KR20170039183A - Method for producing optical member and curable resin composition used therein - Google Patents

Abstract

An optical member which is less susceptible to warping of the substrate and which is excellent in productivity and which is obtained by applying a second curable resin composition having fluidity at the time of uncuring to at least one of a liquid crystal display unit or a protective plate, Is formed as a partition wall between a region filled with the first curable resin composition and a region not filled with the first curable resin composition which is laminated linearly or in a dotted manner between the liquid crystal display unit and the protective plate and in which at least a part of the partition wall And a curable resin composition for use in the method.

Description

TECHNICAL FIELD [0001] The present invention relates to a method of manufacturing an optical member, and a curable resin composition used therefor. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a method of producing an optical member by bonding an optical substrate having a light-shielding portion to another optical substrate, and a curable resin composition therefor.

2. Description of the Related Art Recently, a display device capable of inputting a screen by pasting a touch panel on a display screen of a display device such as a liquid crystal display, a plasma display, or an organic EL display has been widely used. This touch panel has a structure in which a glass plate or a resin film formed with a transparent electrode is adhered to face each other with a slight clearance and, if necessary, a transparent protective plate made of glass or resin is laminated on the touch surface.

BACKGROUND ART There is a technique of using a double-sided pressure-sensitive adhesive sheet for bonding a glass plate or a film on which a transparent electrode is formed in a touch panel with a transparent protective plate made of glass or resin, or bonding the touch panel and a display unit. However, when the double-sided pressure-sensitive adhesive sheet is used, there is a problem that air bubbles easily enter. As a technique for replacing the double-sided pressure-sensitive adhesive sheet, there has been proposed a technique of curing with a flexible curable resin composition.

Thus, as a method of bonding with a flexible ultraviolet-curing resin, two kinds of adhesives as described in Patent Document 1 and Patent Document 2 are used to form a flow stop portion (weir portion) with one adhesive, A filling material is filled in a frame formed by the flow stopper with an adhesive having fluidity of the flowability, and both are cured to form a cured layer, thereby bonding the optical member to the display element.

However, in the case where an image display device is manufactured by forming the peripheral wall portion so that the flow stopping portion is rectangular in shape so as to completely partition the charged region and the outer region of the adhesive, as described in Patent Documents 1 and 2, There is a problem that deformation of the substrate occurs due to the internal stress caused by the shrinkage of the adhesive due to curing when curing and a problem that there is no passage through which the void generated at the time of bonding is discharged to the outer region, .

Thus, in the above situation, development of an image display apparatus and a manufacturing method thereof that can alleviate the stress even when an inner stress due to curing shrinkage of the adhesive occurs, and can reduce the yield due to the presence of voids at the time of bonding .

Japanese Patent Publication No. 5451015 International publication No. 2011/148990 pamphlet

It is an object of the present invention to provide a method of manufacturing an optical member which is less liable to cause warpage of the substrate and can obtain an optical member having excellent productivity, and a curable resin composition used therefor.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention relates to the following (1) to (14).

(1) A method of manufacturing an image display device in which a protective plate is adhered to a liquid crystal display unit,

A second curable resin composition having fluidity at the time of uncured is applied to at least one of the liquid crystal display unit or the protection plate and the application region of the first curable resin composition is defined by the second curable resin composition, A second curable resin composition coating step,

A step of applying a first curable resin composition for applying the first curable resin composition having fluidity at the time of uncured to the application region,

An adhesion step of bonding the liquid crystal display unit and the protective plate via the first curable resin composition,

And a first curable resin composition curing step of curing the first curable resin composition to cement the liquid crystal display unit and the protective plate,

A cured layer obtained by curing the second curable resin composition is laminated as a layer extending in a line or between the liquid crystal display unit and the protective plate or a dotted layer so that the inside of the filling chamber filled with the first curable resin composition And a communicating portion communicating an inner region and an outer region of the filling chamber is formed at least in part of the partition.

(2) The method for manufacturing an image display device according to (1)

The partition wall formed as a layer extending on the line is formed as a rectangular frame,

A plurality of communication portions communicating between the inner region and the outer region,

Wherein the barrier rib has a linearity about a central axis of the image display device when the image display device is viewed from a plane, or the object of rotation is the object of rotation about the axis of the image display device.

(3) The method for manufacturing an image display device according to (1) or (2)

Wherein the partition is formed in a rectangular frame, a partition wall is formed in the obliqueness forming the rectangular frame, and the communicating portion is formed at a square forming a rectangular frame.

(4) The method for manufacturing an image display device according to (1) or (2)

Wherein the partition is formed in a rectangular frame, the communicating portion is formed in the oblique direction forming the rectangular frame, and the partition is formed at a square of the rectangular frame.

(5) A method for producing an optical member according to any one of (1) to (4), wherein the (meth) acrylate (A) and the photopolymerization A curable resin composition containing an initiator (B).

(Meth) acrylate having a polyisoprene skeleton, (meth) acrylate having a polyisoprene skeleton, (meth) acrylate having a polyisoprene skeleton, (meth) acrylate having a polyisoprene skeleton, (Meth) acrylate selected from the group consisting of (meth) acrylate and (meth) acrylate.

(7) The photopolymerization initiator (B) as measured in acetonitrile or methanol has a molar absorptivity of 300 ml / (g · cm) or more at a wavelength of 302 nm or 313 nm and 100 ml / (g · cm) (5) or (6).

(8) The method according to any one of (8) to (9), wherein the protective plate is a transparent glass substrate having a light shielding portion, a transparent resin substrate having a light shielding portion, a glass substrate on which a light shielding portion and a transparent electrode are formed, a glass substrate on which a transparent electrode is formed, (5) to (7), wherein the curable resin composition comprises at least one member selected from the group consisting of compounds represented by the following formulas

(9) The resin composition according to any one of (1) to (9), wherein the storage rigidity at 25 캜 of the resin layer at a curing rate of 80% when the first curing resin composition is irradiated with ultraviolet rays, (5) to (8), wherein the storage stiffness of the layer is 3 to 20 times, and the storage stiffness (25 캜) at a curing rate of 80% is 1 × 10 ² Pa to 1 × 10 ⁵ Pa. Wherein the curable resin composition is a curable resin composition.

(Meth) acrylate having a polyisoprene skeleton, (meth) acrylate having a polyisoprene skeleton, (meth) acrylate having a polybutadiene skeleton, (meth) acrylate having a (5) to (9), wherein the (meth) acrylate is at least one compound selected from the group consisting of

(11) The curable resin composition according to any one of (5) to (10), wherein the protective plate is a touch panel.

(12) A touch panel obtained by the method for manufacturing an image display device according to any one of (1) to (11).

(13) An image display apparatus in which a protective plate is adhered to a liquid crystal display unit,

A first cured layer obtained by curing the first curable resin composition formed on the polarizing plate,

And a second cured layer obtained by curing a second curable resin composition forming a peripheral wall portion of the first cured layer,

The second cured layer is laminated as a layer extending linearly between the liquid crystal display unit and the protective plate so that the first curable resin composition is formed as a partition wall which separates the inner region and the outer region of the filling chamber filled with the first curable resin composition And a communicating portion that communicates an inner region and an outer region of the filling chamber in at least a part of the partition wall.

(14) The curable resin composition according to any one of (14) to (11), wherein the first curable resin composition and the second curable resin composition are a urethane (meth) acrylate compound, a (meth) acrylate compound having a polyisoprene skeleton or a (meth) acrylate compound having a polybutadiene skeleton (Meth) acrylate compound selected from the group consisting of (meth) acrylic acid esters, and a photopolymerization initiator.

1 is a process diagram showing a first embodiment of the production method of the present invention.
Fig. 2 is a schematic view of the configuration of the liquid crystal display unit 1. Fig.
3 is a schematic view of the configuration of the protection plate 2. Fig.
4 is a schematic view showing a specific example of the formation of the partition wall portion.
5 is a process diagram showing a second embodiment of the production method of the present invention.
6 is a process diagram showing a third embodiment of the production method of the present invention.
7 is a schematic view showing an embodiment of an optical member obtained by the present invention.

The present invention relates to a method of manufacturing an image display device in which a protective plate is adhered to a liquid crystal display unit. In the method of manufacturing the image display device, an image display device is manufactured by the following [Step A] to [Step D]. The cured layer obtained by curing the second curable resin composition is laminated as a layer extending linearly between the liquid crystal display unit and the protective plate or a dotted layer as a dotted layer so that the first curable resin composition is filled And a communicating portion which is formed as a partition separating an inner region and an outer region of the charging chamber and communicates an inner region and an outer region of the charging chamber at least in part of the partition.

[Process A] A second curable resin composition having fluidity at the time of non-curing is applied to at least one of the liquid crystal display unit or the protection plate, and the application region of the first curable resin composition is defined by the second curable resin composition A second curable resin composition coating step.

[Step B] The step of applying the first curable resin composition for applying the first curable resin composition having fluidity at the time of uncuring to the application region.

[Step C] An adhesion process for bonding the liquid crystal display unit and the protection plate through the first curable resin composition.

[Step D] A first curable resin composition curing step of curing the first curable resin composition to adhere the liquid crystal display unit and the protective plate.

Hereinafter, the manufacturing method of the present invention and the shape of the image display device manufactured by this method will be described with reference to the drawings. In addition, the first to third embodiments are concrete examples, and the present invention is not limited to these specific examples.

(First Embodiment)

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a process diagram showing a first embodiment of a manufacturing process of an optical member of the present invention. FIG.

This method is a method of obtaining an optical member (image display apparatus) by bonding the liquid crystal display unit 1 and the protective plate 2 together.

The liquid crystal display unit 1 refers to a liquid crystal material sealed between a pair of substrates on which an electrode is formed and provided with a polarizing plate, a driving circuit, a signal input cable, and a backlight unit.

Fig. 2 is a cross-sectional view showing a main part of an example of the liquid crystal display unit 1. Fig. 2, the liquid crystal display unit 1 is provided with a polarizing plate 22 on a liquid crystal display cell 21 and a polarizing plate 22 surrounding the polarizing plate 22 on the liquid crystal display cell 21. [ 23) are disposed. Here, although the structure in which the polarizing plate 22 is directly laminated on the liquid crystal display cell 21 is shown here, it is not necessary to directly laminate the polarizing plate 22, and it is sufficient that the polarizing plate is disposed on the liquid crystal display cell, An optical member such as another functional film may be interposed.

In this state, a gap 24 having a maximum width of several mm is formed between the polarizing plate 22 and the sealing member 23 so that the surface of the liquid crystal display cell 21 is not exposed on the bottom surface of the clearance 24 An example in which the sealing film 25 is disposed is shown. 2, before the second curable resin composition 11 is applied onto the polarizing plate 22, a liquid crystal material (liquid crystal material) is deposited on the bottom surface of the gap 24 between the polarizing plate 22 and the sealing member 23, A sealing film 25 having adhesiveness can be disposed on the surface of the display cell 21 to close a part of the gap 24. One end in the width direction of the sealing film 25 is adjacent to the polarizing plate 22 and the other end is in close contact with the sealing member 23 so that the bottom of the gap 24 is sealed. 2 shows an example in which the sealing film 25 is disposed, the sealing film 25 is not disposed on the bottom surface of the gap 24, but the surface of the liquid crystal display cell 21 is exposed It does not matter.

As such a sealing film 25, a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer such as acrylate or an adhesive layer made of polyethylene terephthalate or the like is preferably used.

As the polarizing plate 22, any known polarizing plate used in an image display apparatus can be used. For example, a film-like absorptive polarizer, a wire grid polarizer, or the like can be used.

In the sealing film 25, the pressure-sensitive adhesive layer or the adhesive layer need not necessarily be solid at the time of disposition, and the sealing film 25 may have a high viscosity so as not to penetrate into the gap between the constituent members of the liquid crystal display unit. More specifically, a curable resin composition having a viscosity of about 65 Pa · s can be used. In order to keep the shape so as not to enter the gap, an adhesive having a stick consumption of about 3 may be used.

The backlight side polarizing plate 27 can be laminated on the liquid crystal display cell 21 on the side opposite to the side where the polarizing plate 22 is formed. Here, the structure is not limited to the structure in which the backlight side polarizing plate 27 is directly laminated on the liquid crystal display cell 21, but the polarizing plate 22 may be disposed on the liquid crystal display cell 21, It is also possible to interpose an optical member such as another functional film between the side polarizing plates 27.

In the backlight side polarizing plate 27, the backlight 28 can be formed on the surface opposite to the surface on which the liquid crystal display cell 21 is disposed. As a light source constituting the backlight, for example, a cold cathode tube or an LED (Light Emitting Diode) can be used. A specific example is an edge light method in which the light source 30 is disposed at one end of the light guide plate 31 and the linear light from the light source 30 is converted into plane light from the light guide plate 31. [ The backlight method is not limited to the edge light method. For example, a direct-type method of disposing the light source 30 directly below the diffusion plate may be employed.

In order to protect the liquid crystal display unit 1, the liquid crystal display unit 1 is usually covered with a casing 26. [ As the casing 26, a metal material is generally used, and specifically, an alloy such as stainless steel, iron, aluminum, or silver can be used.

In the casing 26, a liquid crystal display cell, a backlight, a light guide plate, and an optical film can be accommodated.

In the liquid crystal display unit 1, the plug body 23 is disposed so as to coat the liquid crystal display cell 21. [ 2, the sealing member 23 is disposed so as to surround the polarizing film with the gap 24 interposed therebetween in the peripheral wall portion of the polarizing film 22. As shown in Fig. 2, the sealing member 23 is coated on the liquid crystal display cell 21 with the sealing film 25 interposed therebetween. However, the liquid crystal display cell 21 may be directly coated.

2 shows an example in which the casing 26 disposed directly adjacent to the peripheral wall portion of the liquid crystal display cell 21 is directly coated with the sealing material 23, It is not necessary to be limited to the embodiment. Although not shown, a backlight side polarizing plate 27 is laminated on the surface of the liquid crystal display cell 21 opposite to the surface on which the polarizing plate 22 is formed, and the backlight side polarizing plate 27 is further provided with a backlight It is possible to arrange the backlight unit 28 in such a manner that the casing 26 is adjacent to and covered with the backlight 28 and the casing 26 covers the peripheral wall portion of these members. In addition, the casing 26 may be further coated with the plugs 23. Fig.

As the plug body 23, an organic polymer material is generally used. Specifically, an adhesive film having an adhesive layer or an adhesive layer such as an acrylic polymer film on a film base such as PET can be used.

The protective plate 2 shown in Fig. 3 protects the liquid crystal display unit 1. Fig. The protective plate 2 is a member having a transparent substrate 3 and a light-shielding portion 4 formed on one surface of the transparent substrate 3.

As the transparent substrate 3 used for the protective plate 2, a glass plate or a transparent resin plate can be enumerated. In addition to high transparency to the outgoing light or reflected light from the display panel, , The surface damage property, and the high mechanical strength, a glass plate is preferable.

As a material of the glass plate, a glass material such as soda lime glass can be mentioned, and a highly transparent glass having a lower iron content and a smaller blue color is more preferable. Tempered glass may be used as the surface material to enhance safety. Especially when a thin glass plate is used, it is preferable to use a glass plate subjected to chemical strengthening.

As a material of the transparent resin plate, a resin material having high transparency such as a polymethyl methacrylate (PMMA) plate, a polycarbonate (PC) plate, and an alicyclic polyolefin polymer (COP) plate can be given.

The protective plate 2 may be subjected to surface treatment in order to improve interfacial adhesion with the resin cured layer. Examples of the surface treatment method include a method of treating the surface of the protective plate 2 with a silane coupling agent, a method of forming a thin film of silicon oxide with an oxidizing salt by a frame burner, and the like.

In order to enhance the contrast of the display image, the protective plate 2 is provided with a protective layer 2 which is formed by curing the first cured layer 13 to the second curable resin composition 12 obtained by curing the first curable resin composition 11 The antireflection layer may be formed on the surface opposite to the side where the two cured layer 14 is formed. The antireflection layer can be formed by a method of directly forming an inorganic thin film on the surface of the protective plate 2 or a method of bonding a transparent resin film on which the antireflection layer is formed to the protective plate 2. [

A part or all of the protective plate 2 may be colored or a part or all of the surface of the protective plate 2 may be made an opaque glass to scatter light or a part or whole of the surface of the protective plate 2 Fine irregularities may be formed to refract or reflect the transmitted light. Further, a colored film, a light scattering film, a light refraction film, a light reflection film, or the like may be adhered (adhered) to a part or the whole of the surface of the protection plate 2.

The shape of the protective plate 2 is generally rectangular.

The size of the protective plate 2 is preferably 0.5 m x 0.4 m or more and 0.7 m x 0.4 m or more for the television receiver in that the manufacturing method of the present invention is particularly suitable for manufacturing an image display apparatus having a relatively large area Is particularly preferable. The upper limit of the size of the protective plate 2 is often determined by the size of the display panel. In addition, an image display device that is too large tends to be difficult to handle in installation or the like. The upper limit of the size of the protective plate 2 is usually about 2.5 m x 1.5 m in these limitations.

The thickness of the protective plate 2 is usually 0.5 to 25 mm in the case of a glass plate in view of mechanical strength, transparency and the like. In applications such as a television receiver used indoors and a display for a PC, the distance is preferably 1 to 6 mm from the viewpoint of weight saving of the display device, and 3 to 20 mm is preferable for a public display application installed outdoors. When chemically tempered glass is used, the thickness of the glass is preferably about 0.5 to 1.5 mm in terms of strength. In the case of a transparent resin plate, 2 to 10 mm is preferable.

The light-shielding portion 4 shields the wiring members and the like connected to the display panel by making it possible to prevent a portion other than the image display region of the liquid crystal display cell, which will be described later, from being viewed from the protective plate 2 side. The light shielding portion 4 can be formed on the surface of the second cured layer 14 to be described later on the side where the first cured layer 13 is formed and the parallax between the shielding portion 4 and the image display region Reduce. When the protective plate 2 is a glass plate, it is preferable to use ceramic printing including a black pigment in the light-shielding printing portion because the light-shielding property is high. The light shielding portion 4 may be formed on the surface to be bonded to the protective plate 2 and a film having the antireflection layer formed on the back surface thereof, that is, the outermost surface of the display device may be applied to the protective plate. For example, the light-shielding portion 4 is formed by attaching a tape, applying a paint, or printing.

Although the present invention can be applied to a case in which the light-shielding portion 4 is not provided, in the following description of the first to third embodiments, the case where the light-shielding portion 4 is provided will be described as a specific example do.

[Process A]

1 (a), a second curable resin composition 12 comprising a later-described (meth) acrylate (A) and a photo polymerization initiator (B) (23). Examples of the application method include a screen printing method, a dispensing method, and the like. Here, since the second curable resin composition 12 is a weft part of the first curable resin composition described below at the time of bonding, the first cured resin layer 13 obtained by curing the first curable resin composition 11 can be formed In a desired shape. Specifically, it is formed in the shape of a frame such as a square or a rectangle (that is, on a rectangular frame). The form on the frame will be described later.

Here, the first curable resin composition and the second curable resin composition to be applied to the surfaces of the liquid crystal display unit 1 and the protective plate 2 may be the same or different curable resin compositions may be used.

In order to maintain the gap between the liquid crystal display unit 1 and the protective plate 2, spacer particles having a predetermined particle diameter may be added to the second curable resin composition 12.

Here, the shape of the frame will be described in detail with reference to Fig. In the present invention, the second cured layer 14 is laminated as a layer extending linearly between the liquid crystal display unit 1 and the protective plate 2 or as a dotted layer, whereby the first curable resin composition Is formed as a partition wall (16) that separates an inner region and an outer region of the filled filling chamber (17), and a communication portion communicating an inner region and an outer region of the filling chamber is formed at least in part of the partition. Here, the inner region indicates an inner region of the filling chamber 17 filled with the first curable resin composition partitioned by the partition walls 16 (formed as a second cured layer). The outer region indicates an area on the opposite side of the inner area of the partition 16, and when an image display apparatus is used in the atmosphere, there is usually atmospheric air, and as the structure of the image display apparatus, Are further disposed and spaced apart from the atmosphere, these other members are present.

As shown in Fig. 4 (a) to Fig. 4 (d) as an example of the specific partition wall 16, on the inner surface of the liquid crystal display unit 1 or the protective plate 2 to which the first curable resin composition is applied, A partition wall 16, which is a coating film of the second curable resin composition, is formed on the rectangular frame as the extended coating film.

The barrier rib 16 is formed as a peripheral wall that separates the inner region 18 and the outer region 19 of the filling chamber 17 filled with the first curable resin composition. The application region of the first curable resin composition 11 can be limited so that the first curable resin composition 11 does not leak to the outer region 19 when the first curable resin composition 11 is applied and spread after the composition 11 is applied.

The partition wall 16 can be appropriately designed based on the shape of the image display apparatus and the intended filling state of the filling chamber 17 for filling the first curable resin composition 11. [ As shown in Figs. 4 (a) to 4 (d), a concrete example is formed in a rectangular shape when viewed from the shape plane, and is formed so as to have the object of rotation around the axis of the liquid crystal display unit 1 or the shroud 2 have. Here, the image display device may be formed so as to have a linear property about the center axis when viewed from the plane.

Here, it is preferable to apply the second curable resin composition so that the barrier ribs 16 exist on a pair of sides on the rectangular frame.

In the case where the coating films constituting the partition walls 16 are discrete and exist as in the case of Figs. 4 (b) to 4 (c), they are preferably formed at regular intervals on a rectangular frame, It is desirable to have discrete objectivity.

As a more specific shape, as shown in Fig. 4 (b), the partition wall 16 may have a rotatability about the axis of the liquid crystal display unit 1 or the protective plate 2 on the oblique side or a plane view of the image display device The liquid crystal display unit 1 or the protective plate 2 may be provided on the four corners so as to form rectangular sides from the four corners as shown in Fig. 4 (c) It is preferable that the image forming apparatus is formed so as to have the object of rotation with the axis as the rotation center or with the linearity around the center axis when the image display apparatus is viewed from the plane.

The shape of the partition wall 16 is not particularly limited to the above shape. The partition wall 16 may be formed in a frame shape having a specific shape such as a rectangular shape when the partition wall 16 is grasped as one body and may be formed so as to be spaced apart from the inner region and the outer region of the filling chamber 17, But may be dotted in a dotted pattern.

In this case, when the partition 16 is formed without forming a broken line in the shape of a rectangular frame without the presence of a communicating portion in the filling chamber 17, the inner wall of the filling chamber 17, which is formed by the curing shrinkage due to curing of the first curable resin composition 11 There is no region for relieving the stress, so that deformation such as warping of the liquid crystal display unit 1 or the shielding plate 2 is caused, resulting in display unevenness or the like. In the case where voids are present between the first curable resin composition 11 and the liquid crystal display unit 1 or the protective plate 2 at the time of bonding, there is no air passage, It is likely that there is a problem that it remains.

However, the second cured layer 14 is laminated as a layer extending linearly or as a dotted layer between the liquid crystal display unit 1 and the protective plate 2, so that the first curable resin composition Is formed as a partition wall (16) that separates an inner region and an outer region of the chamber (17), and a communication portion communicating an inner region and an outer region of the filling chamber is formed at least in part of the partition , It is possible to alleviate the internal stress generated at the time of curing the first curable resin composition and to suppress the deformation of the liquid crystal display unit 1 and the shield plate 2. [ In addition, even when a gap is formed when the liquid crystal display unit 1 and the protection plate 2 are bonded to each other, since the gap flows to the communicating portion, it is possible to suppress the problem at the time of bonding.

In the present invention, it is preferable that the second curable resin composition (12) is laminated on the projection area of the plug and not laminated on the projection area of the polarizer. By applying the second curable resin composition (12) to the projected area of the plug in such a manner as to avoid the projection area of the polarizer, the second cured layer obtained by curing the second curable resin composition (12) As shown in FIG. It is possible to prevent ripples from appearing on the image display portion even when pressure is applied on the second cured layer 14 by pressing with a finger or the like by laminating the second cured layer to the point. On the other hand, when the second cured layer 14 is laminated on the polarizing plate, if pressure is applied to the second cured layer and the peripheral wall portion of the image display region, interference is caused by the interference.

The middle point of the width of the coating layer of the second cured layer is disposed so as not to exist in the projection area of the liquid crystal display cell and is present not in the projection area of the gap 24 but surrounding the liquid crystal display cell 21 The pressure applied to the liquid crystal display cell by the pressure is reduced, so that even when the pressure is applied, disturbance of image display of the liquid crystal display cell is reduced, It is possible to prevent such a problem.

Since the area outside the image display area of the liquid crystal display unit 1 is relatively narrow, the width of the coating film formed by the second curable resin composition 12 forming the coating film is preferably narrowed. The width is preferably 0.5 to 3 mm, more preferably 0.5 to 1.6 mm, and further preferably 0.5 to 1.0 mm. The thickness of the coating film of the first curable resin composition 11 to be formed is preferably equal to or more than the average thickness of the coating film of the second curable resin composition 12 to be formed or the thickness of the first curable resin composition 11 to be formed, Is preferably 0.005 to 1 mm thick, more preferably 0.01 to 0.08 mm thick, and more preferably 0.01 to 0.05 mm thick than the thickness of the second curable resin composition (12) to be formed.

It is preferable that the storage rigidity of the second curable resin composition (12) at 25 캜 at the time of curing is higher than the storage rigidity of the cured layer of the first curable resin composition (11) at 25 캜. When the storage rigidity of the second cured layer 14 is greater than the storage rigidity of the first cured layer 13 obtained by curing the first cured resin composition, the liquid crystal display unit 1 and the shield plate 2 are bonded Even if voids remain on the interface between the protective plate 2 and the first cured layer 13 on the periphery of the first cured layer 13, It is easy to become void. Therefore, when the liquid crystal display unit 1 and the protective plate 2 are bonded together under a reduced pressure atmosphere and then the liquid crystal display unit 1 and the protective plate 2 are returned to the atmospheric pressure atmosphere, the pressure in the space (with reduced pressure) The atmospheric pressure), the volume of the gap is reduced, and the void is likely to disappear.

The second curable resin composition 12 and the first curable resin composition 11 are mixed so that the shrinkage ratio at the time of curing of the second curable resin composition 12 becomes larger than the shrinkage rate at the time of curing of the first curable resin composition 11, It is desirable to design. It is considered that the first cured layer 13 formed by curing the first curable resin composition 11 is left in the thickness direction of the first cured layer 13 in the shrinkage stress depending on the shrinkage ratio at the time of curing, The thickness of the first cured layer 13 slightly decreases due to the shrinkage stress in the thickness direction remaining at the top of the layer. By using the first curable resin composition (11) having a smaller shrinkage ratio at the time of curing than the second curable resin composition (12), the stress in the display area can be relaxed and occurrence of display unevenness can be suppressed.

One of the means for increasing the shrinkage rate of the second curable resin composition 12 at the time of curing to be higher than the shrinkage rate of the first curable resin composition 11 at the time of curing is that the number of the curable groups of the second curable resin composition (12) 1 curable resin composition (11). For this purpose, the content of the (i) curable compound (monomer) having a small molecular weight may be increased in the second curable resin composition 12, or (ii) the content of the polyfunctional component having a plurality of reactors in the molecule may be increased.

That is, the viscosity of the second curable resin composition (12) may be higher than that of the first curable resin composition (11). Specifically, the viscosity of the second curable resin composition (12) at the time of uncured is preferably at least two times, more preferably at least five times, the viscosity at the time of uncured first curable resin composition (11) More preferably 10 times or more. In order to form the second curable resin composition (12) on the transparent face material by coating, the viscosity of the second curable resin composition (12) at 25 deg. C at the time of uncured is preferably 3000 Pas Do.

Here, the viscosity of the second curable resin composition (12) is specifically 40 to 70 Pa · s. The second curable resin composition 12 does not maintain its shape and spreads so that it is difficult to control the thickness of the second curable resin composition 12. When the second curable resin composition 12 is bonded to the second curable resin composition 12, There is a possibility that it will be made. On the other hand, when the viscosity exceeds 70 Pa · s, it may be difficult to discharge from the applicator.

The second cured layer 14 is formed with a liquid phase from the interface between the second cured layer 14 and the liquid crystal display unit 1 and the interface between the second cured layer 14 and the shield plate 2. [ 1 curable resin composition 11 is required to have a degree of interfacial adhesion and a rigidity enough to maintain its shape. Therefore, it is preferable to use the second curable resin composition 12 having a high viscosity for the second cured layer 14.

The second curable resin composition (12) may be a photo-curable resin composition or a thermosetting resin composition. The second curable resin composition (12) is preferably a photocurable resin composition comprising a curable compound and a photopolymerization initiator because the curable resin composition (12) can be cured at a low temperature and has a high curing rate.

It is possible to apply the second curable resin composition 12 formed as described above to the next step B by forming the weir portion as it is as a coating film as it is. However, the second curable resin composition 12 may be hardened It is also possible to form a weir part by obtaining a coating film.

In the case of curing, the ultraviolet ray 5 is applied to the second curable resin composition 12 after coating to form a cured portion (in the drawing, not shown in the figure) existing on the lower side of the coated layer (on the liquid crystal display unit side as viewed from the curable resin composition) And a second cured layer 14 having an uncured portion (not shown in the drawing) existing on the upper side (opposite side of the liquid crystal display unit) of the coating layer (on the air side when performed in the air). The irradiation dose is preferably 5 to 2000 mJ / cm2, particularly preferably 10 to 1000 mJ / cm2, and particularly preferably 10 to 500 mJ / cm2. If the irradiation amount is too small, the degree of curing of the resin of the finally joined optical member may become insufficient, and if the irradiation amount is too large, the amount of uncured components decreases, and the adhesion between the liquid crystal display unit 1 and the protective plate 2 becomes poor There is a concern.

In the present invention, " uncured " indicates a state of fluidity under an environment of 25 ° C. Further, when the resin composition layer is contacted with fingers after ultraviolet irradiation and the liquid component adheres to the finger, it is judged that the layer has an uncured portion.

For curing by ultraviolet rays irradiation from ultraviolet to near ultraviolet rays, any light source may be used for a lamp which irradiates a light beam from ultraviolet to near ultraviolet rays. For example, low pressure, high pressure or ultra high pressure mercury lamps, metal halide lamps, (pulse) xenon lamps, LED lamps or electrodeless lamps.

[Process B]

Next, as shown in Fig. 1 (b), a first curable resin composition 11 including a later-described (meth) acrylate (A) and a photo polymerization initiator (B) Is applied to the surface of the surface on which the light-shielding portion 4 of the protective plate 2 is formed. Examples of the application method include a slit coater, a roll coater, a spin coater, and a screen printing method.

The obtained coating film is preferably formed so as to be a frame formed of the second cured layer formed in the step (A). If there is a point outside the frame, there is a possibility that the first curable resin composition 11 may be pushed and a problem may occur when the liquid crystal display unit 1 and the protective plate 2 are bonded. Here, the coating film of the first curable resin composition 11 is not necessarily strictly formed on the second cured layer 14 but is contained in the frame formed of the second cured layer 14, As shown in Fig.

The method of claim 1, the curable resin composition 11, of the elastic modulus in 25 ℃ of the first cured layer obtained by curing a first curable resin composition 11, and the 10 ³ - 10 ⁷ Pa preferably 10 ⁴ to 10 < ⁶ > Pa is more preferred. In order to dissolve the pores at the time of conjugation in a shorter time, 10 ⁴ to 10 ⁵ Pa is particularly preferable. When the elastic modulus is 10 ³ Pa or more, the shape of the first cured layer 13 can be easily maintained. Even if the first curable resin composition 11 to be formed is relatively thick, the thickness of the first cured resin layer 13 can be uniformly maintained throughout the protective layer 2 and the liquid crystal display unit 1 It is difficult for voids to be generated at the interface between the liquid crystal display unit 1 and the first cured layer 13. When the elastic modulus is 10 < ⁷ > Pa or less, good adhesion can be exhibited. In addition, since the molecular mobility of the resin material to be formed is relatively high, when the liquid crystal display unit 1 and the protective plate 2 are bonded together under a reduced pressure atmosphere and then returned to an atmospheric pressure atmosphere, The volume of the air gap tends to decrease due to the differential pressure of the pressure (atmospheric pressure) applied to the cured layer, and the gas in the air gap having a reduced volume is dissolved in the cured layer of the cured material to be easily absorbed.

The thickness of the first curable resin composition 11 is preferably 50 to 500 占 퐉, more preferably 50 to 350 占 퐉, and particularly preferably 100 to 350 占 퐉. If the thickness of the first curable resin composition 11 is 50 m or more, the first cured layer 13 effectively buffs an impact due to an external force at the side of the protective plate 2 and effectively protects the liquid crystal display unit 1 have. In the method of manufacturing an image display apparatus according to the present invention, even if a foreign substance not exceeding the thickness of the first cured layer 13 is mixed between the liquid crystal display unit 1 and the protective plate 2, The thickness of the cargo layer 13 is not largely changed and the influence on the light transmission performance is small. If the thickness of the first cured layer 13 is 500 m or less, the voids do not remain in the first cured layer 13 and the thickness of the entire image display device is not unnecessarily increased.

The thickness of the first cured layer 13 may be adjusted by controlling the thickness of the second cured layer 14 and adjusting the thickness of the liquid second curable resin composition 11 supplied to the surface of the protective plate 2 ) May be controlled.

The viscosity of the first curable resin composition 11 is preferably 0.05 to 50 Pa · s, more preferably 1 to 20 Pa · s. When the viscosity is 0.05 Pa · s or more, deterioration of the physical properties of the first cured layer 13 is suppressed. In addition, since the components having a low boiling point are reduced, volatilization in a reduced-pressure atmosphere to be described later is suppressed, which is preferable. If the viscosity is 50 Pa s or less, voids do not remain in the first cured layer 13.

The viscosity of the first curable resin composition (11) is measured at 25 캜 using an E-type viscometer.

The first curable resin composition (11) may be a photo-curable resin composition or a thermosetting resin composition. As the first curable resin composition, a photocurable resin composition comprising a curable compound and a photopolymerization initiator is preferable because it can be cured at a low temperature and has a high curing speed.

Here, the first curable resin composition 11 may be used for unfolding while being uncured, but it is preferable to cure the first curable resin composition 11 as shown in Fig. 1 (b).

Concretely, ultraviolet rays 5 are applied to the coated film of the first curable resin composition 11 after application to form a cured portion (not shown in the figure) existing on the lower side of the coated layer (on the transparent substrate side as viewed from the curable resin composition) ) And an uncured portion (not shown in the figure) existing on the upper side (opposite side to the transparent substrate side) of the coating layer (on the air side when performed in air). The irradiation dose is preferably 5 to 2000 mJ / cm2, particularly preferably 10 to 1000 mJ / cm2, and particularly preferably 10 to 500 mJ / cm2. If the irradiation amount is too small, the degree of curing of the resin of the finally combined optical member may become insufficient, and if the irradiation amount is too large, the amount of uncured components decreases, and the amount of the cured component of the liquid crystal display unit 1 and the transparent substrate 2 There is a possibility that the coupling becomes poor.

In the present invention, " uncured " indicates a state of fluidity under an environment of 25 ° C. Further, when the resin composition layer is contacted with fingers after ultraviolet irradiation and the liquid component adheres to the finger, it is judged that the layer has an uncured portion.

For curing by ultraviolet rays irradiation from ultraviolet to near ultraviolet rays, any light source may be used for a lamp which irradiates a light beam from ultraviolet to near ultraviolet rays. For example, low pressure, high pressure or ultra high pressure mercury lamps, metal halide lamps, (pulse) xenon lamps, LED lamps or electrodeless lamps.

When the ultraviolet ray to be irradiated onto the curable resin composition has a maximum illuminance in the range of 320 nm to 450 nm as 100, preferably, the ratio of the maximum illuminance at 200 to 320 nm ) Is 30 or less, particularly preferably 200 to 320 nm, and the illuminance is 10 or less. When the maximum illuminance in the range of 320 nm to 450 nm is taken as 100 and the ratio of the maximum illuminance in 200 to 320 nm (illuminance ratio) is more than 30, the adhesive strength of the finally obtained optical member is deteriorated. This is because, if the illuminance at a low wavelength is high, the curing of the curable resin composition excessively proceeds during the hardening of the present step, and the contribution to the adhesion at the time of curing in the irradiation of ultraviolet rays in step D I think it is because it decreases. Further, the roughness is usually 30 to 1000 mW / cm 2 at each wavelength (for example, 365 nm).

Here, the method of irradiating the ultraviolet ray to the illuminance ratio is, for example, a method of applying a lamp that satisfies the condition of the illuminance ratio as a lamp for irradiating a light beam from ultraviolet to near ultraviolet, (For example, a short-wave ultraviolet cut filter, a glass plate, a film, or the like) that cuts ultraviolet rays of a short wavelength at the time of ultraviolet irradiation in the temporary curing of the present step is used, It is possible to investigate the ratio. Examples of the substrate for adjusting the illuminance ratio of ultraviolet rays include, but are not limited to, a glass plate subjected to a short-wave ultraviolet cut treatment, soda lime glass, a PET film, and the like.

In this case, it is preferable to irradiate ultraviolet light from the upper side surface (the side opposite to the transparent substrate side as viewed from the curable resin composition layer) (usually an air surface) on the application side in the atmosphere. It is also possible to irradiate ultraviolet rays while spraying a hardening inhibiting gas on the upper surface of the coating layer after the vacuum is applied. When the resin composition is cured in the air, the side opposite to the liquid crystal display unit side or the side opposite to the transparent substrate side is the atmosphere side.

By spraying oxygen or ozone onto the surface of the ultraviolet curable resin layer (coating layer) during ultraviolet irradiation, the state of the uncured portion and the film thickness of the uncured portion can be adjusted.

In other words, by spraying oxygen or ozone on the surface of the coating layer, oxygen hardening of the curing resin composition is inhibited on the surface thereof, so that the uncured portion of the surface is ensured, or the thickness of the uncured portion It can be thickened.

Here, in the present specification, the curing rate indicates the curing rate as seen from the curing component of the curable resin composition, and indicates that it is calculated excluding the components that are not cured such as a softening agent. In the present invention, the curing rate can be calculated from the following formula (1) from the film specific gravity at 25 캜 obtained by curing the liquid specific gravity before curing at 25 캜 according to the present invention.

[Equation 1]

Cure shrinkage ratio = (film specific gravity - liquid specific gravity) / film specific gravity × 100 (One)

In the first curable resin composition (11) of the present invention, ultraviolet rays are irradiated in the above [Step D] against the storage rigidity at 25 캜 of the resin layer when ultraviolet rays are irradiated in the above [Step B] Is preferably 3 to 20 times (preferably, 3 to 10 times) the storage stiffness of the resin layer at the time when the resin layer is formed.

The storage stiffness can be measured by, for example, the following method. Specifically, two PET films coated with a fluorine-based releasing agent and having a thickness of 40 占 퐉 were prepared, and the resulting curable resin composition was coated on one release agent-applied surface thereof so as to have a film thickness after curing of 600 占 퐉. Thereafter, two PET films were bonded to each other such that the release agent-applied surfaces were opposed to each other. Over the PET film, ultraviolet light of 2000 mJ / cm 2 in total intensity was irradiated with a high-pressure mercury lamp (80 W / cm, ozone resistance) to cure the resin composition. Thereafter, the two PET films are peeled off to produce a cured product for measuring the rigidity. With respect to the stiffness, ARES (TA Instruments) can be used to measure the stiffness in a temperature range of 20 to 40 占 폚.

The curing rate in the main curing in [Process D] is 95% or more.

In the first curable resin composition (11) of the present invention, it is preferable that the storage rigidity at 25 deg. C is 1 x 10 < ² > Pa to 1 x 10 < ⁴ >

When the storage stiffness is higher than 1 x 10 < ⁴ > Pa, the first curable resin composition (11) does not follow the base material, because the first curable resin composition (11) Peeling occurs, the base material is deformed, or the stress is not sufficiently relaxed, so that display irregularity occurs when the optical member is obtained. In addition, in the bonding in a vacuum, since the storage rigidity at the time of temporary hardening is in the above range, it is possible to fill the space formed at the time of the bonding without causing a problem when the substrate is moved under atmospheric pressure. On the other hand, if it is 1 × 10 ² Pa or less, since the rigidity is too low, the shape as a cured product can not be sufficiently maintained, and a cured product suitable for hardening can not be obtained. Here, the storage stiffness is preferably 300 to 3000 Pa, more preferably 500 to 2000 Pa.

As the curing rate of the resin at the time of temporary curing, the curing rate at the time of temporary curing is 60 to 90%, and the storage stiffness of the cured product at the curing rate is the above value and the appropriate value, .

Here, the curing rate at the time of final curing in [Step D] described later is usually 95% or more.

In the present invention, as described above, with respect to the storage stiffness of the resin layer at 25 DEG C during the temporary hardening, the storage stiffness of the resin layer when irradiated with ultraviolet rays in [Step D] described later is 1.5 to 10 And the like. The storage stiffness of the resin layer when irradiated with ultraviolet rays at a curing rate of 80% and the storage stiffness of the resin layer when irradiated with ultraviolet rays at a curing rate of 98% By weight to 10 times by weight.

As described above, by suppressing the stiffness in the case where the hardening rate is low to a certain range as the resin in which the stiffness is rapidly changed according to the hardening rate, it is possible to easily adhere to the substrate in a state where the hardening rate is low, It is possible to easily adhere to each other in terms of adhesion in accordance with the warping of the base material. It is also possible to prevent stress from being generated in the substrate as it follows the change in warp of the substrate. On the other hand, in the state where the curing rate is high, since the bonding of the optical substrates bonded together becomes rigid, the bonding strength can be remarkably increased. Further, in the obtained curing member, a cured product having excellent heat and moisture resistance is obtained while maintaining appropriate flexibility.

Here, with regard to the storage stiffness of the resin layer at 25 deg. C at the time of temporary hardening, the storage stiffness of the resin layer when irradiated with ultraviolet rays in [Step D] to be described later is more preferably 2 to 7, Particularly preferably 5 times. The storage stiffness of the resin layer at ultraviolet light irradiation at a curing rate of 98% with respect to the storage stiffness at 25 占 폚 of the resin layer when irradiated with ultraviolet light at a curing rate of 80% To 7 times, and particularly preferably 2.5 to 5 times.

The curable resin composition of the present invention preferably has a storage rigidity at 25 캜 of 1 x 10 ³ Pa to 1 x 10 ⁶ Pa at the time of the final curing. Here, when the storage stiffness is higher than 1 x 10 < ⁶ > Pa, the base material may be deformed because the shrinkage becomes too large due to curing, but the stress is not sufficiently relaxed, Thereby reducing the risk of this. On the other hand, if it is 1 × 10 ³ Pa or less, the bonding strength becomes low because the rigidity is too low. Here, the storage stiffness is preferably 1.0 x 10 ³ to 1.0 x 10 ⁵ Pa, more preferably 1.0 x 10 ³ to 3.0 x 10 ⁴ Pa.

[Step C]

1 (c), in which the surface of the liquid crystal display unit 1 on which the second curable resin composition 12 is formed and the surface of the protective plate 2 on which the first curable resin composition 11 is formed face each other, The liquid crystal display unit 1 and the transparent substrate 2 having the light shielding portion are bonded. The bonding can be performed either in the air or in vacuum.

Here, in order to make it easier to prevent air bubbles from forming at the time of bonding, it is preferable to perform bonding in vacuum.

Here, when the cured product of the ultraviolet-curable resin having the cured portion and the uncured portion in the first curable resin composition (11) is obtained and then cured, adhesion improvement can be expected.

At the time of bonding, the first curable resin composition 11 is diffused by pressure or the like, and the first curable resin composition 11 is filled in the space. In the case of carrying out under vacuum, a first cured layer 13 having little or no voids is formed when exposed to a high pressure atmosphere thereafter. Here, if the thickness A of the coating film of the first curing resin composition 11 is larger than the thickness B of the coating film of the second curing resin composition 12, the coating film of the first curing resin composition 11 is crushed, The liquid crystal display unit 1 and the protection plate 2 can be bonded firmly.

When the bonding is carried out in a reduced pressure atmosphere, the pressure is preferably 1 kPa, more preferably 10 to 300 Pa, and most preferably 15 to 100 Pa. The decompressed atmosphere state may be immediately released after the bonding. On the other hand, the first curable resin composition 11 flows in the space by maintaining the reduced-pressure atmosphere for a predetermined time (for example, within 10 minutes) to make the gap between the liquid crystal display unit 1 and the protective plate 2 uniform It becomes easy to carry out.

[Process D]

Next, as shown in Fig. 1 (d), ultraviolet rays 5 are irradiated from the side of the protective plate 2 to the optical member obtained by joining the protective plate 2 and the liquid crystal display unit 1 to form a curable resin composition Coating layer) is cured.

The dose of ultraviolet rays is preferably about 100 to 4000 mJ / cm2, particularly preferably about 200 to 3000 mJ / cm2, and more preferably about 1500 to 3000 mJ / cm2, in terms of accumulated light quantity. Regarding the light source used for curing by ultraviolet to near-ultraviolet light irradiation, the light source does not matter whether it is a lamp that emits light other than ultraviolet to near-ultraviolet light. For example, low pressure, high pressure or ultra high pressure mercury lamps, metal halide lamps, (pulse) xenon lamps, LED lamps or electrodeless lamps.

Thus, the optical member shown in Fig. 7 can be obtained.

Thus, the first curable resin composition 11 and the second ultraviolet curable resin composition 12 are cured to form the resin cured layer 15.

The resin cured layer 15 has a first cured layer 13 spreading along the surface of the protective plate 2 and a second cured layer disposed on the periphery of the first cured layer and surrounding the first cured layer 13 . The resin cured layer 15 having the second cured layer can suppress the spreading of the periphery of the first cured layer 13 to the outside, that is, the thinning of the periphery of the first cured layer 13, The thickness of the entire body 13 can be uniformly maintained. It is preferable that the thickness of the entire second resin cured resin layer is made uniform so that it is easy to suppress the remaining of the voids at the interface with the other face material.

In the resin cured layer 15, the thickness of the first curable resin composition 11 and the second curable resin composition 12 is not particularly limited. As a preferable example, the thickness A of the coated film of the first curable resin composition 11 is made equal to or smaller than the thickness B of the coated film of the second curable resin composition 12, or the thickness B of the coated film of the second curable resin composition 12 . Advantages of the setting will be described. When the liquid crystal display unit 1 and the protective plate 2 are bonded to each other, they are usually pressed and bonded. At this time, when the thickness A is equal to or greater than the thickness B, the first curable resin composition 11 is pressed by the pressing force of the first curable resin composition 12 because the coating film of the second curable resin composition 12 is thin, Broken and bonded. Therefore, the second curable resin composition 12 generates stress on the liquid crystal display unit 1 to the protective plate 2 due to the difference between the thickness A and the thickness B, so that the first curable resin composition is stuck It is possible to do it.

In the case where the thickness A of the coating film of the first curable resin composition 11 is smaller than the thickness B of the coating film of the second curable resin composition 12 in the resin cured resin layer 15, The thickness A of the film is more preferably 0.005 mm or thinner than the thickness B of the coating film of the second curable resin composition 12, and more preferably 0.01 mm or thinner.

The thickness A of the coating film of the first curable resin composition 11 is preferably in the range of from 10 to 100 탆 in view of suppressing the generation of voids due to the step difference between the coating film of the second curable resin composition 12 and the coating film of the first curable resin composition 11, The thickness is preferably 0.05 mm or less than the thickness B of the coating film of the second curable resin composition 12, and more preferably 0.03 mm or less.

The coating film of the second curable resin composition 12 in the resin cured layer 15 (the first cured layer and the second cured layer) is close to the coating film of the first curable resin composition 11 When the thickness A of the coating film of the first curable resin composition 11 is smaller than the thickness B of the coating film of the second curable resin composition 12 in at least a part of the region where the first curable resin composition 12 is formed, The thickness B of the thinnest portion of the coating film of the second curable resin composition 12 in the vicinity of the coating film of the curable resin composition 11 is set so that the thickness B of the upper part of the bank formed of the first curable resin composition 11 1/2 or more, more preferably 90/100 or more. When the thickness B of the thinnest portion of the coating film of the second curable resin composition is 1/2 or more of the thickness A of the coating film of the first curable resin composition 11, the voids do not open to the outside, Sufficient to disappear under atmospheric pressure.

The difference between the thickness A of the coating film 11 of the first curable resin composition and the thickness B of the coating film of the second curable resin composition 12 was measured using a laser displacement gauge (LK-H052K, The total thickness of the coating film of the first curable resin composition 11 formed or the coating film of the second curable resin composition 12 is measured and obtained from the difference. The thickness A of the coated film of the first curable resin composition 11 is set to the thickness of the peripheral portion of the coated film of the first curable resin composition 11 adjacent to the coated film of the second curable resin composition 12. Usually, a flat face material is used as the transparent substrate, but a surface shape in which a portion where the coating film of the first curing resin composition 11 is formed and a portion where the coating film of the second curing resin composition 12 is formed is formed in a stepped shape It is preferable that the stepped shape of the surface of the face material having the first curability (the first curable resin composition 11) and the second curable resin composition 12 The difference in height between the thickness A of the coating film of the resin composition 11 and the thickness B of the coating film of the second curing resin composition 12 may be the same. The thickness A of the coating film of the first curable resin composition 11 and the thickness B of the coating film of the second curable resin composition 12 are set so that the coating film of the second curable resin composition 12 becomes the first curable resin composition 11, It is preferable that the thickness of the entire transparent face material is uniform, except for at least a part of the area close to the coated film of the transparent face material.

Depending on the surface shape of the coating film of the first curable resin composition (11) or the coating film of the second curable resin composition (12), it may be difficult to measure the thickness by the laser displacement gauge. In this case, The thickness A of the coating film of the first curing resin composition 11 and the thickness B of the coating film of the second curing resin composition 12 may be measured using a D shape measuring device (high precision shape measuring system KS-1100) or the like.

When the liquid crystal display unit 1 and the protective plate 2 are bonded to each other with the resin composition layer 15 interposed therebetween under the reduced pressure atmosphere as shown in Fig. 1 (c), the liquid crystal display unit 1 or Even if voids separate from the interface between the protective plate 2 and the curable resin composition remain, when the pressure is returned to the atmospheric pressure, the pressure difference between the pressure inside the cavity (depressurization) and the pressure (atmospheric pressure) The volume of the pores decreases, and the fine pores are absorbed by the curable resin composition and disappear.

In the first embodiment, a case is described in which the first curable resin composition is applied to the protective plate 2 and the second curable resin composition is applied to the liquid crystal display unit 1 to form a coating film. However, It is also possible to apply the first curable resin composition to the liquid crystal display unit 1 and coat the second curable resin composition on the protective plate 2 to form a coating film.

(Second Embodiment)

In addition to the first embodiment, the optical member of the present invention may be manufactured by the following modified second embodiment.

[Process A]

5 (a), a second curable resin composition 12 containing (meth) acrylate (A) and a photopolymerization initiator (B) is applied to the light shielding portion 4 on the protective plate 2, Is applied to the surface on which the film is formed.

Here, similarly to the first embodiment, in the present invention, the second cured layer 14 is laminated as a layer extending linearly between the liquid crystal display unit 1 and the protective plate 2 or as a dotted layer , A partition wall (16) that separates an inner area and an outer area of the filling chamber (17) filled with the first curable resin composition, and at least a part of the partition wall And a communicating portion is formed. 4 (a) to 4 (d), on the inner surface of the liquid crystal display unit 1 or the protective plate 2 to which the first curable resin composition is applied, a rectangular A partition wall 16 serving as a coating film of the second curable resin composition is formed.

The barrier rib 16 is formed as a peripheral wall that separates the inner region 18 and the outer region 19 of the filling chamber 17 filled with the first curable resin composition. The application region of the first curable resin composition 11 can be limited so that the first curable resin composition 11 does not leak to the outer region 19 when the first curable resin composition 11 is applied and spread after the composition 11 is applied.

The partition wall 16 can be appropriately designed based on the shape of the image display apparatus and the intended filling state of the filling chamber 17 for filling the first curable resin composition 11. [ As shown in Figs. 4 (a) to 4 (d), a concrete example is formed in a rectangular shape when viewed from the shape plane, and is formed so as to have the object of rotation around the axis of the liquid crystal display unit 1 or the shroud 2 have. Here, the image display device may be formed so as to have a linear property about the center axis when viewed from the plane.

Here, it is preferable to apply the second curable resin composition so that the barrier ribs 16 exist on a pair of sides on the rectangular frame.

[Process B]

5 (b), the first curable resin composition 11 is coated on the surface of the protective plate 2 on which the light shielding portion 4 is formed, and ultraviolet rays 5 are applied to the coating film thus obtained To obtain a cured layer having a non-cured portion existing on the lower side of the coating layer (on the side of the transparent substrate as viewed from the curable resin composition) and on the upper side of the coated layer (the side opposite to the transparent substrate side) .

At this time, when the ultraviolet ray to be irradiated to the curable resin composition has the maximum illuminance in a range of 320 nm to 450 nm as 100, the ratio of the maximum illuminance at 200 to 320 nm is 30 or less, particularly preferably 200 And the illuminance at 320 nm is 10 or less. When the maximum roughness in the range of 320 nm to 450 nm is taken as 100, if the ratio of the maximum roughness at 200 to 320 nm is higher than 30, the adhesive strength of the finally obtained optical member is deteriorated.

[Step C]

Next, as shown in Fig. 5 (c), in the form in which the uncured portions of the first curable resin composition 11 and the second curable resin composition obtained are opposed to the display surface of the liquid crystal display unit 1, (1) and the protective plate (2). The bonding can be performed either in the air or in vacuum.

[Process D]

5 (d), ultraviolet rays 5 are irradiated from the side of the protective plate 2 to the optical member obtained by sticking the protective plate 2 and the liquid crystal display unit 1 to form a cured resin composition The cured layer having uncured portions is cured.

Thus, the optical member shown in Fig. 7 can be obtained.

In the second embodiment, the case where the first and second curable resin compositions are applied to the protective plate 2 together to form a coating film is exemplified. However, the opposite structure is naturally taken, that is, the first curable resin composition and the first curable resin composition 2 curable resin composition may be applied to the liquid crystal display unit 1 to form a coating film and to be applied without any problem.

(Third Embodiment)

In addition to the first and second embodiments, the optical member of the present invention may be manufactured by the following modified third embodiment.

[Process A]

6 (a), a second curable resin composition 12 containing (meth) acrylate (A) and a photopolymerization initiator (B) is applied onto the display surface of the liquid crystal display unit 1 Is applied to the surface of the surface on which the light-shielding portion 4 of the protective plate 2 is formed.

Here, similarly to the first embodiment, in the present invention, the second cured layer 14 is laminated as a layer extending linearly between the liquid crystal display unit 1 and the protective plate 2 or as a dotted layer , A partition wall (16) that separates an inner area and an outer area of the filling chamber (17) filled with the first curable resin composition, and at least a part of the partition wall And a communicating portion is formed. 4 (a) to 4 (d), on the inner surface of the liquid crystal display unit 1 or the protective plate 2 to which the first curable resin composition is applied, a rectangular A partition wall 16 serving as a coating film of the second curable resin composition is formed.

The barrier rib 16 is formed as a peripheral wall that separates the inner region 18 and the outer region 19 of the filling chamber 17 filled with the first curable resin composition. The application region of the first curable resin composition 11 can be limited so that the first curable resin composition 11 does not leak to the outer region 19 when the first curable resin composition 11 is applied and spread after the composition 11 is applied.

The partition wall 16 can be appropriately designed based on the shape of the image display apparatus and the intended filling state of the filling chamber 17 for filling the first curable resin composition 11. [ As shown in Figs. 4 (a) to 4 (d), a concrete example is formed in a rectangular shape when viewed from the shape plane, and is formed so as to have the object of rotation around the axis of the liquid crystal display unit 1 or the shroud 2 have. Here, the image display device may be formed so as to have a linear property about the center axis when viewed from the plane.

Here, it is preferable to apply the second curable resin composition so that the barrier ribs 16 exist on a pair of sides on the rectangular frame.

[Process B]

6 (b), the first curable resin composition 11 containing (meth) acrylate (A) and the photopolymerization initiator (B) is laminated on the display surface of the liquid crystal display unit 1 Is applied to the surface of the surface on which the light-shielding portion 4 of the protective plate 2 is formed.

The obtained coating film is irradiated with ultraviolet rays 5 to form a cured portion existing on the lower side of the coated film (on the side of the transparent substrate as viewed from the curable resin composition) and an uncured portion existing on the upper side of the coated layer To obtain a cured layer.

At this time, when the ultraviolet ray to be irradiated to the curable resin composition has the maximum illuminance in a range of 320 nm to 450 nm as 100, the ratio of the maximum illuminance at 200 to 320 nm is 30 or less, particularly preferably 200 And the illuminance at 320 nm is 10 or less. When the maximum roughness in the range of 320 nm to 450 nm is taken as 100, if the ratio of the maximum roughness at 200 to 320 nm is higher than 30, the adhesive strength of the finally obtained optical member is deteriorated.

[Step C]

Next, as shown in Fig. 6 (c), the liquid crystal display unit 1 and the protection plate 2 are bonded together in such a manner that the uncured portions are opposed to each other. The bonding can be performed either in the air or in vacuum.

Here, in order to make it easier to prevent air bubbles from forming at the time of bonding, it is preferable to perform bonding in vacuum.

As described above, when a cured product of an ultraviolet-curable resin having a cured portion and an uncured portion is obtained in each of the liquid crystal display unit and the transparent substrate, the resultant adhesive can be expected to improve adhesion.

[Process D]

6 (d), ultraviolet rays 5 are irradiated from the side of the protective plate 2 to the optical member obtained by bonding the transparent substrate 2 and the liquid crystal display unit 1 to form a curable resin composition (Coating layer) is cured.

The dose of ultraviolet rays is preferably about 100 to 4000 mJ / cm2, particularly preferably about 200 to 3000 mJ / cm2, and more preferably about 1500 to 3000 mJ / cm2, in terms of accumulated light quantity. Regarding the light source used for curing by ultraviolet to near-ultraviolet light irradiation, the light source does not matter whether it is a lamp that emits light other than ultraviolet to near-ultraviolet light. For example, low pressure, high pressure or ultra high pressure mercury lamps, metal halide lamps, (pulse) xenon lamps, LED lamps or electrodeless lamps.

Thus, the optical member shown in Fig. 7 can be obtained.

Each of the above-described embodiments describes several embodiments of the method for producing an optical member of the present invention with one specific optical substrate. In each of the embodiments, a transparent substrate having a liquid crystal display unit and a light shielding portion is used. However, in the manufacturing method of the present invention, various members described below as an optical substrate can be used in place of the liquid crystal display unit, As the substrate, various members described later can be used.

Furthermore, as optical substrates such as a liquid crystal display unit and a transparent substrate, it is also possible to use various optical substrate layers (for example, films adhered to a cured layer of a curable resin composition or other optical substrate layers ) May be used.

It is also possible to use the coating method of the curable resin composition described in the first embodiment, the thickness of the resin cured product, the irradiation amount and the light source at the time of ultraviolet irradiation, and the ultraviolet curable resin layer by spraying oxygen or ozone onto the surface of the ultraviolet- The method of adjusting the film thickness of the cured portion, and the like are not limited to the above-described embodiment, and can be applied to any manufacturing method included in the present invention.

Specific examples of the optical member that can be manufactured in the first to third embodiments, including the above liquid crystal display unit, are shown below.

(i) the optical substrate having a light-shielding portion is at least one optical substrate selected from the group consisting of a transparent glass substrate having a light-shielding portion, a transparent resin substrate having a light-shielding portion, and a glass substrate having a light- Is an at least one display unit selected from the group consisting of a liquid crystal display unit, a plasma display unit and an organic EL unit, and the obtained optical member is a display body unit having an optical substrate having the light shielding portion.

(ii) an optical member in which one optical substrate is a protective substrate having a light shielding portion, and another optical substrate to which the optical substrate is attached is a display body unit having a touch panel or a touch panel, A touch panel having a protective substrate or a display body unit having the touch panel.

In this case, in the step B, it is preferable to apply the curable resin composition to the surface of the protective substrate having the light-shielding portion on which the light-shielding portion is formed, or to either one of the touch surfaces of the touch panel or both.

(iii) An optical element in which one of the optical substrates is a light-shielding unit, the other optical substrate to which the optical substrate is bonded is a display unit, and the optical member in which at least two optical substrates are bonded is a display unit mode.

In this case, it is preferable that the curable resin composition is applied to either or both of the surface of the optical substrate having the light-shielding portion on which the light shielding portion is formed or the display surface of the display unit in Steps A and B desirable.

Specific examples of the optical substrate having a light-shielding portion include a protective plate for a display screen having a light-shielding portion or a touch panel having a protective substrate having a light-shielding portion formed thereon.

The side of the optical substrate having the light-shielding portion on which the light shielding portion is formed is, for example, the side of the shielding plate on which the light shielding portion is formed when the optical substrate having the light shielding portion is a shielding plate for a display screen having a light shielding portion. When the optical substrate having the light-shielding portion is a touch panel having the protective substrate having the light-shielding portion, the protective substrate having the light-shielding portion has a function of shielding the optical substrate having the light- The face on the side with the added portion means the base face of the touch panel opposite to the touch face of the touch panel.

The light-shielding portion of the optical substrate having the light-shielding portion may be formed on either side of the optical substrate, but is usually fabricated as a frame around a transparent plate-shaped or sheet-shaped optical substrate, and its width is preferably about 0.5 to 10 mm, More preferably about 1 to 8 mm, and even more preferably about 2 to 8 mm.

The curable resin composition usable as the first curable resin composition (11) to the second curable resin composition (12) of the present invention will be described.

The curable resin composition of the present invention preferably contains (meth) acrylate (A) and a photopolymerization initiator (B). In addition, as optional components, other components that can be added to the curable resin composition used for optical purposes may be contained.

The phrase " addable to the curable resin composition for optical use " means that the additive for reducing the transparency of the cured product to such an extent that it can not be used for optical purposes is not included.

When a sheet of a cured product having a thickness of 200 占 퐉 after curing is produced with the curable resin composition used in the present invention, a preferable average transmittance of the sheet in a light having a wavelength of 400 to 800 nm is at least 90% desirable.

A preferable composition ratio of the curable resin composition is 25 to 90% by weight of the (meth) acrylate (A), 0.2 to 5% by weight of the photopolymerization initiator (B) This is the remainder.

As the photopolymerization initiator (B) in the curable resin composition of the present invention, any of the photopolymerization initiators conventionally used may be used.

The (meth) acrylate (A) in the curable resin composition of the present invention is not particularly limited, but examples thereof include urethane (meth) acrylate, (meth) acrylate having polyisoprene skeleton, (meth) acrylate having polybutadiene skeleton, Acrylate, and (meth) acrylate monomer is preferably used. More preferably, at least one of (i) a (meth) acrylate having a urethane (meth) acrylate or polyisoprene skeleton, and (ii) a (meth) acrylate monomer.

In the present specification, "(meth) acrylate" means either or both of methacrylate and acrylate. Quot ;, " (meth) acrylic acid ", and the like.

The urethane (meth) acrylate is obtained by reacting a polyhydric alcohol, a polyisocyanate and a hydroxyl group-containing (meth) acrylate.

Examples of the polyhydric alcohols include alkylenes having 1 to 10 carbon atoms such as neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, Alcohols having a cyclic skeleton such as tricyclodecane dimethylol, bis- (hydroxymethyl) -cyclohexane, etc., and polyhydric alcohols and polybasic acids (for example, , Succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride, etc.), caprolactone alcohol obtained by reaction of polyhydric alcohol and? -Caprolactone, Polycarbonate polyols (e.g., polycarbonate diol obtained by reaction of 1,6-hexanediol with diphenyl carbonate, etc.), polyether polyols (e.g., poly Polypropylene glycol, polytetramethylene glycol, ethylene oxide modified bisphenol A and the like), hydrogenated polybutadiene diol, and other polyolefin polyols. From the viewpoint of compatibility with the other component (A), polypropylene glycol and hydrogenated polybutadiene diol are preferable as the polyhydric alcohol, and polypropylene glycol having a weight average molecular weight of 2000 or more and hydrogenated polybutadiene Diols are particularly preferred. The upper limit of the weight average molecular weight at this time is not particularly limited, but is preferably 10,000 or less, more preferably 5000 or less. The hydrogenated polybutadiene polyol (A) can be used as long as it is a hydrogenation-reduced product of a general polybutadiene polyol. In particular, for the optical use, it is preferable that the residual double bond is small, and the iodine value is particularly preferably 20 or less . With regard to the molecular weight, any molecular weight distribution generally available can be used, and particularly when the balance between flexibility and curability is taken, the molecular weight is particularly preferably from 500 to 3,000.

Examples of the organic polyisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, dicyclopentanyl isocyanate, and the like.

The hydroxyl group-containing (meth) acrylate is a compound having at least one hydroxyl group and at least one (meth) acrylate in one molecule, and specific examples thereof include 2-hydroxyethyl (meth) (Meth) acrylate, glycol mono (meth) acrylate, butanediol mono (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, diethylene glycol mono (Meth) acrylate, triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono Acrylate, neopentyl glycol mono (meth) acrylate, ethoxylated neopentyl glycol mono (meth) acrylate, hydroxy Radiating neopentyl glycol mono (meth) mono (meth) acrylates of divalent alcohols such as acrylate;

(Meth) acrylates such as trimethylolpropane mono (meth) acrylate, ethoxylated trimethylolpropane mono (meth) acrylate, propoxylated trimethylolpropane mono (meth) acrylate, tris (2-hydroxyethyl) isocyanurate mono Acrylate, propoxylated trimethylolpropane di (meth) acrylate, tris (2) acrylate, glycerin mono (meth) acrylate, trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane di Monoacrylates and di (meth) acrylates of trihydric alcohols such as glycerin di (meth) acrylate and glycerin di (meth) acrylate, and di (meth) acrylates of hydroxyl groups of these alcohols, mono- and di (meth) acrylates modified with? -caprolactone;

Acrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, ditrimethylolpropane mono (meth) acrylate, pentaerythritol di (meth) Acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylol propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri (Meth) acrylates of tetravalent or higher alcohols such as tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and ditrimethylolpropane hexa Acrylate having a hydroxyl group or a hydroxyl group in which a part of the hydroxyl groups of these alcohols are modified with an alkyl group or? -Caprolactone Ability (meth) acrylate, and the like.

Among the above (meth) acrylate compounds (C) having at least one hydroxyl group, 2-hydroxyethyl (meth) acrylate is particularly preferable in view of excellent curability and flexibility. In view of ease of workability, the polymerizable compound (F) described later in the present invention may be added during the reaction.

The reaction for obtaining the urethane (meth) acrylate is carried out, for example, in the following manner. That is, the polyol is mixed with the organic polyisocyanate per 1 equivalent of the hydroxyl group so that the isocyanate group is preferably 1.1 to 2.0 equivalents, more preferably 1.1 to 1.5 equivalents, and the reaction temperature is preferably 70 to 90 ° C To synthesize a urethane oligomer (first reaction). Then, the hydroxy (meth) acrylate compound is mixed so that the hydroxyl group is preferably 1 to 1.5 equivalents per equivalent of the isocyanate group of the urethane oligomer, and the reaction is carried out at 70 to 90 ° C to obtain the objective urethane (meth) Rate (second reaction).

In the present invention, the first reaction can be carried out in the absence of a solvent. However, in order to improve workability due to the high viscosity of the product, the first reaction is preferably carried out in a solvent having no alcoholic hydroxyl group or in a polymerizable compound (F) described later. Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene and tetramethylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Glycol ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Propyleneglycol monomethyl ether acetate, dipropyleneglycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, and the like; amines such as gamma -butyrolactone acetate, - cyclic esters such as butyrolactone, Petroleum type solvents such as terpolymer, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, and the like.

The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction is confirmed by a decrease in the amount of isocyanate. In addition, a catalyst may be added for the purpose of shortening the reaction time thereof. As this catalyst, either a basic catalyst or an acidic catalyst is used. Examples of basic catalysts include pyridine, pyrrole, triethylamine, diethylamine, dibutylamine, amines such as ammonia, and phosphines such as tributylphosphine and triphenylphosphine. Examples of the acidic catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, titanium tetraisopropoxide, zirconium tetrabutoxide, aluminum chloride, tin octylate, And Lewis acid catalysts such as tin dilaurate and octyltin diacetate. The addition amount of these catalysts is usually 0.1 to 1 part by weight based on 100 parts by weight of the total weight parts of the diol compound (A + D) and the polyisocyanate compound (B).

The polyurethane compound (E) of the present invention can be obtained by the reaction (second reaction) of a (meth) acrylate compound (C) having at least one hydroxyl group with respect to the isocyanate group remaining after the first reaction.

The second reaction of the present invention is injected in an equivalent relationship such that the isocyanate group of the intermediate obtained after the first reaction is eliminated. Specifically, the OH group of the (meth) acrylate compound (C) having at least one hydroxyl group per 1.0 mol of the NCO group of the intermediate obtained after the first reaction is preferably 1.0 to 3.0 mol, more preferably 1.0 to 2.0 mol, mol.

Although the second reaction of the present invention can be carried out with a solventless agent, it is preferable to carry out the reaction with the polymerizable compound (F) to be described later in the above-mentioned solvent and / or in the present invention in order to improve workability because of high viscosity of the product. The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction is confirmed by a decrease in the amount of isocyanate. The above-mentioned catalyst may be added for the purpose of shortening the reaction time thereof.

The polymerization inhibitor such as 4-methoxyphenol is usually added to the acrylate compound used as the raw material, but the polymerization inhibitor may be added again during the reaction. Examples of such polymerization inhibitors include hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di- p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, phenothiazine, and the like. The amount thereof is 0.01 to 1% by weight based on the reaction mixture.

The weight average molecular weight of the urethane (meth) acrylate is preferably about 7000 to 25000, and more preferably 10,000 to 20,000. If the weight average molecular weight is less than 7000, the shrinkage tends to become large. If the weight average molecular weight is more than 25000, the curability tends to become insufficient.

In the curable resin composition of the present invention, the urethane (meth) acrylate may be used alone or in combination of two or more in an arbitrary ratio. The weight ratio of urethane (meth) acrylate in the photo-curable transparent adhesive composition of the present invention is usually 20 to 80% by weight, more preferably 30 to 70% by weight.

The (meth) acrylate having the polyisoprene skeleton has a (meth) acryloyl group at the terminal or side chain of the polyisoprene molecule. (Meth) acrylate having a polyisoprene skeleton is available as " UC-203 " (Kuraray Co., Ltd.). The (meth) acrylate having a polyisoprene skeleton preferably has a number average molecular weight in terms of polystyrene of 1,000 to 50,000, more preferably 25,000 to 45,000.

The weight ratio of the (meth) acrylate having a polyisoprene skeleton in the photocurable transparent adhesive composition of the present invention is usually preferably 20 to 80% by weight, more preferably 30 to 70% by weight.

The (meth) acrylate having a polybutadiene skeleton has a (meth) acryloyl group at a terminal or a side chain of the polybutadiene molecule. (Meth) acrylate having a polybutadiene skeleton is referred to as "TEAI-1000 (manufactured by Nippon Soda Co., Ltd.)", "TE-2000 (manufactured by Nippon Soda)", "EMA- Organic Chemical Industry Co., Ltd.) ". The (meth) acrylate having a polybutadiene skeleton preferably has a number average molecular weight in terms of polystyrene of 1,000 to 30,000, more preferably 1,000 to 10,000.

As the (meth) acrylate monomer, a (meth) acrylate having one (meth) acryloyl group in the molecule is preferably used.

Here, the (meth) acrylate monomer refers to the (meth) acrylate except for the urethane (meth) acrylate, the following epoxy (meth) acrylate and the (meth) acrylate having the polyisoprene skeleton.

 Specific examples of the (meth) acrylate having one (meth) acryloyl group in the molecule include isooctyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (Meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cetyl (meth) acrylate, isomyristyl (Meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acryloylmorpholine, phenylglycidyl (meth) acrylate, tricyclodecane Dicyclopentanyl (meth) acrylate, 1-adamantyl acrylate, 2-methyl-2 (meth) acrylate, dicyclopentenyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl acrylate, - (Meth) acrylate, dicyclopentadienyloxyethyl (meth) acrylate, 2-ethyl-2-adamantyl acrylate, (Meth) acrylate having 1 to 5 carbon atoms and having a hydroxyl group such as (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) Polyalkylene glycol (meth) acrylates such as ethoxydiethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate and polypropylene oxide-modified nonylphenyl (meth) acrylate, ethylene oxide modified phenoxyphosphoric acid (Meth) acrylate, ethylene oxide modified butoxyphosphoric acid (meth) acrylate, and ethylene oxide-modified octyloxy phosphoric acid (meth) acrylate. All. Among them, an alkyl (meth) acrylate having a carbon number of 10 to 20, 2-ethylhexylcarbitol acrylate, acryloylmorpholine, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl , Isostearyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and polypropylene oxide-modified nonylphenyl (meth) acrylate are preferable, and in view of the flexibility of the resin, (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, polypropylene oxide-modified nonylphenyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

On the other hand, from the viewpoint of improving adhesion to glass, alkyl (meth) acrylates and acryloylmorpholines having 1 to 5 carbon atoms having a hydroxyl group are preferable, and acryloylmorpholine is particularly preferable.

The composition of the present invention may contain (meth) acrylate other than (meth) acrylate having one (meth) acryloyl group within the range that does not impair the properties of the present invention. (Meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, alkylene oxide modified (meth) acrylate, (Meth) acrylate, caprolactone-modified hydroxypivalic neopentyl glycol di (meth) acrylate and ethylene oxide modified di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol Trimethylol C2-C10 alkane tri (meth) acrylate such as trimethylolpropane tri (meth) acrylate, trimethylol propane polyethoxy tri (meth) acrylate, trimethylol propane poly propoxy tri (meth) Trimethylol C2-C10 alkane polyalkoxytri (meth) acrylates such as propane polyethoxy polypropoxy tri (meth) acrylate (Meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, (Meth) acrylate, trimethylolpropane tri (meth) acrylate pentaerythritol polyethoxy tetra (meth) acrylate, pentaerythritol polypropoxytetra (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, have.

In the present invention, when used in combination, (meth) acrylate having one or two functionalities is preferably used in order to suppress curing shrinkage.

In the curable resin composition of the present invention, these (meth) acrylate monomer components may be used alone or in combination of two or more in an arbitrary ratio. The weight ratio of the (meth) acrylate monomer in the photocurable transparent adhesive composition of the present invention is usually 5 to 70% by weight, more preferably 10 to 50% by weight. If it is less than 5% by weight, the curability tends to become insufficient, and if it is more than 70% by weight, shrinkage tends to become large.

(Ii) at least one of (i) a urethane (meth) acrylate or a (meth) acrylate having a polyisoprene skeleton in the curable resin composition, and , The total content of both of (i) and (ii) is preferably from 25 to 90% by weight, more preferably from 40 to 90% by weight, more preferably from 40 to 90% by weight, 40 to 80% by weight.

In the curable resin composition of the present invention, an epoxy (meth) acrylate may be used within a range that does not impair the properties of the present invention. Epoxy (meth) acrylate has a function of improving the curability and improving the hardness and curing rate of the cured product. As the epoxy (meth) acrylate, any of those obtained by reacting a glycidyl ether type epoxy compound with (meth) acrylic acid can be used, but glycidyl ethers for obtaining an epoxy (meth) Type epoxy compounds include diglycidyl ether of bisphenol A or alkylene oxide adduct thereof, diglycidyl ether of bisphenol F or an alkylene oxide adduct thereof, hydrogenated bisphenol A or alkylene oxide adduct thereof Glycidyl ether, hydrogenated bisphenol F or a diglycidyl ether of an alkylene oxide adduct thereof, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol di Glycidyl ether, hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polypropylene glycol Koldi glycidyl ether and the like.

Epoxy (meth) acrylate is obtained by reacting these glycidyl ether type epoxy compounds with (meth) acrylic acid under the following conditions.

(Meth) acrylic acid is reacted at a ratio of 0.9 to 1.5 mol, more preferably 0.95 to 1.1 mol, per equivalent of the epoxy group of the glycidyl ether type epoxy compound. The reaction temperature is preferably 80 to 120 占 폚, and the reaction time is about 10 to 35 hours. In order to accelerate the reaction, it is preferable to use a catalyst such as triphenylphosphine, TAP, triethanolamine, tetraethylammonium chloride or the like. Further, in order to prevent polymerization during the reaction, for example, para-methoxyphenol, methylhydroquinone, etc. may be used as the polymerization inhibitor.

The epoxy (meth) acrylate which can be preferably used in the present invention is a bisphenol A type epoxy (meth) acrylate obtained from an epoxy compound of bisphenol A type. The weight average molecular weight of the epoxy (meth) acrylate is preferably 500 to 10000.

The weight ratio of the epoxy (meth) acrylate in the curable resin composition of the present invention is usually 1 to 80% by weight, preferably 5 to 30% by weight.

The content of the (meth) acrylate (A) in the curable resin composition of the present invention is preferably 25 to 90% by weight, more preferably 40 to 90% by weight based on the total amount of the curable resin composition, More preferably 40 to 80% by weight.

In the curable resin composition of the present invention, the (meth) acrylate (A) is selected from the group consisting of the urethane (meth) acrylate, the (meth) acrylate having the polyisoprene skeleton and the (meth) acrylate monomer Is contained. The content of the urethane (meth) acrylate is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and the content of the (meth) acrylate having the polyisoprene skeleton is preferably Is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and the content of the (meth) acrylate monomer is preferably 5 to 70% by weight, and more preferably 10 to 50% by weight.

In the curable resin composition of the present invention, it is preferable that the (meth) acrylate (A) contains the (meth) acrylate having a urethane (meth) acrylate or polyisoprene skeleton and a content of 20 to 80% More preferably 30 to 70% by weight, further preferably 5 to 70% by weight, and more preferably 10 to 50% by weight, of the (meth) acrylate monomer.

Examples of the photopolymerization initiator (B) contained in the composition of the present invention include, but are not limited to, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 1-hydroxycyclohexyl Phenyl) propanol oligomer (Esacure (ONE), manufactured by Ranbaresh), phenyl ketone (Irgacure (trade name) 184 manufactured by BASF), 2-hydroxy- Hydroxy-2-methyl-1-propan-1-one (Irgacure 2959, BASF), 2-hydroxy- (IRGACURE 127, manufactured by BASF), 2,2-dimethyl-2- (2-methyl-propyl) Dimethoxy-2-phenylacetophenone (Irgacure 651, BASF), 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino propane (manufactured by BASF) 2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid solution 2 (IRGACURE 907; BASF) 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (commercially available from BASF) , 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone and the like.

In the present invention, the photopolymerization initiator (B) preferably has a molar extinction coefficient of 300 ml / (g · cm) or more at 302 nm or 313 nm measured in acetonitrile or methanol, It is preferable to use a photopolymerization initiator having an extinction coefficient of 100 ml / (g · cm) or less. By using such a photopolymerization initiator, it is possible to contribute to the improvement of the bonding strength. When the molar extinction coefficient at 302 nm or 313 nm is 300 ml / (g · cm) or more, the curing at the time of curing in Step D described above is more sufficient. On the other hand, when the molar extinction coefficient at 365 nm is 100 ml / (g · cm) or less, excessive curing can be suitably suppressed at the time of hardening at the steps A and B described above, Lt; / RTI >

Examples of such a photopolymerization initiator (B) include 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by BASF), 2-hydroxy-2-methyl- 1-propan-1-one (Irgacure 2959; BASF, manufactured by BASF), 1- [4- (2- hydroxyethoxy) ), Phenylglyoxylic acid liquid methyl ester (Darocure MBF; manufactured by BASF), and the like.

In the curable resin composition of the present invention, these photopolymerization initiators (B) may be used alone or in combination of two or more in an arbitrary ratio. The weight ratio of the photopolymerization initiator (B) in the photocurable resin composition of the present invention is usually 0.2 to 5 wt%, more preferably 0.3 to 3 wt%. If it is more than 5% by weight, an uncured portion can not be formed or the transparency of the resin cured layer may be deteriorated when a cured layer having uncured portions existing on the side opposite to the cured portion and the optical substrate side is obtained .

The curable resin composition of the present invention contains, in addition to the above (meth) acrylate (A) and the above-mentioned photopolymerization initiator (B), a photopolymerization initiator as the other component, Compounds, later-described softening components, and later additives, and the like. The content of other components relative to the total amount of the curable resin composition of the present invention is the balance obtained by subtracting the total amount of the (meth) acrylate (A) and the photopolymerization initiator (B) in the total amount. Specifically, the total amount of the other components is preferably from 0 to 74% by weight, more preferably from 5 to 70% by weight, based on the total amount of the curable resin composition of the present invention.

In addition, amines or the like which can be a photopolymerization initiator may be used in combination with the photopolymerization initiator. Examples of amines which can be used include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester or p-dimethylaminobenzoic acid isoamyl ester. When a photopolymerization initiator such as an amine is used, the content in the adhesive resin composition of the present invention is preferably 0.005 to 5% by weight, and more preferably 0.01 to 3% by weight.

The curable resin composition of the present invention may contain a compound having a structure represented by the general formula (1), if necessary.

[Chemical Formula 1]

(Wherein n represents an integer of 0 to 40 and m represents an integer of 10 to 50. R ¹ and R ² may be the same or different.) R ¹ and R ² are each an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 1 to 18 carbon atoms, an alkynyl group having 1 to 18 carbon atoms, or an aryl group having 5 to 18 carbon atoms.

The compound having the structure represented by the general formula (1) can be obtained, for example, as UNICEF (trade name) PKA-5017 (polyethylene glycol-polypropylene glycol allyl butyl ether) manufactured by Nichiyu Co.,

The weight ratio in the curable resin composition when the compound having the structure represented by the general formula (1) is used is generally preferably from 10 to 80% by weight, more preferably from 10 to 70% by weight.

In the curable resin composition of the present invention, a softening component may be used if necessary. Specific examples of the softening component that can be used include polymer or oligomer except for the (meth) acrylate and the compound having the structure represented by the general formula (1), phthalic acid esters, phosphoric acid esters, glycol esters, citric acid esters, aliphatic Dibasic acid esters, fatty acid esters, epoxy plasticizers, castor oils, and terpene-based hydrogenated resins. Examples of the oligomer and polymer include oligomers or polymers having polyisoprene skeleton, polybutadiene skeleton, polybutene skeleton, or xylene skeleton, and polymers and esters thereof, and optionally, a polymer or oligomer having a polybutadiene skeleton and It is preferable to use the esterified product. Specific examples of the polymer or oligomer and the esterified product thereof having a polybutadiene skeleton include butadiene homopolymer, epoxy modified polybutadiene, butadiene-styrene random copolymer, maleic acid modified polybutadiene and terminal hydroxyl group modified liquid polybutadiene or liquid hydrogenated poly Butadiene. Further, in the softening component, it is also possible to use the above-mentioned softening components in combination.

The weight ratio of such a softening component in the curable resin composition is usually 10 to 80% by weight, and more preferably 10 to 70% by weight.

The curable resin composition of the present invention may contain additives such as antioxidants, organic solvents, silane coupling agents, polymerization inhibitors, leveling agents, antistatic agents, surface lubricants, fluorescent whitening agents, light stabilizers ), An additive such as a filler may be added.

Specific examples of the antioxidant include BHT, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butyl anilino) (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], triethylene glycol- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5- 4-hydroxyphenyl) propionate, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrosinnamide), 1,3,5-trimethyl- (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- Phenylamine, 2,4-bis [(octylthio) methyl-O-cresol, isooctyl- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], dibutylhydroxytoluene, and the like.

Specific examples of the organic solvent include alcohols such as methanol, ethanol and isopropyl alcohol, dimethylsulfone, dimethylsulfoxide, tetrahydrofuran, dioxane, toluene and xylene.

Specific examples of the silane coupling agent include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4 (Epoxycyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane,? -Mercapropyltrimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxy Silane coupling agents such as silane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane and 3-chloropropyltrimethoxysilane, isopropyl (N-ethylaminoethylamino) titanate , Isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate Titanium coupling agents such as polyoxyethylene (polyoxyethylene) oxyacetate, tetraisopropyl di (dioctylphosphite) titanate and neoalkoxytri (pN- (p-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr- Neoalkoxytris (ethylenediaminoethyl) benzoate sulfonate, neoalkoxytris (dodecanoylethyl) benzene sulfonylate, neoalkoxytris (ethylenediaminoethyl) benzoate, Zirconium such as neoalkoxytris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate and Al-propionate, or aluminum- .

Specific examples of the polymerization inhibitor include p-methoxyphenol and methylhydroquinone.

Specific examples of the light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidyl alcohol, 2,2,6,6-tetramethyl-4-piperidyl alcohol, 2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate (LA-82 manufactured by Adeka Corporation), tetrakis (1,2,2,6,6- 4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane Tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidino and 3,9-bis (2-hydroxy- -Dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, decanedic acid bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis (1-undecaneoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6-tetramethyl- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert- butyl-4-hydroxyphenyl) propionyloxy] Ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, Pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5- Dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, decanedic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, 1,1- N, N ', N''-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethyl) ethylhydroperoxide and the reaction product of octane Yl) -4, 7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N ' Bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butyl Amine Condensate, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl Piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl succinate and 4-hydroxy- Tetramethyl-1-piperidine ethanol, a polymer of 2,2,4,4-tetramethyl-20- (beta -lauryloxycarbonyl) ethyl-7-oxa-3,20-diazadis [ Alanine, N, - (2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / tetradecyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6, -tetramethyl-4-piperidinyl) pyrrolidine- 2,5-dione, 2,2,4,4- -7-oxa-3,20-diazadis pyrrolo [5,1,11,2] heneic acid-21-one, 2,2,4,4-tetramethyl- [(4-methoxyphenyl) -methylene] -bis (1,2,3,4-tetrahydropyran-2-yl) propane dodecyl ester / tetradecyl ester, 2,6,6-pentamethyl-4 (2,2,6,6-tetramethyl-4-piperidino) ester, 1,3-benzenedicarboxamide, N, N'-bis (2,2,6,6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethyl-4-piperidinyl) 2- (2-hydroxy-3- (3,4,5,6-tetrahydropyrimid- yl) phenol, 2- (2-hydroxy- Methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5- chlorobenzotriazole, 2- -tert-pentylphenyl) benzotriazole, the reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert- butyl-4-hydroxyphenyl) propionate with polyethylene glycol, Benzotriazole-based compounds such as 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2,4-di-tert- -4-hydroxybenzoate < / RTI > Based compounds such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 - [(hexyl) oxy] phenol and the like, Is a hindered amine compound.

Specific examples of the filler include powders such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, stearate, spinel, titania, Or spherical beads.

When present in the composition of various additives, the weight ratio of various additives in the photo-curing type transparent adhesive composition is preferably from 0.01 to 3% by weight, more preferably from 0.01 to 1% by weight, still more preferably from 0.02 to 0.5 Weight%.

The curable resin composition of the present invention can be obtained by mixing and dissolving the respective components described above at room temperature to 80 캜, and if necessary, the impurities may be removed by an operation such as filtration. In consideration of the applicability, the resin composition for bonding according to the present invention preferably controls the blending ratio of the components so that the viscosity at 25 캜 is in the range of 300 to 15000 mPa..

The curable resin composition of the present invention is used in a method for producing an optical member by joining at least two optical substrates by the above [Process A] to [Process D].

The curing shrinkage of the cured product of the curable resin composition of the present invention is preferably 3.0% or less, more preferably 2.0% or less in the first curable resin composition. In the second curable resin composition, it is preferably 4.0% or less, and particularly preferably 3.0% or less. Thus, when the curable resin composition is cured, the internal stress accumulated in the resin cured product can be reduced, and deformation of the interface between the substrate and the layer made of the cured product of the curable resin composition can be effectively prevented.

Further, when the base material such as glass is thin, when the hardening shrinkage ratio is large, the warping at the time of hardening becomes large, and the display performance is greatly affected. Therefore, from this viewpoint, the hardening shrinkage ratio is preferably small.

The cured product of the curable resin composition of the present invention preferably has a transmittance of 90% or more at 400 nm to 800 nm. If the transmittance is less than 90%, it is difficult for light to transmit, and visibility may be lowered when used in a display device.

From the viewpoint that a higher transmittance at 400 to 450 nm of the cured product can improve the visibility, it is preferable that the transmittance at 400 to 450 nm is 90% or more.

As the first curable resin composition (11) or the second curable resin composition (12) of the present invention, (I) a (meth) acrylate having a urethane (meth) acrylate or polyisoprene skeleton, Acrylate monomer, and a photopolymerization initiator.

It is preferable that an image display device is obtained by using the resin composition containing both the components (I) and (II) in the first curable resin composition (11) and the second curable resin composition (12).

In addition, it is preferable to further contain the softening component as a softening agent. In particular, it is preferable that both the first curing resin composition (11) and the second curing resin composition (12) contain a softening component. Among the softening components, it is preferable to use a terpene resin (particularly, a solid terpene resin).

Some preferred embodiments of the curable resin composition containing the (meth) acrylate (A) and the photopolymerization initiator (B) used in the production method of the present invention are described below. The " weight% " in the content of each component represents the content ratio with respect to the total amount of the curable resin composition of the present invention.

(A1)

Wherein the (meth) acrylate is at least one (meth) acrylate selected from the group consisting of urethane (meth) acrylate, (meth) acrylate having a polyisoprene skeleton and (meth) (5). ≪ / RTI >

(A2)

As the (meth) acrylate (A)

(i) at least one of (meth) acrylate having a urethane (meth) acrylate or polyisoprene skeleton, and

(ii) (meth) acrylate monomers,

(5) or (A1) above.

(A3)

As the (meth) acrylate (A)

(meth) acrylate obtained by the reaction of (i) a poly C2-C4 alkylene glycol, a diisocyanate and a hydroxy C2-C4 alkyl (meth) acrylate,

(ii) (meth) acrylate monomers,

(5) or (A1) above.

(A4)

The curable resin composition according to any one of (A1) to (A3), wherein the urethane (meth) acrylate has a weight average molecular weight of 7000 to 25000.

(A5)

(B) a curing resin composition containing an acylphosphine oxide compound as a photopolymerization initiator (B), or a photopolymerization initiator (B) as a photopolymerization initiator (B) (A1) to (A4) containing an acylphosphine oxide compound as a curing agent.

(A6)

Wherein the acylphosphine oxide compound is selected from the group consisting of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine The curable resin composition according to the above (A5), wherein the curable resin composition is at least one compound selected from the group consisting of pin oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide.

(A7)

It is preferable that the curable resin composition containing the (meth) acrylate (A) and the photopolymerization initiator (B) further comprises a curable resin composition containing other components in addition to the component (A) The curable resin composition according to any one of (A1) to (A6).

(A8)

The curable resin composition according to the above (A7), wherein the (meth) acrylate (A) is 25 to 90% by weight, the photopolymerization initiator (B) is 0.2 to 5% by weight and the remaining components are remaining.

(A9)

(Meth) acrylate (meth) acrylate and (ii) at least one of urethane (meth) acrylate or polyisoprene (meth) acrylate in an amount of from 5 to 70 (A8), wherein the total amount of both is 40 to 90% by weight based on the total weight of the curable resin composition.

(A10)

The curable resin composition according to any one of the above (A7) to (A9), wherein the other component is 10 to 80% by weight of the compound represented by the general formula (1).

(A11)

A curable resin composition comprising (meth) acrylate (A) and a photopolymerization initiator (B) having a curing shrinkage ratio of a cured product of a curable resin composition of not more than 3% Curable resin composition.

(A12)

Wherein an average transmittance in a wavelength range of 400 to 450 nm is at least 90% and an average transmittance in a wavelength range of 400 to 800 nm is at least 90% with respect to a sheet of a cured product of a curable resin composition having a thickness of 200 m, A curable resin composition comprising (meth) acrylate (A) and a photopolymerization initiator (B), or the curable resin composition according to any one of the above (A1) to (A11).

The curable resin composition of the present invention can be preferably used as an adhesive for producing an optical member by bonding a plurality of optical substrates by the above [Process A] to [Process D].

Examples of the optical substrate used in the method for producing an optical member of the present invention include a protective plate, a transparent plate, a sheet, a touch panel, and a display unit.

In the present invention, " optical substrate " means both an optical substrate having no light-shielding portion on its surface and an optical substrate having a light-shielding portion on its surface. In the method of manufacturing an optical member of the present invention, it is preferable that at least one of the plurality of used optical substrates use an optical substrate having a light-shielding portion.

The position of the light-shielding portion in the optical substrate having the light-shielding portion is not particularly limited. In a preferred embodiment, a band-shaped shielding portion having a width of about 0.05 to 20 mm, preferably about 0.05 to 10 mm, and more preferably about 0.1 to 6 mm is formed at the periphery of the optical substrate have. The light shielding portion on the optical substrate can be formed by attaching a tape, applying a paint, or printing.

As the material of the optical substrate used in the present invention, various materials can be used. Specifically, resins such as PET, PC, PMMA, a complex of PC and PMMA, glass, COC, COP, plastic (acrylic resin, etc.) Examples of the optical substrate, such as a transparent plate or sheet, used in the present invention include a film such as a polarizing plate or a sheet or a laminate in which a plurality of sheets are laminated, a sheet or a transparent plate which is not laminated, and a transparent plate (An inorganic glass plate and processed products thereof, for example, a lens, a prism, and an ITO glass).

The optical substrate used in the present invention may be a laminate composed of a plurality of functional plates or sheets such as a touch panel (touch panel input sensor) or a display unit described below (hereinafter referred to as " functional laminate &Quot;).

Examples of the sheet usable as the optical substrate used in the present invention include an icon sheet, a decorative sheet and a protective sheet. Examples of the plate (transparent plate) that can be used in the method for producing an optical member of the present invention include a bright plate and a protective plate. As a material of these sheets or plates, those listed as materials of transparent plates can be applied.

Examples of the material of the surface of the touch panel that can be used as the optical substrate used in the present invention include glass, PET, PC, PMMA, a complex of PC and PMMA, COC and COP.

The thickness of the plate or sheet-like optical substrate such as a transparent plate or sheet is not particularly limited and is usually about 5 to about 5 cm, preferably about 10 to about 10 mm, more preferably about 50 ~ 3 mm thick.

Preferred examples of the optical member obtained by the production method of the present invention include a plate-shaped or sheet-shaped transparent optical substrate having a light-shielding portion and an optical member in which the functional laminate is formed by a cured product of the curable resin composition of the present invention.

Further, in the manufacturing method of the present invention, by using a display unit such as a liquid crystal display as one of the optical substrates and using an optical functional material as another optical substrate, Panel) can be manufactured. Examples of the display unit include a display device such as an LCD, an EL display, an EL light, an electronic paper or a plasma display in which a polarizing plate is attached to a glass, for example. Examples of optically functional materials include transparent plastic plates such as acrylic plates, PC plates, PET plates, and PEN plates, tempered glass, and touch panel input sensors.

When used as an adhesive material for bonding an optical substrate, the visibility of a display image is further improved when the refractive index of the cured product is 1.45 to 1.55 in order to improve the visibility.

When the refractive index is within the range of this refractive index, the difference in the refractive index from the substrate used as the optical substrate can be reduced, and the light reflection can be suppressed by suppressing irregular reflection of light.

Preferred examples of the optical member obtained by the production method of the present invention include the following (i) to (vii).

(i) An optical member in which an optical substrate having a light-shielding portion and the functional laminate are stacked using a cured product of the curable resin composition of the present invention.

(ii) the optical substrate having the light-shielding portion is an optical substrate selected from the group consisting of a transparent glass substrate having a light-shielding portion, a transparent resin substrate having a light-shielding portion, and a glass substrate having a light-shielding material and a transparent electrode formed thereon, The optical member according to (i) above, wherein the optical member is a display unit or a touch panel.

(iii) The optical member according to (ii), wherein the display unit is any one of a liquid crystal display unit, a plasma display unit, and an organic EL display unit.

(iv) A touch panel (or touch panel input sensor) in which a plate-like or sheet-like optical substrate having a light shielding portion is bonded to the surface of the touch panel side of the touch panel using a cured product of the curable resin composition of the present invention.

(v) A display panel in which a plate-shaped or sheet-shaped optical substrate having a light-shielding portion is superimposed on a display screen of a display unit using a cured product of the curable resin composition of the present invention.

(vi) A display panel according to the above (v), wherein the plate-like or sheet-like optical substrate having the shielding portion is a protective substrate or a touch panel for protecting the display screen of the display unit.

(vii) The optical member, the touch panel or the display panel according to any one of (i) to (vi), wherein the curable resin composition is the curable resin composition according to any one of (A1) to (A12).

By using the curable resin composition of the present invention, a plurality of optical substrates selected from the respective optical substrates are bonded to each other by the method described in the above-mentioned steps A to D, the optical member of the present invention is obtained. In the step B, the curable resin composition may be applied only to one side of the two optical substrates to be bonded to each other with the cured layer interposed therebetween, or may be applied to both sides.

For example, in the case where the functional laminate is the optical member described in (ii) above, which is a touch panel or a display unit, it is preferable that in any one of the surfaces of the protective substrate having the light shielding portion, The resin composition may be applied only to either one of the surface, the touch surface of the touch panel or the display surface of the display unit, or may be applied to both.

In the case of the optical member (vi) in which the protective substrate or the touch panel for protecting the display screen of the display unit is assembled with the display unit, in the processes A and B, The resin composition may be applied only to either one of the substrate surface opposite to the touch surface of the panel and the display surface of the display unit or may be applied to both of them.

The optical member including the display unit and the optical substrate having the light-shielding portion obtained by the manufacturing method of the present invention can be inserted into electronic equipment such as a television, a small game machine, a cellular phone, a PC, and the like.

Example

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto at all.

Preparation of curable resin composition

(Adjustment of first curable resin composition A)

16 parts by weight of a urethane acrylate (reaction product of hydrogenated polybutadiene diol (molecular weight 3000), isophorone diisocyanate and 2-hydroxyethyl acrylate (molar ratio 1: 1.2: 2)), GI-2000 18 parts by weight of a hydroxyl-containing polybutadiene, Nippon Soda Co., Ltd.), 13 parts of Nisseki Polybutene LV-100 (liquid polybutene, JX Nikko Seiki Energy Co., Ltd.) , 16 parts of M105 (aromatic modified hydrogenated terpene resin, Yasuhara Chemical Co., Ltd.), 11 parts of LA (lauryl acrylate, Osaka Organic Chemical Industry Co., Ltd.), S-1800A (isostearyl acrylate (Trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.5 part by weight of Speed Cure (trade name) TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by LAMBSON) (Manufactured by BASF) were heated and mixed. The viscosity at 25 캜 was 4,000 mPa s.

(Adjustment of first curable resin composition B)

9 parts by weight of a reaction product of urethane acrylate (hydrogenated polybutadiene diol (molecular weight 3000), isophorone diisocyanate and 2-hydroxyethyl acrylate (molar ratio 1: 1.2: 2)), GI-2000 55 parts by weight of a hydroxyl group-containing polybutadiene, Nippon Soda Co., Ltd.), 13 parts of Nisseki Polybutene LV-100 (liquid polybutene, JX Nikko Seiki Energy Co., Ltd.) (Trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd.), 3 parts of S-1800A (isostearyl acrylate, Shin-Nakamura Chemical Co., Ltd.), SPEED CURE (trade name) 0.25 part by weight of trimethylbenzoyldiphenylphosphine oxide, manufactured by LAMBSON) and 0.5 part by weight of Irgacure (trade name) 184D (manufactured by BASF). The viscosity at 25 캜 was 3500 mPa s.

(Adjustment of first curable resin composition C)

80 parts by weight of urethane acrylate (reactant of hydrogenated polybutadiene diol (molecular weight 3000), isophorone diisocyanate, and 2-hydroxyethyl acrylate (molar ratio 1: 1.5: 2)), IBXA (isobornyl acrylate (Trade name) TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by LAMBSON), 1 part by weight of Irgacure (trade name) 184D (trade name, manufactured by Shin-Etsu Chemical Co., (Manufactured by BASF) were heated and mixed to prepare a solution. The viscosity at 25 ° C was 14,000 mPa · s.

(Adjustment of second curable resin composition a)

20 parts of LIR-390 (isoprene block polymer, manufactured by Kuraray Co., Ltd.), 50 parts of UC-203 (reactive isoprene polymer, Kuraray Co., Ltd.), FA-512A (dicyclopentenyl acrylate ethyl acrylate, 23 parts of A-NOD-N (nonane diol acrylate, 3 parts, manufactured by Shin-Nakamura Chemical Co., Ltd.), Speed Cure (trade name) TPO (2,4,6-trimethylbenzoyldiphenyl 0.5 part by weight of phosphine oxide, manufactured by LAMBSON Co., Ltd.) and 1 part of Irgacure (trade name) 184D (manufactured by BASF) were heated and mixed to give a viscosity of 65000 mPa · s at 25 ° C.

Using the obtained curable resin composition of the present invention, the following evaluations were carried out.

Example 1

As shown in Fig. 1 (a), the second curable composition a is applied to a projected area of the plug body 23 of the liquid crystal display unit 1 to a thickness of 300 탆, and the coating film is formed in a shape shown in Fig. 4 (b) So as to form a communicating portion for communicating an inside region and an outside region of the application site.

On the other hand, the first curing composition A was applied to the protective plate to a thickness of 250 탆 each. Thereafter, the liquid crystal display unit 1 and the protective plate 2 were bonded to each other in such a manner that the uncured portions were opposed to each other. Finally, an ultraviolet ray 5 with an accumulated light quantity of 2000 mJ / cm 2 was irradiated from the side of the protective plate using an electrodeless ultraviolet lamp (manufactured by Heraeus Noble Light Fusion Co., Ltd., D valve) , And an optical member 7 was prepared.

Example 2

The first curable composition applied to the protective plate was changed to B and the formation of the coated film was applied in the form shown in Fig. 4 (c). The resin cured layer was cured to prepare the optical member Fig.

Comparative Example 1

The resin cured layer was cured in the same manner as the first curable composition except that the application area of the second curable composition was formed by forming it into a rectangular frame so as not to form a communicating part communicating an inside area and an outside area of the application area, .

(Adhesive property)

Optical members were obtained in Examples 1 and 2 and Comparative Example 1 at intervals of 0.1 mm between the substrates. The required stress was measured at room temperature until the obtained optical member substrates were separated from each other. The pressing speed was 5 mm / min, and the obtained stress was divided by the unit area to obtain the adhesive strength.

◎ · · · · 10 N / cm2 or more

O: 5 to 10 N / cm < 2 >

× 5 N / cm 2 or less

(Display unevenness)

The obtained optical member was confirmed by visual inspection.

◎ · · · · Display irregularity and substrate warp are not visible

○ · · · There is no display irregularity, but slight warpage of substrate

× · · · Display unevenness

The obtained curable resin compositions A, B and C of the present invention were evaluated in the following manner.

(Curability) Two slide glasses having a thickness of 1 mm were prepared, and one of them was coated so that the film thickness of the obtained curable resin composition became 200 占 퐉. And the other slide glass was bonded to the coated surface. The resin composition was irradiated with an ultraviolet ray having a cumulative light quantity of 2000 mJ / cm < 2 > with a high-pressure mercury lamp (80 W / cm, ozone resistance) over the glass and the curability was evaluated as follows.

◎ When one side of the substrate is lifted, the entire optical member is heard

When one side of the substrate is lifted, the entire optical member is heard, but it is likely to be peeled once every ten times

X:

(Hardening shrinkage ratio)

Two slide glasses each having a thickness of 1 mm coated with a fluorine-based releasing agent were prepared, and the resulting curable resin composition was coated on one release agent-applied surface thereof so as to have a film thickness of 200 mu m. Thereafter, two pieces of the slide glass were adhered so that the surfaces of the respective releasing agents were opposed to each other. The resin composition was irradiated with ultraviolet light having an accumulated light quantity of 2000 mJ / cm 2 with a high-pressure mercury lamp (80 W / cm, ozone resistance) over the glass, and the resin composition was cured. Thereafter, the two slide glasses were peeled off to produce a cured product for measuring the specific gravity of the film. The specific gravity (DS) of the cured product was measured in accordance with JIS K7112 B method. The liquid specific gravity (DL) of the resin composition was measured at 25 캜. From the measurement results of DS and DL, the hardening shrinkage ratio was calculated by the following formula.

Cure shrinkage (%) = (DS - DL) ÷ DS × 100

(Heat resistance, moisture-resistant adhesive property)

A slide glass having a thickness of 0.8 mm and an acrylic plate having a thickness of 0.8 mm were prepared, and the curable resin composition obtained was applied on one side to a thickness of 200 m, and the other side was bonded to the coated side. Over the glass, the resin composition was irradiated with an ultraviolet ray having an accumulated light quantity of 2000 mJ / cm 2 with a high-pressure mercury lamp (80 W / cm, ozone resistance), and the resin composition was cured to prepare a sample for evaluation of adhesiveness. This was allowed to stand under the environment of 85 ° C and 85% RH for 250 hours. In the sample for evaluation, peeling from a resin cured product of a slide glass or an acrylic plate was confirmed visually.

◎ No peeling after 250 hours

○ · · · · No peeling after 250 hours, with some discoloration

× · · · peeling after 250 hours

(flexibility)

The obtained curable resin composition was sufficiently cured and durometer E hardness was measured by a durometer hardness tester (Type E) by a method in accordance with JIS K7215 to evaluate flexibility. More specifically, the curable resin composition was poured into a cylindrical mold so as to have a film thickness of 1 cm, and irradiated with ultraviolet rays to sufficiently cure the resin composition. The hardness of the resulting cured product was measured with a durometer hardness tester (Type E).

(Stiffness)

Two PET films each having a thickness of 40 占 퐉 on which a fluorine-based releasing agent had been applied were prepared, and the resulting curable resin composition was coated on one releasing agent application surface so that the film thickness after curing became 600 占 퐉. Thereafter, two PET films were bonded to each other such that the release agent-applied surfaces were opposed to each other. Over the PET film, ultraviolet light of 2000 mJ / cm 2 in total intensity was irradiated with a high-pressure mercury lamp (80 W / cm, ozone-less), and the resin composition was cured. Thereafter, the two PET films were peeled off to produce a cured product for measuring the rigidity. Thereafter, the two PET films were peeled off to produce a cured product for stiffness measurement, and the rigidity of the cured product was measured at a temperature range of 20 to 40 캜 using ARES (TA Instruments).

The test results are summarized in the following table.

The rigidity of the first curable composition C is outside the measurement range because the hardness is too high.

Although the present invention has been described in detail with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

The present application is based on Japanese Patent Application (2014-160040) filed on August 6, 2014, which is incorporated by reference in its entirety. Also, all references cited herein are taken as a whole.

Industrial availability

INDUSTRIAL APPLICABILITY The optical member manufacturing method of the present invention can obtain an optical member such as a display unit which is excellent in visibility and hardly causes display unevenness. The optical member obtained by the present invention can be preferably inserted into a display device such as a liquid crystal display, a plasma display, and an organic EL display.

1: Liquid crystal display unit
2: Shield plate
3: transparent substrate
4:
5: ultraviolet ray
11: First curable resin composition
12: Second curable resin composition
13: First cured layer
14: second hard layer
15: Cured resin layer
21: LCD display cell
22: polarizer
23:
24: Clearance
25: Seal film
26: Casing

Claims (14)

A manufacturing method of an image display apparatus in which a protective plate is adhered to a liquid crystal display unit,
A second curable resin composition having fluidity at the time of uncured is applied to at least one of the liquid crystal display unit or the protection plate and the application region of the first curable resin composition is defined by the second curable resin composition, A second curable resin composition coating step,
A step of applying a first curable resin composition for applying the first curable resin composition having fluidity at the time of uncured to the application region,
An adhesion step of bonding the liquid crystal display unit and the protective plate via the first curable resin composition,
And a first curable resin composition curing step of curing the first curable resin composition to cement the liquid crystal display unit and the protective plate,
A cured layer obtained by curing the second curable resin composition is laminated as a layer extending in a line or between the liquid crystal display unit and the protective plate or a dotted layer so that the inside of the filling chamber filled with the first curable resin composition And a communicating portion communicating an inner region and an outer region of the filling chamber is formed at least in part of the partition. The method according to claim 1,
The partition wall formed as a linearly extending layer or a pointed layer is formed as a rectangular frame,
A plurality of communication portions communicating between the inner region and the outer region,
Characterized in that the partition wall has a rotation symmetry about an axis of the image display apparatus or a linear axis about a central axis when the image display apparatus is viewed in a plane,
A method of manufacturing an image display device. 3. The method according to claim 1 or 2,
Wherein the partition is formed in a rectangular frame, a partition wall is formed in the obliqueness forming the rectangular frame, and the communicating portion is formed at a square forming a rectangular frame. 3. The method according to claim 1 or 2,
Wherein the partition is formed in a rectangular frame, the communicating portion is formed in the oblique direction forming the rectangular frame, and the partition is formed at a square of the rectangular frame. (A) and a photopolymerization initiator (B) for use in the first curable resin composition or the second curable resin composition of the optical member manufacturing method according to any one of claims 1 to 4, ). ≪ / RTI > 6. The method of claim 5,
(Meth) acrylate is selected from the group consisting of urethane (meth) acrylate, (meth) acrylate having polyisoprene skeleton, (meth) acrylate having polybutadiene skeleton, (meth) acrylate monomer (Meth) acrylate. The method according to claim 5 or 6,
The curing resin having a molar extinction coefficient of not less than 300 ml / (g · cm) at 302 nm or 313 nm and not more than 100 ml / (g · cm) at 365 nm as measured in acetonitrile or methanol, Composition. 8. The method according to any one of claims 5 to 7,
The protective plate may be selected from the group consisting of a transparent glass substrate having a light shielding portion, a transparent resin substrate having a light shielding portion, a glass substrate having a light shielding portion and a transparent electrode formed thereon, a glass substrate having a transparent electrode formed on a transparent substrate having a light shielding portion, Wherein the curable resin composition is a curable resin composition. 9. The method according to any one of claims 5 to 8,
The storage rigidity of the resin layer at 25 ° C at a curing rate of 80% when the first curable resin composition was irradiated with ultraviolet rays was measured for storage of the resin layer at a curing rate of 98% And a rigidity of 3 to 20 times, wherein the storage rigidity (25 캜) at a curing rate of 80% is 1 × 10 ² Pa to 1 × 10 ⁵ Pa. 10. The method according to any one of claims 5 to 9,
(Meth) acrylate is selected from the group consisting of urethane (meth) acrylate, (meth) acrylate having polyisoprene skeleton, (meth) acrylate having polybutadiene skeleton, (meth) acrylate monomer (Meth) acrylate. 11. The method according to any one of claims 5 to 10,
Wherein the protective plate is a touch panel. A touch panel obtained by the method for manufacturing an image display device according to any one of claims 1 to 11. An image display apparatus in which a protective plate is adhered to a liquid crystal display unit,
A first cured layer obtained by curing a first curable resin composition for bonding the liquid crystal display unit and the protective plate,
And a second cured layer obtained by curing a second curable resin composition for forming a peripheral wall portion of the first cured layer,
The second cured layer is laminated as a layer extending linearly or dotted as a layer between the liquid crystal display unit and the protective plate so that the inner and outer regions of the filling chamber filled with the first curable resin composition And a communicating portion that communicates an inner region and an outer region of the filling chamber is formed in at least a part of the partition. 14. The method of claim 13,
Wherein the first curable resin composition and the second curable resin composition are a mixture of a urethane (meth) acrylate compound, a (meth) acrylate compound having a polyisoprene skeleton or a (meth) acrylate compound having a polybutadiene skeleton Wherein the curable resin composition contains at least one (meth) acrylate compound selected and a photopolymerization initiator.

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