TWI646372B - Optical member manufacturing method, curable resin composition, and touch panel - Google Patents

Abstract

The present invention provides a method for producing an optical member, which is an optical member which is less likely to cause warpage of a substrate and which is excellent in productivity, and which is at least one of a liquid crystal display unit or a protective sheet. A second curable resin composition having fluidity when not cured is applied, and the cured product obtained by curing the composition is layered or dot-likely laminated between the liquid crystal display unit and the protective sheet to form a filling. A region between the region of the first curable resin composition and the region where the first curable resin composition is not filled, and at least a portion of the partition wall is provided with a communication portion between the two regions.

Description

Optical member manufacturing method, curable resin composition, and touch panel

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.

In recent years, a display device in which a touch panel is attached to a display screen of a display device such as a liquid crystal display, a plasma display, or an organic EL (Electroluminescence) display to make a screen input is widely used. The touch panel has a structure in which a glass plate or a resin film having a transparent electrode is formed with a small gap and is attached to each other, and a transparent protective plate made of glass or resin is attached to the touch surface as needed.

There is a technique in which a double-sided adhesive sheet is used for bonding a glass plate or film having a transparent electrode formed in a touch panel to a transparent protective plate made of glass or resin, or bonding a touch panel to a display unit. However, if a double-sided adhesive sheet is used, there is a problem that air bubbles are easily caught. As a technique for replacing a double-sided adhesive sheet, a technique of bonding a curable resin composition which is advantageous in flexibility is proposed.

Here, as a method of bonding with a flexible ultraviolet curable resin, there is proposed a technique in which a stopper is formed by an adhesive using two kinds of adhesives as disclosed in Patent Document 1 and Patent Document 2 (堰)), followed by another fluidity agent Filling is performed in the frame in which the flow stop is formed, and both are hardened to form a cured layer, whereby the optical member is bonded to the display element.

However, as described in Patent Documents 1 and 2, when the peripheral wall portion is formed into a rectangular shape so that the filling portion of the adhesive is completely isolated from the external region, the flow-stop portion has the following problems: When the adhesive is hardened to form the cured layer, the shrinkage of the adhesive is caused by the hardening, and the deformation of the substrate is caused by the inner surface stress generated thereby; or there is no passage for discharging the void generated at the time of bonding to the outer region. Therefore, the remaining space needs to be repaired.

Therefore, under the above circumstances, it has been desired to develop an optical member which can reduce the stress even if the internal surface stress is generated by the curing shrinkage of the adhesive, and can suppress the decrease in yield due to the presence of voids during bonding. method.

Patent Document 1: Japanese Patent No. 5451015

Patent Document 2: International Publication No. 2011/148990

An object of the present invention is to provide a method for producing an optical member which can obtain an optical member which is less likely to cause warpage of a substrate and which is excellent in productivity, and a curable resin composition therefor.

The present inventors conducted intensive studies to solve the above problems, and as a result, completed the present invention. That is, the present invention relates to the following (1) to (14).

(1) A method of producing an optical member, which is a method for producing an optical member in which a liquid crystal display unit is followed by a protective sheet, comprising the steps of: coating a second curable resin composition: the liquid crystal display unit or the above At least one of the protective sheets is coated with a second curable resin composition having fluidity when not cured, and the coating region of the first curable resin composition is defined by the second curable resin composition, and the first hardening is performed. The coating step of the resin composition: the first curable resin composition having fluidity when not cured in the coating region, and a bonding step of: displaying the liquid crystal via the first curable resin composition The unit and the protective sheet are bonded together, and the first curable resin composition is cured by curing the first curable resin composition and bonding the liquid crystal display unit and the protective sheet to form the second curable resin. The cured layer obtained by hardening the composition is laminated in the form of a linearly extending layer or a dot-like layer between the liquid crystal display unit and the protective sheet, thereby forming a partition wall. The partition wall partitions an inner region of the filling chamber filled with the first curable resin composition from the outer region, and a communication portion that communicates between the inner region and the outer region of the filling chamber is provided in at least a portion of the partition wall.

(2) The method of producing an optical member according to (1), wherein the partition wall formed into a linearly extending layer is formed in a rectangular frame shape, and a plurality of communicating portions communicating with the inner region and the outer region are present, The partition wall has rotational symmetry centering on the axis of the optical member, or line symmetry centering on the central axis in the case of observing the optical member.

(3) The method of manufacturing an optical member according to (1) or (2), wherein The partition wall is formed in a rectangular frame shape, and a partition wall is formed on four sides of the frame forming the rectangle, and the communication portion is formed at four corners of the frame forming the rectangle.

(4) The method of producing an optical member according to (1) or (2), wherein the partition wall is formed in a rectangular frame shape, and the communication portion is formed on four sides of the frame forming the rectangle, and is formed at four corners of the rectangular frame. There are the above partition walls.

(5) A curable resin composition, which is used in the method for producing an optical member according to any one of (1) to (4), wherein the first curable resin composition or the second curable resin composition is used ( Methyl) acrylate (A) and photopolymerization initiator (B).

(6) A curable resin composition according to (5), wherein the (meth) acrylate (A) is selected from the group consisting of urethane (meth) acrylate and having a polyisoprene skeleton One or more (meth) acrylates of the (meth) acrylate, the (meth) acrylate having a polybutadiene skeleton, and the (meth) acrylate monomer.

(7) A curable resin composition according to (5) or (6), wherein the photopolymerization initiator (B) measured in acetonitrile or methanol has a molar absorption coefficient of 300 ml/(g.cm at 302 nm or 313 nm). The above is 100 ml/(g.cm) or less at 365 nm.

(8) The curable resin composition according to any one of (5), wherein the protective sheet is made of a transparent glass substrate having a light shielding portion, a transparent resin substrate having a light shielding portion, and a light shielding portion. One or more types of the glass substrate of the transparent electrode, the glass substrate on which the transparent electrode is formed, or the film is bonded to the transparent substrate having the light-shielding portion.

(9) The curable resin composition according to any one of (5) to (8), wherein the resin layer having a curing rate of 80% when irradiated with ultraviolet rays to the first curable resin composition is stored at 25 ° C The rigid modulus, the storage modulus of the resin layer with a curing rate of 98% when irradiated with ultraviolet rays is 3 to 20 times, and the storage rigidity modulus (25 ° C) at the hardening rate of 80% is 1 × 10 ² Pa to 1 × 10 ⁵ Pa.

(10) The curable resin composition according to any one of (5) to (9), wherein the (meth) acrylate (A) is selected from the group consisting of an amine ester (meth) acrylate and having a polyisoprene One or more (meth) acrylates of a group of a (meth) acrylate having a skeleton, a (meth) acrylate having a polybutadiene skeleton, and a (meth) acrylate monomer.

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

(12) A touch panel obtained by the method of producing an optical member according to any one of (1) to (4).

(13) An optical member comprising: a first cured layer: obtained by curing a first curable resin composition formed on the polarizing plate, and a second hardening layer, wherein the liquid crystal display unit is followed by a protective sheet. The material layer is obtained by curing a second curable resin composition that partitions the peripheral wall portion of the first cured material layer, and the second cured material layer is linear between the liquid crystal display unit and the protective plate. The layer of the extended layer is laminated to form a partition wall that partitions an inner region of the filling chamber filled with the first curable resin composition from the outer region, and is provided to communicate with at least a portion of the partition wall A communication portion between the inner region and the outer region of the filling chamber.

(14) The optical member according to the above (13), wherein the first curable resin composition and the second curable resin composition are selected from the group consisting of amine ester (meth) acrylate compounds and polyisoprene At least one (meth) acrylate compound of a group consisting of a (meth) acrylate compound of a skeleton or a (meth) acrylate compound having a polybutadiene skeleton, and a photopolymerization initiator A curable resin composition.

1‧‧‧LCD unit

2‧‧‧protection board

3‧‧‧Transparent substrate

4‧‧‧Lighting Department

5‧‧‧ UV

11‧‧‧1st hardening resin composition

12‧‧‧2nd hardening resin composition

13‧‧‧1st hardened layer

14‧‧‧2nd hardened layer

15‧‧‧Resin hardened layer

21‧‧‧LCD unit

22‧‧‧Polar plate

23‧‧‧ Sealing body

24‧‧‧ gap

25‧‧‧Contained film

26‧‧‧Shell

Fig. 1 is a flow chart showing a first embodiment of the production method of the present invention.

2 is a schematic view showing the configuration of the liquid crystal display unit 1.

Fig. 3 is a schematic view showing the configuration of the protective plate 2.

Fig. 4 is a schematic view showing a specific example of the formation of the partition wall portion.

Fig. 5 is a flow chart showing a second embodiment of the manufacturing method of the present invention.

Fig. 6 is a flow chart showing a third embodiment of the manufacturing method of the present invention.

Fig. 7 is a schematic view showing an aspect of an optical member obtained by the present invention.

The present invention relates to a method for producing an optical member in which a liquid crystal display unit is followed by a protective sheet, and in the method for producing the optical member, an optical member is produced by the following [Step A] to [Step D]. Further, the cured material layer obtained by curing the second curable resin composition is laminated in a layer extending linearly or in a layered manner between the liquid crystal display unit and the protective sheet. This is formed as a partition wall that partitions an inner region of the filling chamber filled with the first curable resin composition from the outer region, and at least a portion of the partition wall is provided with an inner region communicating with the filling chamber and The communication part of the outer area.

[Step A] The second curable resin composition having fluidity when not cured is applied to at least one of the liquid crystal display unit or the protective sheet, and the first hardening resin composition is used to define the first hardening. A second curable resin composition coating step in the coating region of the resin composition.

[Step B] A coating step of applying the first curable resin composition having the fluidity of the first curable resin composition in the coating region to the coating region.

[Step C] A bonding step of bonding the liquid crystal display unit to the protective sheet via the first curable resin composition.

[Step D] The first curable resin composition is cured by curing the first curable resin composition, and the first curable resin composition is bonded to the protective sheet.

Hereinafter, the manufacturing method of the present invention and the form of the optical member manufactured by the method will be described with reference to the drawings. In addition, the first to third embodiments are specific examples, and are not limited to these specific examples.

(First embodiment)

Fig. 1 is a flow chart showing a first embodiment of a manufacturing step of the optical member of the present invention.

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

The liquid crystal display unit 1 is a person having a polarizing plate, a driving circuit, a signal input cable, and a backlight unit, in which a liquid crystal material is sealed between one of the forming electrodes and the substrate.

Fig. 2 is a cross-sectional view showing a main part of an example of the liquid crystal display unit 1. As shown in FIG. 2, the liquid crystal display unit 1 is provided with a polarizing plate 22 on the liquid crystal display unit 21, and a sealing body 23 is disposed on the liquid crystal display unit 21 so as to surround the polarizing plate 22. Here, the structure in which the polarizing plate 22 is directly laminated on the liquid crystal display unit 21 is displayed, but it is not necessary to directly laminate the polarizing plate on the liquid crystal display unit, and optical members such as other functional films may be interposed between the liquid crystal display. Between the unit and the polarizer.

In this state, an example is exemplified in which the maximum width is formed between the polarizing plate 22 and the sealing body 23. The gap 24 is a few mm, and the sealing film 25 is disposed on the bottom surface of the gap 24 so as not to expose the surface of the liquid crystal display unit 21. That is, as shown in the example of FIG. 2, before the second curable resin composition 11 is applied onto the polarizing plate 22, the bottom surface of the gap 24 between the polarizing plate 22 and the sealing body 23 is the liquid crystal display unit 21 On the surface, a sealing film 25 having an adhesiveness is disposed, and one of the gaps 24 is partially closed. One end of the sealing film 25 in the width direction is adjacent to the polarizing plate 22, and the other end is in close contact with the sealing body 23, so that the bottom of the gap 24 is sealed. Here, an example in which the sealing film 25 is disposed is illustrated in FIG. 2, but the sealing film 25 may not be disposed on the bottom surface of the gap 24 to expose the surface of the liquid crystal display unit 21.

The sealing film 25 is preferably a film substrate made of polyethylene terephthalate or the like and having an adhesive layer such as acrylate or an adhesive film of an adhesive layer.

As the polarizing plate 22, a known one for an optical member can be used. For example, a film-shaped absorption type polarizing element, a wire grid type polarizing element, or the like can be used.

Further, the adhesive film or the adhesive layer is not necessarily required to be solid when the sealing film 25 is disposed, and 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 viscosity of 65 Pa can be used. A curable resin composition around s. Further, in terms of maintaining the shape so as not to enter the gap, an adhesive having a thixotropic ratio of about 3 may be used.

In the liquid crystal display unit 21, the backlight-side polarizing plate can be laminated on the surface opposite to the surface on which the polarizing plate 22 is formed. Here, the liquid crystal display unit 21 is not limited to a structure in which a backlight-side polarizing plate is directly laminated, and the polarizing plate 22 may be disposed in the liquid crystal display unit 21, and an optical member such as another functional film may be interposed between the liquid crystal display. The unit 21 is between the backlight 21 and the backlight.

Further, in the backlight-side polarizing plate, a backlight can be formed on and disposed with the liquid crystal display unit 21 The opposite side of the face. As the light source constituting the backlight, for example, a cold cathode tube, an LED (Light Emitting Diode), or the like can be used. As a specific example, an edge light method in which a light source is disposed at one end of the light guide plate and the linear light from the light source is converted into planar light by the light guide plate can be exemplified. Furthermore, the backlight method is not limited to the end face illumination method. For example, a direct-down type in which the light source is disposed directly under the diffusion plate can be employed.

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

The liquid crystal display unit, the backlight, the light guide plate, and the optical film can be housed in the casing 26.

In the liquid crystal display unit 1, a sealing body 23 is disposed so as to form a film on the liquid crystal display unit 21. In FIG. 2, a sealing body 23 is disposed around the polarizing film in a state where the peripheral wall portion of the polarizing film 22 is interposed with a gap 24. Further, in FIG. 2, the sealing film 25 is interposed between the liquid crystal display unit 21 and the film sealing body 23, but may be directly coated on the liquid crystal display unit 21.

In the sealing body 23, a film is formed on the outer wall of the optical member. In the example shown in FIG. 2, the casing 26 disposed adjacent to the peripheral wall portion of the liquid crystal display unit 21 is directly coated. However, the sealing member 23 is not particularly limited. Further, although not shown, the area-side backlight-side polarizing plate of the liquid crystal display unit 21 opposite to the surface on which the polarizing plate 22 is formed may be formed as described above, and the backlight may be laminated on the backlight-side polarizing plate, and the casing 26 may be laminated. The backlight is adjacent and covered, and the casing 26 is disposed to cover the peripheral wall portion of the members. Further, a configuration in which the casing 26 and the film are sealed with the sealing body 23 can be obtained.

As the sealing body 23, an organic polymer material is generally used, and specifically, it can be used for a film substrate such as PET (polyethvlene terephthalate) or the like. Adhesive layer of a polymer system or the like or an adhesive film of an adhesive layer.

The protective panel 2 shown in FIG. 3 can protect the liquid crystal display unit 1 described above. Further, the protective plate 2 is a member having the transparent substrate 3 and the light shielding portion 4, and the light shielding portion 4 is formed on one surface of the transparent substrate 3.

The transparent substrate 3 used for the protective sheet 2 is exemplified by a glass plate or a transparent resin plate, and has high light resistance and low birefringence in terms of high transparency of emitted light or reflected light from the display panel. In terms of high plane precision, surface scratch resistance, and high mechanical strength, a glass plate is preferred.

As a material of the glass plate, a glass material such as soda lime glass is preferable, and a high-transmission glass having a lower iron content and less blue is more preferable. In order to improve safety, tempered glass can also be used as the surface material. Especially in the case of using a thin glass plate, it is preferred to use a glass plate which has been subjected to chemical strengthening.

Examples of the material of the transparent resin sheet include a resin material having high transparency such as a polymethyl methacrylate (PMMA) sheet, a polycarbonate (PC) sheet, or an alicyclic polyolefin polymer (COP) sheet.

For the protective sheet 2, in order to improve the interface adhesion force with the resin cured layer, a surface treatment may be performed. Examples of the surface treatment include a method of treating the surface of the protective sheet 2 with a decane coupling agent, a method of forming a thin film of cerium oxide by an oxidizing flame of a flame burner, and the like.

In order to increase the contrast of the display image, the protective sheet 2 may be provided with an antireflection layer on the surface opposite to the side on which the first cured material layer 13 or the second cured material layer 14 is formed, and the first cured product may be provided. The layer 13 is obtained by curing a first curable resin composition 11 to be described later, and the second cured layer 14 is obtained by curing the second curable resin composition 12 . Anti-reflection layer It is provided by a method of directly forming an inorganic thin film on the surface of the protective sheet 2 or a method of bonding a transparent resin film provided with an antireflection layer to the protective sheet 2.

Moreover, depending on the purpose, one or the whole of the protective sheet 2 may be colored, or One or a part of the surface of the protective sheet 2 may be made into a frosted glass shape to scatter light, or a fine uneven portion or the like may be formed on one or the whole of the surface of the protective sheet 2 to refract or reflect transmitted light. Further, a colored film, a light-scattering film, a light-refractive film, a light-reflecting film, or the like may be bonded to one or the entire surface of the protective sheet 2.

The shape of the protective plate 2 is generally rectangular.

Regarding the size of the protective sheet 2, the manufacturing method of the present invention is particularly suitable for producing a relatively large-area optical member, and therefore, in the case of a television receiver, it is preferably 0.5 m × 0.4 m or more, and particularly preferably 0.7 m × 0.4 m or more. . The upper limit of the size of the protective plate 2 is often determined by the size of the display panel. Further, an operation of setting an optical member such as an excessively large member becomes difficult. Due to these limitations, the upper limit of the size of the protective sheet 2 is usually about 2.5 m x 1.5 m.

Regarding the thickness of the protective sheet 2, in terms of mechanical strength, transparency, and the like, In the case of a glass plate, it is usually 0.5 to 25 mm. Among the applications such as television receivers and PC monitors used in indoors, the weight of the display device is preferably 1 to 6 mm, and is preferably 3 to 20 mm for public display applications installed outdoors. In the case of using chemically strengthened glass, 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 sheet, it is preferably 2 to 10 mm.

The light-shielding portion 4 is incapable of visualizing the liquid crystal display unit described later from the side of the protective sheet 2 In a manner other than the image display area, a concealer such as a wiring member connected to the display panel is attached. The light shielding portion 4 can be formed on the side on which the second cured material layer 14 or the first cured material layer 13 to be described later is formed. The surface is reduced, and the parallax of the light shielding portion 4 and the image display region is reduced. When the protective sheet 2 is a glass plate, if ceramic printing containing a black pigment is used for the light-shielding printing portion, the light-shielding property is high and it is preferable. The light shielding portion 4 may be provided on the surface of the protective sheet 2, and the film provided with the antireflection layer may be bonded to the protective sheet on the back surface of the display device. For example, the light shielding portion 4 is formed by attaching a tape or coating or printing a paint.

Further, in the present invention, the case where the light shielding portion 4 is not provided may be used. However, 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.

[Step A]

As shown in Fig. 1 (a), the second curable resin composition 12 containing the (meth) acrylate (A) and the photopolymerization initiator (B) described later is applied to the liquid crystal display unit 1 as described above. The surface of the sealing body 23. Examples of the coating method include a screen printing method, a dispensing method, and the like. Here, the second curable resin composition 12 forms the crotch portion of the first curable resin composition to be described later at the time of bonding, and therefore, it is applied to the shape of the first cured material layer 13 to be divided, and the first The cured material layer 13 is obtained by curing the first curable resin composition 11 . Specifically, it is formed into a shape of a square or a rectangular frame (that is, a rectangular frame shape). The form of the frame is described later.

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

Moreover, in order to maintain the space between the liquid crystal display unit 1 and the protective sheet 2, the second curable resin composition 12 may be blended with spacer particles having a specific particle diameter.

Here, the shape of the above-described frame will be specifically described based on FIG. 4 . Yu Ben In the invention, the second cured material layer 14 is laminated between the liquid crystal display unit 1 and the protective sheet 2 in the form of a linearly extending layer or a layer-like layer, thereby forming a partition wall 16 which will fill The inner region of the filling chamber 17 filled with the first curable resin composition is spaced apart from the outer region, and at least a portion of the partition wall is provided with a communication portion that communicates between the inner region and the outer region of the filling chamber. Here, the inner region indicates a region in which the inside of the filling chamber 17 filled with the first curable resin composition is divided by the partition wall 16 (formed as the second cured material layer). Further, the outer region indicates a region of the partition wall 16 opposite to the inner region. When an optical member is used in the atmosphere, there is usually an atmosphere, and other members are further disposed as an optical member to be separated from the atmosphere. In the case of opening, the other components exist.

As an example of the partition wall 16, as shown in FIGS. 4(a) to 4(d), the liquid crystal display unit 1 or the protective sheet 2 is coated with the inner surface on one side of the first curable resin composition. A coating film of the second curable resin composition, that is, the partition wall 16 is formed in a rectangular frame shape in the form of a coating film extending in a line shape.

The partition wall 16 is a peripheral wall that partitions the inner region 18 and the outer region 19 of the filling chamber 17, and the filling chamber 17 is filled with a first curable resin composition, and the first curing property can be applied to the first reinforcing layer by the partition wall 16 as follows. The coating region of the resin composition 11 is limited: after the first curable resin composition 11 is applied, the first curable resin composition 11 is not leaked to the outer region 19 during coating diffusion.

The partition wall 16 can be appropriately designed based on the shape of the optical member or the intended filling state of the filling chamber 17 of the first curable resin composition 11. As a specific example, as shown in FIGS. 4( a ) to 4 ( d ), a rectangular shape is formed in a plan view, and a circular symmetry is formed by using the axis of the liquid crystal display unit 1 or the protective plate 2 as a center of rotation. . Here, it may be formed so as to have line symmetry centering on the central axis when the optical member is viewed in plan.

Here, it is preferable that the second curable resin composition is applied so that the partition walls 16 are linearly present on the pair of sides in a rectangular frame shape.

4(b) to (c), when the coating film constituting the partition wall 16 is discrete, it is preferably arranged at equal intervals in a rectangular frame shape, and it is preferable that the coatings are In the case of integration, there is discrete symmetry.

Further, as a more specific shape, it is preferable that the partition wall 16 has rotational symmetry on the four sides with the axis of the liquid crystal display unit 1 or the protective plate 2 as a center of rotation as shown in FIG. 4(b), or The central axis of the optical member is formed to have a line symmetry centering, or is disposed at four corners as shown in FIG. 4(c) and linearly forms the liquid crystal display unit 1 or the protective plate 2 in such a manner as to form a rectangular side. The axis is formed by rotational symmetry of the center of rotation or linear symmetry centering on the central axis when the optical member is viewed in plan.

Further, the shape of the partition wall 16 is not particularly limited to the above shape. When the partition wall 16 is integrally formed, it may be formed in a frame shape having a specific shape such as a rectangular shape, and may be formed so as to partially partition the inner region of the filling chamber 17 from the outer region. The partition wall 16 is not limited to the linear shape. It can also be distributed in the form of dots.

Here, there is no frame in the rectangular shape in the filling chamber 17 When the partition wall 16 is formed at the break, the portion of the inner surface stress generated by the hardening shrinkage caused by the hardening of the first curable resin composition 11 is not present, and thus the liquid crystal display unit 1 or the protective sheet 2 is generated. Deformation such as warpage causes induced display unevenness. Further, when there is a gap between the first curable resin composition 11 and the liquid crystal display unit 1 or the protective sheet 2 at the time of bonding, there is no passage of air, and therefore, it is likely to occur in the filling chamber 17 Bad situation.

However, the second cured layer 14 is formed in the following manner: on the liquid crystal display sheet The element 1 and the protective sheet 2 are laminated in the form of a layer extending in a line or a layer of a dotted pattern, thereby forming a layer The partition wall 16 partitions an inner region of the filling chamber 17 filled with the first curable resin composition from the outer region, and at least a portion of the partition wall is provided with an inner region communicating with the filling chamber. The communication portion of the outer region can reduce the inner surface stress generated during the curing of the first curable resin composition, and can suppress the deformation of the liquid crystal display unit 1 and the protective plate 2. Further, even when a gap is formed when the liquid crystal display unit 1 and the protective sheet 2 are bonded together, the gap flows to the communicating portion, so that the problem at the time of bonding can be suppressed.

Here, in the present invention, the second curable resin composition 12 is preferably laminated on The projection area of the sealing body is not laminated on the projection area of the polarizing plate. By applying the second curable resin composition 12 to the projection region of the sealing body by avoiding the projection region of the polarizing plate, the second cured material layer obtained by curing the second curable resin composition 12 is formed on the projection region. On the sealing body 23. By laminating the second cured material on the portion, even if pressure is applied to the second cured material layer 14 by pressing with a finger or the like, it is possible to prevent the image display portion from being corrugated. On the other hand, when the second cured material layer 14 is laminated on the polarizing plate, when pressure is applied to the peripheral wall portion of the second cured material layer or the image display region, ripples are generated due to interference.

Further, the intermediate portion of the coating film width of the second cured material layer is disposed not in the projection region of the liquid crystal display unit, and is disposed on a projection region of another optical member that surrounds the liquid crystal display unit 21 This is not the projection area of the gap 24, whereby the pressure applied to the liquid crystal display unit by the pressing is lowered. Therefore, even if pressure is applied, the image display which affects the liquid crystal display unit is reduced, and generation of waviness can be prevented.

Since the area on the outer side of the image display area of the liquid crystal display unit 1 is relatively narrow, it is preferable that the width of the coating film formed by the second curable resin composition 12 forming the coating film is narrow. The width is preferably from 0.5 to 3 mm, more preferably from 0.5 to 1.6 mm, still more preferably from 0.5 to 1.0 mm. Moreover, the thickness of the coating film of the first curable resin composition 11 formed is substantially equal to the average thickness of the coating film of the second curable resin composition 12 formed, or the first curable resin composition formed. 11 is preferably 0.005 to 1 mm thick, more preferably 0.01 to 0.08 mm thick, and even more preferably 0.01 to 0.05 mm thick, as compared with the thickness of the second curable resin composition 12 to be formed.

The storage rigidity modulus at 25 ° C of the second curable resin composition 12 at the time of curing is preferably larger than the storage rigidity modulus of the cured layer of the first curable resin composition 11 at 25 ° C. When the storage rigidity modulus of the second cured material layer 14 is larger than the storage rigidity modulus of the first cured material layer 13 obtained by curing the first curable resin composition, the liquid crystal display unit 1 and the protective sheet 2 are bonded together. In the peripheral portion of the first cured material layer 13, even if a gap remains at the interface between the protective sheet 2 and the first cured material layer 13, the void is not easily opened to the outside, and an independent void is easily formed. Therefore, when the liquid crystal display unit 1 and the protective sheet 2 are bonded together under a reduced pressure environment, the pressure in the void (maintaining the reduced pressure) and the pressure applied to the cured layer 15 of the resin are restored when the liquid crystal display unit 1 is returned to the atmospheric pressure environment. The difference between (atmospheric pressure) and the volume of the void is reduced, and the void is easily lost.

It is preferable that the shrinkage ratio of the second curable resin composition 12 at the time of hardening is larger than that of the first The second curable resin composition 12 and the first curable resin composition 11 are designed in such a manner that the curable resin composition 11 has a shrinkage ratio at the time of curing. In the first cured material layer 13 obtained by curing the first curable resin composition 11, it is considered that the shrinkage stress corresponding to the shrinkage ratio at the time of curing remains in the thickness direction of the first cured material layer 13, and remains in the hardening state. The thickness of the first cured material layer 13 is slightly reduced in the shrinkage stress in the thickness direction of the layered portion. By using the first curable resin composition 11 having a shrinkage ratio at the time of curing which is smaller than that of the second curable resin composition 12, stress in the display region can be alleviated, and occurrence of display unevenness can be suppressed.

The shrinkage ratio of the second curable resin composition 12 at the time of curing is greater than that of the first hard One of the means for reducing the shrinkage ratio of the resin composition 11 at the time of curing is that the number of the curable groups of the second curable resin composition 12 is larger than the number of the curable groups of the first curable resin composition 11. Therefore, in the second curable resin composition 12, (i) the content of the curable compound (monomer) having a small molecular weight is large, or (ii) the content of the polyfunctional component having a plurality of reactive groups in the molecule is large. Just fine.

In other words, the viscosity of the second curable resin composition 12 may be higher than the viscosity of the first curable resin composition 11. Specifically, the viscosity of the second curable resin composition 12 when it is not cured is preferably twice or more, more preferably 5 times or more, and more preferably 5 times or more, of the first curable resin composition 11 when it is not cured. More than 10 times. Further, in order to form the second curable resin composition 12 on the transparent surface material by coating, the viscosity of the second curable resin composition 12 when it is not cured at 25 ° C is preferably 3,000 Pa. s below.

Here, the preferred viscosity of the second curable resin composition 12 is specifically 40 to 70 Pa. s. If it is less than 40Pa. In the case where the second curable resin composition 12 is incapable of retaining its shape and diffusing, the second curable resin composition 12 may be broken due to the difficulty in controlling the thickness. On the other hand, the viscosity is over 70Pa. In the case of s, it is difficult to eject from the applicator.

Further, the second cured material layer 14 requires a liquid first curable resin composition 11 The interface adhesion force of the interface between the second cured material layer 14 and the liquid crystal display unit 1 and the interface between the second cured material layer 14 and the protective plate 2 is not more than the hardness of the shape which can maintain the shape. Therefore, in the second cured material layer 14, the second curable resin composition 12 having a high viscosity is preferably used.

The second curable resin composition 12 may be a photocurable resin composition, or It is a thermosetting resin composition. The second curable resin composition 12 preferably contains a curable compound and a photopolymerization initiator in terms of curing at a low temperature and a high curing rate. A curable resin composition.

The second curable resin composition 12 formed as described above is directly coated The film is formed into a crotch portion and can be used in the next step B. However, the second curable resin composition 12 is temporarily cured to obtain a cured coating film, whereby the crotch portion can be formed.

When the second curable resin composition 12 after application is irradiated with the ultraviolet ray 5, it can be obtained on the lower side of the coating layer (the liquid crystal display unit side from the viewpoint of the curable resin composition). The second hardening of the hardened portion (not shown) and the unhardened portion (not shown) existing on the upper side of the coating (the side opposite to the liquid crystal display unit side) (the atmosphere side when it is performed in the atmosphere) Object layer 14. The irradiation amount is preferably 5 ~ 2000mJ / cm ^2, more preferably 10 ~ 1000mJ / cm ^2, particularly preferably 10 ~ 500mJ / cm ^2. When the amount of irradiation is too small, the degree of hardening of the resin of the optical member obtained by final bonding is insufficient. When the amount of irradiation is too large, the amount of unhardened component is reduced, and the adhesion between the liquid crystal display unit 1 and the protective sheet 2 is poor. After that.

In the present invention, the term "unhardened" means a state of fluidity in an environment of 25 ° C. Moreover, after the ultraviolet irradiation, the resin composition layer is touched with a finger, and when the liquid component adheres to the finger, it is judged that it has an unhardened portion.

In the hardening obtained by ultraviolet irradiation of ultraviolet to near ultraviolet light, as long as it is a lamp that irradiates ultraviolet to near ultraviolet light, regardless of the light source. For example, a low pressure, high pressure or ultra high pressure mercury lamp, a metal halide lamp, a (pulse) xenon lamp, an LED lamp or an electrodeless lamp can be cited.

[Step B]

Then, as shown in FIG. 1(b), the first curable resin composition 11 containing the (meth) acrylate (A) and the photopolymerization initiator (B) described later is applied to the light-shielding portion 4 The surface of the protective plate 2 is formed with the surface of the light shielding portion 4. As a method of coating, a slit coater can be cited, Roll coater, spin coater, screen printing method, and the like.

The coating film obtained is preferably formed so as to be in the frame formed by the second cured layer formed in the step A. The reason for this is that when the liquid crystal display unit 1 and the protective sheet 2 are bonded together, the first curable resin composition 11 is pressed. Here, the coating film of the first curable resin composition 11 does not necessarily need to be formed strictly along the second cured material layer 14 , and may be housed in the frame formed by the second cured material layer 14 and filled with the optical member. Formed in the manner of identifying areas.

In the first curable resin composition 11, the first cured layer obtained by curing the first curable resin composition 11 has a modulus of elasticity at 25 ° C of preferably 10 ³ to 10 ⁷ Pa, more preferably 10 ⁴ ~ 10 ⁶ Pa. Further, in order to make the void at the time of bonding disappear in a shorter time, it is particularly preferably 10 ⁴ to 10 ⁵ Pa. When the modulus of elasticity is 10 ³ Pa or more, the shape of the first cured layer 13 is easily maintained. In addition, even when the thickness of the first curable resin composition 11 to be formed is relatively thick, the thickness of the entire first cured layer 13 can be uniformly maintained, and the protective sheet 2 and the liquid crystal display unit 1 can be used. At the time of bonding, it is not easy to generate a void at the interface between the liquid crystal display unit 1 and the first cured material layer 13. When the modulus of elasticity is 10 ⁷ Pa or less, good adhesion can be exhibited. Further, since the molecular movability of the formed resin material is relatively high, when the liquid crystal display unit 1 and the protective sheet 2 are bonded together under a reduced pressure environment, and the pressure is restored to an atmospheric pressure, the pressure in the void is caused ( The pressure difference between the pressure and the pressure (atmospheric pressure) applied to the cured layer of the filler is reduced, and the volume of the void is easily reduced. Further, the gas in the void having a reduced volume is dissolved in the cured layer of the filler and is easily absorbed.

The thickness of the first curable resin composition 11 is preferably 50 to 500 μm, more preferably It is 50 to 350 μm, and particularly preferably 100 to 350 μm. When the thickness of the first curable resin composition 11 is 50 μm or more, the first cured material layer 13 can be effectively buffered from the side of the protective sheet 2 The impact of the force is formed, and the liquid crystal display unit 1 can be protected. Further, in the method for producing an optical member of the present invention, even if a foreign matter not exceeding the thickness of the first cured material layer 13 is mixed between the liquid crystal display unit 1 and the protective sheet 2, the thickness of the first cured material layer 13 is not significantly increased. It has less effect on light transmission properties. When the thickness of the first cured product layer 13 is 500 μm or less, voids are less likely to remain in the first cured material layer 13, and the thickness of the entire optical member is not excessively thick.

The method of adjusting the thickness of the first cured material layer 13 is to adjust the thickness of the second cured material layer 14 and adjust the supply amount of the liquid first curable resin composition 11 supplied to the surface of the protective sheet 2. method.

The viscosity of the first curable resin composition 11 is preferably 0.05 to 50 Pa. s, better It is 1~20Pa. s. When the viscosity is 0.05 Pa.s or more, the decrease in the physical properties of the first cured layer 13 is suppressed. Further, since the component having a low boiling point is reduced, volatilization in a reduced pressure environment to be described later is suppressed, which is preferable. If the viscosity is 50Pa. In the case of s or less, voids are less likely to remain in the first cured product layer 13.

The viscosity of the first curable resin composition 11 was measured at 25 ° C using an E-type viscometer.

The first curable resin composition 11 may be a photocurable resin composition, or may be It is a thermosetting resin composition. The first curable resin composition is preferably a photocurable resin composition containing a curable compound and a photopolymerization initiator in terms of curing at a low temperature and a high curing rate.

Here, the first curable resin composition 11 can be attached without being hardened. It is used in combination, but it is preferably temporarily cured as shown in Fig. 1(b).

Specifically, the coating film of the first curable resin composition 11 after application is irradiated with ultraviolet rays 5 to obtain hardening existing on the lower side of the coating layer (the side of the transparent substrate from the viewpoint of the curable resin composition). A portion (not shown) and a cured layer of an unhardened portion (not shown) existing on the upper side of the coating (the side opposite to the transparent substrate side) (the atmospheric side when it is carried out in the atmosphere). The irradiation amount is preferably 5 ~ 2000mJ / cm ^2, more preferably 10 ~ 1000mJ / cm ^2, particularly preferably 10 ~ 500mJ / cm ^2. When the amount of irradiation is too small, the degree of hardening of the resin of the optical member which is finally bonded is insufficient, and if the amount of irradiation is too large, the unhardened component is reduced, and the liquid crystal display unit 1 and the transparent substrate 2 having the light shielding portion are provided. The bad fit.

In the present invention, the term "unhardened" means a state of fluidity in an environment of 25 ° C. Moreover, after the ultraviolet irradiation, the resin composition layer is touched with a finger, and when the liquid component adheres to the finger, it is judged that it has an unhardened portion.

In the hardening obtained by ultraviolet irradiation of ultraviolet to near ultraviolet light, as long as it is a light that irradiates ultraviolet to near ultraviolet light, regardless of the light source. For example, a low pressure, high pressure or ultra high pressure mercury lamp, a metal halide lamp, a (pulse) xenon lamp, an LED lamp or an electrodeless lamp can be cited.

In the temporary hardening of this step, when the ultraviolet ray irradiated to the curable resin composition has a maximum illuminance in the range of 320 nm to 450 nm of 100, the ratio of the maximum illuminance (irradiation ratio) of preferably 200 to 320 nm is 30. Hereinafter, it is preferable that the illuminance of 200 to 320 nm is 10 or less. When the maximum illuminance in the range of 320 nm to 450 nm is set to 100, if the ratio of the maximum illuminance (irradiation ratio) of 200 to 320 nm is higher than 30, the final strength of the optical member finally obtained deteriorates. The reason for this is that if the illuminance at a low wavelength is high, the curing of the curable resin composition during the temporary curing in this step is excessively performed, and the adhesion at the time of curing by ultraviolet irradiation in the step D described later is considered. Help reduce. Further, the illuminance is usually, for example, 30 to 1000 mW/cm ² at each wavelength (for example, 365 nm).

Here, the method of irradiating ultraviolet rays so as to become the illuminance ratio is, for example, a lamp that uses a condition that satisfies the illuminance ratio as a lamp that irradiates ultraviolet to near-ultraviolet light. The method, or even when the lamp itself does not satisfy the condition of the illuminance, a substrate that cuts off ultraviolet rays of a short wavelength is used for ultraviolet irradiation in the temporary hardening of the step (for example, a short-wave ultraviolet cut filter, a glass plate, The film or the like can be irradiated with the above illuminance ratio. The substrate for adjusting the illuminance ratio of the ultraviolet ray is not particularly limited, and examples thereof include a glass plate, a soda lime glass, a PET film, and the like which have been subjected to short-wave ultraviolet cut-off treatment.

In this case, the irradiation of the ultraviolet ray is generally preferably performed in the atmosphere from the upper side surface of the coating side (the side opposite to the transparent substrate side from the viewpoint of the curable resin composition layer) (usually the atmospheric surface). Further, after the vacuum is applied, the surface of the upper surface of the coating layer may be irradiated with ultraviolet rays by spraying a gas which is hard to inhibit. When the resin composition is cured in the atmosphere, the side opposite to the liquid crystal display unit side or the side opposite to the transparent substrate side becomes the atmosphere side.

At the time of ultraviolet irradiation, by blowing oxygen or ozone to the surface of the ultraviolet curable resin layer (coating layer), the state of the unhardened portion or the film thickness of the uncured portion can be adjusted.

That is, by blowing oxygen or ozone on the surface of the coating layer, the hardened oxygen barrier of the curable resin composition is generated on the surface, so that the uncured portion of the surface can be made sure, or, The film thickness of the hardened portion is thick.

In the present specification, the curing rate is a hardening rate obtained from the curing component of the curable resin composition, and is calculated by removing a component which is not hardened, such as a softening agent. Further, in the present invention, the curing shrinkage ratio can be calculated from the following formula (1) from the specific gravity of the liquid before curing at 25 ° C and the specific gravity of the film at 25 ° C obtained by curing.

(Formula 1) Hardening shrinkage ratio = (film specific gravity - liquid specific gravity) / film specific gravity × 100 (1)

The first curable resin composition 11 of the present invention is preferably a resin composition as follows And a storage rigidity modulus of the resin layer when the ultraviolet ray is irradiated in the above [Step D] with respect to the storage rigidity modulus of the resin layer at 25 ° C when the ultraviolet ray is irradiated in the above [Step B] is 3~ 20 times (preferably 3 to 10 times).

As a method of measuring the storage rigidity modulus, measurement can be performed by, for example, the following method. Specifically, two sheets of a PET film having a thickness of 40 μm coated with a fluorine-based release agent were used, and the hardened coating was applied to one of the release agent-coated surfaces to have a film thickness of 600 μm after curing. Resin composition. Thereafter, two PET films were bonded to each other with the release surfaces of the respective release agents facing each other. The high-performance mercury lamp (80 W/cm, no ozone) was used to irradiate ultraviolet rays having an integrated light amount of 2000 mJ/cm ² through a PET film to cure the resin composition. Thereafter, two PET films were peeled off to prepare a cured product for rigid modulus measurement. Moreover, for rigid modulus, the stiffness modulus can be measured using ARES (TA Instruments) at a temperature range of 20 to 40 °C.

The hardening rate at the time of the main hardening in [Step D] is 95% or more.

The first curable resin composition 11 of the present invention preferably has a storage rigidity modulus at 25 ° C of 1 × 10 ² Pa to 1 × 10 ⁴ Pa at the time of the temporary curing.

When the storage rigidity modulus is more than 1 × 10 ⁴ Pa, the first curable resin composition 11 is contracted when it contracts due to hardening. Therefore, the first curable resin composition 11 does not follow the substrate and peels off. Or the base material is deformed, and the stress cannot be sufficiently relieved, so that display unevenness occurs when the optical member is obtained. Further, in the bonding in a vacuum, when the storage rigidity modulus at the time of temporary hardening is in the above range, it is possible to use a resin to fill the space generated at the time of bonding without causing a problem when moving to atmospheric pressure. . On the other hand, when it is 1 × 10 ² Pa or less, the rigidity modulus is too low, and therefore the shape of the cured product cannot be sufficiently maintained, so that a cured product suitable for temporary curing cannot be obtained. Here, the storage rigidity modulus is preferably from 300 to 3,000 Pa, more preferably from 500 to 2,000 Pa.

The curing rate of the resin during temporary curing is 60 to 90% at the time of temporary curing, and the storage rigidity modulus of the cured product having the curing rate is the above value and a preferable value, so that deformation and display of the substrate can be prevented. Uneven.

Here, the hardening rate at the time of the main hardening in [Step D] described later is usually 95%. the above.

In the present invention, as described above, the resin composition is preferably characterized in that the storage rigidity modulus of the resin layer when irradiated with ultraviolet rays in [Step D] described later is relative to the resin layer at the time of temporary hardening. The storage stiffness modulus at 25 ° C is 1.5 to 10 times. The resin composition is preferably a resin layer which is formed by curing at a curing rate of 98% when the curing rate is 98%, and when the ultraviolet ray is irradiated with ultraviolet rays, the resin layer is irradiated with ultraviolet rays at 80% of the curing rate. The storage modulus at 25 ° C is 1.5 to 10 times.

In this way, the modulus of rigidity of the resin changes drastically in accordance with the hardening rate, and the rigid modulus at a low hardening rate is suppressed to a certain range, and the hardening rate can be easily followed by a state in which the hardening rate is low. The substrate is then warped along the substrate and can therefore be easily followed. Moreover, it is possible to prevent the substrate from being stressed by following the change in the warpage of the substrate. On the other hand, in the state where the hardening rate is high, the bonded optical base materials are rigid next to each other, and therefore, the strength can be remarkably improved. Further, the obtained hardened member is a cured product which maintains moderate flexibility and is excellent in moist heat resistance.

Here, the storage rigidity modulus of the resin layer at the time of ultraviolet irradiation in the [Step D] described later is preferably 2 to 7 times, more preferably 2 to 7 times, relative to the storage rigidity modulus of the resin layer at the time of temporary hardening at 25 ° C. 2.5 to 5 times. When expressed in a hardening rate, the resin is irradiated with ultraviolet rays at a curing rate of 80%. When the layer is stored at 25 ° C, the storage modulus of the resin layer when irradiated with ultraviolet rays at a hardening rate of 98% is preferably 2 to 7 times, more preferably 2.5 to 5 times.

Moreover, the storage rigidity modulus at 25 ° C in the above-described main curing of the curable resin composition of the present invention is preferably from 1 × 10 ³ Pa to 1 × 10 ⁶ Pa. Here, when the storage rigidity modulus is more than 1 × 10 ⁶ Pa and the curable resin composition shrinks too much due to hardening, the substrate is deformed, or the stress is not sufficiently alleviated, so that unevenness occurs when the optical member is obtained. After that, it is lowered. On the other hand, when it is 1 × 10 ³ Pa or less, the rigidity modulus is too low, and thus the strength is lowered. Here, the storage rigidity modulus is preferably 1.0 × 10 ³ to 1.0 × 10 ⁵ Pa, more preferably 1.0 × 10 ³ to 3.0 × 10 ⁴ Pa.

[Step C]

Then, as shown in FIG. 1(c), 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 sheet 2 on which the first curable resin composition 11 is formed are faced. In the form, the liquid crystal display unit 1 is bonded to the transparent substrate 2 having the light shielding portion. The bonding can be carried out in any of the atmosphere and in a vacuum.

Here, in order to prevent generation of air bubbles at the time of bonding, it is preferable to perform bonding in a vacuum.

Here, when the cured material of the ultraviolet curable resin having the cured portion and the uncured portion is obtained in the first curable resin composition 11, the adhesion is expected to be improved.

At the time of bonding, the first curable resin composition 11 is pressed and diffused by pressing or the like, and the first curable resin composition 11 is filled in the space. When it is carried out under vacuum, when exposed to a high pressure environment thereafter, the first cured layer 13 having little or no voids is formed. When the thickness A of the coating film of the first curable resin composition 11 is larger than the thickness B of the coating film of the second curable resin composition 12, the coating of the first curable resin composition 11 is further crushed. The film allows the liquid crystal display unit 1 and the protective sheet 2 to be firmly adhered.

In the case of bonding in a reduced pressure environment, the environment is 1 kPa, preferably 10 to 300 Pa, more preferably 15 to 100 Pa. The decompression environment can be released immediately after bonding. On the other hand, by maintaining the reduced pressure environment for a predetermined period of time (for example, within 10 minutes), the first curable resin composition 11 flows in the space, and the interval between the liquid crystal display unit 1 and the protective sheet 2 is easily made uniform.

[Step D]

Then, as shown in FIG. 1(d), the optical member obtained by bonding the protective sheet 2 and the liquid crystal display unit 1 is irradiated with ultraviolet rays 5 from the side of the protective sheet 2 to harden the curable resin composition (coating). .

The amount of ultraviolet light to be irradiated is preferably about 100 to 4,000 mJ/cm ² , more preferably about 200 to 3,000 mJ/cm ² , and even more preferably 1,500 to 3,000 mJ/cm ² . The light source used in the hardening obtained by irradiation with ultraviolet to near-ultraviolet light is a light source that emits ultraviolet to near-ultraviolet light, regardless of the light source. For example, a low pressure, high pressure or ultra high pressure mercury lamp, a metal halide lamp, a (pulse) xenon lamp, an LED lamp or an electrodeless lamp can be cited.

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

In the above manner, the first curable resin composition 11 and the second ultraviolet curable resin composition 12 are cured, whereby the cured resin layer 15 is formed.

The resin cured layer 15 has a first cured material layer 13 that is diffused along the surface of the protective sheet 2, and a second cured layer that is disposed around the periphery of the first cured layer. When the resin cured layer 15 has the second cured layer, the peripheral portion of the first cured layer 13 can be prevented from diffusing outward, that is, the thin portion of the peripheral portion, and the entire first cured layer 13 can be uniformly held. thickness. By making the thickness of the entire second resin cured material layer uniform, it is preferable to prevent voids from remaining at the interface in adhesion to other surface materials.

In the resin cured material layer 15, the thickness of the first curable resin composition 11 and the second curable resin composition 12 is not particularly limited. In a preferred embodiment, the thickness A of the coating film of the first curable resin composition 11 is the same as the thickness B of the coating film of the second curable resin composition 12 or the second curable resin composition 12 The thickness B of the coating film is thin. The advantages of this setting will be explained. When the liquid crystal display unit 1 and the protective sheet 2 are bonded together, they are usually pressed and then pressed. In this case, since the thickness A is the same as or smaller than the thickness B, and the thickness of the coating film of the second curable resin composition 12 is thicker at the time of pressing, the second curable resin composition 12 is squashed and attached. Hehe. Therefore, the second curable resin composition 12 generates stress on the liquid crystal display unit 1 or the protective sheet 2 due to the difference between the thickness A and the thickness B. Therefore, the first curable resin composition can be more firmly adhered.

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

The thickness A of the coating film of the first curable resin composition 11 is suppressed by 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 to cause voids. In other words, it is preferably 0.05 mm or less thinner than the thickness B of the coating film of the second curable resin composition 12, and more preferably 0.03 mm or less.

In the resin cured layer 15 (layer in which the first cured layer and the second cured layer are combined), the coating film of the second curable resin composition 12 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, the second curable resin composition 12 is at least partially In the region close to the coating film of the first curable resin composition 11, the thickness B of the thinnest portion of the coating film of the second curable resin composition 12 is preferably formed by the first curable resin composition 11. The thickness A of the portion is 1/2 or more, and 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, there is no case where the void is opened to the outside. Form a separate void sufficient to destroy it at 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 is measured by using a laser displacement meter (manufactured by KEYENCE, LK-H052K) to measure the transparent substrate. The total thickness of the coating film of the first curable resin composition 11 or the coating film of the second curable resin composition 12 formed thereon is determined based on the difference. In addition, the thickness A of the coating film of the first curable resin composition 11 is the thickness of the peripheral portion of the coating film of the first curable resin composition 11 adjacent to the coating film of the second curable resin composition 12. In general, a flat surface material is used as a transparent substrate, and a portion where the coating film forming the first curable resin composition 11 and a portion where the coating film of the second curable resin composition 12 are formed are formed into a stepped shape. In the case of the surface-shaped surface material, the step shape of the surface is formed as shown in the previous section regardless of the thickness A of the coating film of the first curable resin composition 11 or the thickness B of the coating film of the second curable resin composition 12. The difference between 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 may be the same step. In addition, the thickness A of the coating film of the first curable resin composition 11 or the thickness B of the coating film of the second curable resin composition 12 is preferably the coating film of the second curable resin composition 12 and the first coating film. The coating film of the curable resin composition 11 is at least a part of the region close to the entire surface of the transparent surface material.

Further, the coating film of the first curable resin composition 11 or the second curable resin composition 12 The surface shape of the coating film is different, and it is sometimes difficult to measure the thickness by the above-described laser displacement meter. In this case, the first hardening resin can also be measured using a 3D shape measuring machine (high-precision shape measuring system KS-1100) or the like. The thickness A of the coating film of the composition 11 and the thickness B of the coating film of the second curable resin composition 12.

When bonding, as shown in FIG. 1(c), even when the liquid crystal display unit 1 and the protective sheet 2 are bonded via a resin composition layer in a reduced pressure environment, even the liquid crystal display unit 1 or the protective sheet 2 is bonded. There is a separate gap between the interface with the curable resin composition, and when it is returned to the atmospheric pressure environment, the pressure in the void (maintaining the reduced pressure) and the pressure applied to the curable resin composition (atmospheric pressure) The volume of the void is reduced by the differential pressure, and the void which is made fine is absorbed by the curable resin composition and disappears.

In the first embodiment, the first curable resin composition is applied to the protective sheet 2, and the second curable resin composition is applied to the liquid crystal display unit 1 to form a coating film. The opposite structure can be used without any problem, that is, the first curable resin composition is applied to the liquid crystal display unit 1 and the second curable resin composition is applied to the protective sheet 2 to form a coating film.

(Second embodiment)

In addition to the first embodiment, the optical member of the present invention can be produced by the second embodiment which is modified as follows.

[Step A]

First, as shown in FIG. 5(a), the second curable resin composition 12 containing the (meth) acrylate (A) and the photopolymerization initiator (B) is applied onto the protective sheet 2. There is a face of the light shielding portion 4.

Here, as in the first embodiment, in the present invention, the second cured material layer 14 is laminated between the liquid crystal display unit 1 and the protective sheet 2 in the form of a layer extending linearly or in a layered manner. Thereby, the partition wall 16 is formed to partition the inner region of the filling chamber 17 filled with the first curable resin composition from the outer region, and at least a portion of the partition wall is provided to communicate with the filling chamber. The communication between the inner area and the outer area. Further, as shown in FIGS. 4(a) to 4(d), the inner surface of the liquid crystal display unit 1 or the protective sheet 2 on the side where the first curable resin composition is applied is in the form of a coating film extending in a line shape. A partition wall 16 which is a coating film of the second curable resin composition is formed in a rectangular frame shape.

The partition wall 16 is a peripheral wall in which the inner region 18 of the filling chamber 17 filled with the first curable resin composition is separated from the outer region 19, and the first curable resin composition is applied by the partition wall 16. After 11th, the application region of the first curable resin composition 11 can be restricted so that the first curable resin composition 11 does not leak to the outer region 19 during coating diffusion.

The partition wall 16 can be appropriately designed based on the shape of the optical member or the intended filling state of the filling chamber 17 filling the first curable resin composition 11. As a specific example, as shown in FIGS. 4( a ) to 4 ( d ), a rectangular shape is formed in a plan view, and the liquid crystal display unit 1 or the protective plate 2 has a rotational center and has rotational symmetry. Here, it may be formed so as to have line symmetry centering on the central axis when the optical member is viewed in plan.

Here, it is preferable that the second curable resin composition is applied in such a manner that the partition walls 16 are linearly present on the pair of sides in a rectangular frame shape.

[Step B]

Thereafter, as shown in FIG. 5( b ), the first curable resin composition 11 is applied onto the surface of the protective sheet 2 on which the light shielding portion 4 is formed, and then the obtained coating film is irradiated with ultraviolet rays 5 to obtain have a hardened portion existing on the lower side of the coating layer (on the side of the transparent substrate from the viewpoint of the curable resin composition) and a hardened layer existing on the upper side of the coating layer (the side opposite to the side of the transparent substrate) .

In this case, when the ultraviolet ray irradiated to the curable resin composition has a maximum illuminance in the range of 320 nm to 450 nm of 100, the ratio of the maximum illuminance at 200 to 320 nm is 30 or less, and particularly preferably the illuminance at 200 to 320 nm is 10 or less. When the maximum illuminance in the range of 320 nm to 450 nm is set to 100, if the ratio of the maximum illuminance at 200 to 320 nm is higher than 30, the final strength of the finally obtained optical member is deteriorated.

[Step C]

Then, as shown in FIG. 5(c), the liquid crystal display unit 1 and the uncured portion of the second curable resin composition are aligned with the display of the liquid crystal display unit 1. The display unit 1 is attached to the protection wrench 2. The bonding can be carried out in any of the atmosphere and in a vacuum.

[Step D]

Then, as shown in FIG. 5(d), the optical member obtained by bonding the protective sheet 2 and the liquid crystal display unit 1 is irradiated with the ultraviolet ray 5 from the side of the protective sheet 2, and the uncured portion having the curable resin composition is used. The hardened layer hardens.

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

In the second embodiment, the first curable resin composition and the second embodiment are listed. In the case where the curable resin composition is applied to the protective sheet 2 to form a coating film, the first curable resin composition and the second curable resin composition may be formed without any problem. The liquid crystal display unit 1 is applied together to form a coating film and used.

(Third embodiment)

In addition to the first and second embodiments, the optical member of the present invention can be produced by the third embodiment of the following modification.

[Step A]

First, as shown in FIG. 6(a), the second curable resin composition 12 containing the (meth) acrylate (A) and the photopolymerization initiator (B) is applied to the display of the liquid crystal display unit 1. The surface of the surface and the protective sheet 2 is formed with the surface of the surface of the light shielding portion 4.

Here, as in the first embodiment, in the present invention, the second cured material layer 14 is laminated between the liquid crystal display unit 1 and the protective sheet 2 in the form of a layer extending linearly or in a layered manner. Thereby, the partition wall 16 is formed to partition the inner region of the filling chamber 17 filled with the first curable resin composition from the outer region, and at least a portion of the partition wall is provided to communicate with the filling chamber. The communication between the inner area and the outer area. Further, as shown in FIGS. 4(a) to 4(d), the inner surface of the liquid crystal display unit 1 or the protective sheet 2 on the side where the first curable resin composition is applied is in the form of a coating film extending in a line shape. A partition wall 16 which is a coating film of the second curable resin composition is formed in a rectangular frame shape.

The partition wall 16 is a peripheral wall in which the inner region 18 of the filling chamber 17 filled with the first curable resin composition is separated from the outer region 19, and the first curable resin composition is applied by the partition wall 16. After 11th, the application region of the first curable resin composition 11 can be restricted so that the first curable resin composition 11 does not leak to the outer region 19 during coating diffusion.

The partition wall 16 may be based on the shape of the optical member or filled with the first curable resin The filling chamber 17 of the composition 11 is appropriately designed in the intended filling state. As a specific example, as shown in FIGS. 4( a ) to 4 ( d ), a rectangular shape is formed in a plan view, and the liquid crystal display unit 1 or The axis of the shield 2 is formed by a rotational center and a rotational symmetry. Here, it may be formed so as to have line symmetry centering on the central axis when the optical member is viewed in plan.

Here, it is preferable that the second curable resin composition is applied in such a manner that the partition walls 16 are linearly present on the pair of sides in a rectangular frame shape.

[Step B]

Thereafter, as shown in FIG. 6(b), the first curable resin composition 11 containing the (meth) acrylate (A) and the photopolymerization initiator (B) is applied to the display of the liquid crystal display unit 1. The surface of the surface and the protective sheet 2 is formed with the surface of the surface of the light shielding portion 4.

The obtained coating film is irradiated with the ultraviolet ray 5 to obtain a hardened portion which exists on the lower side of the coating film (the transparent substrate side as viewed from the above-mentioned curable resin composition) and exists on the upper side of the coating layer (with the transparent substrate) The hardened layer of the uncured portion of the side opposite the side.

In this case, when the maximum illuminance of the ultraviolet ray irradiated to the curable resin composition is in the range of 320 nm to 450 nm, the ratio of the maximum illuminance at 200 to 320 nm is 30 or less, and particularly preferably the illuminance at 200 to 320 nm. It is 10 or less. When the maximum illuminance in the range of 320 nm to 450 nm is set to 100, if the ratio of the maximum illuminance of 200 to 320 nm is higher than 30, the final strength of the optical member finally obtained deteriorates.

[Step C]

Then, the liquid crystal display unit 1 and the protective sheet 2 are bonded together in a form in which the uncured portions face each other as shown in Fig. 6(c). The bonding can be carried out in any of the atmosphere and in a vacuum. Here, in order to prevent generation of air bubbles at the time of bonding, it is preferable to perform bonding in a vacuum.

When the cured product of the ultraviolet curable resin having the cured portion and the uncured portion is obtained by bonding each of the liquid crystal display unit and the transparent substrate, the adhesion can be expected to be improved.

[Step D]

Then, as shown in FIG. 6(d), the optical member obtained by bonding the transparent substrate 2 and the liquid crystal display unit 1 is irradiated with ultraviolet rays 5 from the side of the protective sheet 2 to harden the curable resin composition (coating). .

The amount of ultraviolet light to be irradiated is preferably about 100 to 4,000 mJ/cm ² , more preferably about 200 to 3,000 mJ/cm ² , and even more preferably 1,500 to 3,000 mJ/cm ² . The light source used in the hardening obtained by irradiation with ultraviolet to near-ultraviolet light is a light source that illuminates ultraviolet to near-ultraviolet light regardless of the light source. For example, a low pressure, high pressure or ultra high pressure mercury lamp, a metal halide lamp, a (pulse) xenon lamp, an LED lamp or an electrodeless lamp can be cited.

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

Each of the above embodiments utilizes a specific optical substrate for the optics of the present invention. Several embodiments of the manufacturing method of the member will be described. In each of the embodiments, a liquid crystal display unit and a transparent substrate having a light-shielding portion are used. However, in the manufacturing method of the present invention, various members described below may be used as the optical substrate instead of the liquid crystal display unit, and the transparent substrate may be used. Various members described later were used as the optical substrate.

In addition, as an optical substrate such as a liquid crystal display unit or a transparent substrate, another optical substrate layer may be further used for the various members (for example, a film laminated with a cured layer of a curable resin composition or laminated) Other optical substrate layers).

Furthermore, the coating method of the curable resin composition according to the first embodiment, the film thickness of the cured resin, the irradiation amount at the time of ultraviolet irradiation, the light source, and the blowing of oxygen on the surface of the ultraviolet curable resin layer The method of adjusting the film thickness of the uncured portion by ozone or the like can be applied not only to the above embodiment but also to any of the production methods included in the present invention.

The above liquid crystal display unit is also included, and the first to third embodiments are used. Specific aspects of the optical components that can be fabricated are shown below.

(i) The optical substrate having the light shielding portion is at least one 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 portion and a transparent electrode. The optical substrate to be bonded thereto is at least one 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 has the optical substrate having the light shielding portion. The aspect of the body unit is displayed.

(ii) an optical substrate is a protective substrate having a light-shielding portion, and the other optical substrate to which it is attached is a touch panel or a display unit having a touch panel, and at least two optical substrates are bonded together to obtain an optical The member is a touch panel having a protective substrate having a light shielding portion or a display unit having the touch panel.

In this case, it is preferable that the curable resin composition is applied to any of the surface of the protective substrate having the light shielding portion and the surface of the touch panel or the touch surface of the touch panel. These two.

(iii) An optical substrate is an optical substrate having a light-shielding portion, and the other optical substrate to be bonded thereto is a display unit, and the optical member obtained by bonding at least two optical substrates is an optical base having a light-shielding portion. The appearance of the material display unit.

In this case, it is preferred that the curable resin composition described above is applied to the surface of the optical substrate having the light-shielding portion on the side where the light-shielding portion is provided or the display surface of the display unit. One or both.

Specific examples of the optical substrate having the light-shielding portion include a protective sheet for a display screen having a light-shielding portion, and a touch panel provided with a protective substrate having a light-shielding portion.

The surface of the optical substrate having the light-shielding portion on the side where the light-shielding portion is provided. For example, when the optical substrate having the light-shielding portion is a protective plate for a display screen having a light-shielding portion, the protective plate is provided with a light-shielding portion. Side of the side. Moreover, when the optical substrate having the light shielding portion is a touch panel having a protective substrate having a light shielding portion, the surface of the protective substrate having the light shielding portion having the light shielding portion is bonded to the touch surface of the touch panel. The surface of the optical substrate having the light shielding portion on the side where the light shielding portion is provided refers to the substrate surface of the touch panel opposite to the touch surface of the touch panel.

The light-shielding portion of the optical substrate having the light-shielding portion may be disposed on any optical substrate, and is generally formed into a frame shape around the transparent plate-shaped or sheet-shaped optical substrate, and the width thereof is preferably about 0.5 to 10 mm, more preferably It is about 1 to 8 mm, and more preferably about 2 to 8 mm.

A curable resin composition which can be used as the first curable resin composition 11 or 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). Further, as the optional component, other components which can be added to the curable resin composition for optics can be contained.

In addition, the term "addable to the curable resin composition for optics" means that it does not contain an additive which reduces the transparency of the cured product to such an extent that it cannot be used for optics.

When a cured sheet having a thickness of 200 μm after curing is produced by using the curable resin composition used in the present invention, the sheet preferably has a preferred average transmittance of at least 90% or more at a wavelength of 400 to 800 nm. .

The preferred composition ratio of the curable resin composition is 25 to 90% by weight based on the total amount of the curable resin composition, and the photopolymerization initiator (B) is 0.2. ~5 wt%, the rest are other ingredients.

In the curable resin composition of the present invention, as the photopolymerization initiator (B), any of the photopolymerization initiators which are usually used can be used.

In the curable resin composition of the present invention, as the (meth) acrylate (A), It is not particularly limited, and it is preferably used from (meth) acrylate, (meth) acrylate having a polyisoprene skeleton, (meth) acrylate having a polybutadiene skeleton, (A) Any of a group of acrylate monomer compositions. More preferably, it is at least any one of (i) an amine ester (meth) acrylate or a (meth) acrylate having a polyisoprene skeleton, and (ii) a (meth) acrylate monomer. The situation of the person.

In the present specification, the term "(meth)acrylate" means either or both of methacrylate and acrylate. The same applies to "(meth)acrylic acid".

The above amine ester (meth) acrylate is obtained by using a polyol, a polyisocyanate and a It is obtained by reacting a hydroxyl group (meth) acrylate.

Examples of the polyhydric alcohol include neopentyl glycol and 3-methyl-1,5-pentane. a triol having 1 to 10 carbon atoms such as an alcohol, ethylene glycol, propylene glycol, 1,4-butanediol or 1,6-hexanediol, trimethylolpropane or pentaerythritol, An alcohol having a cyclic skeleton such as tricyclodecane dimethanol or bis-[hydroxymethyl]-cyclohexane; and a polybasic acid (for example, succinic acid, phthalic acid, or the like) Polyester polyol obtained by the reaction of hydrogen phthalic anhydride, terephthalic acid, adipic acid, sebacic acid, tetrahydrophthalic anhydride, etc., by polyol and ε-caprolactone a caprolactone obtained by the reaction, a polycarbonate polyol (for example, a polycarbonate diol obtained by a reaction of 1,6-hexanediol and diphenyl carbonate, etc.), a polyether polyol (for example, a poly A polyolefin polyol such as ethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide modified bisphenol A or the like, or hydrogenated polybutadiene diol. As far as compatibility with other (A) components is concerned, as The polyhydric alcohol, preferably polypropylene glycol or hydrogenated polybutadiene diol, is particularly preferably a polypropylene glycol having a weight average molecular weight of 2,000 or more and a hydrogenated polybutadiene diol from the viewpoint of adhesion to a substrate. . 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 5,000 or less. Further, the hydrogenated polybutadiene polyol (A) can be used as a hydrogenation-reduction product of a usual polybutadiene polyol, and particularly preferably, for optical use, the residual double bond is small, and the iodine value is particularly preferably 20 or less. Further, as for the molecular weight, a generally available molecular weight distribution can be used, and particularly when a balance between flexibility and hardenability is obtained, it is particularly preferably a molecular weight of 500 to 3,000.

Examples of the organic polyisocyanate include isophorone diisocyanate. Hexamethylene diisocyanate, toluene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate or dicyclopentyl isocyanate.

In addition, the hydroxyl group-containing (meth) acrylate is a compound having at least one of a hydroxyl group and a (meth) acrylate group in one molecule, and specific examples thereof include 2-hydroxyl (meth)acrylate. Ethyl ester, propylene glycol mono (meth) acrylate, butane diol mono (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, diethylene glycol single (Meth) acrylate, dipropylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate , polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, ethoxylated neopentyl glycol mono (meth) acrylate, hydroxyl Mono (meth) acrylate of a dihydric alcohol such as neopentyl glycol mono (meth) acrylate; trimethylolpropane mono (meth) acrylate, ethoxylated trimethylolpropane mono Acrylate, trimethylolpropane mono(meth)acrylate, tris(2-hydroxyethyl) Cyanurate mono(meth)acrylate, glycerol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, ethoxylated trimethylolpropane di(meth)acrylate, c Monoacrylic acid such as trimethylolpropane di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate or glycerol di(meth)acrylate Esters and di(meth)acrylates, or mono- and di(meth)acrylates in which one part of the hydroxyl groups of the alcohols are modified with alkyl or ε-caprolactone; pentaerythritol mono(meth)acrylic acid Ester, dipentaerythritol mono (meth) acrylate, di-trimethylolpropane mono (meth) acrylate, neopentyl alcohol di (meth) acrylate, dipentaerythritol di (a) Acrylate, di-trimethylolpropane di(meth)acrylate, neopentyl alcohol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, di-trihydroxyl Propane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate Di-trimethylolpropane a polyfunctional (meth) acrylate having a tetravalent or higher alcohol such as (meth) acrylate having a hydroxyl group, or a part of a hydroxyl group of the alcohol having a hydroxyl group modified by an alkyl group or ε-caprolactone Functional (meth) acrylate and the like.

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

The reaction for obtaining the above amine ester (meth) acrylate is carried out, for example, in the following manner. That is, the organic polyisocyanate is mixed with the polyol in an amount of from 1.1 to 2.0 equivalents, more preferably from 1.1 to 1.5 equivalents, based on 1 equivalent of the hydroxyl group of the polyol, and preferably the reaction temperature is preferably from 1.1 to 2.0 equivalents, more preferably from 1.1 to 1.5 equivalents. The reaction is carried out at 70 to 90 ° C, and the synthesis of the urethane is low. Polymer (first reaction). Then, the (meth)acrylic acid hydroxy ester compound is mixed in an amount of preferably 1 to 1.5 equivalents based on 1 equivalent of the isocyanate group of the urethane oligomer and the hydroxyl group of the (meth)acrylic acid hydroxyester compound. The reaction is carried out at 70 to 90 ° C to obtain the desired amine ester (meth) acrylate (second reaction).

In the present invention, the first reaction can be carried out without solvent, but the viscosity of the product In order to improve workability, it is preferably carried out in a solvent having no alcoholic hydroxyl group or in a polymerizable compound (F) to be 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; and ethylene glycol. Dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether and other glycol ethers, ethyl acetate, butyl acetate, A Fibrin acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl Esters such as ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, cyclic esters such as γ-butyrolactone, petroleum ether, naphtha, It is carried out in a separate or mixed organic solvent such as a petroleum solvent such as hydrogenated naphtha or solvent naphtha.

The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. anti- The end point should be confirmed by the reduction in the amount of isocyanate groups. Further, a catalyst may be added in order to shorten the reaction time. As the catalyst, any of an alkaline catalyst and an acidic catalyst can be used. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine, and ammonia, and phosphines such as tributylphosphine and triphenylphosphine. Further, examples of the acidic catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, aluminum tributoxide, titanium tetraisopropoxide, zirconium tetrabutoxide, aluminum chloride, and stannous octoate. , octyl tin laurate, dibutyl tin dilaurate, octyl tin diacetate, etc. Easy acid catalyst. The amount of the catalyst added is usually 0.1 to 1 part by weight based on 100 parts by weight of the total weight of the diol compound (A+D) and the polyisocyanate compound (B).

The polyurethane compound (E) of the present invention may have a first reaction, followed by The at least one hydroxyl group-containing (meth) acrylate compound (C) is obtained by reacting (second reaction) with the remaining isocyanate group.

The second reaction of the present invention is an isocyanide of the intermediate obtained after the first reaction. The equivalent relationship of the disappearance of the acid ester group is added. Specifically, the OH group of the (meth) acrylate compound (C) having at least one hydroxyl group is preferably 1.0 to 3.0 mol, based on 1.0 mol of the NCO group of the intermediate obtained after the first reaction. More preferably, it is 1.0 to 2.0 mol.

The second reaction of the present invention can also be carried out without solvent, but the viscosity of the product is high, In order to improve workability, it is preferably carried out in the above solvent and/or the polymerizable compound (F) described below in the present invention. Further, the reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction was confirmed by a decrease in the amount of isocyanate groups. In order to shorten the reaction time, the above catalyst may be added.

In the acrylate compound used as a raw material, 4-methoxybenzene is usually added. A polymerization inhibitor such as phenol, but it is also possible to re-add a polymerization inhibitor during the reaction. Examples of the polymerization inhibitor include hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, and 2,6-di-t-butyl-4. - cresol, 3-hydroxythiophenol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, phenothiazine, and the like. It is used in an amount of 0.01 to 1% by weight based on the reaction raw material mixture.

The weight average molecular weight of the above amine ester (meth) acrylate is preferably 7,000~ 25,000 or so, more preferably 10,000 to 20,000. When the weight average molecular weight is less than 7,000, the shrinkage tends to increase, and if the weight average molecular weight is more than 25,000, the curability tends to be insufficient.

In the curable resin composition of the present invention, the amine ester (meth) acrylate can be One type or two or more types are used in combination at any ratio. The weight ratio of the amine ester (meth) acrylate to the photocurable transparent adhesive composition of the present invention is usually preferably from 20 to 80% by weight, more preferably from 30 to 70% by weight.

The above (meth) acrylate having a polyisoprene skeleton is polyisoprene The terminal or side chain of the olefin molecule has a (meth) acrylonitrile group. The (meth) acrylate having a polyisoprene skeleton can be obtained in the form of "UC-203" (manufactured by Kuraray Co., Ltd.). The polystyrene-equivalent number average molecular weight of the (meth) acrylate having a polyisoprene skeleton is preferably from 1,000 to 50,000, more preferably from about 25,000 to 45,000.

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

The above (meth) acrylate having a polybutadiene skeleton is based on polybutadiene The terminal or side chain of the subunit has a (meth) acrylonitrile group. The (meth) acrylate having a polybutadiene skeleton can be "TEAI-1000 (manufactured by Japan Soda Co., Ltd.)" "TE-2000 (manufactured by Japan Soda Co., Ltd.)" "EMA-3000 (manufactured by Japan Soda Co., Ltd.)" "SPBDA- Obtained in the form of S30 (made by Osaka Organic Chemical Industry Co., Ltd.). The number average molecular weight in terms of polystyrene of the (meth) acrylate having a polybutadiene skeleton is preferably from 1,000 to 30,000, more preferably from about 1,000 to 10,000.

As the above (meth) acrylate monomer, it can be preferably used in a molecule One (meth) acrylonitrile-based (meth) acrylate.

Here, the (meth) acrylate monomer means an epoxy group (meth) acrylate, an epoxy (meth) acrylate, and the above polyisoprene. (Meth) acrylate other than the (meth) acrylate of the diene skeleton.

As a (meth) acrylate having one (meth) acrylonitrile group in the molecule, Examples of the body include isooctyl (meth)acrylate, isoamyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, and stearyl (meth)acrylate. , (meth)acrylic acid, such as isostearyl (meth)acrylate, cetyl (meth)acrylate, isomyristyl (meth)acrylate, or tridecyl (meth)acrylate, 5~ 20 alkyl ester, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acryl morpholine, phenyl glycidyl (meth) acrylate, tricyclodecane (meth) acrylate Ester, dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth)acrylate, isodecyl (meth)acrylate, dicyclopentyl (meth)acrylate, 1-adamantyl acrylate Ester, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, 1-adamantyl methacrylate, propylene oxide modified (meth) acrylate (meth) acrylate having a cyclic skeleton such as phenyl phenyl ester or dicyclopentadienyloxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or 4-hydroxy (meth) acrylate (meth)acrylic acid Carbon number 1~5 alkyl ester with hydroxyl group, ethoxy diethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polypropylene oxide modified decyl phenyl (meth) acrylate Polyalkylene glycol (meth) acrylate, ethylene oxide modified benzene oxidized phosphoric acid (meth) acrylate, ethylene oxide modified butyl oxyphosphate (meth) acrylate and ethylene oxide Modified octyl oxyphosphate (meth) acrylate and the like. Among them, preferred are 10 to 20 alkyl (meth)acrylate, 2-ethylhexylcarbitol acrylate, acryloyl morpholine, 4-hydroxybutyl (meth)acrylate, (methyl) ) tetrahydrofurfuryl acrylate, isostearyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, propylene oxide modified (meth) phenyl methacrylate, especially resin From the viewpoint of flexibility, a carbonic acid 10 to 20 alkyl (meth)acrylate, a dicyclopentenyloxyethyl (meth)acrylate, and a polypropylene oxide modified (meth)acrylic acid are preferred. Nonylphenyl ester, tetrahydrofurfuryl (meth)acrylate. On the other hand, from the viewpoint of improving the adhesion to the glass, (meth)acrylic acid preferably has a carbon number of 1 to 5 alkyl esters, acryloyl morpholine, and more preferably acryloyl morpholine. .

The composition of the present invention may contain a (meth) acrylate other than the (meth) acrylate group having one (meth) acrylonitrile group insofar as the characteristics of the present invention are not impaired. For example, tricyclodecane dimethanol di(meth)acrylate, two Alkanediol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, alkylene oxide modified bisphenol A type di(methyl) Acrylate, caprolactone modified hydroxypivalic acid neopentyl glycol di(meth) acrylate and ethylene oxide modified di(meth) acrylate, trimethylolpropane tri (meth) acrylate Trimethylol C2~C10 alkane tri(meth) acrylate such as ester, trimethylol octane tri(meth) acrylate, trimethylolpropane polyethoxy tri(meth) acrylate, three Trimethylol C2~C10 alkane polyalkoxy tris (hydroxymethylpropane) polypropoxy tri(meth)acrylate, trimethylolpropane polyethoxypolypropoxy tri(meth)acrylate Acrylate, tris[(methyl)acryloxyethyl]isocyanurate, pentaerythritol tris(meth)acrylate, ethylene oxide modified trimethylolpropane tris Ethylene oxide modified trimethylolpropane tri(meth)acrylate such as acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, neopentyl alcohol polyethoxy four (meth) acrylate, neopentyl Alcohol polypropoxy tetra (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate Ester, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

In the present invention, in the case of use in combination, in order to suppress hardening shrinkage, a 1 or 2 functional (meth) acrylate is preferably used.

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

At least one of (i) an amine ester (meth) acrylate or a (meth) acrylate having a polyisoprene skeleton, and (ii) (meth)acrylic acid containing the curable resin composition In the aspect of the ester monomer, the total content of both of (i) and (ii) is usually preferably from 25 to 90% by weight, more preferably from 40 to 90% by weight based on the total amount of the resin composition. %, further preferably 40 to 80% by weight.

The curable resin composition of the present invention can be used without impairing the characteristics of the present invention. An epoxy (meth) acrylate is used in the periphery. The epoxy group (meth) acrylate has a function of improving hardenability and increasing the hardness or hardening speed of the cured product. Further, the epoxy group (meth) acrylate can be used as long as it is obtained by reacting a glycidyl ether type epoxy compound with (meth)acrylic acid, and it can be preferably used. Examples of the epoxy propylene ether type epoxy compound of the epoxy group (meth) acrylate used are diglycidyl ether of bisphenol A or an alkylene oxide adduct thereof, bisphenol F or a ring thereof. a diglycidyl ether of an oxyalkylene adduct, a diglycidyl ether of hydrogenated bisphenol A or an alkylene oxide adduct thereof, a diglycidyl ether of hydrogenated bisphenol F or an alkylene oxide adduct thereof, Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexane dimethanol Glycidyl ether, polypropylene glycol diglycidyl ether, and the like.

The epoxy group (meth) acrylate is obtained by reacting the above-mentioned epoxidized epoxy type epoxy compound with (meth)acrylic acid under the following conditions.

The epoxy epoxide type epoxy group is used in an amount of from 0.9 to 1.5 mol, more preferably from 0.95 to 1.1 mol, based on 1 equivalent of the epoxy group of the epoxy propylene ether type epoxy compound and (meth)acrylic acid. The compound is reacted with (meth)acrylic acid. The reaction temperature is preferably from 80 to 120 ° C, and the reaction time is 10~35 hours or so. In order to promote the reaction, a catalyst such as triphenylphosphine, TAP, triethanolamine or tetraethylammonium chloride is preferably used. Further, in the reaction, as the polymerization inhibitor for preventing polymerization, for example, p-methoxyphenol or methyl hydroquinone may be used.

As the epoxy group (meth) acrylate which can be preferably used in the present invention, A bisphenol A type epoxy (meth) acrylate obtained from an epoxy group of a bisphenol A type. The weight average molecular weight of the epoxy (meth) acrylate is preferably from 500 to 10,000.

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

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

In the curable resin composition of the present invention, the (meth) acrylate (A) preferably contains a (meth) acrylate selected from the above amine ester (meth) acrylate and the above polyisoprene skeleton. At least one of the group consisting of an acrylate and the above (meth) acrylate monomer. The content ratio of the above amine ester (meth) acrylate is preferably from 20 to 80% by weight, more preferably from 30 to 70% by weight, and the content ratio of the (meth) acrylate having a polyisoprene skeleton is preferred. The content of the (meth) acrylate monomer is preferably from 5 to 70% by weight, more preferably from 10 to 50% by weight, based on 20 to 80% by weight, more preferably from 30 to 70% by weight.

In the curable resin composition of the present invention, as the (meth) acrylate (A), the above amine ester (meth) acrylate or (meth) acrylate having a polyisoprene skeleton is contained. When the content ratio is 20 to 80% by weight, preferably 30 to 70% by weight, and the (meth) acrylate monomer is contained in a ratio of 5 to 70% by weight, preferably 10 to 50% by weight, More preferably.

The photopolymerization initiator (B) contained in the composition of the present invention is not particularly limited, and examples thereof include 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, and 2,4. ,6-trimethylbenzimidylethoxyethoxyphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, bis(2,6-dimethoxybenzene Mercapto)-2,4,4-trimethylpentylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone (Irgacure (trade name) 184; manufactured by BASF), 2-hydroxy-2-methyl-[4 -(1-Methylvinyl)phenyl]propanol oligomer (Esacure (trade name) ONE; manufactured by Lamberti), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxyl -2-methyl-1-propan-1-one (Irgacure 2959; manufactured by BASF), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl] -Phenyl}-2-methyl-propan-1-one (Irgacure 127; manufactured by BASF), 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651; manufactured by BASF), 2-hydroxy-2 -Methyl-1-phenyl-propan-1-one (Darocure (trade name) 1173; manufactured by BASF), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl Propane-1-one (Irgacure 907; manufactured by BASF), oxy-phenyl-acetic acid 2-[2-o-oxy-2-phenyl-ethoxycarbonyl-ethoxy]-ethyl ester and oxy-benzene base- a mixture of 2-[2-hydroxy-ethoxy]-ethyl acid (Irgacure 754; manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butyl Alkan-1-one, 2-chloro 9-oxosulfur 2,4-dimethyl 9-oxosulfur 2,4-diisopropyl 9-oxosulfur Isopropyl 9-oxosulfur Wait.

In the present invention, the photopolymerization initiator (B) is preferably used in the above. A photopolymerization initiator having a Mohr absorption coefficient of 300 ml/(g.cm) or more and a Mohr absorption coefficient of 655 nm or less at 100 nm/(g.cm) or less at 300 nm or 313 nm in a nitrile or methanol. By using the above photopolymerization initiator, it is possible to contribute to the improvement of the bonding strength. By hardening in the above step D by the Mohr absorption coefficient at 302 nm or 313 nm being 300 ml/(g.cm) or more Hardening is more complete. On the other hand, when the Mohr absorption coefficient at 365 nm is 100 ml/(g.cm) or less, excessive hardening can be appropriately suppressed in the hardening in the temporary hardening of the above steps A and B, and the adhesion can be further improved. .

Examples of the photopolymerization initiator (B) include 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by BASF) and 2-hydroxy-2-methyl-1-phenyl-propan-1-one ( Darocure 1173; manufactured by BASF), 1-[4-(2-hydroxyethoxy)-phenyl-]-2-hydroxy-2-methyl-1-propan-1-one (Irgacure 2959; manufactured by BASF), phenyl Methyl glyoxylate (Darocure MBF; manufactured by BASF).

In the curable resin composition of the present invention, the photopolymerization initiator (B) One type or two or more types may be used in combination at any ratio. The weight ratio of the photopolymerization initiator (B) to the photocurable resin composition of the present invention is usually preferably 0.2 to 5% by weight, more preferably 0.3 to 3% by weight. When it is more than 5% by weight, when the cured layer having the hardened portion and the uncured portion on the side opposite to the side of the optical substrate is obtained, the transparency of the unhardened portion or the cured resin layer may be deteriorated. After that.

In addition to the (meth) acrylate (A) and the photopolymerization initiator (B), the curable resin composition of the present invention may further contain a photopolymerization initiation aid as described below. A compound having a structure represented by the formula (1), a softening component described later, an additive described later, and the like are used as other components. The content ratio of the other component to the total amount of the curable resin composition of the present invention is obtained by subtracting the total amount of the (meth) acrylate (A) and the photopolymerization initiator (B) from the total amount. The rest. Specifically, the total amount of the other components is preferably from 0 to 74% by weight, more preferably from about 5 to 70% by weight, based on the total amount of the curable resin composition of the present invention.

Further, an amine or the like which can be used as a photopolymerization initiation aid can be used in combination with the above-mentioned light. Polymerization initiator. Examples of the amines and the like which can be used include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate or p-dimethylaminobenzene. Isoamyl formate and the like. In the case of using a photopolymerization starter such as an amine, the content of the resin composition for subsequent use of the present invention is usually preferably from 0.005 to 5% by weight, more preferably from 0.01 to 3% by weight.

The curable resin composition of the present invention may optionally contain the formula (1) A compound of the construction shown.

(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 an alkyl group having 1 to 18 carbon atoms, and a carbon number of 1~ Alkenyl group of 18, alkynyl group having 1 to 18 carbon atoms or aryl group having 5 to 18 carbon atoms)

The compound having a structure represented by the formula (1) can be obtained, for example, in the form of Unisafe (trade name) PKA-5017 (polyethylene glycol-polypropylene glycol allyl butyl ether) manufactured by Nippon Oil Co., Ltd., or the like.

When a compound having a structure represented by the formula (1) is used, the weight ratio thereof in the curable resin composition is usually 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 can be used as needed. Specific examples of the softening component which can be used include a polymer or oligomer other than the above (meth) acrylate and a compound having a structure represented by the formula (1), and a phthalic acid ester. Phosphates, glycol esters, citrate esters, aliphatic dibasic acid esters, fatty acid esters, epoxy groups Plasticizers, castor oils, hydrazine-based hydrogenated resins, and the like. Examples of the oligomer or the polymer include an oligomer having a polyisoprene skeleton, a polybutadiene skeleton, a polybutene skeleton, or a xylene skeleton, or an ester thereof, and the like, and In the case, it is preferred to use a polymer or oligomer having a polybutadiene skeleton and an esterified product thereof. Specific examples of the polymer or oligomer having a polybutadiene skeleton and esterified products thereof include butadiene homopolymer, epoxy modified polybutadiene, and butadiene-styrene. A random copolymer, a maleic acid-modified polybutadiene, and a liquid polybutadiene or a liquid hydrogenated polybutadiene whose terminal is hydroxyl-modified. Further, in the softening component, each of the above softening components may be used in combination.

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

In the curable resin composition of the present invention, an antioxidant may be added as needed. Additives such as an organic solvent, a decane coupling agent, a polymerization inhibitor, a leveling agent, an antistatic agent, a surface lubricant, a fluorescent whitening agent, a light stabilizer (for example, a hindered amine compound, etc.), and a filler.

Specific examples of the antioxidant include BHT (butylated hydroxytoluene, dibutylhydroxytoluene) and 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-3 Butylanilino)-1,3,5-three , pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-di-extension ethyl bis[3-(3 ,5-di-t-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionic acid Ester], 1,6-hexanediol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5 -di-t-butyl-4-hydroxyphenyl)propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-phenylpropanamide), 1,3 ,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl) Base)-isocyanurate, octylated diphenylamine, 2,4-bis[(octylthio)methyl-o-cresol, isooctyl-3-(3,5-di-3rd Benzyl-4-hydroxyphenyl)propionate], dibutylhydroxytoluene, and the like.

Specific examples of the organic solvent include alcohols such as methanol, ethanol, and isopropanol, dimethyl hydrazine, dimethyl hydrazine, tetrahydrofuran, and Alkane, toluene, xylene, and the like.

Specific examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane-epoxypropane, 3-glycidoxypropylmethyldimethoxydecane, and 2-( 3,4-Epoxycyclohexyl)ethyltrimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyldimethoxydecane, γ-mercaptopropyltrimethoxydecane , N-(2-Aminoethyl) 3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, vinyltrimethoxy Baseline, N-(2-(vinylbenzylamino)ethyl) 3-aminopropyltrimethoxydecane hydrochloride, 3-methylpropenyloxypropyltrimethoxydecane, 3- a decane coupling agent such as chloropropylmethyldimethoxydecane or 3-chloropropyltrimethoxydecane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triiso Stearic acid titanate, titanium di(dioctyl pyrophosphate)oxyacetate, tetraisopropylbis(dioctylphosphite) titanate, neoalkoxy three (pN-(β-) Titanium coupling agent such as aminoethyl)aminophenyl) titanate; Zr-acetamidopyruvate, Zr-methacrylate, Zr -propionate, neoalkoxy zirconate, neoalkoxytrisinyl zirconate, neoalkoxytris(dodecanoinyl)benzenesulfonyl zirconate, neoalkoxy Tris(ethylideneethylamino)zirconate, neoalkoxytris(m-aminophenyl)zirconate, zirconium ammonium carbonate, Al-acetoxypyruvate, Al-methacrylate A zirconium or aluminum coupling agent such as Al-propionate.

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

Specific examples of the photostabilizer include 1,2,2,6,6-pentamethyl-4-piperidinol and 2,2,6,6-tetramethyl-4-piperidinol. 1,2,2,6,6-pentamethyl-4-piperidinyl (meth) acrylate (made by ADEKA Co., LA-82), four (1, 2, 2, 6, 6-five Methyl-4-piperidinyl-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)-1,2, 3,4-butane tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-double Mixed esterified product of (2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, azelaic acid bis(2,2,6, 6-tetramethyl-4-piperidinyl) sebacate, bis(1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 2, 2,6,6-Tetramethyl-4-piperidyl methacrylate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, double (1,2 ,2,6,6-pentamethyl-4-piperidinyl) sebacate, 4-benzylideneoxy-2,2,6,6-tetramethylpiperidine, 1-[2-[ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoxy]ethyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl) Propyloxy]-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidyl-methacrylate, bis (1, 2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylpropane Acid ester, bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl) sebacate, 1,1-dimethylethyl hydrogen peroxide and octane Reaction product, N, N', N", N'''-tetra-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidine- 4-yl)amino)-three -2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-three -N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetra Polycondensate of methyl-4-piperidinyl)butylamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-tri -2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imido]hexamethylene[(2,2,6,6-tetramethyl- 4-piperidinyl)imido]], dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polymer, 2, 2, 4, 4-tetramethyl-20-(β-lauroyloxycarbonyl)ethyl-7-oxa-3,20-diazapyrosid[5,1,11,2]icosane-21-one , β-alanine, N-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester/myristyl ester, N-acetamido-3-dodecyl 1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3 ,20-diazabispiro[5,1,11,2]icosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diaza Bicyclo-[5,1,11,2]-docosane-20-propionic acid lauryl ester/myristyl ester, malonic acid, [(4-methoxyphenyl)-methylene] - bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1, a hindered amine system such as 3-benzamide, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl) or a benzophenone compound such as octyl benzophenone, 2-( 2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2-hydroxy-5-methylphenyl)benzotriene Oxazole, 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimido-methyl)-5-methylphenyl]benzotriazole, 2-(3 -T-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-p-pentylphenyl)benzotriazole, Reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate with polyethylene glycol, 2-(2H- Benzotriazole-based compound such as benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2,4-di-t-butylphenyl-3,5-di-third Benzoate such as 4-hydroxybenzoate, 2-(4,6-diphenyl-1,3,5-three -2-yl)-5-[(hexyl)oxy]phenol, etc. A compound or the like, but particularly preferably a hindered amine compound.

Specific examples of the filler include, for example, crystalline cerium oxide and molten copper. Powders of cerium oxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, tantalum carbide, tantalum nitride, boron nitride, zirconia, olivine, talc, spinel, titanium oxide, talc, etc. These particles are obtained by spheroidizing.

In the case where various additives are present in the composition, various additives are hardened in the light. The weight ratio in the composition of the transparent adhesive 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% by weight.

The curable resin composition of the present invention can separate the above components at room temperature~ It is obtained by mixing and dissolving at 80 ° C, and it is also possible to remove inclusions by filtration or the like as needed. Considering the coatability, the resin composition for the subsequent use of the present invention preferably has a viscosity at 25 ° C of 300 to 15000 mPa. The blending ratio of the components is appropriately adjusted in the manner of the range of s.

The curable resin composition of the present invention is used for the above [Step A] to [Step Step D] A method of bonding an optical member by bonding at least two optical substrates.

In the curing shrinkage ratio of the cured product of the curable resin composition of the present invention, the first curable resin composition is preferably 3.0% or less, and particularly preferably 2.0% or less. Further, the second curable resin composition is preferably 4.0% or less, and particularly preferably 3.0% or less. Thereby, when the curable resin composition is cured, the stress on the inner surface of the cured resin can be reduced, and the interface between the substrate and the layer formed of the cured product of the curable resin composition can be effectively prevented from being deformed. .

In the case where the substrate such as glass is thin, when the curing shrinkage ratio is large, the warpage at the time of curing increases, and thus the display performance is greatly adversely affected. Therefore, from this viewpoint, the curing shrinkage ratio is preferable. small.

The cured product of the curable resin composition of the present invention is in the range of 400 nm to 800 nm. The transmittance is preferably 90% or more. When the transmittance is less than 90%, the light is hard to transmit, and the visibility is lowered when used in a display device.

Further, when the cured product has a high transmittance at 400 to 450 nm, the visibility can be further improved. Therefore, the transmittance at 400 to 450 nm is preferably 90% or more.

The first curable resin composition 11 or the second curable resin of the present invention The composition 12 preferably contains (I) an amine ester (meth) acrylate or a (meth) acrylate having a polyisoprene skeleton, a (II) (meth) acrylate monomer, and photopolymerization. Starting agent.

In addition, it is preferable to use a resin composition containing the components (I) and (II) described above for each of the first curable resin composition 11 and the second curable resin composition 12 to obtain an optical member.

Moreover, it is preferable to further contain the softening component as a softening agent, and it is preferable that both the first curable resin composition 11 and the second curable resin composition 12 contain a softening component. Among the softening components, a lanthanoid resin (especially a solid lanthanide resin) is preferably used.

The (meth) acrylate (A) used in the production method of the present invention As the curable resin composition of the photopolymerization initiator (B), several preferred aspects are described below. The "% by weight" of the content of each component means the content ratio with respect to the total amount of the curable resin composition of the present invention.

(A1)

The curable resin composition according to the above (5), wherein the (meth) acrylate (A) is selected from the group consisting of an amine ester (meth) acrylate, a (meth) acrylate having a polyisoprene skeleton, and At least one (meth) acrylate of the group consisting of (meth) acrylate monomers.

(A2)

The curable resin composition according to the above (5) or (A1), wherein (i) an amine ester (meth) acrylate or a polyisoprene skeleton is contained as the (meth) acrylate (A) At least one of (meth) acrylate and (ii) a (meth) acrylate monomer.

(A3)

The curable resin composition according to the above (5) or (A1), which comprises (i) a poly C2-C4 alkylene glycol, a diisocyanate, and a hydroxyl group as the (meth) acrylate (A). Both the amine ester (meth) acrylate obtained by the reaction of the C2-C4 alkyl (meth) acrylate, and (ii) the (meth) acrylate monomer.

(A4)

The curable resin composition according to any one of the above (A1) to (A3), wherein the amine ester (meth) acrylate has a weight average molecular weight of 7,000 to 25,000.

(A5)

The curable resin composition according to any one of the above (A1) to (A4), which comprises (meth) acrylate (A) and a photopolymerization initiator (B), and as a photopolymerization initiator (B) The curable resin composition having a mercaptophosphine oxide compound or a mercaptophosphine oxide compound is contained as a photopolymerization initiator (B).

(A6)

The curable resin composition according to the above (A5), wherein the fluorenylphosphine oxide compound is selected from the group consisting of 2,4,6-trimethylbenzimidyldiphenylphosphine oxide and 2,4,6-trimethylbenzene. Methyl phenyl ethoxy ethoxylated phosphine, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide and bis(2,6-dimethoxybenzylidene)-2 At least one compound of the group consisting of 4,4-trimethyl-pentylphosphine oxide.

(A7)

a curable resin composition, or a curable resin as described in any one of the above (A1) to (A6) In the composition, the curable resin composition containing the (meth) acrylate (A) and the photopolymerization initiator (B) contains other components in addition to the components (A) and (B).

(A8)

The curable resin composition of 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 remainder is other components.

(A9)

The curable resin composition according to the above (A8), wherein the (meth) acrylate (A) contains at least (i) an amine ester (meth) acrylate or a polyisoprene (meth) acrylate. One is 20 to 80% by weight and (ii) the (meth) acrylate monomer is 5 to 70% by weight, and the total of the two is 40 to 90% by weight.

(A10)

The curable resin composition according to any one of the above (A7) to (A9), which contains 10 to 80% by weight of the compound represented by the formula (1) as another component.

(A11)

The curable resin composition according to any one of the above-mentioned (A1) to (A10), wherein the cured product of the curable resin composition has a curing shrinkage ratio of 3% or less and contains (methyl group). ) acrylate (A) and photopolymerization initiator (B).

(A12)

A curable resin composition containing a (meth) acrylate (A) and a photopolymerization initiator (B), or a curable resin composition according to any one of the above (A1) to (A11), wherein about 200 μm The cured sheet of the curable resin composition having a thickness has an average transmittance of at least 90% in a wavelength range of 400 to 450 nm and an average transmittance of at least 90% in a wavelength range of 400 to 800 nm.

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

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

In the present invention, the term "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 producing an optical member of the present invention, it is preferred that at least one of the plurality of optical substrates used use an optical substrate having a light shielding portion.

In the optical base material having the light shielding portion, the position of the light shielding portion is not particularly limited. In a preferred embodiment, a strip-shaped light-blocking portion having a width of about 0.05 to 20 mm, preferably about 0.05 to 10 mm, more preferably about 0.1 to 6 mm, is formed in the peripheral portion of the optical substrate. The light-shielding portion on the optical substrate can be formed by attaching a tape or coating or printing a coating or the like.

As the material of the optical substrate used in the present invention, various materials can be used. With Examples of the resin include PET, PC, PMMA, a combination of PC and PMMA, glass, COC (copolymers of cycloolefin), COP (Cyclo-Olefin-Polymer), and plastic (acrylic resin). . As the optical substrate used in the present invention, for example, a transparent plate or sheet, a film or a laminated sheet obtained by using a plurality of polarizing plates or the like, a transparent plate, an unlaminated sheet or a transparent plate, and an inorganic glass can be used. Transparent plate (inorganic glass plate and processed products thereof, such as lens, enamel, ITO glass).

Moreover, the optical substrate used in the present invention includes a touch panel (touch panel input sensor) or a display unit formed of a plurality of functional boards or sheets, in addition to the above-described polarizing plate or the like. (hereinafter also referred to as "functional laminate").

As a sheet which can be used as the optical substrate used in the present invention, an icon sheet can be cited. (icon sheet) Icon sheet, decorative sheet, and protective sheet. A plate (transparent plate) which can be used as a method for producing an optical member of the present invention includes a decorative plate and a protective plate. As the material of the sheets or sheets, those listed as the material of the transparent sheet can be used.

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

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

As a preferred optical member obtained by the production method of the present invention, An optical member obtained by laminating a plate-like or sheet-like transparent optical substrate of the light-shielding portion and a cured layered product of the curable resin composition of the present invention.

Further, in the production method of the present invention, a display unit such as a liquid crystal display device is used as one of the optical substrates, and an optical functional material is used as the other optical substrate, whereby a display unit with an optical functional material can be manufactured (hereinafter Also known as the display panel). Examples of the display unit include a display device such as an LCD, an EL display, an EL illumination, an electronic paper, or a plasma display to which a polarizing plate is attached to a glass. Further, examples of the optical functional material include a transparent plastic plate such as an acrylic plate, a PC plate, a PET plate, and a PEN plate, a tempered glass, and a touch panel input sensor.

In the case of being used as a bonding material for bonding an optical substrate, in order to improve visibility When the refractive index of the cured product is from 1.45 to 1.55, the visibility of the displayed image is further improved, which is preferable.

If it is within the range of the refractive index, the difference in refractive index from the substrate used as the optical substrate can be reduced, and the light reflection can be suppressed, and the optical loss can be reduced.

As a preferred aspect of the optical member obtained by the manufacturing method of the present invention, List the following (i) ~ (vii).

(i) An optical member obtained by laminating an optical substrate having a light-shielding portion and a cured laminate of the curable resin composition of the present invention.

(ii) The optical member according to (i) above, wherein the optical substrate having the light shielding portion is 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 layer and a transparent electrode. The optical substrate in the group, and the functional laminate is a display unit or a touch panel.

(iii) The optical member according to (ii) above, 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 in which a plate-like or sheet-like optical substrate having a light-shielding portion is bonded to a surface of a touch panel side of a touch panel using a cured product of the curable resin composition of the present invention (or Touch panel input sensor).

(v) A display panel obtained by bonding a cured product of the curable resin composition of the present invention to a display screen of a display unit using an optical substrate having a plate-like or sheet-like shape having a light-shielding portion.

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

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

The use of the curable resin composition of the present invention is described by the above steps A to D. In the method, a plurality of optical substrates selected from the above-described optical substrates are bonded together, whereby the optical member of the present invention is obtained. In the above step B, the curable resin composition can be applied to the bonding two Only one side of the surface of the optical substrate facing the cured layer may be applied to both sides.

For example, in the case where the functional laminated body is the optical member of the above (ii) of the touch panel or the display unit, in the steps A and B, the resin composition can be applied only to the protection having the light shielding portion. Any of the surfaces of the substrate, preferably the surface on which the light shielding portion is provided, and the touch surface of the touch panel or the display surface of the display unit may be applied to both of them.

Further, in the case of the optical member of the above (vi) obtained by bonding a protective substrate or a touch panel for protecting a display screen of the display unit to the display unit, in steps A and B, The resin composition may be applied only to the surface of the protective substrate provided with the light shielding portion or the surface of the touch panel opposite to the touch surface and the display surface of the display unit, or may be applied to These two.

Including the display unit obtained by the manufacturing method of the present invention and having shading The optical member of the optical substrate of the portion can be incorporated, for example, into an electronic device such as a television, a mini game machine, a mobile phone, or a computer.

Example

Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited by the Examples.

Preparation of curable resin composition (Preparation of the first curable resin composition A)

A urethane urethane (hydrogenated polybutadiene diol (molecular weight 3000), isophorone diisocyanate, 2-hydroxyethyl acrylate 3 component (mol ratio 1: 1.2: 2) reactant) 16 Parts by weight, GI-2000 (two-terminal hydroxyhydrogenated polybutadiene, manufactured by Nippon Soda Co., Ltd.), 18 parts by weight, Nishite Polybutene LV-100 (liquid polybutene, JX Rigang Risch Energy Co., Ltd.) )) 13 parts, Cleanon (trade name) M105 (aromatically modified hydrogenated terpene resin, Yasuhara) (manufactured by Chemical Co., Ltd.), 16 parts, LA (lauryl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 11 parts by weight, S-1800A (isostearyl acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 0.5 parts by weight of SPEEDCURE (trade name) TPO (2,4,6-trimethylbenzimidyl diphenylphosphine oxide, manufactured by LAMBSON Co., Ltd.), Irgacure (trade name) 184D (manufactured by BASF Corporation), 0.5 parts heating Prepared by mixing. The viscosity at 25 ° C is 4000 mPa. s.

(Preparation of the first curable resin composition B)

A urethane urethane (hydrogenated polybutadiene diol (molecular weight 3000), isophorone diisocyanate, 2-hydroxyethyl acrylate 3 component (mol ratio 1: 1.2: 2) reactant) 9 Parts by weight, GI-2000 (two-terminal hydroxyhydrogenated polybutadiene, manufactured by Nippon Soda Co., Ltd.), 55 parts by weight, Japanese stone polybutene LV-100 (liquid polybutene, JX Rigang Risch Energy Co., Ltd.) )), 13 parts by weight, LA (lauryl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 15 parts by weight, S-1800A (isostearyl acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), SPEEDCURE (trade name) 0.25 parts by weight of TPO (2,4,6-trimethyl benzhydryldiphenylphosphine oxide, manufactured by LAMBSON Co., Ltd.), and Irgacure (trade name) 184D (manufactured by BASF Corporation), 0.5 part by heating and mixing . The viscosity at 25 ° C is 3500 mPa. s.

(Preparation of the first curable resin composition C)

A urethane urethane (hydrogenated polybutadiene diol (molecular weight 3000), isophorone diisocyanate, 2-hydroxyethyl acrylate 3 component (mol ratio 1:1.5:2) reactant) 80 Parts by weight, IBXA (isodecyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 30 parts, SPEEDCURE (trade name) TPO (2,4,6-trimethylbenzhydryldiphenylphosphine oxide, LAMBSON) 1 part by weight of Irgacure (trade name) 184D (manufactured by BASF Corporation) was prepared by heating and mixing 3 parts. The viscosity at 25 ° C is 14000 mPa. s.

(Preparation of the second curable resin composition a)

20 parts of LIR-390 (isoprene block polymer, manufactured by Kuraray Co., Ltd.), UC-203 (reactive isoprene polymer, manufactured by Kuraray Co., Ltd.), 50 parts, FA -512A (dicyclopentenyloxyethyl acrylate, manufactured by Hitachi Chemical Co., Ltd.), 23 parts, A-NOD-N (decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), 3 parts, SPEEDCURE (trade name): 0.5 parts by weight of TPO (2,4,6-trimethyl benzhydryldiphenylphosphine oxide, manufactured by LAMBSON Co., Ltd.), and Irgacure (trade name) 184D (manufactured by BASF Corporation), 1 part by heating and mixing . The viscosity at 25 ° C is 65000 mPa. s.

The following evaluation was carried out using the obtained curable resin composition of the present invention.

Example 1

As shown in Fig. 1(a), a second curable composition a having a thickness of 300 μm is applied to a projection area of the sealing body 23 of the liquid crystal display unit 1, and the formation of the coating film is arranged as follows: b) The shape shown is applied, thereby providing a communication portion that connects the inner region of the coating site with the outer region.

On the other hand, the first curable composition A having a thickness of 250 μm was applied to each of the protective sheets. Thereafter, the liquid crystal display unit 1 and the protective sheet 2 are bonded in the opposite direction to the unhardened portion. Finally, an ultraviolet light 5 having an integrated light amount of 2000 mJ/cm ^{2 was} irradiated from the side of the protective plate by an electrodeless ultraviolet lamp (manufactured by Heraeus Noblelight Fusion UV Co., Ltd., D BULB), whereby the cured resin layer was cured to form the optical member of Fig. 7.

Example 2

The first curable composition applied to the protective sheet is changed to B, and the coating film is formed in the same manner as the shape shown in FIG. 4(c), and the cured resin layer is cured to form a pattern. 7 optics member.

Comparative example 1

The coating place of the second curable composition is formed into a rectangular frame shape so as not to be connected to the communication portion between the inner region and the outer region, and the coating is applied thereto. The operation was carried out in the same manner, and the cured resin layer was hardened to form an optical member.

(adhesive)

The optical members were obtained from Examples 1 to 2 and Comparative Example 1 by leaving the substrates at intervals of 0.1 mm. The stress required to separate the substrates of the obtained optical members from each other was measured at room temperature. The pressing speed was 5 mm/min, and the obtained stress was divided by the unit area as the bonding strength.

(display uneven)

The obtained optical member was confirmed by visual inspection.

Moreover, the following evaluation was performed using the obtained curable resin compositions A, B, and C of the present invention.

(Curability) Two slides each having a thickness of 1 mm were prepared, and one of them was applied so that the film thickness of the obtained curable resin composition was 200 μm. Another slide was attached to the coated side. The resin composition was irradiated with ultraviolet light having a cumulative light amount of 2000 mJ/cm ² by a high-pressure mercury lamp (80 W/cm, no ozone) through a glass, and the hardenability was evaluated as follows.

◎If one of the substrates is lifted, the optical member as a whole is followed up

○If one of the substrates is lifted, the optical member as a whole is picked up, but one of the 10 times is peeled off.

× resin is liquid

(hardening shrinkage rate)

Two glass slides each having a thickness of 1 mm coated with a fluorine-based release agent were prepared, and the obtained curable resin composition was applied to the release coating surface of one of the release coatings so as to have a film thickness of 200 μm. Thereafter, two glass slides were bonded to each other with the respective release agent coating faces facing each other. The resin composition was irradiated with ultraviolet rays having an integrated light amount of 2000 mJ/cm ² by a high-pressure mercury lamp (80 W/cm, no ozone) through a glass to cure the resin composition. Thereafter, two slides were peeled off to prepare a cured product for film specific gravity measurement. The specific gravity (DS) of the cured product was measured in accordance with JIS K7112 B. Further, the liquid specific gravity (DL) of the resin composition was measured at 25 °C. According to the measurement results of DS and DL, the hardening shrinkage ratio was calculated by the following formula.

Hardening shrinkage ratio (%) = (DS-DL) ÷ DS × 100

(heat resistance, wet adhesion)

A glass slide having a thickness of 0.8 mm and an acrylic plate having a thickness of 0.8 mm were prepared, and the obtained curable resin composition was applied so as to have a film thickness of 200 μm, and the other was bonded to the coated surface. The resin composition was irradiated with ultraviolet rays having an integrated light amount of 2000 mJ/cm ² by a high-pressure mercury lamp (80 W/cm, no ozone) through a glass, and the resin composition was cured to prepare a sample for adhesion evaluation. The sample was allowed to stand at 85 ° C, 85% RH for 250 hours. In the sample for evaluation, the peeling of the slide glass or the acrylic plate from the cured resin was visually confirmed.

◎ no peeling after 250 hours

○No peeling after 250 hours, some of them are discolored

× stripped after 250 hours

(softness)

The obtained curable resin composition was sufficiently cured, and the hardness of the durometer E was measured using a hardness meter (type E) according to the method of JIS K7215, and the flexibility was evaluated. More specifically, the curable resin composition was poured into a cylindrical mold so that the film thickness became 1 cm, and the resin composition was sufficiently cured by irradiation with ultraviolet rays. The hardness of the obtained cured product was measured by a durometer (type E).

(rigid modulus)

Two PET films having a thickness of 40 μm coated with a fluorine-based release agent were prepared, and the obtained curable resin composition was applied to the surface of the release agent having a cured film thickness of 600 μm. Coating. Thereafter, two PET films were bonded to each other with the release surfaces of the respective release agents facing each other. The high-performance mercury lamp (80 W/cm, no ozone) was used to irradiate ultraviolet rays having an integrated light amount of 2000 mJ/cm ² through a PET film to cure the resin composition. Thereafter, two PET films were peeled off to prepare a cured product for rigid modulus measurement, and the rigid modulus of the cured product was measured using ARES (TA Instruments) in a temperature range of 20 to 40 °C.

The above test results are summarized in the following table.

The rigid modulus of the first hardenable composition C is in the measurement range because the hardness is too high. Outside. The present invention has been described in detail with reference to the specific embodiments thereof, and it is obvious to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Further, the present application is based on a Japanese patent application (2014-160040) filed on Jan. 6, 2014, which is incorporated by reference. Again, all references cited herein are incorporated in their entirety.

[Industrial availability]

In the method for producing an optical member of the present invention, an optical member such as a display unit which is excellent in visibility and is less likely to cause display unevenness can be obtained. The optical member obtained by the present invention can be preferably incorporated into a display device such as a liquid crystal display, a plasma display, or an organic EL display.

Claims (12)

A method for producing an optical member, which is a method for producing an optical member in which a liquid crystal display unit is followed by a protective sheet, comprising the steps of: coating a second curable resin composition: the liquid crystal display unit or the protective sheet One coating a second curable resin composition having fluidity when not cured, and defining a filling chamber by the second curable resin composition for filling the first hardening having fluidity when not cured And a coating step of the first curable resin composition: the first curable resin composition is stored in the filling chamber when the liquid crystal display unit and the protective sheet are bonded together, and is not coated In the liquid crystal display unit or the protective sheet of the second curable resin composition, the first curable resin composition is applied, and the first curable resin composition is temporarily cured by temporarily suspending the first curable resin composition. The curing step of bonding the liquid crystal display unit and the protective sheet via the first curable resin composition, and the first curable resin composition curing step: the first curable resin group Forming the liquid crystal display unit and the protective sheet, and bonding the cured layer obtained by curing the second curable resin composition to a layer extending linearly between the liquid crystal display unit and the protective sheet or A layer of a dot-like layer is formed as a partition wall, and the partition wall separates an inner region of the filling chamber filled with the first curable resin composition from an outer region, and is provided in at least a portion of the partition wall There is a communication portion that communicates between the inner region and the outer region of the filling chamber. The method of manufacturing an optical member according to the first aspect of the invention, wherein the partition wall formed as a linearly extending layer or a dot-like layer is formed in a rectangular frame shape, and a plurality of the inner region and the outer region are connected The communication portion has a rotational symmetry centering on the axis of the optical member or a line symmetry centered on the central axis of the optical member. The method of manufacturing an optical member according to claim 1 or 2, wherein the partition wall is formed in a rectangular frame shape, and a partition wall is formed on four sides of the frame forming the rectangle, and the four corners of the frame forming the rectangle are formed. Connecting part. The method of manufacturing an optical member according to claim 1 or 2, wherein the partition wall is formed in a rectangular frame shape, and the communication portion is formed on four sides of the rectangular frame, and the rectangular portion is formed at four corners of the rectangular frame. Partition wall. A curable resin composition containing the first curable resin composition or the second curable resin composition in the method for producing an optical member according to any one of claims 1 to 4 (methyl) ) acrylate (A) and photopolymerization initiator (B). The sclerosing resin composition of claim 5, wherein the (meth) acrylate (A) is selected from the group consisting of urethane (meth) acrylate and having a polyisoprene skeleton. One or more (meth) acrylates of the (meth) acrylate, the (meth) acrylate having a polybutadiene skeleton, and the (meth) acrylate monomer. The curable resin composition of claim 5 or 6, wherein the photopolymerization initiator (B) measured in acetonitrile or methanol has a molar absorption coefficient of 300 ml/(g.cm) or more at 302 nm or 313 nm. It is 100 ml/(g.cm) or less at 365 nm. A curable resin composition as claimed in claim 5 or 6, wherein the protective sheet is selected 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, a glass substrate or a film having a transparent electrode formed thereon, and a substrate bonded to a transparent substrate having a light shielding portion One or more of the groups. The curable resin composition of the fifth or sixth aspect of the invention, wherein the resin layer of the curing rate of 80% of the first curable resin composition is irradiated with ultraviolet rays at a storage modulus of 25% at 25 ° C The storage modulus of the resin layer having a 98% hardening rate is 3 to 20 times, and the storage rigidity modulus (25 ° C) at a hardening rate of 80% is 1 × 10 ² Pa to 1 × 10 ⁵ Pa. The curable resin composition of claim 5 or 6, wherein the (meth) acrylate (A) is selected from the group consisting of an amine ester (meth) acrylate and a polyisoprene skeleton (methyl) One or more (meth) acrylates of the group consisting of an acrylate, a (meth) acrylate having a polybutadiene skeleton, and a (meth) acrylate monomer. The curable resin composition of claim 5 or 6, wherein the protective sheet is a touch panel. A touch panel obtained by the method of manufacturing an optical member according to any one of claims 1 to 4.