阅读说明：本技术 衍射导光板及其制造方法 (Diffraction light guide plate and method for manufacturing same ) 是由 郑顺和 崔熙正 金在永 金泳锡 金宪 金惠珉 张影来 于 2020-08-13 设计创作，主要内容包括：本发明涉及衍射导光板和用于制造衍射导光板的方法,所述衍射导光板不仅具有优异的厚度均匀性和平坦度,而且具有低雾度和优异的可见性以及优异的机械特性例如铅笔硬度和强度等。(The present invention relates to a diffractive light guide plate having not only excellent thickness uniformity and flatness but also low haze and excellent visibility as well as excellent mechanical properties such as pencil hardness and strength, and the like, and a method for manufacturing the same.)

1. A diffractive light guide plate includes an optical layer having a diffraction grating pattern formed on one side,

wherein the diffraction grating pattern is formed as a unitary structure without an interface on one side of the optical layer,

a difference in refractive index between the diffraction grating pattern and one side of the optical layer is 0.01 or less, an

The optical layer having a diffraction grating pattern formed on one side is a continuous phase of a polymer comprising an episulfide compound, a thiol compound, and an aromatic cyclic compound having two or more hydroxyl groups.

2. The diffractive light guide plate according to claim 1,

wherein the refractive indices of the diffraction grating pattern and one side of the optical layer are 1.65 or more, respectively.

3. The diffractive light guide plate according to claim 1,

wherein the weight ratio of the thiol compound to the aromatic cyclic compound having two or more hydroxyl groups is 5:5 to 9: 1.

4. The diffractive light guide plate according to claim 1,

wherein the episulfide compound includes a compound represented by the following chemical formula 1,

the thiol compound includes at least one selected from the group consisting of compounds represented by the following chemical formulas 2 and 3, and

the aromatic cyclic compound having two or more hydroxyl groups includes at least one selected from the group consisting of compounds represented by the following chemical formulas 4 and 5:

[ chemical formula 1]

In the chemical formula 1, the first and second organic solvents,

R₁and R₂Each independently hydrogen or C1 to C10 alkyl,

R₃and R₄Each independently a single bond or a C1 to C10 alkylene group,

a is an integer of 0 to 4, and

b is an integer of 0 to 6,

[ chemical formula 2]

In the chemical formula 2,

R₅and R₆Each independently a single bond or a C1 to C10 alkylene group,

c is an integer of 0 to 4, and

d is an integer of 0 to 6,

[ chemical formula 3]

In the chemical formula 3, the first and second organic solvents,

ring A is a 5-or 6-membered aromatic heterocyclic ring containing one or more of nitrogen (N) and sulfur (S) atoms, and

e is an integer of 1 to 3,

[ chemical formula 4]

In the chemical formula 4, the first and second organic solvents,

R₇and R₈Each independently is deuterium, halogen, cyano, nitrile, nitro, amino, C1 to C40 alkyl, C1 to C40 alkoxy, C3 to C40 cycloalkyl, C1 to C40 alkenyl, C6 to C60 aryl, or C1 to C40 heteroaryl comprising one or more of O, N, Si and S,

f and g are each independently an integer from 1 to 7,

h and i are each independently an integer of 0 to 6,

f + h is an integer of 7 or less, and

g + i is an integer of 7 or less,

[ chemical formula 5]

In the chemical formula 5, the first and second organic solvents,

Ar₁and Ar₂Each independently a C6 to C60 aryl group substituted with one or more hydroxyl groups,

R₉and R₁₀Each independently is deuterium, halogen, cyano, nitrile, nitro, amino, C1 to C40 alkyl, C1 to C40 alkoxy, C3 to C40 cycloalkyl, C1 to C40 alkenyl, C6 to C60 aryl, or C1 to C40 heteroaryl comprising one or more of O, N, Si and S, and

m and n are each independently an integer of 0 to 4.

5. The diffractive light guide plate according to claim 1,

wherein the thickness of the diffraction light guide plate is 0.1mm to 10 mm.

6. The diffractive light guide plate according to claim 1,

wherein the diffraction grating pattern comprises one or more pattern units, and

the pattern units have a pitch of 0.1 to 1 μm and a height of 0.1 to 1 μm.

7. The diffractive light guide plate according to claim 1,

wherein the warpage of the diffractive light guide plate is 100 μm or less,

the diffraction light guide plate has a haze of 4.0% or less,

the diffraction light guide plate has a pencil hardness of HB or more, an

The thickness deviation of the diffraction light guide plate is 3.0% or less.

8. The diffractive light guide plate according to claim 1,

wherein the diffraction light guide plate has a transmittance of 80% or more, an

The diffraction light guide plate has a Yellowness Index (YI) of 1 to 30.

9. The diffractive light guide plate according to claim 1,

wherein the diffractive light guide plate is used for a diffractive light guide lens of a wearable device.

10. A method for manufacturing a diffractive light guide plate, comprising the steps of:

preparing a mold apparatus including a flat lower substrate, a flat upper substrate, a buffer spacer between the flat lower substrate and the flat upper substrate, and a template engraved with a diffraction grating pattern included in the flat lower substrate or the flat upper substrate, wherein a molding space is divided by the buffer spacer;

substantially filling the molding space with a curable composition; and

compressing the curable composition with the load of the flat upper substrate and curing the curable composition,

wherein the curable composition comprises an episulfide compound, a thiol compound, and an aromatic cyclic compound having two or more hydroxyl groups, and

performing the steps of compressing the curable composition with the load of the flat upper substrate and curing the curable composition to satisfy the following formula 1:

[ formula 1]

{ (the load of the flat upper substrate + the shrinkage force of the curable composition). times.0.95 }. ltoreq. compressive stress of the cushioning spacer ≦ { (the load of the flat upper substrate + the shrinkage force of the curable composition). times.1.05 }.

11. The method for manufacturing a diffractive light guide plate according to claim 10,

wherein the flexural moduli of the flat lower substrate and the flat upper substrate are respectively 3GPa or more.

12. The method for manufacturing a diffractive light guide plate according to claim 10,

wherein the flexural modulus of the template engraved with the diffraction grating pattern is 1GPa to 20 GPa.

13. The method for manufacturing a diffractive light guide plate according to claim 10,

wherein the flat lower substrate and the flat upper substrate have surface flatness of 5 μm or less, respectively.

14. The method for manufacturing a diffractive light guide plate according to claim 10,

wherein the buffer spacer has a compressive modulus of elasticity of 0.1MPa to 10 MPa.

15. The method for manufacturing a diffractive light guide plate according to claim 10,

wherein the cushioning spacer has a structure in which a non-elastic layer and an elastic layer are laminated, a structure in which an elastic layer is located between non-elastic layers, or a structure in which a non-elastic layer is located between elastic layers.

16. The method for manufacturing a diffractive light guide plate according to claim 10,

wherein the weight ratio of the thiol compound to the aromatic cyclic compound having two or more hydroxyl groups is 5:5 to 9: 1.

17. The method for manufacturing a diffractive light guide plate according to claim 10,

wherein the episulfide compound includes a compound represented by the following chemical formula 1,

the thiol compound includes at least one selected from the group consisting of compounds represented by the following chemical formulas 2 and 3, and

the aromatic cyclic compound having two or more hydroxyl groups includes at least one selected from the group consisting of compounds represented by the following chemical formulas 4 and 5:

[ chemical formula 1]

In the chemical formula 1, the first and second organic solvents,

R₁and R₂Each independently hydrogen or C1 to C10 alkyl,

R₃and R₄Each independently a single bond or a C1 to C10 alkylene group,

a is an integer of 0 to 4, and

b is an integer of 0 to 6,

[ chemical formula 2]

In the chemical formula 2,

R₅and R₆Each independently a single bond or a C1 to C10 alkylene group,

c is an integer of 0 to 4, and

d is an integer of 0 to 6,

[ chemical formula 3]

In the chemical formula 3, the first and second organic solvents,

ring A is a 5-or 6-membered aromatic heterocyclic ring containing one or more of nitrogen (N) and sulfur (S) atoms, and

e is an integer of 1 to 3,

[ chemical formula 4]

In the chemical formula 4, the first and second organic solvents,

R₇and R₈Each independently is deuterium, halogen, cyano, nitrile, nitro, amino, C1 to C40 alkyl, C1 to C40 alkoxy, C3 to C40 cycloalkyl, C1 to C40 alkenyl, C6 to C60 aryl, or C1 to C40 heteroaryl comprising one or more of O, N, Si and S,

f and g are each independently an integer from 1 to 7,

h and i are each independently an integer of 0 to 6,

f + h is an integer of 7 or less, and

g + i is an integer of 7 or less,

[ chemical formula 5]

In the chemical formula 5, the first and second organic solvents,

Ar₁and Ar₂Each independently a C6 to C60 aryl group substituted with one or more hydroxyl groups,

R₉and R₁₀Each independently is deuterium, halogen, cyano, nitrile, nitro, amino, C1 to C40 alkyl, C1 to C40 alkoxy, C3 to C40 cycloalkyl, C1 to C40 alkenyl, C6 to C60 aryl, or C1 to C40 heteroaryl comprising one or more of O, N, Si and S, and

m and n are each independently an integer of 0 to 4.

18. The method for manufacturing a diffractive light guide plate according to claim 10,

wherein the curable composition has a cure shrinkage of 15% or less.

19. The method for manufacturing a diffractive light guide plate according to claim 10,

wherein the viscosity of the curable composition after being held at a temperature of-5 ℃ to 0 ℃ for 12 hours is 4000cP or less.

Technical Field

Cross Reference to Related Applications

This application claims the benefits of korean patent application No. 10-2019-.

The present invention relates to a diffractive light guide plate and a method for manufacturing a diffractive light guide plate.

Background

Recently, apparatuses for providing a three-dimensional image to a user using a virtual reality apparatus, an augmented reality apparatus, and the like are being developed.

Virtual reality devices and augmented reality devices may form diffractive light guide patterns on lenses, such as ordinary eyeglasses, to display desired images to a user.

Generally, glass having a high refractive index is used as a lens for a virtual reality device or an augmented reality device, but although glass may have a high refractive index, light transmittance, flatness, and strength, it may cause serious damage to the eyeball of a user, and its density is high and weight is heavy, thus being inconvenient to wear for a long time.

Therefore, research on such lenses is required: it has high optical transparency and high refractive index and is light and relatively safe when damaged, so that it can be used in virtual reality devices or augmented reality devices.

Although the high refractive index plastic used in place of glass is very light and can realize various colors, characteristics such as surface flatness and thickness uniformity are significantly inferior to existing glass.

Further, during the imprinting process for forming the diffraction grating, it may be deformed due to low strength, or in the case of using inorganic particles in large amounts in order to achieve a high refractive index, haze may be generated in a final product, and interfacial adhesion between the substrate and the high refractive index plastic is poor, and thus, it is difficult to secure a high pencil hardness. Therefore, research into improvement thereof is required.

Disclosure of Invention

Technical problem

An object of the present invention is to provide a diffractive light guide plate which not only has excellent thickness uniformity and flatness, but also has low haze and excellent mechanical properties such as pencil hardness and strength, etc., is lighter than glass or tempered glass, and can realize a high refractive index.

Another object of the present invention is to provide a method for manufacturing a diffractive light guide plate, which prepares a diffractive light guide plate through a simple process.

Technical scheme

There is provided a diffractive light guide plate including an optical layer having a diffraction grating pattern formed on one side, wherein the diffraction grating pattern is formed on one side of the optical layer as an integral structure having no interface, a refractive index difference between the diffraction grating pattern and one side of the optical layer is 0.01 or less, and the optical layer having the diffraction grating pattern formed on one side is a continuous phase of a polymer including an episulfide compound, a thiol compound, and an aromatic cyclic compound having two or more hydroxyl groups.

Also provided is a method for manufacturing a diffractive light guide plate, comprising the steps of: preparing a mold apparatus including a flat lower substrate, a flat upper substrate, a buffer spacer between the flat lower substrate and the flat upper substrate, and a template engraved with a diffraction grating pattern included in the flat lower substrate or the flat upper substrate, wherein a molding space is divided by the buffer spacer; substantially filling the molding space with a curable composition; and compressing the curable composition with a support of a flat upper substrate and curing the curable composition, wherein the curable composition comprises an episulfide compound, a thiol compound, and an aromatic cyclic compound having two or more hydroxyl groups, and the step of compressing the curable composition with a support of a flat upper substrate and curing the curable composition is performed so as to satisfy the following formula 1:

[ formula 1]

{ (the load of the flat upper substrate + the shrinkage force of the curable composition). times.0.95 }. ltoreq. compressive stress of the cushioning spacer ≦ { (the load of the flat upper substrate + the shrinkage force of the curable composition). times.1.05 }.

Hereinafter, a diffractive light guide plate and a method for manufacturing a diffractive light guide plate according to embodiments of the present invention will be described in detail.

Throughout the specification, when it is described that one component "includes" a constituent element, unless specifically described to the contrary, it is not intended to exclude another constituent element, but is intended to include another constituent element as well.

Further, when it is described that one member is located "on" another member, it includes not only a case where one member is in contact with another member but also a case where another member is present between two members.

Further, the term "step of … …" does not mean "step for … …".

As used herein, "episulfide compound" means a compound comprising one or more episulfide compounds, and episulfide means a compound in which the oxygen (O) atom of an epoxide is replaced by a sulfur (S) atom.

As used herein, "thiol compound" means a compound comprising one or more thiol groups (-SH).

As used herein, "curing" means both thermal curing and photocuring, and "curable composition" means a thermally and/or photocurable composition.

As used herein, high refractive index means about 1.6 or greater at a wavelength region of 350nm to 800nm or at a wavelength of 532 nm.

According to one embodiment of the present invention, there is provided a diffractive light guide plate including an optical layer having a diffraction grating pattern formed on one side, wherein the diffraction grating pattern is formed on one side of the optical layer as an integral structure having no interface, a refractive index difference between the diffraction grating pattern and one side of the optical layer is 0.01 or less, and the optical layer having the diffraction grating pattern formed on one side is a continuous phase of a polymer including an episulfide compound, a thiol compound, and an aromatic cyclic compound having two or more hydroxyl groups.

In the optical layer having a diffraction grating pattern formed on one side included in the diffractive light guide plate according to one embodiment, in the case where the diffraction grating pattern is formed as an integral structure having no interface on one side of the optical layer, and such an optical layer is a continuous phase of a polymer including an episulfide compound, a thiol compound, and an aromatic cyclic compound having two or more hydroxyl groups, mechanical characteristics of the diffractive light guide plate, such as pencil hardness and strength, etc., are excellent. Further, since the refractive index difference between the diffraction grating pattern and one side of the optical layer is small, the transmittance reduction or haze generation caused by the interface is not caused, and the total reflection efficiency of light entering the diffraction light guide plate is increased, and thus, when it is used for a virtual reality device or the like, it may display a high resolution image having higher luminance.

Previously, a light guide plate having a pattern portion was prepared by a process of: the imprint resin composition is applied on a substrate and dried to form a resin layer, and then a template engraved with a diffraction grating pattern is imprinted on the resin layer, but the diffraction light guide plate prepared by such a method has an interface between the substrate and the pattern portion, and the interface adhesion is poor, and thus it is difficult to secure mechanical characteristics such as pencil hardness and the like. However, the diffractive light guide plate according to one embodiment may exhibit excellent mechanical characteristics such as high pencil hardness and strength, etc., because the diffraction grating pattern is formed as an integral structure having no interface on one side of the optical layer.

Further, since the optical layer having the diffraction grating pattern formed on one side included in the diffractive light guide plate is a continuous phase of a polymer including an episulfide compound, a thiol compound, and an aromatic cyclic compound having two or more hydroxyl groups, it has a high refractive index similar to glass, and can be used as a diffractive light guide lens of a wearable device. Therefore, it is possible to prevent the conventional problems caused by glass breakage, the difficulty of wearing for a long time due to the heavy weight of glass, and the like. Further, even if the diffractive light guide plate does not additionally include inorganic particles, it can achieve a high refractive index, and thus, it has low haze and high visibility because haze due to the inorganic particles is not generated. In addition, the diffractive light guide plate may be prepared by a manufacturing method of the diffractive light guide plate as described later, and thus it may have excellent thickness uniformity and flatness.

Since the optical layer having the diffraction grating pattern formed on one side is a continuous phase of a polymer including an episulfide compound, a thiol compound, and an aromatic cyclic compound having two or more hydroxyl groups, the refractive index difference between the diffraction grating pattern and one side of the optical layer may be 0.01 or less, 0.05 or less, 0.001 or less, or 0.001 to 0.0001. If the refractive index difference between the diffraction grating pattern and one side of the optical layer is greater than 0.01, the transmittance may be reduced or haze may be generated due to the interface between the diffraction grating pattern and one side of the optical layer. Accordingly, since the refractive index difference between the diffraction grating pattern and one side of the optical layer satisfies the above range, there is no problem of the transmittance reduction or haze generation caused by the interface, and the total reflection efficiency of the guided light may be increased, and thus, when used for a virtual reality device or the like, an image having higher brightness may be displayed.

Fig. 1 is a schematic view showing a cross section of an optical layer included in a diffractive light guide plate according to an embodiment. Specifically, on one side of the optical layer 300, a diffraction grating pattern 200 is formed, and the diffraction grating pattern may include one or more pattern units 400.

In particular, the diffraction grating pattern 200 may include two or more pattern units 400 spaced apart on one side in the direction of the other side. The pattern unit is not particularly limited as long as it can diffract the guided light, but it may be a grating pattern having a quadrangular prism, a hexagonal prism, a triangular pyramid, a cone, an elliptical cone, or a hemispherical shape; or a stripe or stripe pattern. Meanwhile, the shape of the cross section of the pattern unit is not particularly limited, but for example, it may have a quadrangular, triangular, rhombic, trapezoidal, parabolic, or the like shape. The direction of the cross section of the pattern unit may be perpendicular to the diffractive light guide plate.

Further, the pitch of the pattern unit 400 included in the diffraction grating pattern 200 may be 0.1 μm to 1 μm, 0.2 μm to 0.9 μm, 0.3 μm to 0.8 μm, or 0.4 μm to 0.7 μm, and the height may be 0.1 μm to 1 μm, 0.2 μm to 0.9 μm, 0.3 μm to 0.8 μm, or 0.4 μm to 0.7 μm.

The pitch means an interval of the repeating pattern unit 400, and particularly, it may mean a length between one point of one pattern unit and one point of another pattern unit adjacent thereto. Further, one point of one pattern unit and one point of another pattern unit may mean positions corresponding to each other, and the length direction is a direction parallel to the optical layer 300. In addition, the height direction is a direction perpendicular to the optical layer.

In the case where the diffraction grating pattern 200 includes two or more pattern units 400, the two or more pattern units may be the same, and in particular, the shape, pitch, height, etc. of the cross section may be the same as each other. Accordingly, the amount of light diffracted over the entire area of the diffractive light guide plate may be the same. Further, two or more pattern units 400 included in the diffraction grating pattern 200 may be different, and in particular, the shape of the cross section may be the same but the pitch and the height may be different, or the pitch may be the same but the shape and the height of the cross section may be different.

The optical layer 300 may have a thickness of 0.1mm to 10mm, 0.2mm to 9mm, 0.3mm to 8mm, 0.4mm to 7mm, or 0.5mm to 5 mm. If the thickness of the optical layer 300 is too thin, the number of total reflections of light entering the diffractive light guide plate including the optical layer may be unnecessarily increased, and the luminance of light emitted from the diffractive light guide plate may be reduced, and thus, in the case where such a diffractive light guide plate is used for a virtual reality device or the like, the resolution may be reduced. Meanwhile, if the thickness of the optical layer is too thick, the transmittance of external light with respect to a diffractive light guide plate including the optical layer may be reduced, and the brightness of an external image may be reduced, and thus visibility may be reduced.

The optical layer 300 having the diffraction grating pattern 200 formed on one side may be a continuous phase of a polymer including an episulfide compound, a thiol compound, and an aromatic cyclic compound having two or more hydroxyl groups.

The diffractive light guide plate may be manufactured by a one-step method by a manufacturing method of a diffractive light guide plate as described later, and thus, the diffraction grating pattern is formed as an integral structure having no interface on one side of the optical layer, and the optical layer and the diffraction grating pattern formed on one side of the optical layer may contain a cured product of the same curable composition. That is, the optical layer having the diffraction grating pattern formed on one side corresponds to a continuous phase of a polymer including an episulfide compound, a thiol compound, and an aromatic cyclic compound having two or more hydroxyl groups. In addition, the continuous phase of the polymer can achieve a high refractive index without including inorganic particles, thereby preventing haze generated when a large amount of inorganic particles is used.

The weight ratio of the thiol compound to the aromatic cyclic compound having two or more hydroxyl groups can be 5:5 to 9:1, 7:3 to 8.5:1.5, or 7:3 to 8: 2. If the weight ratio of the thiol compound to the aromatic cyclic compound having two or more hydroxyl groups is less than 5:5, it may be difficult to achieve a high refractive index of the diffraction light guide plate, and if the weight ratio is greater than 9:1, it may be difficult to control the curing speed of the curable composition including the same, thus generating striations in the diffraction light guide plate.

The episulfide compound may include a compound represented by the following chemical formula 1.

[ chemical formula 1]

In the chemical formula 1, the first and second,

R₁and R₂Each independently hydrogen or C1 to C10 alkyl,

R₃and R₄Each independently a single bond or a C1 to C10 alkylene group,

a is an integer of 0 to 4, and

b is an integer of 0 to 6,

the episulfide compound represented by chemical formula 1 has an aliphatic chain skeleton in which an episulfide is connected to both ends, and in the aliphatic chain, it may include a thioether repeating unit in which alkylene groups are connected through a sulfur (S) atom.

Due to the above chemical structure, the episulfide compound can contain a high content of sulfur (S) atoms having high atomic refraction in the molecule, and by such a high sulfur atom content, it can increase the refractive index of the diffraction light guide plate. In addition, the episulfide compound can be cured by ring-opening polymerization, and the alkylene sulfide group formed by ring-opening polymerization of the episulfide group can further improve the high refractive index of the diffraction light guide plate.

Meanwhile, in chemical formula 1, R₁And R₂Each of which may independently be hydrogen or methyl, but is not limited thereto.

Furthermore, R₃And R₄Each of which may be independently a single bond, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, or an isobutylene group, but is not limited thereto.

Further, each of a and b may be independently 0 or 1.

A in chemical formula 1 is related to the carbon number of the alkylene group contained in the thioether repeating unit, and if a is too large, the length of a carbon chain in a molecule may become long, and the glass transition temperature of the diffraction light guide plate may decrease, and thus the heat resistance of the diffraction light guide plate may deteriorate, and the relative content of sulfur may decrease, and thus the refractive index of the diffraction light guide plate may decrease.

B in chemical formula 1 is the number of repetitions of the thioether repeating unit in which alkylene groups are connected through a sulfur (S) atom, and if b is too large, the chain length of molecules may become long, the glass transition temperature of the diffraction light guide plate may decrease during curing, and thus the heat resistance of the diffraction light guide plate may deteriorate.

In addition, the compound represented by chemical formula 1 may be used alone, or two or more kinds may be used in combination.

The episulfide compound may include at least one selected from the group consisting of: bis (β -epithiopropyl) sulfide, bis (β -epithiopropyl) disulfide, bis (β -epithiopropylthio) methane, 1, 2-bis (β -epithiopropylthio) ethane, 1, 3-bis (β -epithiopropylthio) propane, 1, 4-bis (β -epithiopropylthio) butane, and the like, but are not limited thereto.

The content of the episulfide compound may be 50 to 99 wt%, 60 to 95 wt%, or 70 to 90 wt% based on 100 wt% of the entire diffractive light guide plate. If the content of the episulfide compound is too large, the glass transition temperature of the diffractive light guide plate may decrease, and the Yellowness Index (YI) may increase. Meanwhile, if the content of the episulfide compound is too small, the glass transition temperature of the diffractive light guide plate may decrease, the Yellowness Index (YI) may increase, and mechanical properties such as hardness and strength may deteriorate.

The thiol compound may include at least one selected from the compounds represented by the following chemical formulas 2 and 3.

[ chemical formula 2]

In the chemical formula 2, the first and second organic solvents,

R₅and R₆Each independently a single bond or a C1 to C10 alkylene group,

c is an integer of 0 to 4,

d is an integer of 0 to 6,

[ chemical formula 3]

In the chemical formula 3, the first and second,

ring A is a 5-or 6-membered aromatic heterocyclic ring containing one or more of nitrogen (N) and sulfur (S) atoms, and

e is an integer of 1 to 3.

Specifically, the thiol compound represented by chemical formula 2 has an aliphatic chain skeleton in which thiol groups (-SH) are attached to both ends, and in the aliphatic chain, it may include a thioether repeating unit in which alkylene groups are connected through a sulfur (S) atom.

Meanwhile, the thiol compound represented by chemical formula 3 may have a structure in which one or more thiol groups are attached to a 5-or 6-membered aromatic ring including a heteroatom, such as nitrogen (N) and/or sulfur (S).

The thiol compound represented by chemical formula 2 or 3 may react with the episulfide group to form a disulfide bond through a curing reaction with the episulfide compound (i.e., ring-opening polymerization of the episulfide group), and it contains a high content of sulfur (S) atoms having high atomic refraction in the molecule, and thus may further increase the refractive index of the diffraction light guide plate and improve the physical strength of the diffraction light guide plate.

Meanwhile, in chemical formula 2, R₅And R₆Each of which may be independently a single bond, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, or an isobutylene group, but is not limited thereto.

Further, each of c and d may be independently 0 or 1.

C in chemical formula 2 is related to the carbon number of the alkylene group contained in the thioether repeating unit, and if c is too large, the length of a carbon chain in a molecule may become long, and the glass transition temperature of the diffraction light guide plate may decrease, and thus the heat resistance of the diffraction light guide plate may deteriorate, and the relative content of sulfur may decrease, and thus the refractive index of the diffraction light guide plate may decrease.

D in chemical formula 2 is the number of repetitions of the thioether repeating unit in which alkylene groups are connected through a sulfur (S) atom, and if d is too large, the chain length of the molecule may become long, the glass transition temperature of the diffraction light guide plate may decrease, and thus the heat resistance of the diffraction light guide plate may deteriorate.

In addition, in chemical formula 3, the a ring may be pyridine, pyrimidine, triazine, imidazole, thiophene, thiazole, or thiadiazole, but is not limited thereto.

Furthermore, e may be 2 or 3.

In addition, the compounds represented by chemical formula 2 or 3 may be used alone, or two or more kinds may be used in combination.

The thiol compound may include, for example, at least one selected from the following compounds.

The content of the thiol compound may be 1 to 30 wt%, 5 to 25 wt%, or 7 to 10 wt% based on 100 wt% of the entire diffractive light guide plate. If the content of the thiol compound is too large, the glass transition temperature of the diffractive light guide plate may decrease, the Yellowness Index (YI) may increase, and physical properties such as hardness and strength may deteriorate. Meanwhile, if the content of the thiol compound is too small, the glass transition temperature of the diffractive light guide plate may decrease and the Yellowness Index (YI) may increase.

The aromatic cyclic compound having two or more hydroxyl groups may include at least one selected from the group consisting of compounds represented by the following chemical formulas 4 and 5:

[ chemical formula 4]

In the chemical formula 4, the first and second organic solvents,

R₇and R₈Each of which isIndependently deuterium, halogen, cyano, nitrile, nitro, amino, C1 to C40 alkyl, C1 to C40 alkoxy, C3 to C40 cycloalkyl, C1 to C40 alkenyl, C6 to C60 aryl, or C1 to C40 heteroaryl comprising one or more of O, N, Si and S,

f and g are each independently an integer from 1 to 7,

h and i are each independently an integer of 0 to 6,

f + h is an integer of 7 or less, and

g + i is an integer of 7 or less,

[ chemical formula 5]

In the chemical formula 5, the first and second organic solvents,

Ar₁and Ar₂Each independently a C6 to C60 aryl group substituted with one or more hydroxyl groups,

R₉and R₁₀Each independently is deuterium, halogen, cyano, nitrile, nitro, amino, C1 to C40 alkyl, C1 to C40 alkoxy, C3 to C40 cycloalkyl, C1 to C40 alkenyl, C6 to C60 aryl, or C1 to C40 heteroaryl comprising one or more of O, N, Si and S, and

m and n are each independently an integer of 0 to 4.

Specifically, the aromatic cyclic compound having two or more hydroxyl groups represented by chemical formula 4 has a skeleton in which two naphthalenes are linked, and one or more hydroxyl groups may be linked to each naphthalene.

Meanwhile, the aromatic cyclic compound having two or more hydroxyl groups represented by chemical formula 5 may have a form in which two aryl groups substituted with one or more hydroxyl groups are substituted at the 9-position of fluorene.

The aromatic cyclic compound having two or more hydroxyl groups represented by chemical formula 4 or 5 may achieve a high refractive index of the diffractive light guide plate through conjugation of the aromatic functional group, and due to such aromatic functional group, even if the aromatic cyclic compound is included in the diffractive light guide plate and the sulfur atom content is reduced, a decrease in refractive index may be minimized, and a glass transition temperature (Tg) of the diffractive light guide plate may be increased, thereby improving mechanical characteristics.

Meanwhile, in chemical formula 4, R₇And R₈Each of which may be independently deuterium, halogen, cyano, nitrile, nitro, amino, methyl or ethyl, but is not limited thereto.

Further, each of f and g may independently be 1 or 2.

Further, each of h and i may independently be 0 or 1.

Further, in chemical formula 5, Ar₁And Ar₂Each of which may be independently phenyl or naphthyl substituted with one or two hydroxyl groups, but is not limited thereto.

Furthermore, R₉And R₁₀Each of which may be independently deuterium, halogen, cyano, nitrile, nitro, amino, methyl or ethyl, but is not limited thereto.

Further, each of m and n may be independently 0 or 1.

In addition, the compounds represented by chemical formula 4 or 5 may be used alone, or two or more kinds may be used in combination.

The aromatic cyclic compound having two or more hydroxyl groups may include, for example, at least one selected from the following compounds.

The content of the aromatic cyclic compound having two or more hydroxyl groups may be 0.1 to 10 wt%, 0.5 to 5 wt%, or 1 to 3 wt% based on 100 wt% of the entire diffractive light guide plate. If the content of the aromatic cyclic compound having two or more hydroxyl groups is too large, the refractive index of the diffractive light guide plate may be decreased, and if the content is too small, the curing speed may be too fast, and thus striations may be generated in the diffractive light guide plate.

In addition, the continuous phase of the polymer may also contain a catalyst. The catalyst may include, for example, amines, ammonium salts or phosphates and the like, and specifically, imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole and the like; amine compounds such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, N-dicyclohexylmethylamine, and the like; hydrazine compounds such as adipic acid dihydrazide, sebacic acid dihydrazide, and the like; phosphorus compounds such as triphenylphosphine and the like. Further, as commercially available products, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (which are trade names of imidazole-based compounds) from Shikoku Chemicals Corporation; U-CAT3503N, UCAT3502T (which is a trade name for block isocyanate compounds of dimethylamine) from Sanapro co., ltd.; and DBU, DBN, U-CATSA102, U-CAT5002 (which is a bicyclic amidine compound and salts thereof); and so on.

The content of the catalyst may be 0.001 to 10 wt%, 0.01 to 5 wt%, or 0.1 to 1 wt% based on 100 wt% of the entire diffraction light guide plate.

In addition, the diffractive light guide plate may further include other additives for imparting specific functions to the display substrate in the art to which the present invention pertains, such as UV absorbers, bluing agents, pigments, and the like.

The continuous phase of the polymer may be a photo-cured product or a thermally cured product.

The refractive indices of one side of the diffraction grating pattern 200 and the optical layer 300 at a wavelength of 532nm may be 1.65 or more, 1.70 or more, 1.72 or more, or 1.73 to 2.5, respectively. The refractive index of a general glass substrate at a wavelength of 532nm is 1.65 or more. Accordingly, a diffractive light guide plate including an optical layer having a diffraction grating pattern formed on one side, although made of plastic, can achieve a refractive index equivalent to that of a glass substrate, and thus can replace the glass substrate. Further, due to the high refractive index, in the case where it is used as a lens of a wearable device, it is possible to minimize optical loss and facilitate transmission of optical information.

Further, the glass transition temperature of the diffractive light guide plate may be 40 ℃ or more, 40 ℃ to 150 ℃, 50 ℃ to 130 ℃, or 80 ℃ to 100 ℃. In the case of wearable devices, the temperature of the lens may increase as successive image transmissions and outputs proceed. Meanwhile, since the diffractive light guide plate can achieve a glass transition temperature of 40 ℃ or more, it can minimize a characteristic variation according to temperature even if used as a lens of a wearable device, thereby achieving high durability.

The haze of the diffractive light guide plate may be 4.0% or less, 3.0% or less, 2.0% or less, or 1.5% to 0.01%. Since the diffractive light guide plate exhibits a refractive index of 1.65 or more without including inorganic particles, it does not cause haze, and thus has high visibility.

Further, the pencil hardness of the diffractive light guide plate may be HB or more, H or more, or 2H or more. Since the diffraction grating pattern 200 is formed as an integral structure having no interface on one side of the optical layer 300, mechanical characteristics such as pencil hardness and strength are excellent.

Further, the diffractive light guide plate may have a thickness deviation of 3.0% or less, 2.5% or less, 1% or less, or 0.1% to 1% although it includes one or more pattern units. The smaller the thickness deviation is, the higher the thickness uniformity of the diffractive light guide plate is, and thus, the diffractive light guide plate according to an embodiment may have excellent thickness uniformity.

Further, the thickness deviation of the diffractive light guide plate can be calculated by the following general formula 1.

[ general formula 1]

Thickness deviation (%) (maximum deviation/average thickness) × 100

The maximum or minimum thickness can be measured by contact measurement at 25 ℃ and 50 RH% atmosphere using a Digimatic Thick 547-401 apparatus from Mitsutoyo. Alternatively, the maximum thickness or the minimum thickness can be measured by non-contact measurement using IFS-2405-1 or IFC-2451-MP equipment from Micro-Epsilon at 25 ℃ and 50 RH% atmosphere.

The average thickness may be an average of thicknesses measured at a radius of 10mm and at intervals of 22.5 ° by contact measurement using a Digimatic Thick 547-401 apparatus from Mitsutoyo under an atmosphere of 25 ℃ and 50 RH% with arbitrary points of randomly arranged specimens as starting points. Alternatively, the average Thickness may be an average value of thicknesses measured at intervals of 1mm width and 1mm length by non-contact Measurement using OWTM (Optical Wafer Thickness Measurement system) equipment from Fiberpro at 25 ℃ and 50 RH% atmosphere with arbitrary points of randomly arranged samples as starting points.

The warping of the diffractive light guide plate may be 100 μm or less, 50 μm or less, 20 μm or less, 10 μm or less, or 0.1 μm to 10 μm. The diffractive light guide plate manufactured by the manufacturing method of the diffractive light guide plate according to one embodiment may satisfy the above warping range, and if the warping of the diffractive light guide plate is greater than 100 μm, the reflection angle of light entering the diffractive light guide plate may not be maintained, and in the case of being used for a virtual reality device or the like, the resolution may be lowered.

The warping is the overall curvature of the diffractive light guide plate expressed as a numerical value, and can be calculated by the following general formula 2.

[ general formula 2]

Warp-the maximum deviation of the center side from the base side-the minimum deviation of the center side from the base side

The center side in general formula 2 is a side surface of the diffractive light guide plate corresponding to the intermediate thickness, and the base side is a side surface calculated by performing least square fitting to the center side in the measurement region. Thus, the warpage corresponds to the difference between the maximum deviation and the minimum deviation of the base side and the center side.

Meanwhile, the center side can be drawn by a non-contact measurement method using an OWTM (optical wafer thickness measuring system) device from Fiberpro at 25 ℃ and 50 RH% atmosphere.

Further, the diffractive light guide plate may have a very high transmittance of 80% or more, 80% to 99%, or 85% to 90%, particularly measured according to JIS K7361 at a thickness of 1 mm.

Further, the diffractive light guide plate can have a low Yellowness Index (YI) of 1 to 30, 2 to 22, 2.1 to 10, 2.2 to 5, or 2.3 to 4, particularly measured according to ASTM E313-1973.

The diffractive light guide plate may be used for a diffractive light guide lens of a wearable device. In particular, the wearable device is an augmented reality device or a virtual reality device, the diffractive light guide plate may be included as a lens of the wearable device, and input, movement, and transmission of optical information may be facilitated due to the inclusion of the diffraction grating pattern in the diffractive light guide plate.

According to another embodiment of the present invention, there is provided a method for manufacturing the above-described diffractive light guide plate.

The inventors have recognized the following and developed the present invention: in the case where the curable composition is injected into a general mold apparatus and cured to prepare a substrate, a cured product may be delaminated from a mold base due to curing shrinkage of the curable composition, and thus, a delamination point may remain on a surface of the prepared substrate, and thickness uniformity may be significantly deteriorated, whereas in the case where an imprint resin composition is applied on a substrate prepared through a molding process and dried to form a resin layer, and then a diffraction light guide plate is manufactured through an imprint process on the resin layer, interfacial adhesion between the substrate and the imprint resin layer may be poor, and thus, it may be difficult to secure high pencil hardness.

A method for manufacturing a diffractive light guide plate according to another embodiment includes the steps of: preparing a mold apparatus including a flat lower substrate, a flat upper substrate, a buffer spacer between the flat lower substrate and the flat upper substrate, and a template engraved with a diffraction grating pattern included in the flat lower substrate or the flat upper substrate, wherein a molding space is divided by the buffer spacer;

substantially filling the molding space with a curable composition; and

compressing the curable composition with a load of a flat upper substrate and curing the curable composition,

wherein the curable composition comprises an episulfide compound, a thiol compound, and an aromatic cyclic compound having two or more hydroxyl groups, and

the step of compressing the curable composition with a load of a flat upper substrate and curing the curable composition is performed to satisfy the following formula 1:

[ formula 1]

{ (the load of the flat upper substrate + the shrinkage force of the curable composition). times.0.95 }. ltoreq. compressive stress of the cushioning spacer ≦ { (the load of the flat upper substrate + the shrinkage force of the curable composition). times.1.05 }.

Since the method for manufacturing a diffractive light guide plate according to another embodiment uses the buffer spacer, delamination of a cured product from the flat lower substrate and the flat upper substrate of the mold apparatus caused by curing shrinkage of the curable composition during curing of the curable composition may be minimized, and thus a diffractive light guide plate having very excellent surface flatness and thickness uniformity may be prepared.

Further, by using a template engraved with a diffraction grating pattern, the diffraction grating pattern engraved in the template is compressed on the upper or lower portion of the cured product while curing the curable composition, and thus the diffraction grating pattern can be formed on one side of the finally prepared diffraction light guide plate. Accordingly, a diffractive light guide plate including an optical layer having a diffraction grating pattern formed on one side can be prepared by a simple one-step process without performing an additional resin layer forming process and imprinting process, and mechanical properties such as pencil hardness and strength, etc. are excellent since the diffraction grating pattern is formed as an integral structure having no interface on one side of the optical layer.

Meanwhile, the compressive stress of the buffer spacer satisfies the above formula 1. Since the variation in the compressive stress of the buffer spacer is within 5% of the sum of the load of the flat upper substrate and the shrinkage force of the curable composition, the flat upper substrate adheres to the curable composition by curing shrinkage of the curable composition in the step of curing the curable composition. Therefore, the prepared diffractive light guide plate exhibits excellent surface flatness, and thus excellent thickness uniformity can be achieved.

Further, since the compressive stress of the buffer spacer satisfies the above formula 1, the template included in the flat lower substrate or the flat upper substrate may also be adhered to the curable composition, and thus, the diffraction grating pattern engraved in the template may be clearly shown as a diffraction grating pattern on one side of the cured product.

Meanwhile, if the compressive stress of the buffer spacer is less than { (load of the flat upper substrate + shrinkage force of the curable composition) × 0.95}, curing may be completed before equilibrium is reached, and thus thickness unevenness of the diffraction light guide plate may be generated and the diffraction grating pattern may not be clearly shown. Further, if the compressive stress of the buffer spacer is greater than { (load of the flat upper substrate + shrinkage force of the curable composition) × 1.05}, shrinkage unevenness may be generated during curing, and thus, the appearance of the diffraction light guide plate may be poor.

Specifically, according to an example of the present invention, formula 1 may satisfy formula 1-1, formula 1-2, or formula 1-3 below.

[ formula 1-1]

{ (the load of the flat upper substrate + the shrinkage force of the curable composition). times.0.97 }. ltoreq. compressive stress of the cushioning spacer ≦ { (the load of the flat upper substrate + the shrinkage force of the curable composition). times.1.03 }.

[ formulae 1-2]

{ (load of flat upper substrate + shrinkage force of curable composition). times.0.98 }. ltoreq. compressive stress of the cushioning spacer ≦ { (load of flat upper substrate + shrinkage force of curable composition). times.1.02 }.

[ formulae 1 to 3]

{ (the load of the flat upper substrate + the shrinkage force of the curable composition). times.0.99 }. ltoreq. compressive stress of the cushioning spacer ≦ { (the load of the flat upper substrate + the shrinkage force of the curable composition). times.1.01 }.

In particular, the variation of the compressive stress of the buffer spacer may be within 3%, 2%, or 1% of the sum of the load of the flat upper substrate and the shrinkage force of the curable composition, and thus the prepared diffractive light guide plate may exhibit more excellent surface flatness and achieve more excellent thickness uniformity.

The load of the flat upper substrate, the shrinkage force of the curable composition, and the compressive stress of the buffer spacer may have a unit of kgf or N.

The buffer spacer can prevent the cured product of the curable composition from delaminating from the flat upper substrate due to curing shrinkage. Specifically, since the cushion spacer has a compressive stress in consideration of the curing shrinkage degree of the curable composition and the load of the flat upper substrate, the cushion spacer can be compressed by the load of the flat upper substrate according to the curing shrinkage of the curable composition, and thus, plays a role of maintaining the adhesion of the curable composition and the flat upper substrate in the step of curing the curable composition. Further, in the case where the template engraved with the diffraction grating pattern is included in and located on the flat upper substrate, the buffer spacer may play a role of maintaining adhesion of the template and the curable composition in the step of curing the curable composition.

The flat upper substrate may have a load of 3.4N to 34N, 5.9N to 27N, or 7N to 25N. In the case where the load of the flat upper substrate is within the above range, deformation caused by curing shrinkage during curing of the curable composition may be minimized, a decrease in transmittance during photocuring of the curable composition may be minimized, and release unevenness of reaction heat during thermal curing of the curable composition may be minimized, thereby causing uniform curing of the curable composition. Meanwhile, in the case where the template engraved with the diffraction grating pattern is included in and located on a flat upper substrate, the load of the flat upper substrate corresponds to the load including the load due to the template engraved with the diffraction grating pattern.

In formula 1, the curing shrinkage force of the curable composition can be measured as follows. Specifically, a certain amount of curable composition was applied on the lower jig at 25 ℃ and 50 RH% atmosphere using a texture analyzer device from TA Corporation, then the upper jig was lowered to contact the curable composition, and the initial value of the force was recorded. In addition, the temperature was raised to 90 ℃ and held for 5 hours, then the final value of the force was recorded, and the difference between the final value and the initial value was measured as the shrinkage force.

In equation 1, the compressive stress of the buffer spacer can be measured as follows. Specifically, 5X 5mm was compressed at a compression rate of 1 mm/min under an atmosphere of 50 RH% at 25 ℃ using a texture analyzer device from TA Corporation²When a specimen is used, the force at which the specimen is deformed ((initial thickness-thickness after deformation)/initial thickness) can be measured.

The molding space may be divided by a buffer spacer. Specifically, in the case where the mold plate engraved with the diffraction grating pattern is located on a flat lower substrate, the molding space is divided by the buffer spacer, and means an empty space between the mold plate and the flat upper substrate. Alternatively, in the case where the template engraved with the diffraction grating pattern is located on a flat upper substrate, the molding space is divided by the buffer spacer, and means an empty space between the template and the flat lower substrate.

The method for manufacturing a light guide plate according to another embodiment may include the step of sufficiently filling the curable composition in the molding space.

Specifically, the step of sufficiently filling the curable composition may mean injecting the curable composition into the molding space and sufficiently filling so that the curable composition may adhere to the flat lower substrate (or the flat upper substrate) and the template engraved with the diffraction grating pattern. In particular, the curable composition may be adhered to the entire engraved pattern surface of the template without a gap. Specifically, the step of sufficiently filling the curable composition may mean injecting the curable composition into the molding space at 95 vol% or more, 97 vol% or more, 99 vol% or more, or 100 vol%.

Further, the step of substantially filling the curable composition may be performed by a variety of methods: a method such as injecting a curable composition into a molding space and a flat lower substrate partitioned by a buffer spacer, and laminating the flat upper substrate including a template; a method of injecting a curable composition into a molding space divided by a buffer spacer and a flat lower substrate including a template, and laminating the flat upper substrate; or a method of providing an inlet in a mold apparatus and injecting a curable composition; and so on.

Meanwhile, the curable composition may be a photocurable composition or a thermally curable composition, and is not limited as long as it is used for preparing a diffractive light guide plate. Specifically, the curable composition is not limited as long as it can be used for producing a diffraction light guide plate by mold casting. For example, the curable composition may contain the above-described episulfide compound, thiol compound, and aromatic cyclic compound having two or more hydroxyl groups. Specifically, the curable composition may include an episulfide compound represented by chemical formula 1, a thiol compound represented by chemical formula 2 or 3, and an aromatic ring compound having two or more hydroxyl groups represented by chemical formula 4 or 5. Meanwhile, with respect to chemical formulas 1 to 5, the above description of the diffractive light guide plate applies.

Further, in the photocurable composition, the weight ratio of the thiol compound to the aromatic cyclic compound having two or more hydroxyl groups may be 5:5 to 9:1, 7:3 to 8.5:1.5, or 7:3 to 8: 2. If the weight ratio of the thiol compound to the aromatic cyclic compound having two or more hydroxyl groups is less than 5:5, it may be difficult to achieve a high refractive index, and if the weight ratio is greater than 9:1, it may be difficult to control the curing speed during curing of the curable composition, and thus striations may be generated in the diffraction light guide plate, and it may be difficult to store the curable composition for a long time.

Further, the content of the episulfide compound may be 50 to 99 wt%, 60 to 95 wt%, or 70 to 90 wt% in the total 100 wt% of the photocurable composition. If the content of the episulfide compound is too large, the content of the cured product of a thiol compound or the like may be relatively reduced, and thus uncured by-products may be generated, whereby the glass transition temperature of the diffraction light guide plate may be lowered, and the Yellowness Index (YI) may be increased. In contrast, if the content of the episulfide compound is too small, the content of the curing agent of a thiol compound or the like may relatively increase, and thus the curing agent may not be sufficiently dissolved in the curable composition, or uncured by-products may be generated, whereby the glass transition temperature of the diffraction light guide plate may decrease, and the Yellowness Index (YI) may increase.

Further, the content of the thiol compound may be 1 to 30 wt%, 5 to 25 wt%, or 7 to 10 wt% in the total 100 wt% of the photocurable composition. If the content of the thiol compound is too large, the solid thiol compound may not be sufficiently dissolved in the curable composition, or the content of other components such as an episulfide compound and the like may be relatively reduced, and thus uncured by-products may be generated, whereby the glass transition temperature of the diffraction light guide plate may be lowered and the Yellowness Index (YI) may be increased. In contrast, if the content of the thiol compound is too small, the content of other components such as an episulfide compound and the like may relatively increase, and thus uncured by-products may be generated, whereby the glass transition temperature of the diffraction light guide plate may decrease, and the Yellowness Index (YI) may increase.

Further, the aromatic cyclic compound having two or more hydroxyl groups contained in the photocurable composition may control the curing reaction speed because, during the curing reaction of the episulfide compound and the thiol compound, a ring-opening polymerization reaction of two or more hydroxyl groups with the episulfide compound occurs to perform crosslinking, and the ring-opening polymerization reaction occurs at a slower reaction speed than the thiol compound, for example, at a reaction speed of 1/1000. Further, in the aromatic cyclic compound having two or more hydroxyl groups, the ring-opening polymerization reaction of the aromatic ring occurs at a slower reaction speed than the aliphatic hydroxyl group, for example, at a reaction speed of 1/2, thereby controlling the curing reaction speed, so that rapid curing can be prevented even after the curable composition is mixed, and the curing reaction can not be allowed to proceed during long-term storage (for example, more than 7 days under a temperature condition of 0 ℃), and further, streaks in the diffraction light guide plate due to rapid curing can be prevented.

Further, the content of the aromatic cyclic compound including two or more hydroxyl groups may be 0.1 to 10 wt%, 0.5 to 5 wt%, or 1 to 3 wt% in the total 100 wt% of the photocurable composition. If the content of the aromatic cyclic compound including two or more hydroxyl groups is too large, it may not be sufficiently dissolved in the curable composition, or the refractive index of the cured product (i.e., the refractive index of the diffractive light guide plate) may be lowered, and if the content is too small, the curing reaction speed may not be controlled.

In addition, the photocurable composition may also contain a catalyst. The catalyst is not particularly limited as long as it functions to accelerate the curing reaction of the curable composition, but for example, imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, and the like; amine compounds such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, N-dicyclohexylmethylamine, and the like; hydrazine compounds such as adipic acid dihydrazide, sebacic acid dihydrazide, and the like; phosphorus compounds such as triphenylphosphine and the like. Further, as commercially available products, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (which are trade names of imidazole-based compounds) from Shikoku Chemicals Corporation; U-CAT3503N, UCAT3502T (which is a trade name for block isocyanate compounds of dimethylamine) from Sanapro co., ltd.; and DBU, DBN, U-CATSA102, U-CAT5002 (bicyclic amidine compounds and salts thereof); and so on.

The catalyst may be present in an amount of 0.001 wt% to 10 wt%, 0.01 wt% to 5 wt%, or 0.1 wt% to 1 wt%, based on 100 wt% of the total curable composition. If the content of the catalyst is too large, the curing reaction may proceed rapidly, and thus, there may be a problem in the operational safety of the curable composition due to overheating, it may be difficult to store for a long period of time, and streaks may be generated. Meanwhile, if the content of the catalyst is too small, the optical and mechanical properties of the cured product, i.e., the diffraction light guide plate, may be deteriorated due to insufficient curing.

In addition, the curable composition may further include other additives for imparting specific functions to the display substrate in the art to which the present invention pertains, such as UV absorbers, bluing agents, pigments, and the like.

The curable composition may be a photocurable composition or a thermally curable composition. In particular, the curable composition may be a heat curable composition.

Meanwhile, the curing shrinkage of the curable composition may be 15% or less, 1% to 15%, 1% to 12%, or 1% to 10%, but is not limited thereto.

Further, the curable composition can be stored for a long time, and in particular, even if the curable composition contains a catalyst, it can be stored for a long time. Further, streaks due to rapid curing can be suppressed. Specifically, the viscosity of the curable composition after being held at a temperature of-5 ℃ to 0 ℃ for 12 hours may be 4000cP or less, 3000cP or less, 2500cP or less, 2000cP or less, 1000cP or less, 500cP or less, 300cP or less, or 100cP to 200 cP.

A method of manufacturing a light guide plate according to another embodiment may include the steps of compressing the curable composition with a load of a flat upper substrate and curing the curable composition.

Fig. 2 is a schematic view showing a cross section of a mold apparatus in a step of curing a curable composition. Specifically, fig. 2 shows: a curable composition 600 is injected and substantially filled in a molding space of a mold apparatus including a buffer spacer 503 between a flat lower substrate 501 and a flat upper substrate 502 including a template 504 engraved with a diffraction grating pattern. Accordingly, after the curable composition is sufficiently filled, photocuring and/or thermal curing may be performed to manufacture a diffractive light guide plate.

When the curable composition is heat-treated to be heat-cured, the temperature rising rate may be 2 ℃/minute or less, 1 ℃/minute or less, or 0.1 ℃/minute to 0.5 ℃/minute. If the temperature rising speed is within the above range, positional deviation of heat transferred to the curable composition can be minimized, and emission unevenness of reaction heat can be minimized, thereby causing uniform curing of the curable composition.

The final temperature may be 50 ℃ to 100 ℃, or 60 ℃ to 80 ℃ during thermal curing, and positional deviation of heat transferred to the curable composition may be minimized by setting three or more isothermal holding intervals at a temperature lower than the final temperature before reaching the final temperature. The temperature difference between the isothermal holding intervals may be 10 ℃ to 20 ℃, and the holding time of the isothermal holding intervals may be 1 hour to 5 hours, respectively. For example, after the curable composition is left at room temperature (25 ℃) for 2 hours, it may be thermally cured at 45 ℃ for 2 hours, at 60 ℃ for 2 hours, at 75 ℃ for 2 hours, and at 90 ℃ for 4 hours to manufacture a diffraction light guide plate.

In the step of curing the curable composition, a diffraction grating pattern may be formed on one side of the optical layer by a template engraved with the diffraction grating pattern. As for the diffraction grating pattern, the above description of the diffraction grating pattern formed on one side of the optical layer included in the diffractive light guide plate applies.

The flexural modulus of the flat lower substrate and the flat upper substrate may be 3GPa or greater, 10GPa or greater, 20GPa or greater, or 40GPa to 300GPa, respectively. If the flexural moduli of the flat lower substrate and the flat upper substrate are within the above ranges, the bending of the flat upper substrate can be minimized, thereby significantly improving the thickness uniformity of the manufactured diffractive light guide plate.

The flexural modulus of the template engraved with the diffraction grating pattern may be 1GPa to 20GPa, 1.5GPa to 15GPa, or 2GPa to 10 GPa. If the flexural modulus of the template engraved with the diffraction grating pattern is less than 1GPa, the uniformity of the diffraction grating pattern may be deteriorated according to the curing shrinkage of the curable composition, and if it is more than 20GPa, the diffraction grating pattern engraved in the template may be deteriorated due to excessive rigidity.

The surface flatness of the flat lower substrate and the flat upper substrate may be 5 μm or less, 2 μm or less, or 0.01 μm to 1 μm, respectively. If the surface flatness of the flat lower substrate and the flat upper substrate is within the above range, the surface flatness of the manufactured diffractive light guide plate can be significantly improved compared to the general diffractive light guide plate.

Surface flatness can be measured as follows. In particular, using an ASI (aspheric tiling interferometry) device from QED Company at 25 ℃ and 50 RH% atmosphere, it is possible to fit every 0.16X 0.16mm in a 200mm diameter area²Measuring one point, or using the three-dimensional shape measuring device from Duckin Corporation, the difference between the highest and lowest values of height measured at 5mm radius and 11.25 deg. intervals at any starting point within a 200mm diameter area can be measured.

The flat lower substrate and the flat upper substrate may be transparent substrates, respectively. Specifically, the flat lower substrate and the flat upper substrate may be glass substrates, respectively, which may effectively perform photocuring of the curable composition due to excellent light transmittance.

The modulus of elasticity in compression of the buffer spacer may be 0.1 to 10MPa, 0.1 to 5MPa, 0.1 to 3MPa, or 0.1 to 2 MPa. If the modulus of compression elasticity of the cushioning spacer is within the above range, the load can be uniformly transferred to the curable composition upon contacting the flat upper substrate, and thus the thickness uniformity of the diffraction light guide plate can be improved, and the diffraction grating pattern engraved in the template can be clearly shown as a diffraction grating pattern on one side of the cured product.

The compression modulus of elasticity of the cushioning spacer was measured as follows. 5X 5mm compression at a compression rate of 1 mm/min using a texture analyzer from TAcorporation at 25 ℃ and 50 RH% atmosphere²When a specimen is used, the slope of the measured force with respect to the deformation of the specimen ((initial thickness-thickness after deformation)/initial thickness) can be measured. Further, in the case where the cushion spacer is composed of two or more different layers, the compression modulus of elasticity of the cushion spacer may be 5 × 5mm in preparation²And (2) a measurement of the slope of the measured force with respect to the deformation of the specimen ((initial thickness-thickness after deformation)/initial thickness) when the specimen is laminated and compressed at a compression rate of 1 mm/min.

The cushioning spacer may have a structure in which a non-elastic layer and an elastic layer are laminated, a structure in which an elastic layer is located between non-elastic layers, or a structure in which a non-elastic layer is located between elastic layers. Meanwhile, in the case where the cushion spacer has a structure in which the inelastic layer and the elastic layer are laminated, a structure in which the elastic layer is located between the inelastic layers, or a structure in which the inelastic layer is located between the elastic layers, the compression elastic modulus of the cushion spacer may be the compression elastic modulus of the elastic layers.

Since the cushion spacer can be designed in consideration of the degree of shrinkage of the curable composition, the inelastic layer can be used as the support, and the elastic layer can be used to control the height variation according to the shrinkage of the curable composition.

The cure shrinkage of the curable composition may be 15% or less, 1% to 15%, 1% to 12%, or 1% to 10%.

The cure shrinkage of the curable composition can be calculated by the following general formula 3.

[ general formula 3]

Cure shrinkage (%) { (volume before cure-volume after complete cure)/volume before cure } × 100.

The method for manufacturing a diffractive light guide plate according to another embodiment may further include the step of obtaining the diffractive light guide plate from a mold apparatus. Specifically, the step of obtaining a diffractive light guide plate may include removing the flat upper substrate, the flat lower substrate, and the template engraved with the diffraction grating pattern to obtain the diffractive light guide plate. The removing of the flat upper substrate, the flat lower substrate, and the template may mean separating the flat upper substrate, the flat lower substrate, and the template from the diffraction light guide plate, which is a cured product of the curable composition, after the curing of the curable composition is completed.

The above description of the diffractive light guide plate applies to the characteristics of the diffractive light guide plate manufactured by the manufacturing method of the diffractive light guide plate according to another embodiment, such as thickness and thickness uniformity, refractive index, glass transition temperature, haze, and the like. Further, as described above, the diffractive light guide plate may be used for a diffractive light guide lens of a wearable device.

Meanwhile, the thickness of the diffractive light guide plate may be controlled according to the distance between the flat lower substrate and the flat upper substrate and the curing shrinkage of the curable composition, and the thickness of the diffractive light guide plate may be controlled within the above range according to the use of the diffractive light guide plate.

The surfaces of the flat lower substrate, the flat upper substrate, and the template engraved with the diffraction grating pattern may be treated with a release agent, respectively. The release agent is not limited as long as it is generally used in the art. For example, the surface treatment with the release agent may be surface coating with a fluorine-containing silane coupling agent. In the case where the surface is coated with the release agent, in the step of obtaining the diffractive light guide plate, the flat lower substrate, the flat upper substrate, and the mold plate may be removed while minimizing damage to the surface of the diffractive light guide plate.

Advantageous effects

According to the present invention, there are provided a diffractive light guide plate which has not only excellent thickness uniformity and flatness but also low haze, excellent mechanical properties such as pencil hardness and strength, etc., which is lighter than glass or tempered glass, and can realize a high refractive index, and a method of manufacturing the same, which can manufacture such a diffractive light guide plate through a simple one-step process.

Drawings

Fig. 1 is a schematic view of a cross section of an optical layer included in a diffractive light guide plate according to an embodiment of the present invention.

Fig. 2 is a schematic view of a cross section of a mold device in a step of curing a curable composition in a method of manufacturing a diffractive light guide plate according to another embodiment of the present invention.

Detailed Description

The present invention will be illustrated in detail in the following examples. However, these examples are presented only as illustrations of the present invention, and the scope of the present invention is not limited thereto.

Preparation example 1: preparation of curable compositions

A curable composition comprising 89.0 parts by weight of bis (. beta. -epithiopropyl) sulfide, 7.0 parts by weight of 2,2' -thiodiethylene thiol, 3.0 parts by weight of 2.2' -dihydroxy-1, 1' -binaphthyl, and 1.0 part by weight of catalyst N, N-dicyclohexylmethylamine was prepared.

The curing shrinkage of the prepared curable composition was measured by the above-described method for measuring curing shrinkage, and the modulus of compressive stress calculated by dividing the measured curing shrinkage by the volume of the sample was 2.5 x 10³N/m³。

Preparation example 2: preparation of curable compositions

A curable composition comprising 89.5 parts by weight of bis (. beta. -epithiopropyl) sulfide, 9.5 parts by weight of 2,2' -thiodiethanol and 1.0 part by weight of catalyst N, N-dicyclohexylmethylamine was prepared.

The curing shrinkage of the prepared curable composition was measured by the above-described method for measuring curing shrinkage, and the modulus of compressive stress calculated by dividing the measured curing shrinkage by the volume of the sample was 2.5 x 10³N/m³。

Preparation example 3: preparation of impression resin composition

An imprint resin composition containing 8.3 parts by weight of zirconium oxide particles having a diameter of 20nm, 8.3 parts by weight of dipentaerythritol hexaacrylate (DPHA), 83.0 parts by weight of butyl carbitol acetate, and 0.4 parts by weight of ethyl (2,4, 6-trimethylbenzoyl) phenylphosphinate was prepared.

< examples and comparative examples: production of diffraction light guide plate

Example 1

A glass substrate having a flexural modulus of 70GPa, a surface flatness of 0.5 μm, a thickness of 30mm, and a diameter of 200mm was prepared as a lower substrate, and on the lower substrate, a template engraved with a diffraction grating pattern (flexural modulus: 3GPa) was attached. Wherein the template is attached such that the center of the lower substrate is in contact with the center of the template, the template is polyethylene terephthalate (PET) having a diameter of 150mm and a thickness of 200 μm, and the engraved diffraction grating pattern has a pitch of 405nm and a depth of 500 nm.

Thereafter, the resulting steel sheet was adjusted to have a compressive modulus of elasticity of 1.0MPa, a height of 1007 μm and a cross section of 10X 10mm²Are placed in contact with the periphery of the lower substrate at intervals of 120 deg., thereby forming a moldA space, and then the curable composition prepared according to preparation example 1 was injected into the molding space, and the molding space was sufficiently filled with the curable composition using a glass substrate having a flexural modulus of 70GPa, a load of 8.2N, a diameter of 200mm, and a surface flatness of 0.5 μm as an upper substrate.

Further, the curable composition was put in a convection oven from Jeio Tech co., ltd. and left at room temperature for 2 hours, and then the temperature rise rate was set to 1 ℃/min and allowed to be photocured at 45 ℃ for 2 hours, 60 ℃ for 2 hours, 75 ℃ for 2 hours, and 90 ℃ for 4 hours to manufacture a diffraction light guide plate having a thickness of 0.8 mm.

Comparative example 1

A diffractive light guide plate was manufactured by the same method as example 1, except that the curable composition prepared according to preparation example 2 was used instead of the curable composition prepared according to preparation example 1.

Comparative example 2

A glass substrate having a flexural modulus of 70GPa, a surface flatness of 0.5 μm, a thickness of 30mm and a diameter of 200mm was used as a lower substrate, and a compressive modulus of elasticity of 1.0MPa, a height of 804 μm and a cross-section of 10X 10mm were used²The buffer spacers made of silicon were placed in contact with the periphery of the lower substrate at intervals of 120 deg. to thereby form a molding space, and then the curable composition prepared according to preparation example 1 was injected into the molding space, and the curable composition was sufficiently filled in the molding space using a glass substrate having a flexural modulus of 70GPa, a load of 8.2N, a diameter of 200mm, and a surface flatness of 0.5 μm as an upper substrate.

Further, the curable composition was put into a convection oven from Jeio Tech co., ltd. and left at room temperature for 2 hours, and then the temperature rising rate was set to 1 ℃/min and heat-cured at 45 ℃ for 2 hours, at 60 ℃ for 2 hours, at 75 ℃ for 2 hours, and at 90 ℃ for 4 hours to manufacture a plastic substrate.

The imprint resin composition (refractive index 1.70) prepared according to preparation example 3 was applied on a plastic substrate and dried to form an imprint having a thickness of 1 μmAnd a resin layer. Then, a template (150 mm in diameter, 200 μm in thickness, polyethylene terephthalate) engraved with a diffraction grating pattern having a 405nm pitch and a1 μm depth was compressed on the imprinting resin layer at a temperature of 40 ℃ and a pressure of 20 bar to form a diffraction grating, and then passed through 1000mJ/cm²Was irradiated with UV (360nm light source) to prepare a diffractive light guide plate having a thickness of 0.8mm, and cut into a form of 6cm × 5cm rectangle.

Comparative example 3

A diffraction light guide plate was manufactured by the same method as comparative example 2, except that the curable composition prepared according to preparation example 2 was used instead of the curable composition prepared according to preparation example 1.

Evaluation of

1. Measurement of refractive index

The refractive indexes of the diffraction light guide plates of examples and comparative examples were measured using a spectroscopic ellipsometer from Ellipso Technology co.ltd., and the results are shown in table 1 below.

2. Measurement of haze

The haze of the diffraction light guide plates of the examples and comparative examples was measured by ASTM D-1003, and the results are shown in table 1 below.

3. Measurement of Pencil hardness

After a pencil was fixed on the surface of each of the diffractive light guide plates of the examples and comparative examples at a load of 0.5kg and an angle of 45 °, the surface was scratched according to pencil hardness and judged whether or not scratched with naked eyes, and the maximum pencil hardness at which scratches were not generated was shown in table 1 below.

4. Measurement of warpage

For the diffraction light guide plates of examples and comparative examples, rectangular test pieces having a long axis of 600mm and a short axis of 400mm were prepared, the warpage was calculated by the following general formula 2, and the results are shown in table 1 below.

[ general formula 2]

Warp-the maximum deviation between the central side and the base side-the minimum deviation between the central side and the base side

The center side can be plotted at 25 deg.c and 50 RH% atmosphere by measuring the thickness of the diffractive light guide plate and the distance between the base optical body mounted at the lower portion of the diffractive light guide plate and the diffractive light guide plate through a non-contact measuring method using OWTM (optical wafer thickness measuring system) equipment from Fiberpro. Meanwhile, the base side may be calculated by performing least square fitting on the center side.

5. Measurement of glass transition temperature

For the diffractive light guide plates of examples 1 and 2 and the plastic substrates of comparative examples 2 and 3, the glass transition temperature (Tg) was measured using a Pyris6DSC (Differential Scanning Calorimetry) from Perkin Elmer inc, and the results are shown in table 1 below.

[ Table 1]

	Example 1	Comparative example 1	Comparative example 2	Comparative example 3
					Refractive index	1.73	1.71	1.73	1.71
Haze (%)	1.4	1.4	4.1	4.2
					Hardness of pencil	2H	2H	6B	6B
Warp (μm)	20	24	55	68
					Glass transition temperature (. degree. C.)	85	74	85	74

According to table 1, it was determined that the diffractive light guide plate of example 1 having a continuous phase of a polymer including an episulfide compound, a thiol compound, and an aromatic cyclic compound having two or more hydroxyl groups, in which a diffraction grating pattern is formed on one side of an optical layer as an integral structure having no interface, has high refractive index and glass transition temperature, excellent pencil hardness, and low haze and high visibility.

In contrast, it was confirmed that the diffractive light guide plate of comparative example 1, which did not use the aromatic cyclic compound, had a lower refractive index and glass transition temperature and a higher warpage than example 1. Further, it was confirmed that the diffractive light guide plates of comparative examples 2 and 3, in which there is an interface between the diffraction grating pattern and the optical layer, had significantly high warpage and haze, and reduced pencil hardness, as compared to example 1.

Reference numerals

200: diffraction grating pattern 300: optical layer

400: the pattern unit 501: flat lower substrate

502: flat upper substrate 503: buffer spacer

504: template engraved with diffraction grating pattern 600: a curable composition.