KR20200134652A - Transparent resin composition - Google Patents

Abstract

The present application relates to a transparent resin composition, a substrate including a transparent column spacer, and a method of manufacturing a substrate including a transparent column spacer. The transparent resin composition of the present application includes a ball, and thus can implement a uniform pattern height of the transparent column spacer and secure pattern adhesion. Also, by controlling the physical properties or composition of the transparent resin composition, it is possible to ensure uniform dispersibility of balls, corrosion resistance of an electrode layer, and the like.

Description

Transparent resin composition

The present application relates to a transparent resin composition, a substrate including a transparent column spacer, and a method of manufacturing a substrate including a transparent column spacer.

An optical device in which a light modulating material containing a liquid crystal compound is disposed between opposing substrates so as to control light transmittance, color, or reflectivity is known. For example, Patent Document 1 discloses a so-called GH cell (Guest host cell) to which a mixture of a liquid crystal host and a dichroic dye guest is applied. In such devices, so-called spacers are placed between the substrates to maintain the spacing between the substrates.

Patent Document 1: European Patent Publication No. 0022311

The present application provides a transparent resin composition, a substrate including a transparent column spacer, and a method of manufacturing a substrate including a transparent column spacer.

The present application relates to a transparent resin composition. The transparent resin composition may include transparent resin and balls. In the present specification, a composition excluding balls in the transparent resin composition may be referred to as a transparent resin, and a composition including a transparent resin and a ball may be referred to as a transparent resin composition. The transparent resin may include a photocurable monomer, an initiator, and various additives to be described later.

The transparent resin composition may be used to manufacture a substrate including a pattern of transparent column spacers. When the transparent resin composition includes a ball, it is possible to implement a uniform height of the pattern of the transparent column spacer and secure pattern adhesion. In addition, by controlling the physical properties and composition of the transparent resin and/or the transparent resin composition, it is possible to ensure uniform dispersibility of balls and corrosion resistance of the electrode layer.

In the present specification, the transparent resin may mean a resin having a transmittance of about 80% or more, about 85% or more, or 90% or more before or after curing. The upper limit of the transmittance may be, for example, 99% or less or 95% or less. A cured product of a transparent resin to be described later to a transparent column spacer including the cured product may also satisfy the transmittance range. When using a transparent resin, it can be advantageous in that it can increase the transmittance of the product by increasing the transmittance of the spacer pattern itself.

The transmittance is determined by applying a transparent resin on the transparent layer of a laminate in which a transparent layer (indium tin oxide (ITO) layer) is formed on a transparent PET (poly(ethylene terephthalate)) base film, and then irradiating ultraviolet rays (wavelength: about 365 nm). , UV irradiation dose: 100 to 200 mJ/cm ² ) It may be a value measured for a layer formed by curing and forming a layer having a thickness of about 10 μm. The transmittance may mean an average transmittance within a visible light wavelength range, for example, 400 nm to 700 nm wavelength range.

The pH value of the transparent resin may be 1 or more. The pH value of the transparent resin can be measured using, for example, an OACTON model instrument manufactured by Eutech Instrument. The pH value of the transparent resin may be specifically 1.2 or more, 1.4 or more, 1.6 or more, 1.8 or more, or 2.0 or more. The upper limit of the pH value of the transparent resin may be specifically 4 or less, 3 or less, or 2.4 or less. The transparent resin composition may secure corrosion resistance of the electrode layer by including a transparent resin having a pH value within the above range.

The contact angle of the transparent resin to water may be 50° or more. The contact angle of the transparent resin with respect to water may be measured using, for example, a Drop Shpae Analyzer (Model: KRUSS DSA 100). The contact angle of the transparent resin with water may be specifically 52° or more, 54° or more, 56° or more, 58° or more, 60° or more, or 61° or more. The upper limit of the contact angle of the transparent resin with water may be specifically 80° or less, 78° or less, 76° or less, 74° or less, 72° or less, or 71° or less. The transparent resin composition may secure uniform dispersibility of balls by including a hydrophobic transparent resin having a contact angle with water within the above range.

The viscosity of the transparent resin may be in the range of 50 cP to 700 cP. The viscosity may be a viscosity at room temperature. The viscosity may be specifically 50 cp or more, 75 cp or more, 100 cp or more, 125 cp or more, or 150 cp or more. The viscosity may be specifically 700 cp or less, 600 cp or less, 500 cp or less, 400 cp or less, or 300 cp or less. The transparent resin composition may be advantageous in securing the manufacturability of the pattern of the transparent column spacer and the adhesion of the pattern by including a transparent resin having a viscosity at room temperature within the above range.

In the present specification, the normal temperature may mean a temperature in which temperature is not artificially controlled. Room temperature may mean, for example, a temperature in the range of 20°C to 40°C, a temperature in the range of 20°C to 30°C, specifically, a temperature of about 25°C.

The refractive index of the transparent resin composition may be in the range of 1.39 to 1.51. The refractive index may be a value measured for a wavelength of 587 nm. When the refractive index of the transparent resin composition is within the above range, it may be advantageous in terms of versatility and ease of manufacture.

The color of the transparent resin composition ^* a ^* b ^* color coordinate standard L b ^* values can be from 0.65 to 0.75 range tomorrow. When the color coordinate of the transparent resin composition is within the above range, it may be advantageous in terms of implementing a pattern having transparency indicating a transmittance of 80% or more.

The transparent resin may contain a photocurable monomer. In the present specification, the "photocurable monomer" may mean a monomer having at least one photocurable group.

The transparent resin is a photocurable monomer, and may include a low molecular weight monomer having 1 to 3 photocurable groups. In the present specification, "low molecular weight monomer" may mean a monomer having a molecular weight of 500 g/mol or less. The lower limit of the molecular weight of the low molecular weight monomer may be, for example, 100 g/mol or more.

In the present specification, "n-functional monomer" may mean a monomer having n photocuring groups. In the present specification, the photocuring group may be an ultraviolet curable functional group. The photocuring group may be, for example, an alkenyl group, an epoxy group, a carboxyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, or a methacryloyloxy group, but is not limited thereto.

The low molecular weight monomer may serve as a binder. The low molecular weight monomer may be included in an amount of 75 parts by weight or more, 80 parts by weight or more, 85 parts by weight or more, or 90 parts by weight or more based on 100 parts by weight of the total transparent resin. The low molecular weight monomer may be included in an amount of 99 parts by weight or less or 95 parts by weight or less based on 100 parts by weight of the total transparent resin.

The low molecular weight monomer may include at least one selected from the group consisting of a monofunctional monomer, a bifunctional monomer, and a trifunctional monomer. The monofunctional monomer, the bifunctional monomer, and the trifunctional monomer may each independently have a molecular weight of 500 g/mol or less. The lower limit of the molecular weight may be 100 g/mol or more.

The low molecular weight monomer may include a trifunctional monomer. As the trifunctional monomer, for example, TMPTA (Trimethylolpropane triacrylate) may be exemplified. The low molecular weight monomer may include a trifunctional monomer in the range of 30 parts by weight to 40 parts by weight based on 100 parts by weight of the total low molecular weight monomer. Through this, it may be advantageous to provide a transparent resin composition having uniform dispersibility of balls and corrosion resistance of an electrode layer.

The low molecular weight monomer is a monofunctional monomer, and may further include a monofunctional monomer having a ring structure. As a monofunctional monomer having a cyclic structure, IBOA (Isobornyl acrylate) may be exemplified. The monofunctional monomer having the cyclic structure may be included in the range of 10 to 20 parts by weight based on 100 parts by weight of the total transparent resin. Through this, it may be advantageous to provide a transparent resin composition having uniform dispersibility of balls and corrosion resistance of an electrode layer.

The low molecular weight monomer may further include other monomers other than a trifunctional monomer and a monofunctional monomer having a cyclic structure. Other monomers may include at least one selected from the group consisting of HMDA (Hexamethylene diacrylate), HEA (Hydroxyethyl acrylate), HEMA ((Hydroxyethyl methacrylate), BMA (Butyl methacrylate), and MMA (Methyl methacrylate). It may be advantageous to provide a transparent resin composition having uniform dispersibility of balls and corrosion resistance of an electrode layer.

In one example, the low molecular weight monomer may include all of a monofunctional monomer, a bifunctional monomer, and a trifunctional monomer.

When a pattern of a transparent column spacer is manufactured from the transparent resin composition, the ball may play a role of controlling the height of the pattern. In addition, the ball may play a role of securing the manufacturability of a pattern having a uniform dimension, for example, a uniform height, and adhesion or adhesion of the pattern to the substrate layer.

The balls may include white balls and/or black balls. When the transparent resin composition contains white balls, light can penetrate the inside of the ball, so the transmittance of the pattern can be increased, and when the transparent resin composition contains black balls, the light is blocked inside the ball, so the transmittance of the pattern can be reduced. have. Therefore, the white ball and/or black ball may be appropriately selected and used according to the transmittance characteristics required for the product. The transparent resin composition may include a plurality of balls, and the plurality of balls may be all white balls, all black balls, or white balls and black balls may be mixed.

The main component of the ball may be a polymer. In the present specification, the material of the main component means that the material of the main component is included in about 80% by weight or more, about 85% by weight or more, about 90% by weight, or about 95% by weight or more, based on the total 100% by weight of the ball. I can.

The ball may include, for example, one or more polymers selected from the group consisting of polystyrene (PS) and polymethylmethacrylate (PMMA). In the case of black balls, carbon particles, dyes or pigments representing black may be further included. In the case of a black ball, for example, a black ball in which the entire ball is made black, or a black ball coated with black on the outside of the ball can be used. In the above, the coating material is carbon black or CNT (Carbon Nano Tube) or Carbon-based materials such as graphene or various known dyes or pigments are applied.

The size of the ball used as the role of controlling the height of the column spacer may be larger than the height of the pattern of the column spacer. For example, the height (H) of the column spacer and the particle diameter (D) of the ball may satisfy the relationship of H/D <1. The ratio of H/D may be more specifically in the range of 0.7 to 0.99.

The transparent resin composition and/or a plurality of balls included in the substrate to be described later may have a standard deviation of particle diameter of 0.8 μm or less. In another example, the standard deviation may be about 0.7 µm or less, about 0.6 µm or less, or about 0.5 µm or less, or 0 µm or more, 0 µm or more, about 0.1 µm or more, about 0.2 µm or more, about 0.3 µm or more, or about 0.4 µm or more. I can. When the ball has a standard deviation of the particle diameter within the above range, it may be advantageous in terms of securing the manufacturability of the pattern having a uniform height and the adhesion of the pattern of the transparent column spacer.

The CV (Coefficient of Variation) value of the particle diameters of the plurality of balls included in the transparent resin composition and/or the substrate to be described later may be about 8% or less. The CV value is a value defined as a standard deviation of 100×ball particle diameter/average particle diameter of balls. In other examples, this CV value is approximately 7% or less, 6% or less, or 5% or less, or 0% or more, more than 0%, 1% or more, 2% or more, 3% or more, or 4 It can be about% or more. When the ball has a CV value of a particle diameter within the above range, it may be advantageous in terms of securing the manufacturability of the pattern having a uniform height and the adhesion of the pattern of the transparent column spacer.

The ball may be included in an amount greater than 1 part by weight based on 100 parts by weight of the total transparent resin. In another example, the ratio is about 1.1 parts by weight or more, about 1.2 parts by weight or more, about 1.3 parts by weight or more, about 1.4 parts by weight or more, or 1.5 parts by weight or more, or about 10 parts by weight or less, about 9 parts by weight or less, about 8 parts by weight. It may be less than or equal to about 7 parts by weight, less than about 6 parts by weight, or less than about 5.5 parts by weight. When the ball is included in an amount within the above range, it may be advantageous in terms of securing manufacturability of a pattern having a uniform height of the transparent column spacer and adhesion of the pattern.

The transparent resin may further include an initiator. The initiator may be a photo initiator. The photoinitiator may be, for example, a radical initiator. The photoinitiator is, for example, a benzoin-based 　 initiator, a hydroxyketone-based 　 initiator, an amino ketone-based 　 initiator 　, or a phosphine oxide-based 　 initiator 　, etc. The initiator can be used without limitation. The transparent resin may contain an initiator as described above in the range of about 0.5% to 10% by weight.

The transparent resin may further include an additive. Examples of these additives include curing agents, initiators, thixotropic agents, leveling agents, defoaming agents, antioxidants, radical generating substances, organic/inorganic pigments or dyes, dispersants, thermally conductive fillers, insulating fillers, etc. Various fillers, functional polymers, light stabilizers, and the like may be exemplified, but are not limited thereto. In particular, the dispersant can improve the dispersibility of the transparent resin composition. In addition, the coupling agent may improve the adhesion between the substrate layer and the transparent resin composition, and for example, a Silan or Acid-based coupling agent may be used. The transparent resin may contain the above additives in the range of about 0.5% to 10% by weight.

The present application relates to a substrate including a transparent column spacer. In the present specification, a transparent column spacer may mean a resin having a transmittance of about 80% or more, about 85% or more, or 90% or more. The upper limit of the transmittance may be, for example, 99% or less or 95% or less.

The substrate may include a substrate layer and a transparent column spacer that is present on the substrate layer and includes a cured product of transparent resin. For the transparent resin, the description of the above-described transparent resin may be equally applied.

As the substrate layer, without particular limitation, any substrate layer used for the substrate in the configuration of a known optical device such as, for example, a liquid crystal display (LCD) may be applied. For example, the base layer may be an inorganic base layer or an organic base layer. As the inorganic substrate layer, a glass substrate layer and the like may be exemplified, and as the organic substrate layer, various plastic films may be exemplified. As a plastic film, a triacetyl cellulose (TAC) film; Cycloolefin copolymer (COP) films such as norbornene derivatives; Acrylic film such as PMMA (poly(methyl methacrylate)); PC (polycarbonate) film; Polyolefin film such as PE (polyethylene) or PP (polypropylene); PVA (polyvinyl alcohol) film; DAC (diacetyl cellulose) film; Pac (Polyacrylate) Film; PES (polyether sulfone) film; PEEK (polyetheretherketon) film; PPS (polyphenylsulfone) film, PEI (polyetherimide) film; PEN (polyethylenemaphthatlate) film; PET (polyethyleneterephtalate) film; PI (polyimide) film; PSF (polysulfone) A film or a polyarylate (PAR) film may be exemplified, but the present disclosure is not limited thereto. As the base layer, a functional film such as a super retardation film (SRF) or an optical-axis control film (OCF) may also be used.

In the substrate of the present application, the thickness of the substrate layer is not particularly limited, and an appropriate range may be selected according to the use.

The meaning of the column spacer is the same as known in the art. For example, the column spacer has a columnar shape and may be fixed on the base layer. In the above, that the spacer is fixed to the base layer means that the spacer is fixed in direct contact with the base layer, or when another layer exists between the base layer and the spacer, the spacer is fixed on the other layer. Includes the case. In the above, other types of layers include known layers required for driving the optical device, and for example, an electrode layer to be described later may be exemplified.

A plurality of column spacers may be present on the base layer. The plurality of column spacers may exist in a state spaced apart from each other. The spacing, arrangement, and the like between the plurality of column spacers may be controlled according to the spacing and arrangement of patterns of the shading layer of the mask to be described later.

The substrate may further include an electrode layer between the base layer and the column spacer, and the column spacer may be in contact with the electrode layer. As described above, when the transparent resin composition of the present application is used, corrosion resistance to the electrode layer can be secured.

The columnar shape of the column spacer is not particularly limited, and includes, for example, an elliptical columnar shape, a cylindrical shape, a square columnar shape, a triangular columnar shape, other polygonal columnar shape, and an irregularly shaped columnar shape. In one example, the column spacer may be manufactured to have a cylindrical shape or a hemispherical upper surface.

The substrate may further include a ball. The ball may exist on the base layer in a state attached to the transparent column spacer. In this case, the ball may be attached to the side of the column spacer. The substrate may further include a transparent column spacer to which balls are not attached. That is, the substrate may include a plurality of column spacers, among which the balls may be attached to at least some of the column spacers, and the balls may not be attached to some of the column spacers.

1 is a schematic side view of a substrate including a transparent column spacer of the present application. 1A is a schematic side view of a substrate in which a plurality of column spacers 201 in a cylindrical shape are formed on a base layer 100 and a ball 202 is attached to at least a part of the column spacers 201 to be. (B) of FIG. 1 shows a substrate in which a plurality of column spacers 201 having a hemispherical top surface are formed on a base layer 100 and a ball 202 is attached to at least a portion of the column spacers 201. It is a schematic side view. 1 shows a structure in which the column spacers 201 and the balls 202 are directly formed on the base layer 100, but as shown in FIG. 2, the base layer 100, the column spacers 201, and the balls 202 are shown. Between ), another layer 300 such as an electrode layer is additionally present, and the column spacer 201 and the ball 202 may be in contact with the other layer 300.

The ratio (A/B) of the number of column spacers to which the balls are attached (A) and the number of column spacers to which the balls are not attached (B) in the substrate may be in the range of 0.01 to 10. In another example, the ratio may be about 0.05 or more, about 0.1 or more, about 0.15 or more, or about 0.2 or more, or about 8 or less, about 6 or less, about 4 or less, about 2 or less, 1 or less, or about 0.5 or less. Within the above range, a column spacer having a desired dimensional uniformity, adhesion, opening ratio, etc. can be manufactured, and this ratio can be controlled by adjusting the content ratio of the transparent resin and balls in the manufacturing process described later.

The column spacer as described above may have an appropriate range of dimensions according to the purpose, and the range is not particularly limited.

For example, the average height of the plurality of column spacers may be in the range of about 2 μm to 100 μm. In other examples, the average value may be 3 μm or more, 4 μm or more, 5 μm or more, 6 μm or more, 7 μm or more, or 8 μm or more, 80 μm or less, 60 μm or less, 40 μm or less, 20 μm or less, or 15 μm or less. May be.

The average diameter of the plurality of column spacers may be in the range of 4 μm to 60 μm. In other examples, the average value may be 5 µm or more, 10 µm or more, 15 µm or more, 20 µm or more, or 25 µm or more, 55 µm or less, 50 µm or less, 45 µm or less, 40 µm or less, 35 µm or less, or 30 µm or less. May be.

In the above, the diameter of the column spacer is the length of the long axis or short axis in case the cross section of the column spacer is elliptical, the diameter in case of circular shape, and the largest or smallest dimension among the measured dimensions in case of other polygonal or irregular shapes. Or it may be the average value.

The column spacer as described above may have excellent dimensional uniformity. For example, the standard deviation of the heights of the plurality of column spacers may be in the range of 0.05 μm to 0.5 μm. In another example, the standard deviation may be 0.1 µm or more, 0.15 µm or more, or 0.20 µm or more, 0.5 µm or less, 0.45 µm or less, 0.4 µm or less, 0.35 µm or less, 0.3 µm or less, or 0.25 µm or less. The standard deviation of the diameters of the plurality of column spacers may be in the range of 0.3 μm to 1.5 μm. In other examples, the standard deviation is 0.31 µm or more, 0.32 µm or more, 0.33 µm or more, 0.34 µm or more, 0.35 µm or more, 0.36 µm or more, 0.37 µm or more, 0.38 µm or more, 0.39 µm or more, 0.4 µm or more, 0.41 µm or more , 0.42 µm or more, 0.43 µm or more, 0.44 µm or more, 0.45 µm or more, or 0.46 µm or more, 1.4 µm or less, 1.3 µm or less, 1.2 µm or less, 1.1 µm or less, 1 µm or less, or 0.9 µm or less. The standard deviation referred to in this specification is a value determined by the square root of the positive variance.

The occupied areas of the column spacers and balls on the substrate layer are not particularly limited, and may be selected in consideration of the purpose of the substrate. For example, based on the total area of the surface of the base layer, the ratio of the areas of the column spacers and the balls present on the surface of the base layer may be in the range of about 0.5% to 20%.

As described above, FIGS. 1B and 2B are schematic side views of a substrate including a spacer having a hemispherical top surface of the column spacer. The spacer may be a hemispherical spacer having at least a hemispherical portion formed thereon. By applying a spacer having such a hemisphere, even when an alignment treatment such as rubbing orientation or photo-alignment is performed after forming an alignment layer on the substrate layer on which the spacer is formed, even in the area where the spacer is present without the effect of the step difference due to the spacer. One orientation treatment becomes possible. Accordingly, the optical device to which the substrate of the present application is applied may exhibit uniform optical performance.

In the present application, the term hemisphere may mean a portion of a spacer including a curved shape in which the trajectory of the cross section has a predetermined curvature. In addition, the trajectory of the cross section of the hemisphere may include a curved portion in which at least a center of curvature exists inside the cross-sectional trajectory.

In one example, the hemisphere may have a maximum curvature of 2,000 mm ^-1 or less of its cross-sectional trajectory. As is known, the curvature is a numerical value expressing the degree of bending of a line, and is defined as the reciprocal of the radius of curvature, which is the radius of the contact circle at a predetermined point of the curve. In the case of a straight line, the curvature is 0, and the larger the curvature, the more curved the curve exists.

By controlling the degree of bending of the hemisphere so that the maximum curvature of the cross-sectional trajectory of the hemisphere is 2,000 mm ^-1 or less, uniform alignment treatment may be performed even when the alignment treatment is performed on the hemisphere. In the above, the cross section for confirming the cross-sectional trajectory of the hemisphere may be an arbitrary normal plane with respect to the base layer. In addition, the maximum curvature may mean the largest curvature among curvatures for all contact sources that can be obtained on the cross-sectional trajectory of the hemisphere. In other words, the cross-sectional trajectory of the hemisphere may not include a portion bent such that the curvature exceeds 2,000 mm ^{- 1} .

In other examples, the maximum curvature is 1,800 mm ^-1 or less, 1,600 mm ^-1 or less, 1,400 mm ^-1 or less, 1,200 mm ^-1 or less, 1,000 mm ^-1 or less, 900 mm ^-1 or less, 950 mm ^-1 or less, 850 mm ^-1 or less, 800 mm ^-1 or less, 750 mm ^-1 or less, 700 mm ^-1 or less, 650 mm ^-1 or less, 600 mm ^-1 or less, 550 mm ^-1 or less, 500 mm ^-1 or less, 450 mm ^{- 1} or less, 400 mm ^-1 or less, 350 mm ^-1 or less, 300 mm ^-1 or less, 250 mm ^-1 or less, 200 mm ^-1 or less, or 150 mm ^-1 or less. The maximum curvature is, in another example, 5 mm ^-1 or more, 10 mm ^-1 or more, 15 mm ^-1 or more, 20 mm ^-1 or more, 25 mm ^-1 or more, 30 mm ^-1 or more, 35 mm ^-1 or more, It may be 40 mm ^-1 or more, 45 mm ^-1 or more, or 50 mm ^-1 or more.

The cross-sectional trajectory of the hemisphere may or may not include a portion having a curvature of 0 mm ^-1 , that is, a portion of a straight line.

As long as the spacer includes the hemisphere, it may be formed in various shapes. For example, the hemispherical spacer has a shape in which the hemisphere is directly formed on the surface of the base layer 100 as shown in FIG. 3 or 4, or in a column shape including the hemisphere on an upper portion as shown in FIG. 5 or 6 It may be a spacer.

3 to 6, H2 is the height of the hemisphere, R is the radius of curvature of the hemisphere, W1 is the length (width) of the flat surface of the flat hemisphere, W2 is the width of the spacer, and H1 is the hemisphere at the total height of the spacer. It is the value minus the negative height (H2).

Even when the upper surface of the column spacer is hemispherical, the ball may be attached to at least a part of the column spacer. In this case, the ball may be attached next to the area H1 of FIG. 5 or 6, for example. A substrate of such a form can be manufactured by further including balls in the transparent resin composition in a method for manufacturing a hemispherical spacer to be described later. Accordingly, a column spacer having excellent dimensional uniformity and adhesion to the substrate layer can be formed, and the height of the H1 region of the hemispherical spacer can be increased.

The hemisphere may have a complete hemisphere shape or may have an approximate hemisphere shape. The complete hemisphere shape may be a hemisphere shape that satisfies the following relational equation 1, and the approximate hemisphere shape may be a hemisphere shape that satisfies any one of the following relational equations 2 to 4.

The hemisphere portion may have a cross-sectional shape that satisfies any one of the following relational equations 1 to 4.

[Relationship 1]

a = b = R

[Relationship 2]

a ≠ b = R or b≠a = R

[Relationship 3]

a = b <R

[Relationship 4]

a ≠ b <R

In the relations 1 to 4, a is the horizontal length of the hemisphere section measured from the center of the virtual contact circle of the hemisphere section, b is the vertical length of the hemisphere section measured from the center of the virtual contact circle of the hemisphere section, and R Is the radius of curvature of the virtual contact circle in the section of the hemisphere.

The radius of curvature in relations 1 to 4 corresponds to the length indicated by R in FIGS. 3 to 6.

In the relations 1 to 4, the virtual contact source may mean a contact source having the largest radius of curvature among a plurality of virtual contact sources in contact with the curve forming the hemisphere.

If the hemisphere is a normal hemisphere as shown in Figs. 3 and 5, since the cross section of the entire hemisphere is curved, the contact sources with the largest radius of curvature among the plurality of virtual contact sources at any point of the curve are the relations 1 to 4 It may be a virtual contact source. In addition, if the hemisphere is a flat hemisphere as shown in Figs. 4 and 6, the contact source with the largest radius of curvature among a plurality of virtual contact sources at any point of the curve on both sides except the flat line at the top of the hemisphere section is It becomes a virtual contact source in relational expressions 1 to 4.

In the relations 1 to 4, the horizontal length is a length measured in a direction horizontal to the base layer surface (reference numeral 100 in FIGS. 3 to 6) at the center point of the virtual contact source, and the vertical length is the base layer surface at the center point of the virtual contact source. It is a length measured in a direction perpendicular to (reference numeral 100 in FIGS. 3 to 6).

Accordingly, in relations 1 to 4, a is the length from the center of the virtual contact circle of the cross section of the hemisphere to the point where the hemisphere is measured while traveling in the horizontal direction. These horizontal lengths may be divided into two lengths: a length measured while proceeding from the center of the virtual contact circle in a right direction and two lengths measured while proceeding in a left direction, and a is applied in the relational equations 1 to 4 is the shorter of the two lengths. Means length. In the case of the hemisphere in the shape of FIGS. 3 and 5, the horizontal length (a) is a value corresponding to 1/2 of the width W2 of the spacer. In addition, in the case of FIGS. 4 and 6, a value (2a+W1) obtained by adding the length (width) W1 of the flat part to twice the horizontal length (a) may correspond to the width W2 of the spacer.

In the relational equations 1 to 4, b is the length from the center of the virtual contact circle of the cross section of the hemisphere to the point where it first meets the hemisphere while moving upward in the vertical direction. This vertical length (b) may be generally the same as the height of the hemisphere, for example, the length indicated by the symbol H2 in FIGS. 3 to 6.

The dimension of the spacer of the above-described shape is not particularly limited, and may be appropriately selected in consideration of, for example, a cell gap or an aperture ratio of a target optical device.

For example, the height of the hemisphere (H2 in FIGS. 3 to 6) may be in the range of 1 μm to 20 μm. In another example, the height may be 2 μm or more, 3 μm or more, 4 μm or more, 5 μm or more, 6 μm or more, 7 μm or more, 8 μm or more, 9 μm or more, 10 μm or more, or 11 μm or more. The height may also be 19 μm or less, 18 μm or less, 17 μm or less, 16 μm or less, 15 μm or less, 14 μm or less, 13 μm or less, 12 μm or less, or 11 μm or less in another example.

In addition, the width of the hemisphere (W2 in FIGS. 3 to 6) may be in the range of 2 μm to 40 μm. In another example, the width may be 4 μm or more, 6 μm or more, 8 μm or more, 10 μm or more, 12 μm or more, 14 μm or more, 16 μm or more, 18 μm or more, 20 μm or more, or 22 μm or more. In another example, the width may be 38 μm or less, 36 μm or less, 34 μm or less, 32 μm or less, 30 μm or less, 28 μm or less, 26 μm or less, 24 μm or less, or 22 μm or less.

The height of the spacer is the same as the height of the hemisphere described above when the spacer is in the shape as shown in FIG. 3 or 4, and in the case of the shape as shown in FIGS. 5 and 6, the height of the columnar portion (H1) is added to the height of the hemisphere. It can be a number. The height may be in the range of 1 μm to 50 μm in one example.

The height is 3㎛ or more, 5㎛ or more, 7㎛ or more, 9㎛ or more, 11㎛ or more, 13㎛ or more, 15㎛ or more, 17㎛ or more, 19㎛ or more, 21㎛ or more, 23㎛ or more, 25 It may be greater than or equal to µm or greater than or equal to 27 µm. In other examples, the height is 48㎛ or less, 46㎛ or less, 44㎛ or less, 42㎛ or less, 40㎛ or less, 38㎛ or less, 36㎛ or less, 34㎛ or less, 32㎛ or less, 30㎛ or less, 28㎛ or less or 26 It may be less than or equal to µm.

By controlling the dimensions of the hemispherical spacer or the hemispherical columnar spacer as described above, uniform alignment treatment is possible even for the alignment layer formed on the spacer, and it is possible to maintain a uniform cell gap, so that the substrate may have been applied to the manufacture of optical devices. At that time, the performance of the device can be maintained excellently.

The substrate of the present application may include other elements required for driving the optical device in addition to the base layer and the spacer. Various such elements are known, and representatively, there are electrode layers and the like. In one example, the substrate may further include an electrode layer between the base layer and the spacer. As the electrode layer, a known material may be applied. For example, the electrode layer may include a metal alloy, an electrically conductive compound, or a mixture of two or more of the above. Such materials include metals such as gold, CuI, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), Zinc Tin Oxide (ZTO), zinc oxide doped with aluminum or indium, magnesium indium oxide, nickel tungsten oxide, An oxide material such as ZnO, SnO ₂ or In ₂ O ₃ , a metal nitride such as gallium nitride, a metal serenide such as zinc serenide, and a metal sulfide such as zinc sulfide may be exemplified. The transparent hole injection electrode layer may also be formed by using a laminate of a metal thin film such as Au, Ag, or Cu and a high refractive transparent material such as ZnS, TiO ₂ or ITO.

The electrode layer may be formed by any means such as vapor deposition, sputtering, chemical vapor deposition, or electrochemical means. Patterning of the electrode layer is also possible in a known manner without any particular limitation, and for example, it may be patterned through a process using a known photolithography or a shadow mask.

In one example, the electrode layer may be a transparent electrode layer. The transparent electrode layer may include a metal oxide. As such a metal oxide, for example, ITO may be used, and may have an amorphous or crystalline structure. Various materials and methods for forming a transparent electrode layer are known, and all of these methods can be applied.

The substrate of the present application may further include an alignment layer on the base layer and the spacer.

Accordingly, another exemplary substrate of the present application includes a substrate layer; A spacer on the base layer; And an alignment layer formed on the base layer and the spacer.

In the above, specific details of the base layer and the spacer are as described above.

In addition, the type of alignment layer formed on the base layer and the spacer is not particularly limited, and a known alignment layer, for example, a known rubbing alignment layer or a light alignment layer may be applied.

A method of forming the alignment layer on the base layer and the spacer and performing an alignment treatment thereon also follows a known method.

However, the alignment layer may also have a unique shape by being formed on the spacer having a unique shape as described above. The shape of the alignment layer may have a shape that follows the shape of the spacer existing under the alignment layer. 7 is a diagram schematically showing a cross-sectional trajectory of such an alignment film. 7 is an example of a cross-sectional shape of an alignment layer formed on the spacer, and shows a hemispherical shape having a predetermined width W3 and a height H3 and a center of curvature formed inside the cross-section.

For example, the alignment layer may also include the above-described hemisphere portion thereon. In this case, the hemisphere may have a maximum curvature of 2,000 mm ^-1 or less of its cross-sectional trajectory as in the case of a spacer. In other examples, the maximum curvature is 1,800 mm ^-1 or less, 1,600 mm ^-1 or less, 1,400 mm ^-1 or less, 1,200 mm ^-1 or less, 1,000 mm ^-1 or less, 900 mm ^-1 or less, 950 mm ^-1 or less, 850 mm ^-1 or less, 800 mm ^-1 or less, 750 mm ^-1 or less, 700 mm ^-1 or less, 650 mm ^-1 or less, 600 mm ^-1 or less, 550 mm ^-1 or less, 500 mm ^-1 or less, 450 mm ^{- It may be about 1} or less, 400 mm ^-1 or less, 350 mm ^-1 or less, 300 mm ^-1 or less, 250 mm ^-1 or less, 200 mm ^-1 or less, or 150 mm ^-1 or less. The maximum curvature is, in another example, 5 mm ^-1 or more, 10 mm ^-1 or more, 15 mm ^-1 or more, 20 mm ^-1 or more, 25 mm ^-1 or more, 30 mm ^-1 or more, 35 mm ^-1 or more, It may be 40 mm ^-1 or more, 45 mm ^-1 or more, or 50 mm ^-1 or more.

The cross-sectional trajectory of the hemisphere of the alignment layer may or may not include a portion having a curvature of 0, that is, a portion having a linear shape.

The height or width of the alignment layer formed on the spacer as described above is also determined according to the height and width of the spacer present under the spacer, and the thickness of the alignment layer formed thereon, and is not particularly limited.

For example, the height of the hemisphere (H3 in FIG. 7) may be in the range of 1 μm to 50 μm. In another example, the height may be 2 μm or more, 3 μm or more, 4 μm or more, 5 μm or more, 6 μm or more, 7 μm or more, 8 μm or more, 9 μm or more, 10 μm or more, or 11 μm or more. The height is also 48 μm or less, 46 μm or less, 44 μm or less, 42 μm or less, 40 μm or less, 38 μm or less, 36 μm or less, 34 μm or less, 32 μm or less, 30 μm or less, 28 μm or less, It may be 26µm or less, 24µm or less, 22µm or less, 19µm or less, 18µm or less, 17µm or less, 16µm or less, 15µm or less, 14µm or less, 13µm or less, 12µm or less, or 11µm or less.

In addition, the width of the hemisphere (W3 in FIG. 7) may be in the range of 1 μm to 80 μm. The width is 2㎛ or more, 3㎛ or more, 4㎛ or more, 6㎛ or more, 8㎛ or more, 10㎛ or more, 12㎛ or more, 14㎛ or more, 16㎛ or more, 18㎛ or more, 20㎛ or more or It may be 22㎛ or more. In other examples, the width is 78 μm or less, 76 μm or less, 74 μm or less, 72 μm or less, 70 μm or less, 68 μm or less, 66 μm or less, 64 μm or less, 62 μm or less, 60 μm or less, 58 μm or less, 56µm or less, 54µm or less, 52µm or less, 50µm or less, 48µm or less, 46µm or less, 44µm or less, 42µm or less, 40µm or less, 38µm or less, 36µm or less, 34µm or less, 32µm Hereinafter, it may be 30 μm or less, 28 μm or less, 26 μm or less, 24 μm or less, or 22 μm or less.

In the case of the substrate of the present application, the alignment treatment of the alignment layer formed on the spacer by adjusting the shape of the spacer to a unique hemispherical shape can be uniformly performed without being affected by the step difference of the spacer.

In order to maximize this effect, the shape of the alignment layer may be additionally controlled.

For example, as shown in FIGS. 7 and 8, the cross-section of the alignment layer may have a curved shape in which a center of curvature is formed outside the cross-section from a point in contact with the base layer in the cross-section of the alignment layer toward the top. Such a shape may be formed according to, for example, the shape of the spacer and the formation condition of the alignment layer. Accordingly, even when an alignment treatment such as a rubbing treatment is performed on the alignment layer, a uniform alignment treatment can be performed that is not affected by the step difference of the spacer.

The base layer may include a plurality of spacers by including the hemispherical spacers as mentioned above, and including spacers identical to or different from those. The plurality of spacers may be disposed on the base layer while simultaneously having a predetermined regularity and irregularity. Specifically, at least some of the spacers on the substrate layer are irregular in terms of being arranged to have different pitches, but may be regular in terms of being arranged while having substantially the same density between regions determined according to a predetermined rule. .

The present application is also directed to a method of manufacturing the substrate. The manufacturing method may include irradiating light through a light shielding mask to the layer of the transparent resin composition applied on the substrate layer. In this case, the light irradiation may be performed in a state in which the light shielding mask is in contact with or in close contact with the layer of the transparent resin composition.

The layer of the transparent resin composition may be cured through the light irradiation.

The columnar column spacers and the hemispherical column spacers may each be manufactured by an appropriate method.

In one example, in the case of manufacturing a column spacer having a columnar shape, the ball has an average particle diameter that satisfies the above-described ratio with the average height and diameter of the target column spacer, while the standard of the aforementioned particle diameter It is possible to use those with deviation. The ratio (D/H) of the average particle diameter (D) of the balls to the average height (H) of the formed column spacers may exceed 1. Meanwhile, the ratio (T/D) of the average value (T) of the diameter of the column spacer to the average particle diameter (D) of the balls may be greater than 1 or greater than 2.

In manufacturing a column spacer having a cylindrical shape, a general mask may be used as a light blocking mask. In such a light-shielding mask, for example, as shown in FIG. 9, a pattern of a light-shielding layer 902 is formed on one surface of a light-transmitting, for example, ultraviolet-transmitting body 901, and the light-shielding layer 902 And a release layer 903 formed on the surface of the body 901.

The light transmitting body may be, for example, a glass or a transparent film. The transparent film may include, for example, poly(ethylene terephthalate) (PET) or polycarbonate (PC). The light-shielding layer is, for example, AlOxNy (0 ≤ x ≤ 1.5, 0 ≤ y ≤ 1, x and y Is the ratio of the number of atoms of each O and N to the Al 1 atom) or CrOx ((0 ≤ x ≤ 1.5 x is the ratio of the number of each O atoms to Cr 1 atom) or Metal Halide material (AgX, X= Cl, F, Br, I) The release layer may include, for example, Si or F-based materials.

In the above, the light blocking layer 902 may be formed in a certain pattern on the body 901, and the shape of this pattern may be determined in consideration of the shape and/or arrangement of the desired spacer. Various types of light-shielding masks of this type are known, and all of these known masks can be applied in the above method.

10, in a state in which the masks 901, 902, and 903 are in close contact with the layer 1000 of the transparent resin composition formed on the base layer 100, light is irradiated through the mask to cure the transparent resin composition. I can.

Although not described in the drawings, other elements such as an electrode layer may be formed between the base layer 100 and the layer 1000 of the transparent resin composition.

At this time, the state of the irradiated light, for example, the wavelength, amount of light, intensity, etc. are not particularly limited, and may be determined according to the degree of curing and the type of the black resin composition.

In the manufacturing method of the present application, a so-called developing process of removing the uncured transparent resin composition after irradiation of the light may be performed, and this method may be performed in a known manner. Through this process, the substrate may be manufactured.

In another example, when a hemispherical column spacer is to be manufactured, an imprinting mask may be applied as a shading mask.

11 exemplarily shows an imprinting mask. In the mask of FIG. 11, a concave hemispherical shape 9011 is formed on one surface of a light-transmitting, for example, ultraviolet-transmissive body 901, and the surface of the body 901 on which the hemispherical shape 9011 is formed In the portion where the hemispherical shape is not formed, the light blocking layer 902 is formed. If necessary, a release layer may be formed on the surface of the light blocking layer 902 and the body 901.

The light transmitting body may be, for example, a glass or a transparent film. The transparent film may include, for example, poly(ethylene terephthalate) (PET) or polycarbonate (PC). The light-shielding layer is, for example, AlOxNy (0 ≤ x ≤ 1.5, 0 ≤ y ≤ 1, x and y Is the ratio of the number of atoms of each O and N to the Al 1 atom) or CrOx ((0 ≤ x ≤ 1.5 x is the ratio of the number of each O atoms to Cr 1 atom) or Metal Halide material (AgX, X= Cl, F, Br, I) The release layer may include, for example, Si or F-based materials.

An exemplary process of manufacturing the spacer using a mask of such a shape is shown in FIG. 12. As shown in FIG. 12, first, a layer 200 of a transparent resin composition is formed on the surface of the base layer 100, and the mask 900 is pressed onto the layer 200. Thereafter, when the layer 200 is cured by irradiating ultraviolet rays or the like from the top of the mask 900, the photocurable monomer is cured according to the hemispherical shape formed in the mask 900 to form a spacer. Then, by removing the mask 900 and removing the uncured compound, the spacer may be formed in a fixed form on the base layer 100.

A desired hemispherical or hemispherical columnar spacer may be manufactured by controlling the amount of ultraviolet rays irradiated in the above process, the degree of compression of the mask, and/or the shape of the hemispherical shape of the mask 900.

Although not described in the drawings, other elements such as an electrode layer may be formed between the base layer 100 and the layer 200 of the transparent resin composition.

At this time, the state of the irradiated light, for example, the wavelength, amount of light, intensity, etc. are not particularly limited, and may be determined according to the degree of curing and the type of the black resin composition.

In the manufacturing method of the present application, a so-called development process of removing the uncured transparent resin composition composition after irradiation of the light may be performed, and this method may be performed in a known manner. Through this process, the substrate may be manufactured.

The present application also relates to an optical device formed using the substrate as described above.

The exemplary optical device of the present application may include the substrate and a second substrate disposed opposite to the substrate, and maintaining a distance between the substrate and the substrate by a spacer of the substrate.

In the optical device, an optical modulation layer may exist in the gap between the two substrates. In the present application, the term light modulation layer may include all types of known layers capable of changing at least one of characteristics such as polarization state, transmittance, color tone, and reflectance of incident light according to the purpose.

For example, the light modulation layer is a layer containing a liquid crystal material, and is a liquid crystal layer that is switched between a diffusion mode and a transmission mode by on-off of a voltage, for example, a vertical electric field or a horizontal electric field. , A liquid crystal layer that is switched between a transmission mode and a blocking mode, a liquid crystal layer that is switched between a transmission mode and a color mode, or a liquid crystal layer that switches between color modes of different colors.

Various light modulation layers, for example, a liquid crystal layer, capable of performing the above-described functions are known. As an exemplary light modulation layer, a liquid crystal layer used in a conventional liquid crystal display may be used. In another example, the light modulation layer is a so-called guest host liquid crystal layer in various forms, a polymer dispersed liquid crystal layer, a pixel-isolated liquid crystal layer. , A suspended particle device, or an electrochromic display.

In the above, the polymer dispersed liquid crystal layer (PDLC layer) is a higher concept including so-called PILC (pixel isolated liquid crystal), PDLC (polymer dispersed liquid crystal), PNLC (Polymer Network Liquid Crystal) or PSLC (Polymer Stablized Liquid Crystal). to be. The polymer dispersed liquid crystal layer (PDLC layer) may include, for example, a polymer network and a liquid crystal region including a liquid crystal compound dispersed in a phase-separated state from the polymer network.

The implementation method or form of the optical modulation layer as described above is not particularly limited, and a known method may be adopted without limitation depending on the purpose.

In addition, the optical device may further include an additional known functional layer, for example, a polarizing layer, a hard coating layer and/or an antireflection layer, if necessary.

The present application relates to a transparent resin composition, a substrate including a transparent column spacer, and a method of manufacturing a substrate including a transparent column spacer. By including the ball, the transparent resin composition of the present application can implement a uniform pattern height of the transparent column spacer, secure pattern adhesion, and control the properties or composition of the transparent resin composition to achieve uniform dispersibility of the ball, Corrosion resistance of the electrode layer, etc. can be ensured.

1 and 2 are schematic diagrams of the form of the substrate of the present application.
3 to 6 are schematic diagrams of a shape of a spacer having a hemispherical top surface.
7 and 8 are schematic diagrams of cross-sections of an alignment film formed on a spacer.
9 is a schematic diagram of a shading mask applied in the manufacturing method of the present application.
10 is a diagram illustrating a state of a manufacturing process of the substrate according to the present application.
11 is a schematic diagram of a shading mask applied in the manufacturing method of the present application.
12 is a view showing an exemplary state of a manufacturing process of the substrate of the present application.
13 is a result of measuring contact angles of Example 1 and Comparative Example 1. FIG.
14 is a result of evaluation of corrosion resistance of Example 1 and Comparative Example 1.
15 is a result of measuring the transmittance of Example 1.
16 is a result of measuring transmittance of Comparative Example 1.
17 is an SEM image of a substrate including a transparent column spacer of Example 1. FIG.

Hereinafter, the present application will be specifically described through examples according to the present application and comparative examples not according to the present application, but the scope of the present application is not limited by the examples presented below.

Measurement example 1. Analysis of molecular weight distribution of monomers

The molecular weight distribution of the monomer was measured using GPC (equipment device name: PLgel Mixed E*2, manufacturer: Waters).

Measurement example 2. Monomer Number of functional groups analysis

The number of functional groups of the monomer was measured using GC and pyrolysis-GC/MS (equipment instrument name: GC-2010 ultraMS, manufacturer: Shimadzu), and LC/MS (equipment instrument name: LTQ XL, manufacturer: Thermo Scientific).

Measurement example 3. Measurement of viscosity of transparent resin

The viscosity of the transparent resin was measured using a Brookfield viscometer DV1 Prime instrument and a No. 62 spindle.

Measurement example 4. pH measurement of transparent resin

The pH of the transparent resin was measured using an OACTON model instrument manufactured by Eutech Instrument.

Measurement example 5. Of transparent resin Contact angle Measure

A transparent resin was applied on the ITO surface of PET-ITO substrate by spin coating. And after adding 3μl of water dropwise to the surface of the coated transparent resin, the contact angle was measured using a Drop Shpae Analyzer (Model: KRUSS DSA 100).

Measurement example 6. Spacer Measurement of height, diameter and standard deviation

The height of the spacer described below was confirmed using a measuring equipment (Optical profiler, Nano System, Nano View-E1000). The diameter of the spacer was confirmed using an optical microscope (Olympus BX 51). The standard deviation for each of the height and diameter was obtained as the square root of the amount of variance for each mean (the standard deviation was obtained for spacers existing in an area of 300 mm in width and height, respectively, and approximately 50 To 250 spacers were obtained).

Example 1. Transparent resin composition

Low molecular weight monomeric binder with a content of 90 wt% (TMPTA: 35 wt%, IBOA: 18 wt%, HMDA 8 wt%, HEA 8 wt%, HEMA 7 wt%, BMA 7 wt%, MMA 7 wt%), 5 wt % Content of initiator (Photo-initiator, mixed with Darocure-1173 and Darocure-TPO), 5 wt% of additive (dispersant 0.6 wt%, coupling agent [KBM-503, AA] 3 wt%, antioxidant [BHT] 2 wt%) and 2.5 parts by weight of white balls relative to 100 parts by weight of the transparent resin were added, and then blended using a shaker to prepare the transparent resin composition of Example 1. The white ball (manufacturer: Sekisui Chemical, brand name: SP 210) has a size distribution with an average size of 10 µm, a CV value of 4%, and a standard deviation of 0.4 µm. The room temperature viscosity of the transparent resin of Example 1 was 150 cP to 210 cP, the pH was 2 to 2.4, and the contact angle with water was 61° to 71.0°. 13 is a result of measuring a contact angle.

Comparative example 1. Transparent resin composition

65 wt% of a low molecular weight monomeric binder (IBOA: 37 wt%, HMDA 5 wt%, HEMA 5 wt%, EGDA 4 wt%, EGDMA 4 wt%, PEGDA (Poly(ethylene glycol) diacrylate, molecular weight: 308 g/ mol) 5 wt%, IPDI 5 wt%), 25 wt% Urethane Acrylate binder, 5 wt% initiator (Photo-initiator, Darocure-1173 and Darocure-TPO mixed), 5 wt% additive (dispersant After adding a transparent resin composed of 0.6 wt%, a coupling agent [KBM-503, AA] 3 wt%, and an antioxidant [BHT] 2 wt%) and 2.5 parts by weight of white balls relative to 100 parts by weight of the transparent resin, a mixer The transparent resin composition of Comparative Example 1 was prepared by blending using a (shaker). The white ball (manufacturer: Sekisui Chemical, brand name: SP 210) has a size distribution with an average size of 10 µm, a CV value of 4%, and a standard deviation of 0.4 µm. The room temperature viscosity of the transparent resin of Comparative Example 1 was 200 cP to 270 cP, the pH was 0.15 to 0.3, and the contact angle with water was 34.1 ° to 44.7 °. 13 is a result of measuring a contact angle.

Evaluation example 1. Amorphous ITO of transparent resin Of the electrode layer Corrosion evaluation

The transparent resins prepared in Example 1 and Comparative Example 1 were applied to one surface of an amorphous ITO (Indium tin oxide) electrode layer, respectively, and stored in a yellow dark room for 21 hours, and then the transparent resin was removed from the ITO electrode layer. Changes in the appearance of the amorphous ITO electrode layer were observed, and the sheet resistance (Ω/sq) of the amorphous ITO was measured using the Mitsubishi Chemical MCP-T600 instrument. 14 is an external image of an ITO electrode layer after corrosion evaluation of Example 1 and Comparative Example 1, and Table 1 shows the results of measuring sheet resistance. In Table 1, the sheet resistance value before corrosion evaluation is the sheet resistance value measured for the amorphous ITO layer before applying the transparent resin.

In the appearance comparison, in the case of the transparent resin of Example 1, there was no change before and after the evaluation, but in the case of the transparent resin of Comparative Example 1, it could be observed that the ITO layer of yellow color changes to the white layer after evaluation. In the amorphous ITO layer to which the transparent resin of Comparative Example 1 was applied, the sheet resistance of the white region was not measured (0 Ω/sq), and through this, it can be seen that the ITO was corroded by the transparent resin of Comparative Example 1. . In Example 1, it was confirmed that there was no change in sheet resistance before and after evaluation. The different results of the above two transparent resins are thought to be caused by the fact that the pH value (2 to 2.4) of the transparent resin of Example 1 is higher than that of the transparent resin of Comparative Example 1 (0.15 to 0.3).

Example 1 Comparative Example 1 Before corrosion evaluation 320 Ω/sq 320 0Ω/sq After corrosion evaluation 320 Ω/sq Measurement X (0 Ω/sq)

Evaluation example 2. Evaluation of ball dispersibility of transparent resin composition

The ball dispersibility of the transparent resin composition was confirmed by measuring the transmittance using Turbiscan equipment (Formulaction). Specifically, the transparent resin composition prepared in Example 1 and Comparative Example 1 was put into a 20 mL cylindrical cell (diameter 25.4 mm, height 55 mm). After shaking by hand, the transparent resin composition of Example 1 and Comparative Example 1 were compared with each other by measuring the transmittance of light at 880 nm for up to 4 hours by placing it in a Turbiscan device in a dispersed state. In addition, the transparent resin composition of Example 1 was additionally measured for transmittance of 880 nm light up to 54 hours in 5 hours increments.

15 shows the transmittance measurement result of Example 1, and FIG. 16 shows the transmittance measurement result of Comparative Example 1. In FIGS. 15 and 16, Delta Transmission (%) refers to a change in transmittance (transmittance change rate) after a lapse of time when the transmittance before measurement is 0%. The state before the measurement refers to a state immediately after the transparent resin composition is added to a cylindrical cell and dispersed by shaking.

The transparent resin composition of Example 1 showed a transmittance of less than 1% even after 54 hours elapsed after dispersion. On the other hand, the transparent resin composition of Comparative Example 1 shows a transmittance of 20% or more after 4 hours. In Example 1, the transmittance was lower than that of Comparative Example 1, and thus the dispersibility to the balls was excellent, which means that aggregation of balls in the transparent resin composition of Example 1 was suppressed. Since the transparent resin composition of Example 1 does not contain the hydrophilic material (EGDA, EGDMA, PEGDA) included in Comparative Example 1, it is estimated that the dispersibility is excellent because it has excellent affinity with the balls having hydrophobicity. These experimental results show that the contact angle of the transparent resin with respect to water is higher in Example 1 than in Comparative Example 1, so that Example 1 is consistent with the measurement result having higher hydrophobicity compared to Comparative Example 1.

Example 2. Transparent column Spacer Containing substrate

A substrate including a transparent spacer column was prepared using the transparent resin composition of Example 1. The refractive index of the transparent resin composition of Example 1 is in the range of 1.47 to 1.48. The refractive index was measured as a value for a wavelength of 587 nm using an Abbe refractometer.

About 2 to 3 mL of the transparent resin composition of Example 1 was dropped onto the electrode layer of a PET base film having an amorphous ITO electrode layer formed on the surface, and the dropwise added transparent resin composition was pressed with a mask, and the base layer , An electrode layer, a layer of the resin composition, and a layer of the resin composition were cured by irradiating ultraviolet rays toward the mask in a state in which a layered body including the mask was formed (ultraviolet irradiation amount: 100 mJ/cm ² ).

As the mask applied during the manufacture of the substrate, a mask in which a patterned light-shielding layer (AgX, X=Cl, F, Br or I) and a release layer are sequentially formed on a PET film, which is a transparent base film (body), is used. I did. In the above, the pattern of the shading layer was formed to form a triangular closed figure in which the length of each side of the triangle was substantially the same, and regions (diameter: about 20 μm) in which the circular shading layer was not formed were regularly arranged. The length (pitch) of each side of the triangle was about 125 μm.

After ultraviolet irradiation, the uncured resin composition was removed (developed) to form a transparent column spacer. 17 is an SEM image of a substrate on which a column spacer is formed manufactured in the same manner as described above. As shown in FIG. 17, the substrate includes a column spacer to which white balls are attached and a column spacer to which white balls are not attached. In the above, the ratio (A:B) of the number of column spacers with white balls (A) and the number of column spacers without white balls (B) was about 1:5 to 3:7. The white balls had an average particle diameter of 10 μm and a distribution of 9 μm to 10.8 μm. The height of the column spacer was about 8.2 μm to 9.8 μm, with an average of about 9 μm, and a diameter of about 25 μm to 30 μm, with an average of about 28 μm. It can be seen through the SEM image that the column spacer height is measured lower than that of the white ball. In addition, the ratio of the area of the spacer on the surface of the substrate was about 3.6% to 5.2%. In the above, the standard deviation of the height of the column spacers was about 0.25 μm, and the standard deviation of the diameter was about 0.89 μm.

On the other hand, the transparent spacer, which is an ultraviolet cured product of transparent resin, increased the refractive index to 1.51 to 1.52, and the color changed to neutral (when comparing before and after curing, the color coordinate b ^* value decreased from 0.7 to 0.6), and it appeared transparent compared to the substrate. Can be seen. The color coordinates were measured using a COH-400 device manufactured by Nippon Denshoku.

Reference Numerals 100: base layer, 1000: 200: transparent resin composition layer, 201: column spacer, 202: ball 300: electrode layer, 900: mask, 901: ultraviolet transmissive body, 902: light-shielding layer, 903: release layer, 9011: hemisphere shape

Claims (18)

A molecular weight of 500 g/mol or less, and a transparent resin containing a low molecular weight monomer having 1 to 3 photocuring groups and balls,
The low molecular weight monomer includes a trifunctional monomer in the range of 30 to 40 parts by weight based on 100 parts by weight of the total low molecular weight monomer,
The transparent resin composition has a pH value of 1 or more. The transparent resin composition according to claim 1, wherein the transparent resin has a pH value of 2 or more. The transparent resin composition of claim 1, wherein the transparent resin has a contact angle of 50° or more with respect to water. The transparent resin composition of claim 1, wherein the viscosity of the transparent resin is in the range of 50 cP to 700 cP. The transparent resin composition of claim 1, wherein the refractive index of the transparent resin composition is in the range of 1.39 to 1.51. The method of claim 1, wherein the color of the transparent resin composition ^* a ^* b ^* color coordinate standard L b ^* value is from 0.65 to 0.75 within a range of the transparent resin composition. The transparent resin composition of claim 1, wherein the low molecular weight monomer is included in a range of 75 parts by weight or more based on 100 parts by weight of the total transparent resin. The transparent resin composition of claim 1, wherein the low molecular weight monomer comprises a monofunctional monomer having a cyclic structure in a range of 10 to 20 parts by weight based on 100 parts by weight of the total transparent resin. The transparent resin composition of claim 1, wherein the photocuring group includes an alkenyl group, an epoxy group, a carboxyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, or a methacryloyloxy group. The transparent resin composition according to claim 1, wherein the low molecular weight monomer includes all of a monofunctional monomer, a bifunctional monomer, and a trifunctional monomer. The transparent resin composition of claim 1, wherein the ball has a size distribution of 0.8 μm or less based on a standard deviation and 8% or less based on a coefficient of variation (CV). The transparent resin composition of claim 1, wherein the ball comprises at least one selected from the group consisting of polystyrene (PS) and polymethylmethacrylate (PMMA). A substrate comprising a substrate layer, a transparent column spacer present on the substrate layer and including a cured product of transparent resin, and a ball present on the substrate layer in a state attached to the transparent column spacer, wherein the transparent resin has a molecular weight It is 500 g/mol or less and includes a low molecular weight monomer having 1 to 3 photocuring groups, and the low molecular weight monomer includes a trifunctional monomer in the range of 30 to 40 parts by weight based on 100 parts by weight of the total low molecular weight monomer And, the transparent resin has a pH value of 1 or more. The substrate of claim 13, further comprising an electrode layer between the base layer and the transparent column spacer, wherein the transparent column spacer contacts the electrode layer. The substrate of claim 13, wherein the substrate further comprises a transparent column spacer to which balls are not attached. The substrate of claim 13, wherein the transparent column spacer has a transmittance of 80% or more. A method of manufacturing a substrate comprising a transparent column spacer comprising the step of irradiating light through a light shielding mask to the transparent resin composition of claim 1 applied on the substrate layer. The method of claim 17, wherein the irradiation of light is performed while the mask is in contact with the transparent resin composition.

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