in the art may be used without limitation. For example, it may be an adhesive composition comprising an epoxy-based photopolymerizable compound and a photocationic polymerization initiator.

The epoxy-based photopolymerizable compound is, for example, 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, vinylcyclohexenedioxide dicyclopentadiene dioxide, bisepoxycyclopentyl ether, bisphenol A-based epoxy compound , Bisphenol F-based epoxy compound, 1,4-cyclohexanedimethanol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl diglycidyl ether, Resorcinol diglycidyl ether, diethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, o-Cresyl glycidyl ether, and the like. These can be used individually or in mixture of 2 or more types.

Preferably, the adhesive composition according to the present invention may include a first epoxy compound having a glass transition temperature of 120° C. or higher of the homopolymer and a second epoxy compound having a glass transition temperature of 60° C. or lower of the homopolymer.

The first epoxy compound may be used without particular limitation as long as the glass transition temperature of the homopolymer is an epoxy compound of 120° C. or higher, for example, an alicyclic epoxy compound and/or an aromatic epoxy having a glass transition temperature of 120° C. or higher of the homopolymer. It can be used as the first epoxy compound of the invention. Specific examples of the epoxy compound having a glass transition temperature of the homopolymer of 120° C. or higher include 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide dicyclopentadiene dioxide, bisepoxycyclo Pentyl ether, a bisphenol A type|system|group epoxy compound, a bisphenol F type|system|group epoxy compound, etc. are mentioned. As for the first epoxy compound, it is more preferable that the homopolymer has a glass transition temperature of about 120°C to 200°C.

The second epoxy compound is, for example, 1,4-cyclohexanedimethanol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl diglycidyl ether , Resorcinol diglycidyl ether, diethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether dil ether, phenyl glycidyl ether, o-cresyl glycidyl ether, and the like. These can be used individually or in mixture of 2 or more types. As for the second epoxy compound, it is more preferable that the glass transition temperature of the homopolymer is about 0°C to 60°C.

The second epoxy compound is preferably included in an amount of 30 to 100 parts by weight based on 100 parts by weight of the first epoxy compound. When the content of the second epoxy compound exceeds 100 parts by weight, the glass transition temperature of the entire adhesive composition is lowered to lower heat resistance, and when it is less than 30 parts by weight, adhesive strength may be lowered.

More preferably, a weight ratio of the first epoxy compound and the second epoxy compound is about 1:1 to 3:1, more preferably, a weight ratio of 1: 1 to 2:1, and most preferably, the first epoxy compound and the second epoxy compound may be mixed and used in a weight ratio of 1:1. When the weight ratio of the first epoxy compound and the second epoxy compound satisfies the above range, it is possible to obtain the most desirable physical properties in terms of glass transition temperature and adhesive strength.

If necessary, the adhesive composition may further include an oxetane-based compound, a vinyl-based compound, etc. as the photopolymerizable compound, and may further include a radically polymerizable compound.

Examples of the radically polymerizable compound include (meth)acrylates, (meth)acrylamides, maleimides, (meth)acrylic acid, maleic acid, itaconic acid, (meth)acrylaldehyde, (meth)acryloylmorph. Pauline, N-vinyl-2-pyrrolidone, triallyl isocyanurate, etc. are mentioned.

A photocationic polymerization initiator is a compound that produces a cationic species or a Lewis acid by irradiation with an active energy ray, for example, an onium salt such as an aromatic diazonium salt, an aromatic iodine aluminum salt or an aromatic sulfonium salt, an iron-arene complex and the like, but is not limited thereto.

The photocationic polymerization initiator may be included, for example, in an amount of 0.5 to 20 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the first epoxy compound.

When the adhesive composition contains a radical polymerizable monomer, it is preferable to incorporate a radical photopolymerization initiator in order to accelerate the radical polymerizability and improve the curing rate.

As the radical photopolymerization initiator, for example, an acetophenone-based photopolymerization initiator, a benzoin ether-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, or a thioxanthone-based photopolymerization initiator may be used.

The radical photopolymerization initiator may be included, for example, in an amount of 0.5 to 20 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, based on the total weight of the composition.

In addition, the adhesive composition may further include a leveling agent, a photosensitizer, an antioxidant, an oligomer, an adhesion enhancer, and the like, if necessary.

The cover window substrate of the present invention may include a plurality of organic and inorganic layers alternately stacked on one side of the polymer base film. In such a case, since the thickness of each layer can be reduced, hardness and flexibility can be improved by suppressing grain growth, and the effect of improving flexibility due to stress offset can be maximized.

In addition, the cover window substrate of the present invention may further include at least one of an organic layer and an inorganic layer on the other side of the polymer base film. In such a case, it is possible to prevent the other side of the polymer base film from being deformed when pressed.

The cover window substrate of the present invention may further include a layer configuration known in the art in addition to. For example, a UV-blocking layer, an anti-fingerprint layer, etc. are mentioned. These layers have the effect of further improving hardness by reducing the friction coefficient in addition to basic functions such as UV protection and fingerprint protection. These layers may be included in the outermost surface of the one side of the polymer base film.

In addition, the present invention provides an image display device including the above-described cover window substrate.

The image display device including the cover window substrate may include a liquid crystal display device, an OLED, a flexible display, and the like, but is not limited thereto, and all image display devices known in the art that are applicable may be exemplified.

In addition, the image display apparatus of the present invention may further include a configuration known in the art in addition to the above configuration.

Hereinafter, preferred embodiments are presented to help the understanding of the present invention, but these examples are merely illustrative of the present invention and do not limit the appended claims, and are within the scope and spirit of the present invention. It is obvious to those skilled in the art that various changes and modifications are possible, and it is natural that such variations and modifications fall within the scope of the appended claims.

manufacturing example. Preparation of a composition for forming an organic layer

(1) Preparation of polyfunctional (meth)acryl alkoxy silane oligomer

A polyfunctional (meth)acryl alkoxy silane oligomer was prepared through the following Scheme 2:

[Scheme 2]

247 parts by weight of 3-isocyanatopropyl triethoxy silane (Shin-Etsu, KBE-9007), dipentaerythritol hexa/pentaacrylate mixture ( 1345 parts by weight of Nippon Pharmaceutical Co., Ltd. DPHA), 0.7 parts by weight of dibutyl tin dilaurate (Akemi, Fascat 4202), and 1.5 parts by weight of methoxy hydroquinone (Eastman, HQMME) were added and reacted at 60° C. for 5 hours. Oligomers were prepared.

At this time, the reaction was terminated when the isocyanate characteristic peak (2260cm ^-1 ) completely disappeared by measuring FT-IR.

The molecular weight of the obtained compound was 741 g/cm ³ as a result of measurement, and it was confirmed that amide stretch peaks of urethane were generated at 3400 cm ^-1 and 1190 cm ^-1 through FT-IR measurement. In addition, the viscosity of the completed oligomer was 9800 cps at 25 degrees.

(2) Preparation of a composition for forming an organic layer

A composition for forming an organic layer was prepared by mixing the components shown in Table 1 below, stirring with a high-speed stirrer, and defoaming with a rotational revolution degassing machine. At this time, a composition was prepared to have a concentration of 78% using a mixed solvent of MEK/IPA (methyl ethyl ketone/isopropyl alcohol, 2.5:1 volume ratio) as the solvent.

division Preparation Example 1 Polyfunctional (meth)acryl alkoxy silane oligomer Preparation Example (1) 23 Polyfunctional (meth)acrylate oligomers EB-1290
(SK Cytec) 45 (meth)acrylate monomer M300
(Miwon Specialty) 23 photoinitiator I-184 (BASF) 8 additive BYK-333 (BYK Chemisa) One

(3) Preparation of a composition for forming an organic layer

A composition for forming an organic layer having the composition and content (wt%) shown in Table 2 was prepared.

division Preparation 2 Acrylic photopolymerizable compound M-4004
(Miwon Specialty Chemical) 32 SOU-1700B
(Shinah T&C) 8 photoinitiator I-184
(BASF) 1.8 additive BYK-333 (BYK Chemisa) 0.2 solvent methyl ethyl ketone 38 Normal Butyl Acetate 20

Example 1

The composition for forming an organic layer of Preparation Example 1 was coated on both sides of a polyethylene naphthalate film having a thickness of 50 μm and photocured to form an organic layer having a thickness of 3 μm.

Next, an inorganic material layer having a thickness of 0.5 μm was formed on the organic layer by PE CVD using Si(CH ₃ ) ₄ as a precursor to prepare a cover window substrate.

Example 2

An organic layer, an inorganic layer, and an organic layer were sequentially laminated on the inorganic layer of the cover window substrate of Example 1 in the same manner.

And, 25% by weight of 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate having a glass transition temperature of 190 degrees on the inorganic layer on the inorganic layer to strengthen the adhesion of the organic layer on the upper portion of each inorganic layer (Dicel's) Celloxide 2021P), 25% by weight of 1,4-cyclohexane dimethanol diglycidyl ether having a glass transition temperature of 25 degrees of homopolymer, 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxy Methyl] oxetane (Toagosei Aaron oxetane DOX221) 50 wt% of a resin composition prepared by adding 5 parts by weight of CPI 100P (Sanapro) to 100 parts by weight of a resin composition prepared by adding 5 parts by weight of a cationic initiator CPI 100P (Sanapro Co.) An adhesive layer was formed.

Example 3

Substance AF-COAT® Fluid (W-880, W-550) containing a composition of MMT's PFPE Polyrimethylene oxide and Ethyl Nonafluoroisobutyl Ether on the outermost side of the one surface on which a plurality of organic and inorganic layers of the cover window substrate of Example 2 are laminated A cover window substrate was prepared in the same manner as in Example 2, except that the AF solution of the product was coated and dried at 80° C. for 30 minutes to further form an anti-fingerprint layer having a thickness of 0.02 nm.

Example 4

A cover window substrate was manufactured in the same manner as in Example 1, except that the thickness of the inorganic layer was 1.5 μm.

Example 5

A cover window substrate was manufactured in the same manner as in Example 1, except that the inorganic layer had a thickness of 1.7 μm.

Example 6

A cover window substrate was manufactured in the same manner as in Example 1, except that the thickness of the inorganic layer was 2 μm.

Example 7

A cover window substrate was prepared in the same manner as in Example 1, except that the composition for forming an organic layer of Preparation Example 2 was used.

Example 8

A cover window substrate was manufactured in the same manner as in Example 2, except that the silicon carbide bonding ratio of the inorganic layer was adjusted by changing the ratio of the vaporization amount of the precursor Si(CH ₃ ) ₄ and the O ₂ gas.

Example 9

A cover window substrate was manufactured in the same manner as in Example 2, except that the silicon carbide bonding ratio of the inorganic layer was adjusted by changing the ratio of the vaporization amount of the precursor Si(CH ₃ ) ₄ and the O ₂ gas.

Comparative Example 1

A cover window substrate was prepared by forming an organic layer having a thickness of 5 μm on one surface of the polymer base film in the same manner as in Example 1, and forming an organic layer having a thickness of 10 μm on the other surface.

Comparative Example 2

A cover window substrate was manufactured by forming an organic layer having a thickness of 5 μm on one surface of the polymer base film in the same manner as in Example 1, and forming an organic layer having a thickness of 3 μm on the other surface.

Comparative Example 3

A cover window substrate was prepared by forming an organic layer having a thickness of 3 μm on one surface of the polymer base film in the same manner as in Example 1.

Comparative Example 4

A cover window substrate was prepared by forming an inorganic layer having a thickness of 0.5 μm on both sides of the polymer substrate film in the same manner as in Example 1.

Comparative Example 5

A cover window substrate was manufactured in the same manner as in Example 1, except that the thickness of the organic layer and the inorganic layer was set to 0.5 μm.

Comparative Example 6

A cover window substrate was manufactured in the same manner as in Example 1, except that the thickness of the organic layer and the inorganic layer was set to 3 μm.

Comparative Example 7

A cover window substrate was prepared by forming an inorganic layer having a thickness of 0.5 μm on both sides of the polymer substrate film using PE CVD.

Experimental example

(1) Pencil hardness evaluation

The surface hardness of the obtained cover window substrate was measured. Surface hardness is measured using a Pencil Hardness Tester by bringing a Mitsu-Bish Pencil into contact with the board, and then placing a 1,000g weight on it to increase the load and speed of 50mm/sec to the board. The surface hardness was measured by scraping the surface of the and observing the surface. The measurement standard was evaluated on the basis of when the shape of the surface abrasion, peeling, tearing, or scratching was not observed at a level corresponding to the pencil hardness, and the results are shown in Table 2 below .

(2) Evaluation of crack occurrence for flexural fatigue (flexibility)

The cover window substrates manufactured in Examples and Comparative Examples were repeatedly subjected to bending fatigue in a U shape so that the bending radius R was 2 mm as shown in FIG. 2, and then observed with an optical microscope to observe whether cracks occurred, and cracks were observed. The number of times this occurred is shown in Table 2 below.

(3) Measurement of transmittance

Transmittance of the cover window substrates of Examples and Comparative Examples was measured. The transmittance was measured using a haze meter (HM-150, Murakami Corporation), and the results are shown in Table 2 below.

(4) Haze measurement

Haze of the cover window substrates of Examples and Comparative Examples was measured. Haze was measured using a haze meter (HM-150, Murakami Corporation), and the results are shown in Table 2 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Silicon carbide bonding ratio of inorganic layer 48% 48% 48% 48% 48% 48% 48% 35% 28% pencil
Hardness 4H 6H 7H 6H 6H 7H 4H 5H 4H curve
characteristic 2R 230,000 times 2R 200,000 times 2R 200,000 times 2R
180,000 times 2R
150,000 times 2R
130,000 times 2R
230,000 times 2R 200,000 times 2R 200,000 times transmittance 91.8% 91.2% 91.1% 90.8% 89.2% 88.9% 91.8% 92.1% 92.5% haze 0.6% 0.7% 0.8% 0.7% 0.8% 0.8% 0.9% 0.7% 0.8%

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Silicon carbide bonding ratio of inorganic layer - - - 48% 48% 48% 62% pencil
Hardness 4H 1H HB 2H 2H 8H 3H curve
characteristic 2R
160,000 times 2R
230,000 times 2R
230,000 times 2R 200,000 times 2R
250,000 times 2R
10,000 times 2R
200,000 times transmittance 91.3% 92.2% 92.4% 91.1% 92.1% 87.1% 88.3% haze 0.5% 0.6% 0.7% 0.6% 0.7% 0.9% 0.8%

Referring to Tables 3 and 4, it can be seen that the cover window substrate of the embodiment simultaneously exhibits excellent hardness and flexibility.

However, it can be seen that the cover window substrate of the comparative example has low hardness or low flexibility.

Claims (10)

polymer base film; and an organic layer and an inorganic layer laminated on one side of the polymer base film; and
A primer layer comprising a compound represented by the following formula (8),
The primer layer is formed between the organic layer and the inorganic layer, or is laminated in this order of the polymer base film, the inorganic layer, and the organic layer, and the primer layer is formed between the polymer base film and the inorganic layer,
The organic layer is formed of a composition for forming an organic layer comprising a polyfunctional (meth) acryl alkoxy silane oligomer represented by the following Chemical Formula 1, or has a polyfunctional (meth) acrylate (A) having an ethylene glycol group and a cyclohexyl group It is formed of a composition for forming an organic layer comprising a functional urethane (meth)acrylate (B),
wherein the organic layer is thicker than the inorganic layer;
[Formula 1]

(Wherein, R ₁ and R ₂ are the same as or different from each other, and each independently represents a C1 to C10 aliphatic or aromatic hydrocarbon, R ₃ is a C1 to C15 aliphatic or aromatic hydrocarbon, and R ₄ is a C3 to C50 aliphatic or aromatic hydrocarbon. Hydrocarbon or a functional group derived from a polyol having at least one molecular structure selected from the group consisting of polyether, polyester, polyolefin, polyacrylate and polycarbonate, Y is an acrylate group or a methacrylate group, and m is an integer from 1 to 3, and n is an integer from 3 to 21)
[Formula 8]

(Wherein, R ₁ and R ₃ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms,
R ₂ is a functional group represented by the following Chemical Formula 9 or 10)
[Formula 9]

(Wherein, R ₄ is an alkylene group having 1 to 6 carbon atoms, and R ₅ is hydrogen or an alkyl group having 1 to 6 carbon atoms)
[Formula 10]

(Wherein, R ₆ is an alkylene group having 1 to 6 carbon atoms).
The cover window substrate of claim 1 , wherein a thickness ratio of the organic layer and the inorganic layer is 1:0.05 to 0.5.
delete delete delete The cover window substrate of claim 1 , wherein the inorganic layer is formed from an inorganic material including silicon, silicon oxide, and silicon carbide.
The cover window substrate according to claim 6, wherein the ratio of the silicon carbide in the inorganic material is 30 to 60 wt%.
The cover window substrate according to claim 1, comprising a plurality of organic and inorganic layers alternately stacked on one side of the polymer base film.
The cover window substrate of claim 1, further comprising at least one of an organic layer and an inorganic layer on the other side of the polymer base film.
The cover window substrate according to claim 1, further comprising an anti-fingerprint layer on the outermost side of the one side of the polymer base film.