KR20220091369A - Optical laminate and flexible display device including the same - Google Patents

Abstract

The present invention includes a hard coating layer comprising polysiloxane, a primer layer and an anti-fingerprint layer comprising a fluorine-containing compound, and an optical laminate having a specific water contact angle change amount and friction coefficient change amount before and after a friction test is performed on the anti-fingerprint layer; and It relates to a flexible display device including the same.

Description

Optical laminate and flexible display device including the same

The present invention relates to an optical laminate and a flexible display device including the same.

Recently, with the development of mobile devices such as smartphones and tablet PCs, thinning and slimming of substrates for displays are required. Glass or tempered glass is generally used as a material having excellent mechanical properties for a window or a front panel for a display of such a mobile device. However, glass and tempered glass have their own heavy weight, which causes the mobile device to become heavy, and has a problem of being easily damaged by an external impact, and has low flexibility, so there is a limit to applying it to a flexible or foldable display device. In addition, antifouling properties have been imparted to a window or front panel for a display by coating an anti-fingerprint layer on glass, but there is a low limit in durability such as scratch resistance due to low adhesion between the glass and the anti-fingerprint layer.

Plastic resin is being researched as a material to replace such glass. Plastic resin is lightweight, less likely to break, and has flexibility, so it is more suitable for weight reduction and flexibility of mobile devices. Typical examples include polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), polyacrylate (PAR), polycarbonate (PC), polyimide (PI), and polyamideimide (PAI). However, in the case of a substrate using these plastic resins, there is a problem in that hardness and scratch resistance are insufficient compared to the glass material. Accordingly, methods for supplementing high hardness and abrasion resistance by coating a resin composition on a plastic resin substrate to form a hard coating layer have been tried.

For example, an acrylate-based resin capable of UV curing is mainly used for hard coating on a foldable display substrate. However, the acrylate-based resin has a high shrinkage rate upon curing, and as a result, severe curvature occurs, so it should be processed as a thin coating, which has a low impact resistance limit.

In addition, although an anti-fingerprint additive is added to the resin composition for the hard coating layer to impart antifouling properties to a display window or front panel, since the hardness and antifouling properties of the coating layer are in a trade-off relationship, these two properties It is necessary to secure a technology that satisfies all of them.

The present invention has excellent antifouling and high hardness properties, and improved adhesion and scratch resistance, and can replace a tempered glass cover window. Provided is an optical laminate that can be easily applied to a flexible, rollable, or foldable mobile device or a display device.

In addition, the present invention provides a flexible display device including the optical laminate.

In the present specification, a hard coating layer comprising polysiloxane; primer layer; and an anti-fingerprint layer comprising a fluorine-containing compound, wherein the water contact angle with respect to the surface of the anti-fingerprint layer is 100° or more, and before and after 1000 reciprocations with steel wool at a load of 500 g with respect to the surface of the anti-fingerprint layer, the surface of the anti-fingerprint layer The amount of change in the water contact angle of the anti-fingerprint layer is 10° or less, and the amount of change in the friction coefficient of the anti-fingerprint layer surface is 0.2 or less before and after 1000 reciprocations with steel wool under a 500 g load with respect to the anti-fingerprint layer.

In addition, the present specification provides a flexible display device including the optical laminate.

Hereinafter, an optical laminate according to a specific embodiment of the present invention and a flexible display device including the same will be described in more detail.

As used herein, "flexible" means a state having a degree of flexibility that does not cause cracks with a length of 3 mm or more when wound on a cylindrical mandrel having a diameter of 3 mm, and thus , The optical laminate may be applied as a cover film of a bendable, flexible, rollable, or foldable display.

In addition, in this specification, "(meth)acrylate" is meant to include both acrylates and methacrylates.

In addition, in this specification, "(meth)acryloxy group" is meant to include both an acryloxy group or a methacryloxy group.

In addition, as used herein, the term “fluorine-containing compound” refers to a compound in which one or more fluorine atoms (F) are included in the compound.

In addition, in this specification, "organosilane compound" or "modified silane compound" is meant to further include not only the organosilane compound, but also a partial hydrolysis-condensation product of the organosilane compound.

In addition, in this specification, curing is meant to include both photocuring and thermal photocuring.

In this specification, the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the polystyrene equivalent weight average molecular weight measured by the GPC method, a commonly known analyzer, a detector such as a differential refraction detector, and a column for analysis may be used, and the temperature at which it is normally applied Conditions, solvents, and flow rates can be applied. As a specific example of the measurement conditions, the evaluation temperature is 160 ° C. using a Waters PL-GPC220 instrument using a Polymer Laboratories PLgel MIX-B 300 mm long column, and 1,2,4-trichlorobenzene is used as a solvent The flow rate was 1 mL/min, and the sample was prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 200 μL, and the value of Mw can be obtained using a calibration curve formed using a polystyrene standard. The molecular weight of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

Also, as used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; a phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; Or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more, or substituted or unsubstituted, two or more of the above-exemplified substituents are linked. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

According to one embodiment of the invention, a hard coating layer comprising polysiloxane; primer layer; and an anti-fingerprint layer comprising a fluorine-containing compound, wherein the water contact angle with respect to the surface of the anti-fingerprint layer is 100° or more, and before and after 1000 reciprocations with steel wool at a load of 500 g with respect to the surface of the anti-fingerprint layer, the surface of the anti-fingerprint layer The amount of change in the water contact angle of the anti-fingerprint layer is 10° or less, and the amount of change in the friction coefficient on the surface of the anti-fingerprint layer is 0.2 or less before and after 1000 reciprocations with steel wool under a 500 g load with respect to the anti-fingerprint layer may be provided.

The present inventors conducted research on an optical laminate applicable to a cover window of a flexible display device, and in an optical laminate having a multilayer structure of two or more layers, on a hard coating layer having a specific composition, a primer layer and a fluorine-containing compound Including an anti-fingerprint layer, the water contact angle with respect to the surface of the anti-fingerprint layer is 100° or more, the amount of change in the water contact angle on the surface of the anti-fingerprint layer is 10° or less And, when the amount of change in the friction coefficient on the surface of the anti-fingerprint layer is 0.2 or less after 1000 reciprocations with steel wool under a 500 g load for the anti-fingerprint layer, the adhesion between the layers is excellent, and damage such as abrasion due to external impact is prevented, , The invention was completed after confirming that it is possible to realize excellent touch resistance as well as antifouling properties by implementing excellent water and oil repellency properties while remarkably excellent in scratch resistance and abrasion resistance.

In addition, the optical laminate has almost no damage to the film even by repeated bending or folding operations, and specifically, the hard coating layer or the anti-fingerprint layer is turned inside to have a curvature diameter of 3 mm. When the operation is repeated 200,000 times, it shows bending durability to a degree that cracks of 3 mm or more do not occur.

Specifically, a water contact angle with respect to the surface of the anti-fingerprint layer included in the optical laminate may be 100° or more, 105° or more, 110° or more, or 115° to 150°. Because the water contact angle of the surface of the anti-fingerprint layer is 100° or more, excellent water-repellent and oil-repellent properties can be realized, thereby implementing excellent antifouling and slip properties. On the other hand, if the water contact angle of the surface of the anti-fingerprint layer is less than 100°, water and oil repellency properties may be deteriorated, and thus resistance to contamination and scratches may be deteriorated.

In addition, the amount of change in water contact angle on the surface of the anti-fingerprint layer is 10° or less, 9° or less, 8° or less, 7° or less, 5° to 0.1° can be The anti-fingerprint layer has a small change in water contact angle even if the surface is partially deformed due to external rubbing or friction, etc., because the change in water contact angle before and after reciprocating steel wool is 10° or less. can indicate However, if the amount of change in the water contact angle exceeds 10°, the degree of durability decline according to use time increases, and thus excellent antifouling properties and slip properties may not be maintained.

On the other hand, after 1000 rounds of reciprocating with steel wool under a 500 g load on the surface of the anti-fingerprint layer, the water contact angle of the surface of the anti-fingerprint layer exceeds 100°, 101° or more, 102° or more, 102° to 160°, 103° to 150 ° or 104° to 130°.

In addition, the amount of change in the friction coefficient of the surface of the anti-fingerprint layer is 0.20 or less, 0.01 to 0.19, 0.01 to 0.18, 0.05 to 0.17, or 0.05 to 0.15 before and after 1000 reciprocations with steel wool under a 500 g load on the surface of the anti-fingerprint layer. have. The coefficient of friction may be a coefficient of static friction measured according to ASTM D1894 for the anti-fingerprint layer using a friction tester (Toyoseiki, Model TR type) device.

The anti-fingerprint layer has less than 0.20 change in friction coefficient before and after reciprocating steel wool, so even if the surface is partially deformed by external rubbing or friction, the friction coefficient change is small, and excellent antifouling and slip properties are maintained by maintaining excellent water and oil repellency properties. can indicate However, when the friction coefficient change amount exceeds 0.20, the degree of decrease in durability according to use time increases, and thus excellent antifouling properties and slip properties may not be maintained.

The hard coating layer included in the optical laminate according to the exemplary embodiment may include polysiloxane including 70 mol% or more of a repeating unit including an epoxy group-containing functional group, and an elastic polymer.

On the other hand, the epoxy group-containing functional group is not particularly limited as long as it is a functional group containing an epoxy group, for example, it may be any one selected from the group consisting of an alicyclic epoxy group and a functional group represented by the following formula (1).

[Formula 1]

In Formula 1,

R _a is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 20 carbon atoms, -R _b -CH= CH-COO-R _c -, -R _d -OCO-CH=CH-R _e -, -R _f OR _g -, -R _h COOR _i -, or -R _j OCOR _k -;

R _b to R _k are each independently, a single bond; or a substituted or unsubstituted C 1 to C 6 alkylene group.

The functional group represented by Chemical Formula 1 includes an epoxy group, and not only improves the physical properties of high hardness and scratch resistance of the optical laminate, but also causes almost no damage to the film even by repeated bending or folding operations, so bendable, flexible, roller It can be easily implemented in a portable or foldable mobile device, a display device, or the like.

For example, in the epoxy group-containing functional group represented by Formula 1, R _a is methylene, ethylene, propylene, allylene, -R _b -CH=CH-COO-R _c -, -R _d -OCO-CH=CH- R _e -, -R _f OR _g -, -R _h COOR _i -, or -R _j OCOR _k -.

For example, in Formula 1, R _b to R _k may be a single bond, methylene, ethylene, propylene, or butylene.

For example, R _a may be methylene, ethylene, or -R _f OR _g -, where R _f and R _g may be a direct bond, methylene or propylene.

For example, the functional group represented by Formula 1 is not limited thereto, but may be glycidoxy, glycidoxyethyl, glycidoxypropyl, or glycidoxybutyl.

In addition, the alicyclic epoxy group is not limited thereto, but may be, for example, epoxycyclohexyl.

In addition, the polysiloxane may be represented by the following formula (2).

[Formula 2]

(R ¹ SiO _3/2 ) _a (R ² SiO _3/2 ) _b (O _1/2 R) _c

In Formula 2,

R ¹ is the epoxy group-containing functional group, and includes 70 mol% or more of a repeating unit including a substituent of R ¹ with respect to the total molar ratio content of Formula 2,

R ² is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 of an alkynyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 20 carbon atoms, an epoxy group, a hydrogen atom, an amino group , a mercapto group, an ether group, an ester group, a carbonyl group, a carboxyl group, a (meth)acrylate or a sulfone group,

R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,

a / (a + b) ≥ 0.7,

a is a positive number,

b and c are each independently 0 or a positive number.

The polysiloxane represented by Formula 2 includes a silsesquioxane unit of (R ¹ SiO _3/2 ) as a T3 unit.

In the silsesquioxane structural unit of (R ¹ SiO _3/2 ), R ¹ is a functional group represented by Formula 1, which is 70 mol% or more, 70 to 99 based on the total molar ratio content of Formula 2 It may be included in mol%, or 80 to 90 mol%, or 50 to 70 mol%. When the content of the functional group represented by Chemical Formula 1 is less than 70 mol%, there is a problem in that it is difficult for the upper and lower coating layers to exhibit sufficient surface hardness due to a decrease in curing density.

In addition, the polysiloxane may further include a silsesquioxane unit of (R ² SiO _3/2 ) as a T3 unit together with the silsesquioxane unit of (R ¹ SiO _3/2 ). The (R ² SiO _3/2 ) silsesquioxane unit may increase the curing density of the polysiloxane to improve the surface hardness characteristics of the hard coating layer.

Wherein R ² is specifically a substituted or unsubstituted C1 to C12 alkyl group, a substituted or unsubstituted C3 to C12 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted carbon number It may be selected from the group consisting of an arylalkyl group of 7 to 12, a substituted or unsubstituted alkylaryl group having 7 to 12 carbon atoms, an epoxy group, and a hydrogen atom. Among them, in that it is possible to further increase the curing density of the polysiloxane to further improve the surface hardness properties of the hard coating layer, R ² is more specifically an acryl group, a methacryl group, a vinyl group, an allyl group, an epoxy group, and an oxetane group. It may be an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 carbon atoms, or an epoxy group, which is unsubstituted or substituted with one or more substituents selected from the group. Meanwhile, the epoxy group is a functional group including an oxirane ring, and includes an alicyclic epoxy group, an aliphatic epoxy group, and an aromatic epoxy group, except for the epoxy group-containing functional group represented by Formula 1 above.

In addition, the polysiloxane may include a structural unit of (O _1/2 R). By including the structural unit, it is possible to improve flexibility while maintaining excellent hardness properties. R is specifically a hydrogen atom, or may be an alkyl group having 1 to 12 carbon atoms, more specifically, a hydrogen atom, or a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, etc. having 1 carbon number to 4 may be a straight-chain or branched alkyl group.

The polysiloxane including the above-mentioned structural units is prepared by hydrolysis between the siloxane monomer of each structural unit, specifically, an alkoxysilane having a functional group of Formula 1, or an alkoxysilane having a functional group of Formula 1 and a heterogeneous alkoxysilane. It can be prepared by a condensation reaction, in which case the molar ratio of each constituent unit can be controlled by controlling the content ratio of the alkoxysilane. Specifically, in Formula 2, a, b, and c are (R ¹ SiO _3/2 ) units, (R ² SiO _3/2 ) units, and (O _1/2 R) units constituting the polysiloxane, respectively represents the molar ratio of , and may be 0<a<1, 0≤b<1, and 0≤c<1.

In addition, the polysiloxane is 70 mol% with respect to the total amount of T units constituting the polysiloxane, that is, 100 mol% of the structural unit of (R ¹ SiO _3/2 ) under the conditions satisfying the content range of each of the above-described structural units. More specifically, by including 70 mol% or more and 100 mol% or less, the curing density is increased when the hard coating film is formed, and as a result, the optical laminate can exhibit significantly improved surface hardness (in terms of molar ratio, 0.7 ≤ a / (a + b) ≤ 1). If the molar content of the (R ¹ SiO _3/2 ) constituent unit in the polysiloxane is less than 70 mol%, it is difficult for the upper and lower coating layers to exhibit sufficient surface hardness due to a decrease in curing density. More specifically, the constituent unit of (R ¹ SiO _3/2 ) may be included in an amount of 70 mol% or more and less than 85 mol%, or 85 mol% or more and 100 mol% or less with respect to the total amount of T units, that is, 100 mol%. can

In addition, when the polysiloxane further includes the structural unit of (R ² SiO _3/2 ), it may be included in a molar ratio corresponding to b (0<b<1), and more specifically, 0<b<0.5 Or 0.01≤b≤0.5, more specifically, in a molar ratio that satisfies 0.1≤b≤0.3 (R ² SiO _3/2 ) may further include a structural unit. When the constituent unit of (R ² SiO _3/2 ) is included in the above content range, it is possible to increase the curing density of the polysiloxane to improve the surface hardness properties of the hard coating layer.

In addition, when the polysiloxane further includes the structural unit of (O _1/2 R), it may be included in a molar ratio corresponding to c (0<c<1), and more specifically, 0<c<0.5; More specifically, it may further include (O _1/2 R) units in a molar ratio that satisfies 0.01≤c≤0.3 or 0.01≤c≤0.05. When the (O _1/2 R) unit is included in the above content range, flexibility can be improved while maintaining excellent hardness properties.

In addition, under the conditions satisfying the above-described content range, the sum of the molar ratios of each constituent unit included in the polysiloxane (a+b+c) may be 1. On the other hand, the content of each structural unit constituting the polysiloxane can be obtained by ¹ H-NMR or ²⁹ Si-NMR spectrum measurement.

Meanwhile, the polysiloxane may have an equivalent weight of the epoxy group-containing functional group of 3.0 to 6.3 mmol/g or 4.0 to 6.0 mmol/g. When the equivalent weight of the functional group represented by the formula (1) is too small, the density of the hard coating layer is reduced and a problem occurs that the surface hardness is lowered. This happens. The equivalent weight of these functional groups is a value obtained by dividing the molecular weight of the polysiloxane by the number of functional groups, and can be analyzed by H-NMR or chemical titration.

In addition, the polysiloxane may have a weight average molecular weight, number average molecular weight, molecular weight distribution, etc. controlled by controlling the reaction temperature, amount of catalyst, and reaction rate using a solvent, etc. mol, or may have a weight average molecular weight of 1,200 to 15,000 g/mol. By having a weight average molecular weight in the above range, superior hardness characteristics may be exhibited. If the weight average molecular weight is less than 1,000 g / mol, hardness is not implemented, but rather there is a fear that ductility is expressed, and if it exceeds 50,000 g / mol, high hardness is exhibited, but there is a fear that the film processability is reduced.

In addition, the polysiloxane may have a number average molecular weight (Mn) of 1,000 to 10,000 g/mol, more specifically, 1,000 to 8,000 g/mol, along with the above-described Mw. When the above-described number average molecular weight condition is satisfied, compatibility with other components in the resin composition for forming a hard coating layer is increased, and the surface hardness of the cured product is improved, so that the heat resistance and abrasion resistance of the cured product can be further improved. Meanwhile, the weight average molecular weight and the number average molecular weight of the polysiloxane are standard polystyrene conversion values by gel permeation chromatography.

In addition, the polysiloxane may have a molecular weight distribution (Mw/Mn) of 1.0 to 10.0, more specifically, 1.1 to 5.0. When the molecular weight distribution is within the above range, the surface hardness improvement effect is more excellent, and the polysiloxane is present in a liquid state, so handling is easy.

The hard coating layer included in the optical laminate according to the embodiment includes an elastic polymer. The elastic polymer can minimize shrinkage during curing by imparting stress resistance properties through toughness of the hard coating layer, and as a result, improve flexural properties, improve flexibility such as flexibility, and improve hardness properties.

Specifically, the content of the elastic polymer included in the hard coating layer is 20 to 80 parts by weight, 30 to 75 parts by weight of the elastomer, based on 100 parts by weight of the polysiloxane containing 70 mol% or more of the repeating unit including the epoxy group-containing functional group. , 35 to 70 parts by weight, 40 to 65 parts by weight may be included. If the content of the elastomer is too large, the surface hardness characteristics may be lowered, and if the content of the elastomer is too small, the improvement effect due to the inclusion of the elastomer may not be sufficiently obtained, and there is a risk of deterioration of the flexural properties and flexibility.

The elastic polymer is not limited thereto, but includes, for example, at least one selected from the group consisting of alkanediol having 1 to 20 carbon atoms, polyolefin polyol, polyester polyol, polycaprolactone polyol, polyether polyol, and polycarbonate polyol. can do. These elastomers can be crosslinked and polymerized by UV irradiation compared to conventional elastomers such as rubber, and high hardness and flexibility can be realized without lowering other properties.

Among them, the elastic polymer may include polycaprolactone diol, polycarbonate diol, or a mixture thereof. In particular, the polycaprolactone diol includes an ester group and an ether group in the repeating unit and is repeated, so that the combination with the polysiloxane When used, it can exhibit superior effects in terms of flexibility, hardness, and impact resistance.

The elastic polymer may have a number average molecular weight (Mn) of 500 to 10,000 Da, or 530 to 5,000 Da. When the above-described number average molecular weight condition is satisfied, compatibility with other components in the hard coating layer is increased, the surface hardness of the cured product is improved, and heat resistance and abrasion resistance of the cured product can be further improved.

The hard coating layer included in the optical laminate according to the embodiment may further include a reactive monomer including at least one functional group crosslinkable with the polysiloxane. The reactive monomer includes at least one functional group crosslinkable with the polysiloxane described above, thereby serving as a crosslinking agent between the polysiloxane networks, thereby increasing the tensile strength of the hard coating layer.

The reactive monomer is a functional group crosslinkable with the polysiloxane, for example, an alicyclic epoxy group, a glycidyl group And it may include one or more selected from the group consisting of oxetanyl group.

In addition, the reactive monomer comprising at least one functional group crosslinkable with the polysiloxane is, for example, bisphenol A diglycidyl ether, 4-vinylcyclohexene dioxide, cyclohexene vinyl monoxide, (3,4-epoxycyclohexyl ) methyl 3,4-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl)-1, 3-dioxolane, bis(3,4-epoxycyclohexylmethyl)adipate, p-butyl phenol glycidyl ether, butyl glycidyl ether, cresyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether Cydyl ether, diglycidyl ether, butanediol diglycidyl ether, limonene dioxide, diethylene glycol diglycidyl ether, 3-methyloxetane, 2-methyloxetane, 3-oxetanol, 2- Methyleneoxetane, 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3,3-oxetane dimanethiol, 2-ethylhexyloxetane, 4- (3 -Methyloxetan-3-yl)benzonitrile, N-(2,2-dimethylpropyl)-3-methyl-3-oxetanemethanamine, N-(1,2-dimethylbutyl)-3-methyl- 3-oxetanemethanamine, xylene bis oxetane, 3-ethyl-3[{(3-ethyloxetan-3-yl)methoxy}methyl]oxetane, (3-ethyloxetan-3-yl) methyl methacrylate, and at least one selected from the group consisting of 4-[(3-ethyloxetan-3-yl)methoxy]butan-1-ol.

The weight ratio of the polysiloxane and the reactive monomer included in the hard coating layer may be 99:1 to 70:30, 95:5 to 72:28, 90:10 to 74:26, or 80:20 to 75:25. When the polysiloxane is included in an excessive amount compared to the reactive monomer, the improvement effect due to the inclusion of the reactive monomer may be insignificant. On the other hand, when the polysiloxane is included in an excessively small amount compared to the elastomer, the distance between curing sites is narrowed due to an excessive amount of reactive monomer, and the internal stress of the coating film is increased due to curing shrinkage due to this, thereby reducing crack resistance.

The hard coating layer may further include an acrylate-based compound to improve surface hardness.

Examples of the acrylate-based compound include 2-ethylhexyl acrylate, octadecyl acrylate, isodecyl acrylate, 2-phenoxyethyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, tridecyl meta Krylate, nonylphenolethoxylate monoacrylate, β-carboxyethyl acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, 4-butylcyclohexyl acrylate, dicyclophene Tenyl acrylate, dicyclopentenyl oxyethyl acrylate, ethoxyethoxyethyl acrylate, ethoxylated monoacrylate, 1,6-hexanediol diacrylate, triphenylglycol diacrylate, butanediol diacrylate , 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate acrylate, tetraethylene glycol, diacrylate, tetraethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, diphoro Phylene glycol diacrylate, ethoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, penta Erythritol tetramethacrylate, pentaerythritol tetraacrylate, ethoxylated triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, dipentaerythritol pentaacrylate, di and trimethylolpropane tetraacrylate, alcohol sylated tetraacrylate, and the like, preferably pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, or and polyfunctional acrylate-based compounds such as pentaerythritol tetraacrylate, and any one or a mixture of two or more thereof may be used. have.

In addition, there may be mentioned acrylate-based oligomers such as polyester acrylate, polyether acrylate, urethane acrylate, or epoxy acrylate, and any one or a mixture of two or more thereof may be used. Among the above-described acrylate-based compounds, urethane acrylate oligomer may be more preferably used in consideration of the remarkable effect of improving surface hardness when used in combination with the above-described polysiloxane.

The urethane acrylate oligomer may have 6 to 9 functional groups. If the functional group is less than 6, the effect of improving the hardness may be insignificant, and if it is more than 9, the hardness may be excellent, but the viscosity may increase. In addition, the urethane (meth)acrylate oligomer may be used without limitation those used in the art, but preferably a compound having at least one isocyanate group in the molecule and a (meth)acrylate compound having at least one hydroxyl group in the molecule One prepared by reacting may be used.

When the acrylate-based compound is further included, it may be included in an amount of 0.1 to 20 parts by weight, 1 to 15 parts by weight, or 5 to 10 parts by weight based on 100 parts by weight of the polysiloxane. If the content of the reactive monomer is less than 0.1 parts by weight, the improvement effect due to the inclusion of the acrylate-based compound is insignificant, and if it exceeds 20 parts by weight, the surface hardness improvement effect may be rather inhibited due to the excess acrylate-based compound.

Together with the above components, the hard coating layer may independently include one or more commonly used additives such as antioxidants, surfactants, anti-yellowing agents, inorganic fillers, lubricants, coating aids, and antifouling agents.

As described above, since the hard coating layer contains the polysiloxane, it is possible to impart excellent hardness characteristics and improved flexibility and bending characteristics to the optical laminate. In addition, a primer layer and an anti-fingerprint layer may be sequentially laminated on the hard coating layer. Since the hard coating layer, the primer layer and the anti-fingerprint layer are sequentially stacked, excellent antifouling properties, anti-fingerprint properties, high strength and scratch resistance can be imparted.

Specifically, since the anti-fingerprint layer includes a fluorine-containing compound, antifouling and anti-fingerprint properties of the optical laminate may be improved. In addition, the primer layer can prevent shear breakdown and loss of the hard coating layer and the anti-fingerprint layer due to shear stress by increasing the adhesion between the hard coating layer and the anti-fingerprint layer. For this reason, the optical laminate may be applicable as a cover window for a display by replacing the tempered glass.

In addition, this optical laminate has little damage to the film even by repeated bending or folding operations. Specifically, with the hard coating layer or the anti-fingerprint layer inside, the continuous operation of folding and unfolding 90 degrees so that the curvature diameter becomes 3 mm 20 It can exhibit bending durability to the extent that cracks of 3 mm or more do not occur when repeated retrieval is performed.

1 schematically shows a method for evaluating dynamic bending properties.

Referring to Figure 1, after the optical laminate is placed so that it is level with the floor, the interval between the folds in the middle of the optical laminate is 3 mm, and both sides of the optical laminate are folded and unfolded at 90 degrees with respect to the bottom surface. Durability against bending can be measured by repeating 200,000 times at 25°C at a rate of once per 1.5 seconds. At this time, in order to keep the distance between the folds constant, for example, the optical laminate is placed in contact with a rod having a diameter (R) of 3 mm and the rest of the optical laminate is fixed, and the optical laminate is centered on the rod. You can take a method that repeats folding and unfolding both sides. In addition, the folded portion is not particularly limited as long as it is inside the optical laminate, and for convenience of measurement, the central portion of the optical laminate may be folded so that both sides of the optical laminate except for the folded portion are symmetrical.

In the evaluation of the dynamic bending properties, cracks of 1 cm or more or 3 mm or more do not occur, and cracks do not occur in the optical laminate even after bending 200,000 times. In particular, cracks do not occur even when bent to either side of the inner and outer sides of the optical laminate, for example, folding the anti-fingerprint layer of the optical laminate inward, or folding the hard coating layer inward, or of the hard coating layer When the support base layer is included on one surface, cracks do not occur even when the support base layer is folded inward. Therefore, the possibility of cracks occurring even in an actual use state such as repeatedly folding, rolling, or bending is very low, and thus it can be suitably applied to a cover window of a flexible display device.

The primer layer included in the optical laminate according to the exemplary embodiment may include an organic silane compound. The organosilane compound is a compound having a functional group acting as a silane coupling agent, and may have at least one organic functional group in one molecule. The organic functional group may be at least one selected from the group consisting of an epoxy group, a (meth)acryloxy group, a mercapto group, an amino group, a vinyl group, and a ureido group. In addition, the organosilane compound may be a compound having at least one hydrolysable group, and the hydrolyzable group is an alkoxy group bonded to a silicon atom or the like.

Specifically, the organic silane compound having an organic functional group is 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldiethoxy Silane, 3-glycidoxypropyl triethoxysilane, glycidoxypropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)- 3-Aminopropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3-ureido propyl Trimethoxy silane, 3-ureido propyltrialkoxy silane, vinyltrimethoxy silane, vinyltriethoxy silane, methacryloxytrimethoxy silane, methacryloxytriethoxy silane, N-phenyl-γ-aminopropyl At least one selected from the group consisting of trimethoxy silane and mercaptopropyltrimethoxy silane may be used.

The organic silane compound having the organic functional group may be 40 to 95 wt%, 50 to 90 wt%, 60 to 85 wt%, or 70 to 80 wt% based on 100 wt% of the total weight of the primer layer. If the content of the organosilane compound is too small, the adhesive force is lowered due to a decrease in the density of the primer layer, thereby reducing the scratch resistance of the optical laminate. Due to this, there is a problem in that haze occurs and durability is reduced.

The primer layer is an organic silane compound having at least one organic functional group selected from the group consisting of the epoxy group, (meth)acryloxy group, mercapto group, amino group, vinyl group, and ureido group, as well as other organic functional groups. It may further include a compound. For example, from the group consisting of methyltrimethoxy silane, methyltriethoxy silane, ethyltrimethoxy silane, ethyltriethoxy silane, propyltrimethoxy silane, propyltriethoxy silane, and methyltributoxy silane It may further include one or more selected organosilane compounds.

In addition, the primer layer may further include silica nanoparticles, aluminum oxide particles, titanium oxide particles, zinc oxide particles, or polysilazane in addition to the organic silane compound.

In addition, in order to form the primer layer, it may further include a solvent. The type of the solvent is not limited, but preferably at least one selected from the group consisting of trifluorotoluene, chlorofluorocarbon, hydrofluorocarbon, hydrofluoroether, alcohol, and alkoxyfluoroalkane having 2 to 20 carbon atoms. can

The method of forming the primer layer may be formed through general thermal curing or photocuring after mixing the above-described components, but the curing method is not particularly limited. In addition, the primer layer may include a structure including at least one layer on the hard coating layer.

The anti-fingerprint layer included in the optical laminate according to the embodiment may include a fluorine-containing compound. The fluorine-containing compound may include at least one selected from the group consisting of a perfluoro polyether compound, a compound containing an oxyperfluoroalkylene group, a fluoro-modified silane compound, and a compound containing a fluoroalkyl group. .

For example, the compound containing the oxyperfluoroalkylene group is not limited thereto, but for example, perfluoropolyethylene urethane acrylate, perfluoropolyethylene polymethacrylate or perfluoropolymethacrylate can be

In addition, the fluoro-modified silane compound is not limited thereto, but may be, for example, perfluoro-modified silane or perfluoropolyethylene-modified silane.

In addition, the compound including the fluoroalkyl group is not limited thereto, but may be, for example, perfluoropolyethylene.

The fluorine-containing compound may have a weight average molecular weight of 300 to 200,000 g/mol, 450 to 150,000 g/mol, 480 to 130,000 g/mol, or 520 to 100,000 g/mol. If the weight average molecular weight of the fluorine-containing compound is too small, it may be difficult for the anti-fingerprint layer to exhibit antifouling properties and slip properties, and if the weight average molecular weight is too large, it may be difficult to exhibit scratch resistance or abrasion resistance.

The fluorine-containing compound may be 50 wt% or more, 50 to 100 wt%, or 70 to 99% based on 100 wt% of the total weight of the anti-fingerprint layer. When the content of the fluorine-containing compound is too small, there is a problem in that antifouling properties and slip properties are lowered.

The anti-fingerprint layer may further include inorganic fine particles surface-modified with silane or silazane, in addition to the fluorine-containing compound. Here, the inorganic fine particles may include a group of silica nanoparticles, aluminum oxide fine particles, titanium oxide fine particles, or zinc oxide fine particles.

In addition, in order to form an anti-fingerprint layer, a solvent may be further included. The type of the solvent is not limited, but preferably at least one selected from the group consisting of trifluorotoluene, chlorofluorocarbon, hydrofluorocarbon, hydrofluoroether, alcohol, and alkoxyfluoroalkane having 2 to 20 carbon atoms. can

The method of forming the anti-fingerprint layer may be formed through general thermosetting or photocuring after mixing the above-described components, and the curing method is not particularly limited. In addition, the anti-fingerprint layer may include a structure including at least one layer on the primer layer.

Meanwhile, the thickness ratio of the primer layer and the anti-fingerprint layer included in the optical laminate may be 1:0.01 to 10,000, 1: 0.05 to 100, and 1: 0.1 to 500. When the thickness of the anti-fingerprint layer is too thin compared to the primer layer, there is a problem in that the surface modification degree is lowered and the antifouling property is lowered. There is a problem of lowering the characteristics.

Specifically, the primer layer may have a thickness of 1 nm to 5 μm, 10 nm to 900 nm, or 20 nm to 800 nm, and the anti-fingerprint layer has a thickness of 1 nm to 20 μm, 5 nm to 10 μm, or It may be 10 nm to 1 μm.

In addition, the hard coating layer may have a thickness of 10 to 100 μm, 30 to 90 μm, or 40 to 80 μm. As the thickness of the hard coating layer increases, the strength increases, but if the thickness is too thick, it is easily broken when folded, and if the thickness is too thin, the strength may be poor even if the foldability is secured. In addition, when the hard coating layer is formed on both surfaces of the support base layer to be described later, the upper hard coating layer and the lower hard coating layer may have the same or different thicknesses.

The optical laminate sequentially includes the hard coating layer, the primer layer and the anti-fingerprint layer, and may further include a support substrate layer positioned on one surface of the hard coating layer to face the primer layer. In addition, the optical laminate may further include another hard coating layer on one surface of the support base layer to face the hard coating layer. That is, the hard coating layer may be positioned on both sides of the support base layer, and these may be divided into an upper hard coating layer and a lower hard coating layer.

The support base layer may have a transmittance of 50% or more, 75% or more, 85% or more, or 95% or more at a wavelength of 300 nm or more.

In addition, the support base layer may include a transparent plastic resin. Specific examples of the plastic resin include polyester-based resins, cellulose-based resins, polycarbonate-based resins, acrylic resins, styrene-based resins, polyolefin-based resins, polyimide-based resins, polyethersulfone-based resins, or sulfone-based resins. and any one or a mixture of two or more thereof may be used.

More specifically, the support base layer may include polyethyleneterephthalate (PET), cyclic olefin copolymer (COC), polyacrylate (PAC), polycarbonate (PC), polyethylene ( polyethylene, PE), polymethylmethacrylate (PMMA), polyetheretherketone (PEEK), polyethylenenaphthalate (PEN), polyetherimide (PEI), polyimide (PI) ), polyamideimide (PAI) and triacetylcellulose (TAC) may include at least one.

In addition, the support base layer may be a single layer, or may have a multilayer structure of two or more layers made of the same or different materials. For example, the support base layer is a multilayer structure of polyethylene terephthalate (PET), a multilayer structure formed by coextrusion of polymethyl methacrylate (PMMA)/polycarbonate (PC), or polymethyl methacrylate (PMMA) It may be a single-layer structure including a copolymer of polycarbonate (PC) and and polycarbonate (PC).

In addition, the support base layer may be plasma surface-treated if necessary, and the method is not specifically suggested and may be performed according to a conventional method.

In addition, when the thickness of the support base layer is too thick or too thin, there are problems in surface hardness, lowering of impact resistance, or folding characteristics, and it may be preferable to appropriately set the range. For example, the support base layer may have a thickness of 30 to 100 μm, more specifically, 50 to 80 μm.

The optical laminate according to the embodiment is It may further include an adhesive layer positioned on one surface of the support base layer to face the hard coating layer. The pressure-sensitive adhesive layer may be implemented as an adhesive or a pressure-sensitive adhesive film, and is not particularly limited as long as it is known in the art. Meanwhile, the adhesive film is not particularly limited as long as it is known in the art, but a double-sided adhesive film such as an optically clear adhesive (OCA) film may be used.

The optical laminate having the above-described structure and configuration is formed by applying a resin composition for forming a hard coat layer on one surface of the support base layer and curing it to form a hard coat layer, and applying the resin composition for forming a primer layer on the hard coat layer It can be prepared by coating and curing to form a primer layer, and applying a resin composition for forming an anti-fingerprint layer on the primer layer and curing it to form a primer layer. In addition, before or after applying the hard coat layer to one surface of the support base layer, a resin composition for forming a hard coat layer similar or identical to the resin composition for forming the hard coat layer is applied to the other side of the support base layer, and It can be cured to form a lower hard coating layer.

In addition, the entirety of applying the resin composition for forming a primer layer on the hard coat layer, the surface of the hard coat layer may be surface treated by plasma or corona to improve adhesion.

In the above-described optical laminate manufacturing method, the composition and weight ratio of polysiloxane, elastomer, reactive monomer, etc. contained in the resin composition for forming the hard coating layer and the weight ratio thereof are as described above, and the organosilane contained in the resin composition for forming the primer layer. The composition of the compounds and their contents are as described above, and the compositions and their contents of the fluorine-containing compound included in the resin composition for forming an anti-fingerprint layer are as described above.

In addition, the resin composition for forming the hard coat layer, the resin composition for forming the primer layer, and the resin composition for forming the anti-fingerprint layer may further include an initiator. The initiator may be a photopolymerization or thermal polymerization initiator well known in the art, and the type thereof is not particularly limited. For example, the photopolymerization initiator is aryl sulfonium hexafluoroantimonate salt, aryl sulfonium hexafluorophosphate salt, diphenyldiodonium hexafluorophosphate salt, diphenyldiodonium hexaantimonium salt , Ditorilliodonium hexafluorophosphate salt and 9- (4-hydroxyethoxyphenyl) may be at least one selected from the group consisting of cyanrhenium hexafluorophosphate salt, but is not limited thereto. The thermal polymerization initiator is 3-methyl-2-butenyltetramethylenesulfonium hexafluoroantimonate salt, ytterbium trifluoromethenesulfonate salt, samarium trifluoromethenesulfonate salt, erbium trifluoromethene sulfonate salt, dysprosium trifluoromethenesulfonate salt, lanthanum trifluoromethenesulfonate salt, tetrabutylphosphonium methenesulfonate salt, ethyltriphenylphosphonium bromide salt, benzyldimethylamine, dimethyl It may include at least one selected from the group consisting of aminomethylphenol, triethanolamine, Nn-butylimidazole and 2-ethyl-4-methylimidazole, but is not limited thereto.

The initiator may be included in an amount of 0.1 to 10% by weight, 0.5 to 5% by weight, or 1 to 4% by weight based on 100% by weight of the total content of the composition. If the content of the initiator is less than 0.1% by weight, only surface hardening or epoxy curing may not occur sufficiently, so that the hardness may be low, and if it exceeds 10% by weight, cracks and peeling may occur due to a fast curing rate.

The resin composition for forming the hard coat layer, the resin composition for forming the primer layer, and the resin composition for forming the anti-fingerprint layer can be used as solvent-free if there is no problem in the process, but selectively control the viscosity and fluidity of the composition during coating and may optionally further include an organic solvent in order to increase the applicability of the composition.

When the organic solvent is further included, the organic solvent may include an alcohol-based solvent such as methanol, ethanol, isopropyl alcohol, or butanol; alkoxy alcohol solvents such as 2-methoxyethanol, 2-ethoxyethanol, and 1-methoxy-2-propanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, and cyclohexanone; Propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethyl glycol monoethyl ether, diethyl glycol monopropyl ether , ether solvents such as diethyl glycol monobutyl ether and diethylene glycol-2-ethylhexyl ether; acetate-based solvents such as propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate; Alternatively, an aromatic solvent such as benzene, toluene, or xylene may be used alone or in combination.

In addition, The resin composition for forming the hard coat layer, the resin composition for forming the primer layer, and the resin composition for forming the anti-fingerprint layer are In addition to the above-described components, antioxidants, surfactants, anti-yellowing agents, inorganic fillers, lubricants, coating aids, antifouling agents, and the like may be further included. In addition, the content can be variously adjusted within a range that does not reduce the physical properties, so it is not particularly limited, but may include, for example, 0.1 to 10% by weight based on 100% by weight of the total content of the composition.

For example, the antioxidant is for inhibiting the oxidation reaction resulting from the polymerization initiator, and may include a mixture of one or more selected from the group consisting of phenolic, phosphate, amino, thioester, and the like. may not be limited. The surfactant may be a fluorine-based acrylate, a fluorine-based surfactant, or a silicone-based surfactant having 1-2 functional properties. In this case, the surfactant may be included in a dispersed or cross-linked form in the cross-linked copolymer. In addition, examples of the anti-yellowing agent include a benzophenone-based compound or a benzotriazole-based compound.

The coating process of the resin composition for forming the hard coat layer, the resin composition for forming the primer layer and the resin composition for forming the anti-fingerprint layer is a die coater, air knife, reverse roll, spray, blade, casting, gravure, spin coating, or bar coating, etc. It can be carried out by a known method of

In addition, after each resin composition is applied, a process for curing may be performed, and the curing may be performed by thermal curing or light curing according to a conventional method. The heat treatment or light irradiation conditions for the thermal curing and light curing may be appropriately controlled by adjusting the wavelength region and the amount of light, or the heat treatment temperature, depending on the type of the initiator.

According to another embodiment of the present invention, a flexible display device including the optical laminate may be provided.

The flexible display device includes a curved, bendable, flexible, rollable, or foldable mobile communication terminal, a smart phone, a touch panel of a tablet PC, and a wearable device. It may include both devices and various displays. According to various embodiments, the wearable device is an accessory type (eg, a watch, a ring, a bracelet, an anklet, a necklace, glasses, contact lenses, or a head-mounted-device (HMD)), a fabric or a clothing integrated type ( It may include at least one of: electronic clothing), body attachable (eg skin pad or tattoo), or bioimplantable (eg implantable circuit).

On the other hand, the flexible display device is, for example, a liquid crystal display (LCD) device, a light emitting diode (LED) display device, an organic light emitting diode (OLED) display device, a microelectromechanical system (MEMS) display device or a rollable display device (rollable display or foldable display).

For example, in the organic light emitting diode (OLED) display device, the cover window of the flexible organic light emitting diode display device may be positioned at an outer portion in a direction in which light or a screen is emitted, and a cathode providing electrons; An electron transport layer, an emission layer, a hole transport layer, and an anode providing holes may be sequentially formed. In addition, the organic light emitting diode (OLED) display may further include a hole injection layer (HIL) and an electron injection layer (EIL).

In order for the organic light emitting diode (OLED) display to function and operate as a flexible display, the cathode and anode electrodes and each component may be used as a material having a predetermined elasticity.

Another example of the flexible display device may be a rollable display or foldable display.

On the other hand, the retractable display device may have various structures depending on the field of application and specific form, for example, including a cover window, a touch panel, a polarizing plate, a barrier film, a light emitting device (OLED device, etc.), a transparent substrate, etc. can be a structure.

As another example of the flexible display device, a pair of polarizing plates facing each other; a thin film transistor, a color filter and a liquid crystal cell sequentially stacked between the pair of polarizing plates; And it may be a liquid crystal display device including a backlight unit.

In the display device, the optical laminate may be provided on the outermost surface of the viewer side or the backlight side of the display panel.

According to the present invention, while exhibiting both excellent antifouling properties and high hardness properties, the adhesive strength and scratch resistance are excellent, and in particular, there is little damage to the film even by repeated bending or folding operations, and a flexible display device including the same may be provided.

In addition, the optical laminate exhibits improved bending properties, and has excellent properties of flexibility, high hardness and scratch resistance. It can be usefully applied to a flexible, rollable, or foldable mobile device, a display device, a front panel of various instrument panels, a display unit, and the like.

1 schematically shows a method for evaluating dynamic bending properties.

The invention is described in more detail in the following examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

<Production Example>

Preparation Example 1-1: Preparation of a resin composition for forming an anti-fingerprint layer (AF-1)

1 g of perfluoro-modified silane compound (product name: KY-185, manufacturer: Shinetsu, weight average molecular weight: 520), 0.01 g of water, and hydrofluoroether as a fluorine-based solvent (product name: HFE-7200, manufacturer: Novec) ) was mixed to prepare a resin composition (AF-1) for forming an anti-fingerprint layer.

Preparation 1-2: Preparation of a resin composition for forming an anti-fingerprint layer (AF-2)

0.1 g of perfluoropolyethylene urethane acrylate (product name: AD1700, manufacturer SOLVAY, weight average molecular weight: 3000) and 100 g of fluorine-based solvent hydrofluoroether (product name: HFE-7200, manufacturer: Novec) are mixed and fingerprinted A resin composition for forming an barrier layer (AF-2) was prepared.

Preparation Example 1-3: Preparation of a resin composition for forming an anti-fingerprint layer (AF-3)

3-methacryloxypropyl trimethoxysilane (product name: KBM-503, manufactured by Shinetsu) 50 g, trimethoxyphenylsilane (product name: phenyltrimethoxysilane, manufactured by Aldrich, molecular weight 198) 50 g, photoinitiator (Irgacure 127) ) 1 g, 400 g of 2-butanone as an organic solvent, and 2 g of perfluoropolyethylene polymethacrylate were mixed to prepare a resin composition (AF-3) for forming an anti-fingerprint layer.

Preparation Example 1-4: Preparation of a resin composition for forming an anti-fingerprint layer (AF-4)

An anti-fingerprint layer by mixing 15 g of perfluoropolyethylene urethane acrylate (product name: AD1700, manufacturer SOLVAY), 0.7 g of N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, and 84.3 g of trifluorotoluene A resin composition for formation (AF-4) was prepared.

Preparation Example 2: Preparation of resin composition (P-1) for forming a primer layer

A resin composition for forming a primer layer by mixing 1 g of N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 0.3 g of methyltrimethoxysilane, 100 g of ethanol, and 20 g of t-amyl alcohol (P -1) was prepared.

Preparation Example 3-1: Preparation of resin composition (H-1) for forming a hard coating layer

In a 1000 mL 3-neck flask, 3-glycidoxypropyltrimethoxysilane (GPTMS, KBM-403™, Shinetsu Corporation), water and toluene as a silane monomer were added and stirred (GPTMS: water: toluene ratio = 4 mol: 1 mol:3 mol). To the resulting mixed solution, 1 part by weight of a basic catalyst (TMAH) was added with respect to 100 parts by weight of the silane monomer and reacted at 100° C. for 2 hours to obtain 100 mol% of glycidoxypropyl modified silicone (hereinafter referred to as GP). A polysiloxane containing was prepared (number average molecular weight: 2,000 g/mol, molecular weight distribution (PDI): 1.4, glycypropyl group equivalent: 6.0 mmol/g).

10 g of the polysiloxane, 3 g of bisphenol A diglycidyl ether (Merck Corporation), 4 g of polycaprolactone diol (Mn: 530, Merck Corporation) and iodinium as an initiator, (4-methylphenyl) [4-2- Methylpropyl]phenyl]-, hexafluorophosphate (1-) (Iodinium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -, hexafluorophosphate (1-), (IGM resins) 0.3 g of mixing) to prepare a resin composition (H-1) for forming a hard coat layer.

Preparation Example 3-2: Preparation of resin composition (H-2) for forming a hard coating layer

Polycaprolactone diol (Mn: 530, Merck Co.) 4 g instead of polycaprolactone diol (Mn: 530, Merck Co.) Except that 8 g was used in the same manner as in Preparation Example 3-1 A resin composition (H-2) for forming a coating layer was prepared.

Preparation 3-3: Preparation of resin composition (H-3) for forming a hard coating layer

A resin composition (H-3) for forming a hard coat layer was prepared in the same manner as in Preparation Example 3-1, except that 6 g of bisphenol A diglycidyl ether was used instead of 3 g of bisphenol A diglycidyl ether. did

<Example>

Example 1

As shown in Table 1 below, an optical laminate was prepared by sequentially coating and curing the compositions prepared in Preparation Examples, respectively.

Specifically, after applying the resin composition (H-1) for forming a hard coat layer prepared in Preparation Example 3 on one surface of a polyethylene terephthalate (PET) substrate (support substrate layer) having a thickness of 15 cm x 20 cm and a thickness of 50 μm (H-1), a UV lamp By irradiating ultraviolet rays (irradiation dose: 400 mJ/cm 2 ) to form a lower hard coating layer with a thickness of 80 μm by photocuring using The resin composition (H1) was applied, and ultraviolet rays were irradiated using a UV lamp (irradiation amount: 400 mJ/cm 2 ) to form an upper hard coating layer having a thickness of 80 μm by photocuring.

Then, after the upper hard coating layer was surface-treated with plasma, the resin composition for forming a primer layer (P-1) prepared in Preparation Example 2 was applied, and then heat-cured at 110° C. for 30 minutes to form a 30 nm-thick primer layer. was formed. After coating the resin composition (AF-1) for forming an anti-fingerprint layer prepared in Preparation Example 1-1 on the primer layer, thermosetting at 110° C. for 30 minutes to form an anti-fingerprint layer with a thickness of 10 nm, an optical laminate was prepared.

Example 2

Instead of the resin composition for forming an anti-fingerprint layer prepared in Preparation Example 1-1 (AF-1), the resin composition for forming an anti-fingerprint layer prepared in Preparation Example 1-2 (AF-2) was used, and the lower hard coating layer was not formed. Except for the point, an optical laminate was prepared in the same manner as in Example 1.

Example 3

Except for using the resin composition for forming an anti-fingerprint layer prepared in Preparation Example 1-2 instead of the resin composition for forming an anti-fingerprint layer (AF-1) prepared in Preparation Example 1-1 (AF-2), An optical laminate was manufactured in the same manner as in Example 1.

Comparative Example 1

The point that the resin composition (AF-2) for forming an anti-fingerprint layer prepared in Preparation Example 1-2 was used instead of the resin composition for forming an anti-fingerprint layer (AF-1) prepared in Preparation Example 1-1, and a primer layer was not formed Except for, an optical laminate was prepared in the same manner as in Example 1.

Comparative Example 2

After applying the resin composition (H-1) for forming a hard coating layer prepared in Preparation Example 3 on one surface of a polyethylene terephthalate (PET) substrate having a thickness of 15 cm × 20 cm and a thickness of 50 μm, using a UV lamp to irradiate ultraviolet rays (irradiation amount) : 400 mJ/cm 2) to form a lower hard coating layer with a thickness of 80 μm by photocuring, and the resin composition for forming an anti-fingerprint layer prepared in Preparation Example 1-3 on the opposite side of the PET substrate on which the lower coating layer is formed (AF-3 ), and photocuring by irradiating ultraviolet rays using a UV lamp (irradiation amount: 400 mJ/cm 2 ) to form an anti-fingerprint layer with a thickness of 10 nm to prepare an optical laminate.

Comparative Example 3

The point that the resin composition (AF-4) for forming an anti-fingerprint layer prepared in Preparation Example 1-4 was used instead of the resin composition for forming an anti-fingerprint layer (AF-1) prepared in Preparation Example 1-1, and a primer layer was not formed Except for, an optical laminate was prepared in the same manner as in Example 1.

Comparative Example 4

Except for using the resin composition (H-2) for forming a hard coat layer prepared in Preparation Example 3-2 instead of the resin composition (H-1) for forming a hard coat layer prepared in Preparation Example 3-1, An optical laminate was manufactured in the same manner as in Example 1.

Comparative Example 5

Except that the resin composition (H-3) for forming a hard coat layer prepared in Preparation Example 3-3 was used instead of the resin composition (H-1) for forming a hard coat layer prepared in Preparation Example 3-1, An optical laminate was manufactured in the same manner as in Example 1.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 anti-fingerprint layer Preparation 1-1
(AF-1) Preparation 1-2
(AF-2) Preparation 1-2
(AF-2) Preparation 1-2
(AF-2) - Preparation Example 1-4
(AF-4) Preparation 1-1
(AF-1) Preparation 1-1
(AF-1) primer layer Preparation Example 2
(P-1) Preparation Example 2
(P-1) Preparation Example 2
(P-1) - - - Preparation Example 2
(P-1) Preparation Example 2
(P-1) upper hard coating layer Preparation Example 3-1
(H-1) Preparation Example 3-1
(H-1) Preparation Example 3-1
(H-1) Preparation Example 3-1
(H-1) Preparation 1-3
(AF-3) Preparation Example 3-1
(H-1) Preparation 3-2
(H-2) Production Example 3-3
(H-3) support base layer PET PET PET PET PET PET PET PET lower hard coating layer Preparation Example 3-1
(H-1) - Preparation Example 3-1
(H-1) Preparation Example 3-1
(H-1) Preparation Example 3-1
(H-1) Preparation Example 3-1
(H-1) Preparation 3-2
(H-2) Production Example 3-3
(H-3)

< Experimental example >

For the optical laminates prepared in Examples and Comparative Examples, physical properties were measured by the following method, and the results are shown in Table 2 below.

1. Measurement of water contact angle before and after steel wool evaluation

For the anti-fingerprint layer of Examples and Comparative Examples (in the case of Comparative Example 2, the upper hard coating layer), the contact angle was measured using a contact angle measuring instrument (CAX-150). When measuring the contact angle, the size of each droplet is 3 μl, and to check the uniformity of the coating, the contact angle of 5 points per coated sample is measured and averaged, and the result is the water contact angle before evaluation of steel wool in Table 2 below. indicated.

Thereafter, after reciprocating 1000 times with steel wool (#0000) under a 500 g load on the surface of the anti-fingerprint layer, the water contact angle was measured in the same manner as described above for the surface of the anti-fingerprint layer, and the results are shown in Table 2 It is shown in the water contact angle after evaluation of steel wool.

2. Measurement of friction coefficient before and after steel wool evaluation

For the anti-fingerprint layer (in case of Comparative Example 2, the upper hard coating layer) of Examples and Comparative Examples, the coefficient of static friction was measured according to ASTM D1894 using a friction tester (Toyoseiki, Model TR type), and the results are obtained from the steel of Table 2 below. It is shown in the friction coefficient before wool evaluation.

Then, after reciprocating 1000 times with steel wool (#0000) under a 500 g load on the surface of the anti-fingerprint layer, the static friction coefficient was measured according to ASTM D1894 for the surface of the anti-fingerprint layer, and the result is shown in the steel of Table 2 below. It is shown in the friction coefficient after wool evaluation.

3. Scratch resistance evaluation

After reciprocating 1,000 times with steel wool (#0000) under a 500 g load on the surface of the anti-fingerprint layer (upper hard coating layer in the case of Comparative Example 2) of Examples and Comparative Examples, visually check whether scratches occur, and scratches of 3 mm or less When it occurred, it was set as “O.K.”, and when a scratch exceeding 3 mm occurred, it was judged as “N.G.”.

4. Eraser wear evaluation

After reciprocating the minnow eraser 1,500 times under a 500 g load on the surface of the anti-fingerprint layer (in the case of Comparative Example 2, the upper hard coating layer) of Examples and Comparative Examples, visually check whether the scratch coating film is worn (scratch, haze), and when there is no deformation is set to “O.K.”, and when wear deformation occurs, it is judged as “N.G.”.

5. Dynamic bending properties evaluation

1 is a diagram schematically illustrating a method for evaluating dynamic bending characteristics for an optical laminate according to an embodiment of the present invention.

The optical laminate was cut, but laser cut to a size of 80 x 140 mm to minimize microcracks in the edge region. Place the laser-cut film on the measuring equipment, put the lower hard coating layer (supporting substrate layer in the case of Example 2) inside, and make the gap (inner curvature diameter) of the folded part to be 3 mm, so that both sides of the film at room temperature was repeated 200,000 times in a continuous operation of folding and unfolding at 90 degrees with respect to the bottom surface (the film folding speed is once per 1.5 seconds), and the dynamic bending characteristics were evaluated according to the following criteria.

O.K.: No cracks

N.G.: Cracking

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 water contact angle Steel wool before evaluation 115˚ 115˚ 110˚ 110˚ 80˚ 112˚ 111˚ 111˚ After evaluation of steel wool 107˚ 110˚ 103˚ 75˚ 65˚ 75˚ 103˚ 75˚ coefficient of friction Steel wool before evaluation 0.09 0.09 0.05 0.10 0.40 0.09 0.09 0.08 After evaluation of steel wool 0.24 0.22 0.18 0.41 0.70 0.45 0.25 0.40 scratch resistance O.K. O.K. O.K. N.G. N.G. N.G. N.G. N.G. eraser wear O.K. O.K. O.K. N.G. N.G. N.G. N.G. N.G. dynamic bending properties O.K. O.K. O.K. O.K. O.K. O.K. O.K. O.K.

According to Table 2, the optical laminates of Examples 1 to 3 sequentially include a hard coat layer, a primer layer, and an anti-fingerprint layer, and the amount of change in water contact angle before and after steel wool evaluation is 10° or less, and the change in friction coefficient is 0.2 or less. Therefore, it was confirmed that it exhibits excellent scratch resistance and eraser abrasion properties, and exhibits dynamic bending characteristics in which cracks do not occur even when the continuous operation of folding and unfolding is repeated 200,000 times.

On the other hand, the optical laminate of Comparative Example does not include a primer layer or uses a hard coating layer of a different composition from that of the present application, so the adhesion between the upper hard coating layer and the anti-fingerprint layer is weak, and thus scratch resistance and abrasion resistance are poor. Also, it was confirmed that the amount of change in water contact angle and friction coefficient before and after steel wool evaluation was large.

Claims (15)

a hard coating layer comprising polysiloxane; primer layer; and an anti-fingerprint layer comprising a fluorine-containing compound;
The water contact angle with respect to the surface of the anti-fingerprint layer is 100° or more,
Before and after 1000 reciprocations with steel wool under a 500 g load on the surface of the anti-fingerprint layer, the amount of change in the water contact angle of the surface of the anti-fingerprint layer is 10° or less,
The amount of change in the coefficient of friction on the surface of the anti-fingerprint layer is 0.2 or less, before and after 1000 reciprocations with steel wool under a 500 g load with respect to the anti-fingerprint layer.
According to claim 1,
The polysiloxane is an optical laminate comprising at least 70 mol% of a repeating unit including an epoxy group-containing functional group.
3. The method of claim 2,
The epoxy group-containing functional group is any one selected from the group consisting of an alicyclic epoxy group and a functional group represented by the following Chemical Formula 1, an optical laminate:
[Formula 1]

In Formula 1,
R _a is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 20 carbon atoms, -R _b -CH= CH-COO-R _c -, -R _d -OCO-CH=CH-R _e -, -R _f OR _g -, -R _h COOR _i -, or -R _j OCOR _k -;
R _b to R _k are each independently, a single bond; or a substituted or unsubstituted C 1 to C 6 alkylene group.
3. The method of claim 2,
The polysiloxane has the epoxy group-containing functional group equivalent of 3.0 to 6.3 mmol/g, the optical laminate.
The method of claim 1,
The polysiloxane has a weight average molecular weight of 1,000 to 50,000 g/mol, a number average molecular weight of 1,000 to 10,000 g/mol, and a molecular weight distribution of 1.0 to 10.0, an optical laminate.
The method of claim 1,
An optical laminate comprising 20 to 80 parts by weight of an elastic polymer based on 100 parts by weight of the polysiloxane.
7. The method of claim 6,
wherein the elastomeric polymer comprises polycaprolactone polyol.
According to claim 1,
The primer layer includes an organic silane compound having at least one organic functional group selected from the group consisting of an epoxy group, a (meth)acryloxy group, a mercapto group, an amino group, a vinyl group, and a ureido group. .
9. The method of claim 8,
The organosilane compound is 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-glycidoxy Propyl triethoxysilane, glycidoxypropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxy Silane, N-2-(aminoethyl)-3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3-ureido propyltrimethoxy silane, 3- Ureido propyltrialkoxy silane, vinyltrimethoxy silane, vinyltriethoxy silane, methacryloxytrimethoxy silane, methacryloxytriethoxy silane, N-phenyl-γ-aminopropyltrimethoxy silane and mercapto An optical laminate comprising at least one selected from the group consisting of propyltrimethoxy silane.
9. The method of claim 8,
The primer layer is from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and methyltributoxysilane. The optical laminate further comprising one or more selected organic silane compounds.
The method of claim 1,
The fluorine-containing compound comprises at least one selected from the group consisting of a perfluoro polyether compound, a compound containing an oxyperfluoroalkylene group, a fluoro-modified silane compound, and a compound containing a fluoroalkyl group. Optical, laminate.
According to claim 1,
The thickness ratio of the primer layer and the anti-fingerprint layer is 1:0.01 to 10,000, the optical laminate.
The method of claim 1,
The hard coating layer, the primer layer and the anti-fingerprint layer are sequentially laminated,
The optical laminate further comprising a support base layer positioned on one surface of the hard coat layer to face the primer layer.
14. The method of claim 13,
The optical laminate further comprising an adhesive layer positioned on one surface of the support base layer to face the hard coating layer.
A flexible display device comprising the optical laminate according to claim 1 .

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