TW201640193A - Method for producing image display device, curable resin composition to be used therein, touch panel, and image display device - Google Patents

Abstract

A method for producing an image display device having a protective plate adhered to a liquid crystal display unit equipped with a liquid crystal display cell, a polarizing plate, and a sealed body or a housing, the method involving: (A) a step for coating the liquid crystal display unit or the protective plate with a first curable resin composition; (B) a step for sticking the liquid crystal display unit and the protective plate to one another with the first curable resin composition interposed therebetween; and (C-I)-(C-III) the subsequently described steps which follow step (B). (C-I) a step for adhering the liquid crystal display unit and the protective plate to one another by curing the first curable resin composition; (C-II) a step for coating the outer-peripheral-side surface section of the protective plate, the sealed body or the housing with a second curable resin composition, so as to connect the liquid crystal display unit and the protective plate with one another; and (C-III) a step for, after step (C-II), providing the outer-peripheral side surface section of the protective plate, the sealed body or the liquid crystal display unit housing with a cured-article layer by curing the second curable resin composition.

Description

Method for manufacturing image display device, curable resin composition therefor, touch panel and image display device

The present invention relates to a method of manufacturing an image display device in which an optical substrate having a light-shielding portion is bonded to another optical substrate to produce an image display device, a curable resin composition therefor, a touch panel, and an image display device .

In recent years, a display device that realizes screen input by attaching a touch panel to a display screen of a display device such as a liquid crystal display, a plasma display, or an organic EL display has been widely used. The touch panel has a structure in which a glass plate or a resin film having a transparent electrode is formed with a gap and is relatively bonded to each other, and a glass or resin transparent protective plate is attached to the touch surface as needed.

Regarding the bonding of a glass plate or a film having a transparent electrode formed on a touch panel to a transparent protective plate made of glass or resin, or a bonding between a touch panel and a display body assembly, there is a technique of using a double-sided adhesive sheet. However, if a double-sided adhesive sheet is used, there is a problem that air bubbles are easily entered. As a technique for replacing a double-sided adhesive sheet, a technique of bonding with a curable resin composition having flexibility has been proposed.

Therefore, it is bonded by using a soft ultraviolet curable resin. According to the method, a two-layer adhesive as described in Patent Document 1 is used, and a stopper (a crotch portion) is formed by an adhesive, and thereafter, a flow-stopping agent is used to stop the flow. The frame formed in the portion is filled and the both are cured to form a cured layer, whereby the optical member is bonded to the display element.

However, in the case where the image display device is produced by the above method, when the cured portion is formed, and the crotch portion of the cured ultraviolet curable resin is pressed with a finger or the like, the liquid is locally applied by pressing the portion to be pressed. The gap of the unit changes, so that ripples are generated, and the visibility of the pressing causes problems.

On the other hand, as described in Patent Document 2, a method of using a single adhesive without using two kinds of adhesives has been proposed. However, even in the case of a single adhesive, the occurrence of the above-mentioned corrugations was confirmed. Therefore, under the above circumstances, the industry has desired to develop an image display device that does not generate ripples regardless of which portion of the screen of the touch image display device.

Patent Document 1: Japanese Patent No. 5451015

Patent Document 2: International Publication No. 2013/111810

An object of the present invention is to provide a method of manufacturing an image display device and a curable resin composition therefor, which can be used in an image display device which is excellent in visual recognition without causing ripples when pressed against any portion of the image display device. , touch panel and image display device.

The inventors of the present invention have made an effort to solve the above problems, and as a result, have completed the present invention. That is, the present invention relates to the following (1) to (12).

(1) A method of manufacturing an image display device, wherein a protective plate is attached to a liquid crystal display device, and the liquid crystal display device includes a liquid crystal display unit, a polarizing plate disposed on the liquid crystal display unit, and a polarizing plate surrounding the liquid crystal display unit a sealing body or a housing for fixing the liquid crystal display unit by surrounding a peripheral wall portion of the liquid crystal display unit, and the manufacturing method includes: (A) when at least one of the liquid crystal display unit and the protective sheet is not hardened a coating step of the first curable resin composition having fluidity, and (B) a bonding step of bonding the liquid crystal display unit and the protective sheet through the first curable resin composition, in the above step ( B), comprising the following steps (CI) to (C-III): (CI) curing the first curable resin composition, and forming the liquid crystal display device and the first curable resin next to the protective sheet And a solidification step (C-II) for connecting the liquid crystal display unit and the protective sheet to the outer peripheral side surface portion of the protective sheet, the outer peripheral side portion of the sealing body covering the liquid crystal display unit, or the solid portion The coating step of applying the second curable resin composition to the outer peripheral side surface portion of the casing of the liquid crystal display unit, and (C-III) curing the second curable resin composition after the step (C-II) The step of providing a cured layer on the outer peripheral side surface portion of the protective plate, the outer peripheral side surface portion of the sealed body covering the liquid crystal display unit, or the outer peripheral side surface portion of the casing for fixing the liquid crystal display unit.

(2) The method of producing an image display device according to the above aspect, wherein the step (A) is performed by applying the first curable resin composition onto the surface of the protective sheet to form a cured or uncured coating. In the film, the step (B) is to bond the protective sheet on which the coating film is formed to the liquid crystal display device. The step (C-II) is to apply the second curable composition to form a hardened or uncured coating on the outer peripheral side surface portion of the sealing body of the liquid crystal display unit or the outer peripheral side portion of the housing of the fixed liquid crystal display unit. membrane.

(3) The method of producing a video display device according to the above aspect, wherein the coating film of the first curable resin composition has an average thickness of the second curable resin composition. The average thickness of the film is below.

The method of manufacturing the image display device according to any one of the above aspects, wherein the protective plate is composed of one or more selected from the group consisting of the following substrates, and the substrate is 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, and a glass substrate having a transparent electrode formed on a transparent substrate having a light shielding portion or a substrate bonded with a film .

(5) The method of manufacturing the image display device according to any one of (1) to (4) wherein the protective plate is a touch panel.

(6) A curable resin composition, wherein the first curable resin composition or the second curable resin is used in the method for producing a video display device according to any one of (1) to (5) And containing (meth) acrylate (A) and photopolymerization initiator (B).

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

(8) The curable resin composition as described in (6) or (7), wherein the photo-polymerization initiator (B) measured in acetonitrile or methanol has a molar absorption coefficient at 302 nm or 313 nm. The lower part is 300 ml/(g.cm) or more, and the 365 nm is 100 ml/(g.cm) or less.

(9) The curable resin composition according to any one of (6), wherein the first curable resin composition is a resin layer at a curing rate of 80% when irradiated with ultraviolet rays at 25 The storage modulus of rigidity at °C, the storage rigidity modulus of the resin layer at a curing rate of 98% under ultraviolet irradiation is 3 to 20 times the resin composition, and the storage rigidity modulus at a hardening rate of 80% (25 ° C) is 1 × 10 ² Pa to 1 × 10 ⁵ Pa.

(10) A touch panel obtained by the method of manufacturing the image display device according to any one of (1) to (5).

(11) An image display device in which a protective plate is attached to a liquid crystal display device, and the liquid crystal display device includes a liquid crystal display unit, a polarizing plate disposed on the liquid crystal display unit, and a polarizing plate surrounding the liquid crystal display unit a sealing body or a casing that fixes the liquid crystal display unit by surrounding a peripheral wall portion of the liquid crystal display unit, and the image display device has a first cured layer formed of a first curable resin formed on the polarizing plate And the second cured layer is attached to the outer peripheral side surface portion of the protective plate, the outer circumferential side surface portion of the sealing body covering the liquid crystal display unit, or the outer circumferential side surface portion of the casing for fixing the liquid crystal display member The liquid crystal display device and the second curable resin composition of the protective sheet are cured and obtained.

(12) The image display device according to the above aspect, wherein the first curable resin composition and the second curable resin composition contain a (meth) acrylate compound and a photopolymerization initiator a curable resin composition selected from the group consisting of (meth)acrylic acid amine ester compounds and (meth)acrylates having a polyisoprene skeleton At least one of a compound and a group of (meth) acrylate compounds having a polybutadiene skeleton.

1‧‧‧LCD components

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

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

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

Fig. 6 is a flow chart showing a fourth embodiment of the production 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 of manufacturing an image display device, and a method of manufacturing the image display device, wherein the protection panel is followed by a liquid crystal display device, and the liquid crystal display device includes a liquid crystal display unit and a polarized light disposed on the liquid crystal display unit. a plate, and a casing surrounding the polarizing plate and covering the liquid crystal display unit or a casing for fixing the liquid crystal display member by surrounding a peripheral wall portion of the liquid crystal display unit, in the method of manufacturing the image display device, by the following [ Steps A] to [Step B], [Step CI] to [Step C-III], a video display device was manufactured. Further, the second cured material layer obtained by curing the second cured resin composition is formed on the outer peripheral side surface portion of the protective sheet and covers the sealing body of the liquid crystal display unit. The outer peripheral side surface portion or the outer peripheral side surface portion of the casing in which the liquid crystal display member is fixed by surrounding the peripheral wall portion of the liquid crystal display unit.

[Step A] The first step of applying the first curable resin composition is to apply the first curable resin composition having fluidity when at least one of the liquid crystal display device or the protective sheet is applied.

[Step B] The bonding step is to bond the liquid crystal display unit and the protective sheet via the first curable resin composition.

[Step C-I] The first curable resin composition curing step is performed by curing the first curable resin composition and adhering the liquid crystal display unit and the protective sheet.

[Step C-II] The coating step is applied to the outer peripheral side surface portion of the protective sheet, the outer peripheral side surface portion of the sealing body, or the second curable resin composition, by connecting the liquid crystal display unit and the protective sheet. The outer peripheral side portion of the housing.

[Step C-III] The second curable resin composition curing step is followed by the step [C-II], and the second curable resin composition is cured to bond the liquid crystal display unit and the protective sheet.

The above [Step A] and [Step B] are performed in accordance with the arrangement, and [Step C-I] to [Step C-III] can be performed in different orders. However, [Step C-III] is set to be performed after [Step C-II].

Hereinafter, the manufacturing method of the present invention and the form of the image display device manufactured by the method will be described with reference to the drawings. Further, the first to fourth embodiments are specific examples, but are not limited to these specific examples.

(First embodiment)

Figure 1 is a diagram showing the manufacturing steps of the image display device (also referred to as "optical member") of the present invention. A step diagram of the first embodiment.

This method is a method of obtaining an optical member by laminating the liquid crystal display unit 1 and the protective sheet 2.

The liquid crystal display unit 1 is a member including a polarizing plate, a driving circuit, a signal input cable, and a backlight assembly, in which one of the forming electrodes is filled with a liquid crystal material between the substrates.

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 has a configuration in which a polarizing plate 22 is disposed 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 exemplified, but it is not necessary to directly laminate, and a polarizing plate may be disposed on the liquid crystal display unit, and optical members such as other functional films may be incorporated. Placed between the liquid crystal display unit and the polarizing plate.

In this state, a gap 24 having a maximum width of several mm is formed between the polarizing plate 22 and the sealing body 23, and it is exemplified that "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". example. That is, as shown in the example of FIG. 2, the liquid crystal display unit 21 which is the bottom surface of the gap 24 between the polarizing plate 22 and the sealing body 23 before the second curable resin composition 11 is applied onto the polarizing plate 22 A sealing film 25 having an adhesiveness is disposed on the surface, and one of the gaps 24 is partially closed. Since 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, the bottom of the gap 24 is sealed. Here, in FIG. 2, an example in which the sealing film 25 is disposed is exemplified, but the sealing film 25 may not be disposed on the bottom surface of the gap 24, and the surface of the liquid crystal display unit 21 may be exposed.

As such a sealing film 25, an adhesive film such as polyethylene terephthalate or the like as a film substrate and having an adhesive layer such as an acrylate or an adhesive layer is preferable.

As the polarizing plate 22, a known image display device 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 sealing film 25 does not necessarily have to be solid at the time of arrangement, and may have a high viscosity as long as it does not penetrate into the gap between the constituent members of the liquid crystal display device. More specifically, a viscosity of 65 Pa can be used. A curable resin composition around s. Further, an adhesive having a thixotropy ratio of about 3 may be used in terms of maintaining the shape so as not to enter the gap.

The liquid crystal display unit 21 can be an area-side backlight-side polarizing plate (not shown) on the side opposite to the surface on which the polarizing plate 22 is formed. Here, the configuration is not limited to the structure in which the backlight-side polarizing plate is directly laminated on the liquid crystal display unit 21, and the polarizing plate 22 may be disposed on the liquid crystal display unit 21, and optical members such as other functional films may be interposed. It is between the liquid crystal display unit 21 and the backlight-side polarizing plate.

Further, in the backlight-side polarizing plate, a backlight (not shown) can be formed on the surface opposite to the surface on which the liquid crystal display unit 21 is disposed. 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 illumination method in which a light source (not shown) is disposed at one end of a light guide plate (not shown) 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 edge illumination method. For example, a direct type in which a light source is disposed directly under the diffusion plate may be employed.

In order to protect the liquid crystal display unit 1, the liquid crystal display unit 1 is usually covered with a casing 26. The casing 26 is generally 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 cover the liquid crystal display unit 21. In FIG. 2, the sealing body 23 is disposed so as to surround the polarizing film in a state in which the gap 24 is interposed in the peripheral wall portion of the polarizing film 22. Further, in FIG. 2, the sealing body 23 is coated on the liquid crystal display unit 21 via the sealing film 25, but may be directly coated on the liquid crystal display unit 21.

The sealing body 23 covers the outer wall of the image display device, and is an example in which the casing 26 disposed adjacent to the peripheral wall portion of the liquid crystal display unit 21 is directly covered in FIG. 2, but it is not particularly limited to this. Further, although not shown, the backlight layer side polarizing plate of the liquid crystal display unit 21 opposite to the surface on which the polarizing plate 22 is formed may be laminated as described above, and the backlight may be laminated on the backlight side polarizing plate to form a case. The body 26 abuts and covers the backlight, with the housing 26 covering the configuration of the peripheral wall portion of the members. Further, the sealing body 23 may be further configured to cover the casing 26.

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

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

As the transparent substrate 3 for the protective sheet 2, a glass plate or a transparent resin plate is mentioned, and it is self-evident in terms of high transparency to emitted light or reflected light from the display panel, and has light resistance and low doubleness. A glass plate is preferred in terms of refractive index, high planar precision, surface damage resistance, and high mechanical strength.

The material of the glass plate may, for example, be a glass material such as soda lime glass, and more preferably a high light-transmissive glass having a lower iron content and less blue color. In order to improve safety, tempered glass can also be used as the surface material. Especially in the case of using a thinner glass plate, it is preferred to use a chemical that has been implemented. Strengthened glass panels.

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, a surface treatment may be performed in order to improve the interfacial adhesion with the resin cured layer. 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 ruthenium oxide film by using an oxidizing flame obtained by a flame burner, and the like.

In order to improve the contrast of the display image, the protective sheet 2 may be obtained by curing the first cured material layer 13 obtained by curing the first curable resin composition described below or by curing the second curable resin composition. An antireflection layer is provided on the surface on the side opposite to the side of the second cured material layer 14. The antireflection layer can be 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.

Further, a part or the whole of the protective sheet 2 may be colored according to the purpose, or a part or the whole of the surface of the protective sheet 2 may be made into a glassy shape to scatter light, or a part or the whole of the surface of the protective sheet 2 may be finely formed. The concave and convex or the like refracts or reflects the 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 plate 2, since the manufacturing method of the present invention is particularly suitable for the manufacture of a relatively large-area image display device, it is preferably 0.5 m × 0.4 m or more, and more preferably 0.7 m × in the case of a television receiver. 0.4m or more. The upper limit of the size of the protective plate 2 is often determined by the size of the display panel. Moreover, an image display device that is too large may easily cause difficulty in operation when it is installed or the like. In terms of these constraints, the upper limit of the size of the protective plate 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, it is usually 0.5 to 25 mm in the case of a glass plate. For applications such as television receivers and PC monitors that are used indoors, it is preferably 1 to 6 mm in terms of weight reduction of the display device, and is preferably 3 to 20 mm in 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 unit 4 is a concealer such as a wiring member that is connected to the display panel so that the image display area of the liquid crystal display unit described below cannot be visually recognized from the side of the protective sheet 2 . The light shielding portion 4 can be formed on the surface on the side where the second cured material layer 14 or the first cured material layer 13 is formed to reduce the parallax between the light shielding portion 4 and the image display region. In the case where the protective sheet 2 is a glass plate, it is preferable to use a ceramic printing containing a black pigment for the light-shielding printing portion, since the light-shielding property is high. A film having a light-shielding portion 4 attached to the surface of the protective sheet 2 and having an anti-reflection layer on the back surface thereof, that is, the outermost surface of the display device may be bonded to the protective sheet. For example, the light shielding portion 4 is formed by attaching a tape, applying a paint, printing, or the like.

Furthermore, in the present invention, the case where the light shielding portion 4 is not provided can be applied. However, in the following description of the first to fourth embodiments, the case where the light shielding portion 4 is provided will be described as a specific example.

[Step A]

Next, as shown in Fig. 1 (a), the first curable resin composition 11 containing the following (meth) acrylate (A) and photopolymerization initiator (B) is applied to the light-shielding portion 4 The surface of the protective plate 2 on which the surface of the light shielding portion 4 is formed is formed. Examples of the coating method include slit coating, roll coating, spin coating, and screen printing. Furthermore, in the present embodiment, an example is given Although the first curable resin composition is applied to the shield 2, it may be applied to the liquid crystal display unit 1 side, or may be applied to the respective substrates of the protective sheet 2 and the liquid crystal display unit 1.

Here, the first curable resin composition 11 may be applied so as to fill the visual recognition region of the image display device, and other optical members may be interposed between the first curable resin composition 11 and the coated portion. Between the substrates.

In the first curable resin composition 11, the first cured layer obtained by curing the first curable resin composition 11 has a storage rigidity modulus at 25 ° C of preferably 10 ² to 10 ⁷ Pa, more preferably 10 ² ~ 10 ⁵ Pa. Further, in order to make the void at the time of bonding disappear in a shorter time, it is particularly preferably 10 ² to 10 ⁴ Pa. When the storage rigidity modulus is 10 ³ Pa or more, the shape of the first cured material 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 entire first cured layer 13 can be uniformly maintained in thickness, and the protective sheet 2 and the liquid crystal display unit 1 can be attached. At the same time, voids are less likely to occur at the interface between the liquid crystal display unit 1 and the first cured material layer 13. When the storage rigidity modulus is 10 ⁷ Pa or less, good adhesion can be exhibited. Moreover, since the molecular mobility of the formed resin material is relatively high, when the liquid crystal display device 1 and the protective sheet 2 are bonded together in a reduced pressure environment and restored to an atmospheric pressure environment, the pressure in the void is utilized ( In the state of decompression and the pressure (atmospheric pressure) applied to the hardened material layer of the filler, the volume of the void is easily reduced, and after the volume is reduced, the gas in the void is easily dissolved in the hardened layer of the filler. absorb.

The thickness of the first curable resin composition 11 is preferably 50 to 500 μm, more preferably 50 to 350 μm, still more 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 effectively absorb the impact or the like caused by the force from the side of the protective sheet 2, and protect the liquid crystal display unit 1. Moreover, in the image display device of the present invention In the manufacturing method, even if a foreign matter not exceeding the thickness of the first cured material layer 13 is mixed between the liquid crystal display element 1 and the protective sheet 2, the thickness of the first cured material layer 13 does not largely change, and the light transmission property is transmitted. The impact is less. When the thickness of the first cured material 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 image display device is not unnecessarily thick.

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

The viscosity of the first curable resin composition 11 is preferably 0.05 to 50 Pa. s, more preferably 1~20Pa. s. If the viscosity is 0.05Pa. When s or more, the deterioration of the physical properties of the first cured product layer 13 can be suppressed. Moreover, since the low boiling point component is small, it is preferable to suppress volatilization in the following reduced pressure environment. If the viscosity is 50Pa. In the case of s or less, voids are less likely to remain in the first cured 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 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 being cured at a low temperature and having a high curing rate.

Here, the first curable resin composition 11 may be used for bonding in an uncured state, but it is preferably temporarily cured as described in FIG. 1(a).

Specifically, the coating film of the first curable resin composition 11 after application is irradiated with ultraviolet rays 5 to obtain a cured layer having a lower side of the coating layer (self-curing resin composition) The hardened portion (not shown) on the transparent substrate side when the object is observed, and the unhardened portion which is present on the upper side of the coating layer (the side opposite to the transparent substrate side) (the atmospheric side when it is carried out in the atmosphere) Not shown in the figure). 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 finally bonded is insufficient. When the amount of irradiation is too large, the amount of unhardened component is small, and the liquid crystal display unit 1 and the protective sheet having the light shielding portion are provided. The fit of 2 becomes bad.

In the present invention, "unhardened" means a state of fluidity in an environment of 25 ° C.

Moreover, when the resin composition layer is touched with a finger after ultraviolet irradiation, and a liquid component is attached to a finger, it is judged that it has an unhardened part.

When it is hardened by ultraviolet irradiation of ultraviolet to near ultraviolet light, it is not limited to a light source as long as it is a light that irradiates ultraviolet to near ultraviolet light. 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.

Further, in the step 1 of the present invention, the ratio of the maximum illuminance at 200 to 320 nm (illuminance ratio) when the maximum illuminance in the range of 320 nm to 450 nm of ultraviolet rays irradiated to the curable resin composition is 100 It 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 (illuminance ratio) is higher than 30, the final strength of the finally obtained optical member is inferior. The reason for this is considered to be that if the illuminance at a low wavelength is high, the hardening of the curable resin composition during the curing in the step 1 is excessively performed, and the contribution to the adhesion during the curing of the ultraviolet ray in the step 3 is reduced. . 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 above-described illuminance ratio is, for example, a method of using a lamp satisfying the condition of the illuminance ratio as a method of irradiating a light of ultraviolet to near-ultraviolet light, or a lamp When the illuminance condition is not satisfied by itself, the illuminance ratio may be used by the substrate (for example, a short-wave ultraviolet cut filter, a glass plate, a film, or the like) that cuts off short-wavelength ultraviolet rays by the irradiation of the step 1. Irradiation is performed. 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 are subjected to short-wave ultraviolet ray cutting treatment.

In this case, it is preferred that the ultraviolet ray is irradiated in the atmosphere from the upper side surface of the coating side (the side opposite to the transparent substrate side when viewed from the curable resin composition layer) (usually the atmospheric surface). . Further, after the vacuum is applied, the curing inhibitory gas may be sprayed onto the surface of the upper surface of the coating layer to perform ultraviolet irradiation. 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.

In other words, by blowing oxygen or ozone onto the surface of the coating layer, oxygen which is hardened by the curable resin composition is generated on the surface thereof, so that the unhardened portion of the surface can be made sure and the uncured portion can be made hard. Part of the film thickness becomes thicker.

Here, in the present specification, the curing ratio indicates the curing rate in terms of the hardening component of the curable resin composition, and is calculated by removing a component that does not harden, such as a softening agent. Further, in the present invention, the curing shrinkage ratio can be calculated from the specific gravity of the film at 25 ° C obtained by the specific gravity of the pre-hardening liquid at 25 ° C and the hardening according to the following formula (1).

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

The first curable resin composition 11 used in the present invention is preferably a storage rigidity modulus of the resin layer at 25 ° C when irradiated with ultraviolet rays in the above [Step B], the above [Step C-I] Or the storage rigid modulus of the resin layer when irradiated with ultraviolet rays in [Step C-III] is 3 to 20 times (preferably 3 to 10 times).

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

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

The first curable resin composition 11 used in 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 by hardening, so that the first curable resin composition 11 cannot follow the substrate and peels off, or the substrate The deformation, or the stress is not sufficiently alleviated, causes display unevenness when the optical member is obtained. Further, when bonding in a vacuum, the storage rigidity modulus at the time of temporary hardening is within the above range, and the space generated at the time of bonding can be filled with a resin without causing a problem when moving to atmospheric pressure. On the other hand, when it is 1 × 10 ² Pa or less, since the shape of the cured product cannot be sufficiently maintained because the rigidity modulus is too low, 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 hardening rate of the resin as a temporary hardening is 60 to 90%, and hardening at the hardening rate The storage rigidity modulus is the above value and a preferred value, and the deformation and display unevenness of the substrate can be prevented.

Here, the hardening rate at the time of the main hardening in the following [Step C-I] is usually 95% or more.

In the present invention, as described above, it is preferable to use a storage rigidity modulus at 25 ° C with respect to the resin layer at the time of temporary hardening, and the storage rigidity modulus of the resin layer when irradiated with ultraviolet rays in the following [Step CI] is 1.5 to 10 Double the resin composition. When it is represented by a hardening rate, it is preferable to use a storage rigidity modulus of the resin layer at 25 ° C when irradiated with ultraviolet rays with respect to a curing rate of 80%, and a storage rigidity modulus of the resin layer when irradiated with ultraviolet rays having a curing rate of 98% is 1.5. ~10 times the resin composition.

In this way, by the resin which changes rapidly according to the hardening rate in the rigid modulus, and the rigidity modulus at the time of the low hardening rate is suppressed to a certain range, the substrate can be easily adhered to the substrate in a state where the curing rate is low. The warpage along the substrate is followed by, and thus can be easily followed. Moreover, it becomes possible to follow the change in the warpage of the substrate, and also to prevent stress from occurring in the substrate. On the other hand, in a state where the curing rate is high, the optical substrates such as the liquid crystal display unit or the protective sheet to be bonded are rigidly attached to each other, so that the bonding strength can be remarkably improved. Further, the obtained optical 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 is preferably 2 to 7 in the case of irradiating ultraviolet rays in the following [Step CI] or [Step C-III] with respect to the storage rigidity modulus of the resin layer at the time of temporary hardening at 25 ° C. Double, especially good for 2.5 to 5 times. When expressed by the hardening rate, the storage rigidity modulus of the resin layer at 25 ° C when irradiated with ultraviolet rays with respect to the curing rate of 80%, and the storage rigidity modulus of the resin layer when irradiated with ultraviolet rays of 98% of the curing rate is preferably 2 to 7. Double, especially good for 2.5 to 5 times.

Further, the curable resin composition used in the method of the present invention (hereinafter also referred to simply as "the curable resin composition of the present invention") preferably has a storage rigidity modulus of 1 × at 25 ° C at the time of the above-described main curing. 10 ³ Pa~1×10 ⁶ Pa. Here, there is a concern that the storage rigidity modulus is larger than 1×10 ⁶ Pa, and the curable resin composition shrinks excessively due to hardening, so that the base material is deformed or the stress is not sufficiently alleviated. There is a concern that display unevenness occurs when an optical member is obtained. On the other hand, when it is 1 × 10 ³ Pa or less, the rigidity is low, and the strength is lower. Here, the storage rigidity modulus is preferably 1.0 × 10 ³ Pa to 1.0 × 10 ⁵ Pa, more preferably 1.0 × 10 ³ Pa to 3.0 × 10 ⁴ Pa.

[Step B]

Next, in the form in which the liquid crystal display unit 1 and the protective sheet 2 are formed with the first curable resin composition 11, as shown in FIG. 1(b), the liquid crystal display unit 1 and the protective sheet having the light shielding portion are provided. 2 fit. The bonding can be carried out in any environment in 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 product of the ultraviolet curable resin having the cured portion and the uncured portion in the first curable resin composition 11 is obtained and bonded, the adhesion can be expected to be improved.

At the time of bonding, the first curable resin composition 11 is dispersed by pressing or the like, and the space is filled with the first curable resin composition 11. When it is carried out under vacuum, when it is exposed to a high pressure environment, the first cured layer 13 having little or no voids is formed.

In the case of bonding in a reduced pressure environment, it is 1 kPa or less, preferably 10 to 300 Pa, and more preferably 15 to 100 Pa. The decompression environment can also be released immediately after lamination. 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 C-I]

Next, as shown in FIG. 1(b), the protective board 2 and the liquid crystal display unit 1 are facing from the side of the protective board 2 The optical member obtained by bonding is irradiated with the ultraviolet ray 5, and the curable resin composition (coating layer) is hardened.

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 for hardening by ultraviolet to near-ultraviolet light is not limited to a light source as long as it is a light that illuminates ultraviolet to near-ultraviolet light. 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 C-II]

Further, as shown in FIG. 1(c), the second curing of the (meth) acrylate (A) and the photopolymerization initiator (B) is carried out so that the liquid crystal display unit 1 and the protective sheet are connected to each other. The resin composition 12 is applied to the outer peripheral side surface portion of the sealing body 23 on the protective sheet 2. Here, a specific example of application to the outer peripheral side surface portion of the sealing body 23 is exemplified, but the second curable resin composition 12 may be applied to the outer side surface portion of the sealing body 23 or the casing 26 as long as the result is The liquid crystal display unit 1 can be connected to the protective plate. Moreover, the example in which "the second curable resin composition 12 is applied to the protective sheet 2" is exemplified, but another optical member may be interposed between the protective sheet 2 and the second curable resin composition 12.

As a form in which the second curable resin composition is applied to the outer peripheral side surface portion of the casing 26, for example, the liquid crystal display unit 1 in which only the sealing body 23 is not provided in FIG. 2 is applied to the outer peripheral side of the casing 26 The form of the liquid crystal display unit 1 or the form to be applied is not particularly limited to this form as long as the second curable resin composition is applied to the outer side surface portion of the casing 26 .

Examples of the method of coating include a dispensing method and the like. Here, applied to liquid crystal The first curable resin composition and the second curable resin composition on the surface of the display unit 1 and the protective sheet 2 may be the same, and different curable resin compositions may be used.

In the present invention, the second curable resin composition 12 is applied to the sealing body 23 or the outer circumferential side surface portion of the casing so as to connect the liquid crystal display unit and the protective plate. In this manner, the second curable resin composition 12 is applied to the outer peripheral side surface portion of the sealing body 23 or the casing 26 of the fixed liquid crystal display unit 1 by avoiding the projection area of the liquid crystal display unit, and the outer peripheral side of the sealing body 23 is provided. A second cured material layer obtained by curing the second curable resin composition 12 is formed on the outer peripheral side surface portion of the casing 26 of the fixed liquid crystal display unit. When the second cured material is laminated on the portion, even if pressure is applied to the second cured material layer 14 by pressing with a finger or the like, the pressure is not easily transmitted to the liquid crystal display unit, and thus the image display portion can be prevented from being generated. ripple. On the other hand, when the second cured material layer 12 is laminated on the display region or the polarizing plate of the liquid crystal display unit, 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. .

In addition, by stacking the second cured material layer 14, the distance between the protective plate 2 and the liquid crystal display unit 1 can be maintained, and the pressure can be prevented from being transmitted to the liquid crystal display unit or the polarizing plate even when pressed with a finger or the like. Since the interval is maintained, it is possible to effectively prevent the occurrence of waviness due to interference.

In addition, it is preferable that the coating of the second curable resin composition 12 is formed in a rectangular frame shape along the sealing body 23 or the outer peripheral side surface portion of the casing 26 of the liquid crystal display unit 1. Further, it may be applied in a form in which a broken portion is formed in one of the second cured material layers 14.

The coating thickness of the second curable resin composition 12 may be sufficient for connecting the liquid crystal display unit and the protective sheet, but is thicker than the first one formed. The thickness of the curable resin composition 11. It is preferable that the thickness of the first curable resin composition 11 formed is 0.01 to 10 mm thick, more preferably 0.1 to 5 mm thick, and still more preferably 0.5 to 3 mm thick.

The storage rigidity modulus at 25 ° C in the curing of the second curable resin composition 12 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, when the liquid crystal display device 1 and the protective plate 2 are connected It is more resistant to deformation due to deformation due to external pressure, so that the influence of the first curable resin layer on the gap thickness can be reduced.

It is preferable to design the second curable resin composition 12 and the first curability so that the shrinkage ratio at the time of curing of the second curable resin composition 12 is larger than the shrinkage ratio at the time of curing of the first curable resin composition 11. Resin composition 11. 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 layer 13 is slightly reduced by the contraction 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, the stress in the display region can be alleviated, and the occurrence of display unevenness can be suppressed.

One of the means for causing the shrinkage ratio at the time of curing the second curable resin composition 12 to be larger than the shrinkage ratio at the time of curing of the first curable resin composition 11 is to make the second curable resin composition 12 have more curing bases. The hardening base 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 increased, or (ii) the polyfunctional component having a plurality of reactive groups in the molecule is increased. The content can be.

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 application, 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 not able to maintain its shape and is diffused, it is difficult to control the thickness, and the second curable resin composition 12 may be broken by the second curable resin composition 12. On the other hand, the viscosity is over 70Pa. In the case of s, there is a case where it is not easy to eject from the applicator.

The second curable resin composition 12 may be a photocurable resin composition or a thermosetting resin composition. The second curable resin composition 12 is preferably a photocurable resin composition containing a curable compound and a photopolymerization initiator in terms of being cured at a low temperature and having a high curing rate.

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

When it is hardened by ultraviolet irradiation of ultraviolet to near ultraviolet light, it is not limited to a light source as long as it is a light that irradiates ultraviolet to near ultraviolet light. 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.

The thickness of the coating film 11 of the first curable resin composition and the second hardenability tree The thickness of the coating film of the lipid composition 12 can be measured using a laser displacement meter (manufactured by Keyence Corporation, LK-H052K) to measure the transparent substrate and the coating film of the first curable resin composition 11 formed thereon or the second. The total thickness of the coating film of the curable resin composition 12 was determined.

Further, depending on the surface shape of the coating film of the first curable resin composition 11 or the coating film of the second curable resin composition 12, it is not easy to measure the thickness by the above-described laser displacement meter. In the case, the thickness of the coating film of the first curable resin composition 11 and the coating film of the second curable resin composition 12 can be measured using a 3D shape measuring machine (high-precision shape measuring system KS-1100) or the like. thickness.

When bonding, as shown in FIG. 1(b), when the liquid crystal display device 1 and the protective sheet 2 are interposed in a resin composition layer in a reduced pressure environment, even when the liquid crystal display device 1 or the protective sheet 2 is bonded The interface with the curable resin composition has a separate void, and when it is returned to the atmospheric pressure environment, the pressure in the void (under a reduced pressure) and the pressure applied to the curable resin composition ( The difference in pressure at the atmospheric pressure reduces the volume of the voids, and the fine pores are absorbed by the curable resin composition and disappear.

[Step C-III]

Finally, as shown in FIG. 1(d), the second curable resin composition 12 is cured to form the second cured layer 14.

As a means for hardening, heat or light is mentioned, and it is preferable to harden by irradiating light. The direction of irradiation of the light is not particularly limited, and it is preferable to irradiate from the side surface portion of the obtained image display device or to irradiate from the side of the liquid crystal display unit 1.

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 for hardening by irradiation of ultraviolet to near-ultraviolet light is not limited to a light source as long as it is a light that illuminates ultraviolet to near-ultraviolet light. 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 image display device shown in Fig. 7 can be obtained.

(Second embodiment)

Fig. 4 is a flow chart showing a second embodiment of the manufacturing process 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. In addition, the parts other than the change of the first embodiment can be reflected and incorporated in the above-described first embodiment, and a part of the description will be omitted.

[Step A]

First, as shown in FIG. 4( a ), the first curable resin composition 11 including the following (meth) acrylate (A) and photopolymerization initiator (B) is applied to the light-shielding portion 4 . The surface of the protective plate 2 on which the surface of the light shielding portion 4 is formed is formed. Examples of the coating method include slit coating, roll coating, spin coating, and screen printing. In the present embodiment, the first curable resin composition is applied to the protective sheet 2, but it may be applied to the liquid crystal display unit 1 side, or may be applied to the protective sheet 2 and the liquid crystal. The respective components of the display unit 1 are on the substrate.

Here, the first curable resin composition 11 may be applied so as to fill the visual recognition region of the image display device, and other optical members may be interposed between the first curable resin composition 11 and the coated portion. Between the substrates.

The first curable resin composition 11 may be a photocurable resin composition or a thermosetting resin composition. As a first curable resin composition, it can be hardened at low temperatures. Further, in terms of a faster curing rate, a photocurable resin composition containing a curable compound and a photopolymerization initiator is preferred.

Here, the first curable resin composition 11 may be used for bonding in an uncured state, but it is preferably temporarily cured as described in FIG. 4(a).

Specifically, the coating film of the first curable resin composition 11 after the application is irradiated with the ultraviolet ray 5, and the coating film is provided on the lower side of the coating layer (the transparent substrate side when viewed from the curable resin composition). The hardened portion (not shown) and the hardened portion of the unhardened portion (not shown) present on the upper side of the coating layer (the side opposite to the transparent substrate side) (the atmospheric side when it is carried out in the atmosphere) Floor. 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 finally bonded is insufficient, and if the amount of irradiation is too large, the amount of unhardened component is small, and the liquid crystal display unit 1 and the protective sheet having the light shielding portion are provided. The fit of 2 becomes bad.

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

[Step B]

Next, in the form in which the liquid crystal display unit 1 and the protective sheet 2 are formed with the first curable resin composition 11, as shown in FIG. 1(b), the liquid crystal display unit 1 and the protective sheet having the light shielding portion are provided. 2 fit. The bonding can be carried out in any environment in 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 product of the ultraviolet curable resin having the cured portion and the uncured portion in the first curable resin composition 11 is obtained and bonded, the adhesion can be expected to be improved.

At the time of bonding, the first curable resin composition 11 is dispersed by pressing or the like, and the space is filled with the first curable resin composition 11. When it is carried out under vacuum, when it is exposed to a high pressure environment, the first cured layer 13 having little or no voids is formed.

In the case of bonding in a reduced pressure environment, it is 1 kPa or less, preferably 10 to 300 Pa, and more preferably 15 to 100 Pa. The decompression environment can also be released immediately after lamination. 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 C-II]

Further, as shown in FIG. 4(b), the second curability of the (meth) acrylate (A) and the photopolymerization initiator (B) is included so as to connect the liquid crystal display unit 1 to the protective sheet. The resin composition 12 is applied to the outer peripheral side surface portion of the sealing body 23 on the protective sheet 2. Here, a specific example of application to the outer peripheral side surface portion of the sealing body 23 is exemplified, but the second curable resin composition 12 may be applied to the outer side surface portion of the sealing body 23 or the casing 26 as long as the result is The liquid crystal display unit 1 can be connected to the protective plate. Further, although the second curable resin composition 12 is applied to the protective sheet 2, other optical members may be interposed between the protective sheet 2 and the second curable resin composition 12.

As a form in which the second curable resin composition is applied to the outer peripheral side surface portion of the casing 26, for example, the liquid crystal display unit 1 in which only the sealing body 23 is not provided in FIG. 2 is applied to the outer peripheral side of the casing 26 The form of the liquid crystal display unit 1 or the form to be applied is not particularly limited to this form as long as the second curable resin composition is applied to the outer side surface portion of the casing 26 .

As a method of coating, a dripping method etc. are mentioned. Here, it is applied to the liquid crystal display assembly 1 The first curable resin composition and the second curable resin composition on the surface of the protective sheet 2 may be the same, and different curable resin compositions may be used.

In addition, it is preferable that the coating of the second curable resin composition 12 is formed in a rectangular frame shape along the sealing body 23 or the outer peripheral side surface portion of the casing 26 of the liquid crystal display unit 1. Further, it may be applied in a form in which a broken portion is formed in one of the second cured material layers 14.

The coating thickness of the second curable resin composition 12 may be a thickness sufficient for connecting the liquid crystal display unit and the protective sheet, but is thicker than the thickness of the first curable resin composition 11 to be formed. It is preferable that the thickness of the first curable resin composition 11 formed is 0.01 to 10 mm thick, more preferably 0.1 to 5 mm thick, and still more preferably 0.5 to 3 mm thick.

The storage rigidity modulus at 25 ° C in the curing of the second curable resin composition 12 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, when the liquid crystal display device 1 and the protective plate 2 are connected It is more resistant to deformation due to deformation due to external pressure, so that the influence of the first curable resin layer on the gap thickness can be reduced.

The second curable resin composition 12 may be a photocurable resin composition or a thermosetting resin composition. The second curable resin composition 12 is preferably a photocurable resin composition containing a curable compound and a photopolymerization initiator in terms of being cured at a low temperature and having a high curing rate.

[Step C-I] and [Step C-III]

Then, as shown in Fig. 1(c), the optical member obtained by bonding the protective sheet 2 and the liquid crystal display unit 1 to the protective sheet 2 is irradiated with ultraviolet rays 5, and the curable resin composition (coating layer) is hard. Chemical. At the same time, the second curable resin composition 12 is cured to form the second cured layer 14 .

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 for hardening by irradiation of ultraviolet to near-ultraviolet light is not limited to a light source as long as it is a light that illuminates ultraviolet to near-ultraviolet light. 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 image display device shown in Fig. 7 can be obtained.

(Third embodiment)

Fig. 5 is a flow chart showing a third embodiment of the manufacturing process 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. In addition, the parts other than the change of the first embodiment can be reflected and incorporated in the above-described first embodiment, and a part of the description will be omitted.

[Step A]

First, as shown in Fig. 5 (a), the first curable resin composition 11 containing the following (meth) acrylate (A) and photopolymerization initiator (B) is applied to the light-shielding portion 4 The surface of the protective plate 2 on which the surface of the light shielding portion 4 is formed is formed. Examples of the coating method include slit coating, roll coating, spin coating, and screen printing. In the present embodiment, the first curable resin composition is applied to the protective sheet 2, but it may be applied to the liquid crystal display unit 1 side, or may be applied to the protective sheet 2 and On each of the substrates of the liquid crystal display device 1.

Here, the first curable resin composition 11 may be applied so as to fill the visual recognition region of the image display device, and other optical members may be interposed in the first curable resin composition. 11 between the coated substrate.

The first curable resin composition 11 may be a photocurable resin composition or 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 being hardenable at a low temperature and having a high curing rate.

Here, the first curable resin composition 11 may be used for bonding in an uncured state, but it is preferably temporarily cured as described in FIG. 5(a).

Specifically, the coating film of the first curable resin composition 11 after the application is irradiated with the ultraviolet ray 5, and the coating film is provided on the lower side of the coating layer (the transparent substrate side when viewed from the curable resin composition). The hardened portion (not shown) and the hardened portion of the unhardened portion (not shown) present on the upper side of the coating layer (the side opposite to the transparent substrate side) (the atmospheric side when it is carried out in the atmosphere) Floor. 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 finally bonded is insufficient, and if the amount of irradiation is too large, the amount of unhardened component is small, and the liquid crystal display unit 1 and the protective sheet having the light shielding portion are provided. The fit of 2 becomes bad.

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

[Step B]

Next, in the form in which the liquid crystal display unit 1 and the protective sheet 2 are formed with the first curable resin composition 11, as shown in FIG. 5(b), the liquid crystal display unit 1 and the protective sheet having the light shielding portion are provided. 2 fit. The bonding can be carried out in any environment in 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 product of the ultraviolet curable resin having the cured portion and the uncured portion in the first curable resin composition 11 is obtained and bonded, the adhesion can be expected to be improved.

At the time of bonding, the first curable resin composition 11 is dispersed by pressing or the like, and the space is filled with the first curable resin composition 11. When it is carried out under vacuum, when it is exposed to a high pressure environment, the first cured layer 13 having little or no voids is formed.

In the case of bonding in a reduced pressure environment, it is 1 kPa or less, preferably 10 to 300 Pa, and more preferably 15 to 100 Pa. The decompression environment can also be released immediately after lamination. 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 C-II]

Further, as shown in FIG. 5(b), the second curability of the (meth) acrylate (A) and the photopolymerization initiator (B) is contained so that the liquid crystal display unit 1 and the protective sheet are connected to each other. The resin composition 12 is applied to the outer peripheral side surface portion of the sealing body 23 on the protective sheet 2. Here, a specific example of application to the outer peripheral side surface portion of the sealing body 23 is exemplified, but the second curable resin composition 12 may be applied to the outer side surface portion of the sealing body 23 or the casing 26 as long as the result is The liquid crystal display unit 1 can be connected to the protective plate. Further, although the second curable resin composition 12 is applied to the protective sheet 2, other optical members may be interposed between the protective sheet 2 and the second curable resin composition 12.

As a form in which the second curable resin composition is applied to the outer peripheral side surface portion of the casing 26, for example, the liquid crystal display unit 1 in which only the sealing body 23 is not provided in FIG. 2 is applied to the outer peripheral side of the casing 26 The form of the part, etc., but the form or coating form of the liquid crystal display unit 1 is as long as The second curable resin composition is applied to the outer circumferential side surface portion of the casing 26, and is not particularly limited to this embodiment.

As a method of coating, a dripping method etc. are mentioned. Here, the first curable resin composition and the second curable resin composition applied to the surfaces of the liquid crystal display element 1 and the protective sheet 2 may be the same, and different curable resin compositions may be used.

In addition, it is preferable that the coating of the second curable resin composition 12 is formed in a rectangular frame shape along the sealing body 23 or the outer peripheral side surface portion of the casing 26 of the liquid crystal display unit 1. Further, it may be applied in a form in which a broken portion is formed in one of the second cured material layers 14.

The coating thickness of the second curable resin composition 12 may be a thickness sufficient for connecting the liquid crystal display unit and the protective sheet, but is thicker than the thickness of the first curable resin composition 11 to be formed. It is preferable that the thickness of the first curable resin composition 11 formed is 0.01 to 10 mm thick, more preferably 0.1 to 5 mm thick, and still more preferably 0.5 to 3 mm thick.

The storage rigidity modulus at 25 ° C in the curing of the second curable resin composition 12 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, when the liquid crystal display device 1 and the protective plate 2 are connected It is more resistant to deformation due to deformation due to external pressure, so that the influence of the first curable resin layer on the gap thickness can be reduced.

The second curable resin composition 12 may be a photocurable resin composition or a thermosetting resin composition. The second curable resin composition 12 is preferably a photocurable resin composition containing a curable compound and a photopolymerization initiator in terms of being cured at a low temperature and having a high curing rate.

[Step C-III]

Then, as shown in FIG. 5( c ), the second curable resin composition 12 is cured to form the second cured material layer 14 with respect to the optical member obtained by bonding the protective sheet 2 and the liquid crystal display unit 1 .

As a means for hardening, heat or light is mentioned, and it is preferable to harden by irradiating light. The direction of irradiation of the light is not particularly limited, and it is preferable to irradiate from the side surface portion of the obtained image display device or to irradiate from the side of the liquid crystal display unit 1.

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 for hardening by irradiation of ultraviolet to near-ultraviolet light is not limited to a light source as long as it is a light that illuminates ultraviolet to near-ultraviolet light. 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 C-I]

Finally, 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 ultraviolet rays 5 from the side of the protective sheet 2 to form a curable resin composition (coating layer). hardening.

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 for hardening by irradiation of ultraviolet to near-ultraviolet light is not limited to a light source as long as it is a light that illuminates ultraviolet to near-ultraviolet light. 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 image display device shown in Fig. 7 can be obtained.

(Fourth embodiment)

Fig. 6 is a flow chart showing a fourth embodiment of the manufacturing process 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. In addition, the parts other than the change of the first embodiment can be reflected and incorporated in the above-described first embodiment, and a part of the description will be omitted.

[Step A]

First, as shown in Fig. 6 (a), the first curable resin composition 11 containing the following (meth) acrylate (A) and photopolymerization initiator (B) is applied to the light-shielding portion 4 The surface of the protective plate 2 on which the surface of the light shielding portion 4 is formed is formed. Examples of the coating method include slit coating, roll coating, spin coating, and screen printing. In the present embodiment, the first curable resin composition is applied to the protective sheet 2, but it may be applied to the liquid crystal display unit 1 side, or may be applied to the protective sheet 2 and the liquid crystal. The respective components of the display unit 1 are on the substrate.

Here, the first curable resin composition 11 may be applied so as to fill the visual recognition region of the image display device, and other optical members may be interposed between the first curable resin composition 11 and the coated portion. Between the substrates.

The first curable resin composition 11 may be a photocurable resin composition or 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 being hardenable at a low temperature and having a high curing rate.

Here, the first curable resin composition 11 may be used for bonding in an uncured state, but it is preferably temporarily cured as described in FIG. 6(a).

Specifically, the coating film of the first curable resin composition 11 after the application is irradiated with the ultraviolet ray 5, and the coating film is provided on the lower side of the coating layer (the transparent substrate side when viewed from the curable resin composition). The hardened portion (not shown) and the hardened portion of the unhardened portion (not shown) present on the upper side of the coating layer (the side opposite to the transparent substrate side) (the atmospheric side when it is carried out in the atmosphere) Floor. 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 finally bonded is insufficient, and if the amount of irradiation is too large, the amount of unhardened component is small, and the liquid crystal display unit 1 and the protective sheet having the light shielding portion are provided. The fit of 2 becomes bad.

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

[Step B]

Next, in the form in which the liquid crystal display unit 1 and the protective sheet 2 are coated with the first curable resin composition 11, as shown in FIG. 6(b), the liquid crystal display unit 1 and the light-shielding portion are protected. Plate 2 fits. The bonding can be carried out in any environment in 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 product of the ultraviolet curable resin having the cured portion and the uncured portion in the first curable resin composition 11 is obtained and bonded, the adhesion can be expected to be improved.

At the time of bonding, the first curable resin composition 11 is dispersed by pressing or the like, and the space is filled with the first curable resin composition 11. When it is carried out under vacuum, when it is exposed to a high pressure environment, the first cured layer 13 having little or no voids is formed.

In the case of bonding in a reduced pressure environment, it is 1 kPa or less, preferably 10 to 300 Pa, and more preferably 15 to 100 Pa. The decompression environment can also be released immediately after lamination. On the other hand, by When the reduced-pressure environment is maintained 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 C-II]

Further, as shown in FIG. 6(b), the second curability of the (meth) acrylate (A) and the photopolymerization initiator (B) is contained so that the liquid crystal display device 1 and the protective sheet are connected to each other. The resin composition 12 is applied to the sealing body 23 of the liquid crystal display unit 1 so as to surround the outer peripheral side surface portion of the protective sheet. Here, a specific example of application to the outer peripheral side surface portion of the protective sheet 2 is exemplified, but the second curable resin composition 12 may be applied to the outer peripheral side surface portion of the protective sheet 2 as long as the liquid crystal display unit 1 is obtained as a result. It can be connected to the protective plate 2. Further, although the second curable resin composition 12 is applied to the sealing body 23, other optical members may be interposed between the sealing body 23 and the second curable resin composition 12. Further, it may be applied to the casing 26 surrounding the liquid crystal display unit, or another optical member may be interposed between the sealing body 23 or the casing 26 and the second curable resin composition 12.

As a form in which the second curable resin composition is applied to the outer peripheral side surface portion of the protective sheet 2, for example, the liquid crystal display unit 1 in which only the sealing body 23 is not provided in FIG. 6 is provided on the casing 26 to be surrounded and protected. The form of the sheet 2 is applied to the outer peripheral side surface portion, and the form of the liquid crystal display unit 1 or the form to be applied is not particularly limited as long as the second curable resin composition is applied to the outer side surface portion of the protective sheet 2 . Limited to this form.

As a method of coating, a dripping method etc. are mentioned. 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 sealing body 23 or the casing 26 may be the same, and different curable resin compositions may be used.

Further, the coating of the second curable resin composition 12 is preferably performed along the outer periphery of the protective sheet 2 The side portion is formed in a rectangular frame shape. Further, it may be applied in a form in which a broken portion is formed in one of the second cured material layers 14.

The coating thickness of the second curable resin composition 12 may be a thickness sufficient for connecting the liquid crystal display unit and the protective sheet, but is thicker than the thickness of the first curable resin composition 11 to be formed. It is preferable that the thickness of the first curable resin composition 11 formed is 0.01 to 10 mm thick, more preferably 0.1 to 5 mm thick, and still more preferably 0.5 to 3 mm thick.

The storage rigidity modulus at 25 ° C in the curing of the second curable resin composition 12 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, when the liquid crystal display device 1 and the protective plate 2 are connected It is more resistant to deformation due to deformation due to external pressure, so that the influence of the first curable resin layer on the gap thickness can be reduced.

The second curable resin composition 12 may be a photocurable resin composition or a thermosetting resin composition. The second curable resin composition 12 is preferably a photocurable resin composition containing a curable compound and a photopolymerization initiator in terms of being cured at a low temperature and having a high curing rate.

[Step C-I] and [Step C-III]

Then, as shown in FIG. 6(c), the optical member obtained by bonding the protective sheet 2 and the liquid crystal display unit 1 to the protective sheet 2 is irradiated with the ultraviolet ray 5, and the curable resin composition (coating layer) is hardened. . At the same time, the second curable resin composition 12 is cured to form the second cured layer 14 .

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 for hardening by irradiation of ultraviolet to near-ultraviolet light is not limited to a light source as long as it is a light that illuminates ultraviolet to near-ultraviolet light. 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 image display device shown in Fig. 7 can be obtained.

The specific aspect of the optical member which can also be manufactured by the above embodiment is also 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 selected from at least one of the liquid crystal display module, the plasma display module, and the organic EL component, and the obtained optical member is an optical base including the light shielding portion. The appearance of the display component of the material.

(i) an optical substrate is a protective plate having a light shielding portion, and the other optical substrate to which it is attached is a touch panel or a display body assembly having a touch panel, and at least two optical substrates are bonded together. The optical member is a touch panel including a protective plate having a light shielding portion or a display body assembly having the same.

In this case, it is preferable to apply the curable resin composition to the surface of the protective plate having the light-shielding portion or the touch surface of the touch panel or both surfaces thereof in step B. .

(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 body assembly, and the optical member obtained by bonding at least two optical substrates includes a light-shielding portion. The aspect of the display body assembly of the optical substrate.

In this case, it is preferable that in step 1, the optical substrate having the light shielding portion is provided The curable resin composition is applied to either the side of the light shielding portion or the display surface of the display body member or both surfaces thereof.

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 sheet having a light-shielding portion.

The optical substrate having the light-shielding portion is provided with a surface on the side of the light-shielding portion. For example, when the optical substrate having the light-shielding portion is a protective sheet for a display screen having a light-shielding portion, the protective plate is provided with a side of the light-shielding portion. The face. Moreover, when the optical substrate having the light-shielding portion is a touch panel including a protective plate having a light-shielding portion, since the protective plate having the light-shielding portion bonds the surface having the light-shielding portion to the touch surface of the touch panel, the so-called The optical substrate having the light shielding portion is provided with a side surface of the light shielding portion, and means a 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 at any position of the 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 further 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 used in the method of the present invention will be described.

The curable resin composition of the present invention preferably contains a (meth) acrylate (A) and a photopolymerization initiator (B). Further, other components which can be added to the curable resin composition for optical use can be contained as an optional component.

In addition, the term "addable to a curable resin composition for optical use" 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 optical applications.

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, a preferred average of the sheet at a wavelength of 400 to 800 nm is obtained. The light transmittance is preferably at least 90% or more.

With respect to the preferred composition ratio of the curable resin composition, the (meth) acrylate (A) is 25 to 90% by weight based on the total amount of the curable resin composition, and the photopolymerization initiator (B) is 0.2 to 5% by weight, the other components are the remainder.

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

The (meth) acrylate (A) in the curable resin composition of the present invention is not particularly limited, and it is preferred to use (methyl methacrylate) having a polyisoprene skeleton (methyl group). Any one of a group consisting of an acrylate, a (meth) acrylate having a polybutadiene skeleton, and a (meth) acrylate monomer. More preferably, it comprises at least either (i) (meth) acrylate or a (meth) acrylate having a polyisoprene skeleton, and (ii) a (meth) acrylate monomer. The way.

In addition, in this specification, "(meth)acrylate" means either or both of methacrylate and acrylate. The same applies to "(meth)acrylic acid".

The above (meth)acrylic acid amide can be obtained by reacting a polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate.

Examples of the polyhydric alcohol include carbon numbers such as neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol. 1 to 10 alkyl alcohol such as alkyl diol, trimethylolpropane or neopentyl alcohol, tricyclodecane dimethanol, bis-[hydroxymethyl]-cyclohexane, etc. And by using the polyol and polybasic acid (for example, succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, sebacic acid, tetrahydrophthalic anhydride) The polyester polyol obtained by the reaction of the reaction, obtained by the reaction of a polyol with ε-caprolactone a caprolactone, a polycarbonate polyol (for example, a polycarbonate diol obtained by a reaction of 1,6-hexanediol and diphenyl carbonate), a polyether polyol (for example, polyethylene glycol) Polyolefins such as polypropylene glycol, polytetramethylene glycol, ethylene oxide modified bisphenol A, and hydrogenated polybutadiene diol. From the viewpoint of the compatibility with the other component (A), the polyhydric alcohol is preferably a polypropylene glycol or a hydrogenated polybutadiene diol, and particularly preferably a weight in terms of adhesion to a substrate. Polypropylene glycol having an average molecular weight of 2,000 or more and hydrogenated polybutadiene diol. 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 can be used as long as it is a hydrogenated reduction product of a general polybutadiene polyol, and particularly for optical use, it is preferred that the residual double bond is less, as an iodine value, It is especially good for 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, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate or two. Cyclopentyl isocyanate and the like.

Further, the (meth) acrylate having a hydroxyl group is a compound having at least one of a hydroxyl group and a (meth) acrylate in one molecule, and specific examples thereof include 2-hydroxyethyl (meth)acrylate. , propylene glycol mono (meth) acrylate, butane diol mono (meth) acrylate, pentanediol mono (meth) acrylate, hexane diol mono (meth) acrylate, diethylene glycol mono (A) Acrylate, dipropylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, poly Ethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, new Pentyl glycol mono (meth) acrylate, ethoxylated neopentyl glycol mono (meth) acrylate, hydroxy pivalic acid neopentyl glycol mono (meth)acrylate) a mono (meth) acrylate of a glycol; Trimethylolpropane mono(meth)acrylate, ethoxylated trimethylolpropane mono(meth)acrylate, propoxylated trimethylolpropane mono(meth)acrylate, three (2) -hydroxyethyl)isocyanurate mono(meth)acrylate, glycerol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, ethoxylated trimethylolpropane II (Meth) acrylate, propoxylated trimethylolpropane di(meth) acrylate, tris(2-hydroxyethyl)isocyanurate di(meth) acrylate, glycerol di(methyl) a mono- (meth) acrylate of a trihydric alcohol such as acrylate or a di(meth) acrylate, or a part of a hydroxyl group of the alcohol modified by an alkyl group or ε-caprolactone And di(meth)acrylate; Pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, bis (trimethylolpropane) mono (meth) acrylate, neopentyl alcohol di (methyl) Acrylate, dipentaerythritol di(meth)acrylate, bis(trimethylolpropane)di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (Meth)acrylate, bis(trimethylolpropane)tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, bis(trimethylolpropane)tetra(meth)acrylic acid a polyfunctional (meth) acrylate having a tetravalent or higher alcohol such as an ester, dipentaerythritol hexa(meth) acrylate or bis(trimethylolpropane) hexa(meth) acrylate, and having a hydroxyl group, or A polyfunctional (meth) acrylate having a hydroxyl group, such as a part of a hydroxyl group of the alcohol, is modified with an alkyl group or ε-caprolactone.

Among the above (meth) acrylate compounds having at least one or more hydroxyl groups, 2-hydroxyethyl (meth) acrylate is preferred in terms of excellent hardenability and flexibility. ester. In terms of ease of workability, a polymerizable compound may be added during the reaction.

The reaction for obtaining the above (meth) acrylate is carried out, for example, in the following manner. That is, the organic polyisocyanate is mixed with the isocyanate group in an amount of preferably 1.1 to 2.0 equivalents, more preferably 1.1 to 1.5 equivalents per 1 equivalent of the hydroxyl group of the polyol, and is reacted at a reaction temperature. The reaction is carried out at 70 to 90 ° C to synthesize an amine ester oligomer (first reaction). Then, the hydroxy ester (meth) acrylate compound is mixed with a hydroxyl group of preferably 1 to 1.5 equivalents per equivalent of the isocyanate group of the amine ester oligomer, and the reaction is carried out at 70 to 90 ° C. The target (meth) acrylate (second reaction) can be obtained.

The first reaction can be carried out without a solvent, but in order to improve the workability of the product, the workability is preferably carried out in a solvent having no alcoholic hydroxyl group or in a polymerizable compound. Specific examples of the solvent can be carried out in the following separate or mixed organic solvents: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, benzene, toluene, xylene, and tetramethylbenzene. a glycol ether such as an aromatic hydrocarbon, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether or triethylene glycol diethyl ether, Ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol Esters such as diethyl ether acetate, dipropylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, and cyclic esters such as γ-butyrolactone Petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, solvent petroleum brain, etc.

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. 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 pyridines, pyrrole, triethylamine, diethylamine, dibutylamine, amines such as 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 tin octylate. , Lewis acid octyl tin citrate, dibutyl tin dilaurate, octyl tin diacetate and other Lewis 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 (polyol + hydroxyl group-containing (meth) acrylate) and polyisocyanate compound.

The above (meth)acrylic acid amide can be obtained by reacting (second reaction) a (meth) acrylate compound having at least one hydroxyl group with a residual isocyanate group after the first reaction.

The second reaction is added in an equivalent relationship in which the isocyanate group of the intermediate obtained after the first reaction disappears. Specifically, it is preferred to set the OH group of the (meth) acrylate compound (C) having at least one hydroxyl group to 1.0 to 3.0 with respect to 1.0 mol of the NCO group of the intermediate obtained after the first reaction. The mol is further preferably set to 1.0 to 2.0 mol.

The second reaction may be carried out in the absence of a solvent. However, in order to improve the workability of the product, it is preferred to carry out the above-mentioned solvent and/or polymerizable compound. 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. The above catalyst may also be added in order to shorten the reaction time.

It is common to add a polymerization inhibitor such as 4-methoxyphenol to the acrylate compound used as a raw material, but it is also possible to re-add a polymerization inhibitor during the reaction. Examples of such polymerization inhibitors 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, phenolthiophene Wait. 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 (meth) acrylate is preferably from 7,000 to 25,000, more preferably from 10,000 to 20,000. When the weight average molecular weight is less than 7,000, the shrinkage tends to be large, and when 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 (meth)acrylic acid amide can be used singly or in combination of two or more kinds in any ratio. The weight ratio of the (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 has a (meth) acrylonitrile group at the terminal or side chain of the polyisoprene molecule. The (meth) acrylate having a polyisoprene skeleton can be obtained by "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 has a (meth) acrylonitrile group at the terminal or side chain of the polybutadiene molecule. 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-S30 (made by Osaka Organic Chemical Industry Co., Ltd.)" was acquired. 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 the molecule. One (meth) acrylonitrile-based (meth) acrylate.

Here, the (meth) acrylate monomer means (meth) acrylate, the following epoxy (meth) acrylate, and the above (meth) acrylate having a polyisoprene skeleton. Other than (meth) acrylate.

Examples of the (meth) acrylate having one (meth) acrylonitrile group in the molecule include isobutyl (meth)acrylate, isoamyl (meth)acrylate, and (methyl). Lauryl acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cetyl (meth) acrylate, isomyristyl (meth) acrylate And alkyl (meth) acrylate having a carbon number of 5 to 20 such as tridecyl (meth) acrylate; benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, propylene ruthenium porphyrin , (meth)acrylic acid phenyl glycidyl ester, tricyclodecane (meth) acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acrylate Oxime ester, dicyclopentanyl (meth)acrylate, 1-adamatyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantane acrylate a base ester, 1-adamantyl methacrylate, propylene oxide modified (meth) phenyl methacrylate, dicyclopentadienyl (meth) acrylate, etc. having a cyclic skeleton ( Methyl) propylene Ethyl ester of (meth)acrylic acid having 2 to 5 carbon atoms having a hydroxyl group; 2-ethoxypropyl (meth)acrylate; 4-hydroxybutyl (meth)acrylate; Polyalkylene glycol (meth) acrylate such as methyl acrylate, polypropylene glycol (meth) acrylate, polypropylene oxide modified (meth) phenyl methacrylate, modified with ethylene oxide Phenoxylated phosphoric acid (meth) acrylate, ethylene oxide modified butoxylated phosphoric acid (meth) acrylate, and ethylene oxide modified octoxylated phosphoric acid (meth) acrylate. Among them, preferred are alkyl (meth) acrylates having a carbon number of 10 to 20, 2-ethylhexyl carbitol acrylate, propylene ruthenium porphyrin, 4-hydroxybutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isostearyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, modified by polypropylene oxide The mercaptophenyl (meth)acrylate is preferably an alkyl (meth)acrylate or a dicyclopentene (meth)acrylate having a carbon number of 10 to 20, particularly from the viewpoint of flexibility of the resin. Ethyloxyethyl ester, polypropylene oxide modified decyl phenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate.

On the other hand, from the viewpoint of improving the adhesion to the glass, it is preferably an alkyl (meth)acrylate having a hydroxyl group of 1 to 5, an acryloquinone, or a propylene fluorene. Porphyrin.

In the composition of the present invention, a (meth) acrylate other than the (meth) acrylate having one (meth) acrylonitrile group may be contained in the range which does not impair the characteristics of the present invention. For example, tricyclodecane dimethylol 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 hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate and ethylene oxide modified di(meth)acrylate, trimethylolpropane tri(methyl) Trimethylol C2~C10 alkane tri(meth)acrylate such as acrylate or trimethylol octane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylate, a trimethylol C2~C10 alkane polyalkoxy three such as trimethylolpropane polypropoxy tri(meth)acrylate or trimethylolpropane polyethoxypolypropoxy tri(meth)acrylate Methyl) acrylate, tris[(methyl)acryloxyethyl]isocyanurate, pentaerythritol tri(meth)acrylate, ethylene oxide modified trimethylolpropane III Ethylene oxide such as methyl acrylate, propylene oxide modified trimethylolpropane tri(meth) acrylate, modified trimethylolpropane tri(meth) acrylate, neopentyl alcohol polyethoxylate Tetra(meth)acrylate, new Tetraol polypropoxy tetra(meth)acrylate, neopentyltetrakis(meth)acrylate, bis(trimethylolpropane)tetra(meth)acrylate, dipentaerythritol tetra(methyl) Acrylate, 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 monofunctional or bifunctional (meth) acrylate is preferably used.

In the curable resin composition of the present invention, the (meth) acrylate monomer component may be used singly or in combination of two or more kinds in any ratio. The weight ratio of the (meth) acrylate monomer to 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 be large.

The curable resin composition comprises (i) at least one of (meth) acrylate or a (meth) acrylate having a polyisoprene skeleton, and (ii) (meth) acrylate In the aspect of the 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.

In the curable resin composition of the present invention, epoxy (meth) acrylate can be used without departing from the characteristics of the present invention. The epoxy (meth) acrylate has a function of improving hardenability or increasing the hardness or hardening speed of the cured product. Further, the epoxy (meth) acrylate can be used as long as it is obtained by reacting a glycidyl ether type epoxy compound with (meth)acrylic acid, and is preferably used for obtaining an epoxy ( The glycidyl ether type epoxy compound of a methyl acrylate may, for example, be a diglycidyl ether of bisphenol A or an alkylene oxide adduct thereof, or a diglycidyl ether of bisphenol F or an alkylene oxide adduct thereof. , diglycidyl ether of hydrogenated bisphenol A or its alkylene oxide adduct, diglycidyl ether of hydrogenated bisphenol F or its alkylene oxide adduct, ethylene glycol condensate Glycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, polypropylene glycol diglycidyl Ether, etc.

The epoxy (meth) acrylate can be obtained by reacting the glycidyl ether type epoxy compound with (meth)acrylic acid under the conditions described below.

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

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

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

The curable resin composition of the present invention preferably contains a (meth) acrylate selected from the above (meth) acrylate, the above polyisoprene skeleton, and the above (meth) acrylate. At least one of the groups consisting of the bodies is (meth) acrylate (A). Above The content ratio of the (meth) acrylate is preferably from 20 to 80% by weight, more preferably from 30 to 70% by weight, and the content of the (meth) acrylate having the polyisoprene skeleton is preferably 20 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 80% by weight, more preferably from 30 to 70% by weight.

In the curable resin composition of the present invention, the (meth) acrylate (A) is further preferably a case where the (meth)acrylic acid amide or the polyisoprene skeleton (meth) is contained. The acrylate has a content ratio of 20 to 80% by weight, preferably 30 to 70% by weight, and contains a (meth) acrylate monomer in a ratio of 5 to 70% by weight, preferably 10 to 50% by weight. The % is further preferred.

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. - Trimethyl benzhydryl phenyl ethoxy phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzoate Indenyl)-2,4,4-trimethyl-pentylphosphine 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- Lolinylpropan-1-one (Irgacure 907; manufactured by BASF), oxy-phenyl-acetic acid 2-[2-o-oxy-2-phenyl-ethyloxy-ethoxy]-ethyl ester and oxygen Mixture of 2-phenyl-2-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester (Irgacure 754; manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)-butan-1-one, 2-chloro 9-oxosulfur 2,4-dimethyl 9-oxosulfur 2,4-diisopropyl 9-oxosulfur Isopropyl 9-oxosulfur Wait.

In the present invention, with respect to the above photopolymerization initiator (B), it is preferred that the Mohr absorbance at 302 nm or 313 nm measured in acetonitrile or methanol is 300 ml/(g.cm) or more and 365 nm. The photopolymerization initiator having a Mohr absorption coefficient of 100 ml/(g.cm) or less. By using such a photopolymerization initiator, it is possible to contribute to the improvement of the bonding strength. By the molar absorption coefficient at 302 nm or 313 nm being 300 ml/(g.cm) or more, hardening at the time of hardening in the step C-I or the step C-III becomes more sufficient. 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 at the time of hardening in the step B, and the adhesion can be further improved.

As such a photopolymerization initiator (B), for example, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propane-1- Ketone (Darocure 1173; manufactured by BASF), 1-[4-(2-hydroxyethoxy)-phenyl-]-2-hydroxy-2-methyl-1-propan-1-one (Irgacure 2959; manufactured by BASF ), methyl phenylglyoxylate (Darocure MBF; manufactured by BASF), and the like.

In the curable resin composition of the present invention, the photopolymerization initiator (B) may be used singly or in combination of two or more kinds in 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 uncured portion cannot be formed, or the transparency of the cured resin layer becomes Poor situation.

The curable resin composition of the present invention contains the above (meth) acrylate (A) and the above photopolymerization initiator (B), and may further contain the following photopolymerization initiation aid, and has the following The compound of the structure represented by the formula (1), the following softening component, and the following additives are used as other components. The content ratio of the other components to the total amount of the curable resin composition of the present invention is the total amount obtained by subtracting the total amount of the above (meth) acrylate (A) and the photopolymerization initiator (B) section. 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 may be used in combination with the above photopolymerization initiator. Examples of the amines and the like which can be used include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate or isoamyl p-dimethylaminobenzoate. Wait. 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 a compound having a structure represented by the formula (1).

(wherein, n represents an integer of 0 to 40, and m represents an integer of 10 to 50. R ¹ and R ² may be the same or different. R ¹ and R ² are 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, from Unisafe (trade name) PKA-5017 (polyethylene glycol-polypropylene glycol allyl butyl ether) manufactured by Nippon Oil Co., Ltd., or the like.

The weight ratio in the curable resin composition when the compound having the structure represented by the formula (1) is used 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 may 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 general formula (1), and a phthalic acid ester. Phosphates, glycol esters, citrate esters, aliphatic dibasic acid esters, fatty acid esters, epoxy plasticizers, castor oils, terpene hydrogenated resins, and the like. Examples of the oligomer or the polymer include an oligomer or polymer having a polyisoprene skeleton, a polybutadiene skeleton, a polybutene skeleton or a xylene skeleton, and an ester thereof, and preferably Polymers or oligomers having a polybutadiene skeleton and esterified products thereof are used as appropriate. Specific examples of the polymer or oligomer having a polybutadiene skeleton and esterified products thereof include butadiene homopolymer, epoxy modified polybutadiene, and butadiene-styrene random copolymer. A modified polybutadiene of maleic acid and a liquid polybutadiene or a liquid hydrogenated polybutadiene modified with a terminal hydroxyl group. Further, in the softening component, each of the above-mentioned 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, an organic solvent, a decane coupling agent, a polymerization inhibitor, a leveling agent, an antistatic agent, a surface lubricant, a fluorescent whitening agent, and a light stabilizer may be added as needed. Additives such as a hindered amine compound or the like, and a filler.

Specific examples of the antioxidant include BHT and 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-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-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 3-(3,5-di-t-butyl-4 -hydroxyphenyl)octadecyl propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamate) (N,N'-hexamethylenebis ( 3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide)), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl) Benzo, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, octylated diphenylamine, 2,4-bis[(octylthio) A Base-O-cresol, 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid isooctyl ester], 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, 3-glycidoxypropylmethyldimethoxydecane, and 3-glycidoxypropyl group. Dimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyldimethoxydecane, γ-Mercaptopropyltrimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-mercaptopropyl Trimethoxydecane, vinyltrimethoxydecane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxydecane hydrochloride, 3-methylpropenyloxy a decane coupling agent such as propyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane or 3-chloropropyltrimethoxydecane; isopropyl (N-ethylaminoethylamino) Titanate, isopropyl triisostearate titanate, bis(dioctylpyridiniumoxy)titanium glycolate, tetraisopropylbis(dioctylphosphonium oxy) titanate a titanium-based coupling agent such as neoalkoxytris(p-N-(β-aminoethyl)aminophenyl) titanate; Zirconium pyruvate, zirconium methacrylate, zirconium propionate, neoalkoxy zirconate, neoalkoxy trisynyl zirconate, neoalkoxytris(dodecacarbyl)benzenesulfonate Zirconate, neoalkoxytris(ethylideneethylamine)zirconate, neoalkoxytris(m-aminophenyl)zirconate, carbonic acid A zirconium or aluminum coupling agent such as ammonium zirconium, acetonitrile pyruvate, aluminum methacrylate or aluminum propionate.

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

Specific examples of the light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidyl alcohol and 2,2,6,6-tetramethyl-4-piperidinyl. Alcohol, 1,2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate (Manufactured by ADEKA (LA), LA-82), four (1, 2, 2, 6, 6) -pentamethyl-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 a mixed ester of bis(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, bismuth Bis(1,2,2,6,6-pentamethyl-4-piperidinyl), 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-hydroxyl) Phenyl)propenyloxy]-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate , bis(1,2,2,6,6-pentamethyl-4-piperidinyl) malonate [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl) ]methyl]butyl ester, bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl) sebacate, 1,1-dimethylethylhydrogen Reaction product of oxide and octane, N, N', N", N'''-tetra-(4,6-bis-(butyl-(N-methyl-2,2,6,6-four) Methylpiperidin-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-tetramethyl) Polycondensate of phenyl-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-lauryloxycarbonyl)ethyl-7-oxa-3,20-diazaspiro[5,1,11,2]octadec-21-one , β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester/tetradecyl ester, N-ethylindolyl-3-ten Dialkyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxygen Hetero-3,20-diazabispiro[5,1,11,2]icosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20- Diazabicyclo-[5,1,11,2]-docosane-20-propane acid lauryl/tetradecyl ester, propane dioic acid, [(4- Methoxyphenyl)-methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl), 2,2,6,6-tetramethyl-4- Higher fatty acid ester of piperidinol, 1,3-phenyldicarboxyguanamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl) and other hindered amines, octane Benzophenone-based compound such as benzophenone, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol , 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimido-methyl )-5-methylphenyl]benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl -3,5-di-t-amylphenyl)benzotriazole, 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propane a reaction product of methyl ester and polyethylene glycol, a benzotriazole compound such as 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2,4 a benzoate such as di-tert-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2-(4,6-diphenyl-1,3,5- three -2-yl)-5-[(hexyl)oxy]phenol, etc. A compound or the like is particularly preferably a hindered amine compound.

Specific examples of the filler include, for example, crystalline cerium oxide, molten cerium oxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, cerium carbide, cerium nitride, boron nitride, zirconia, magnesium. A powder such as fosterite, talc, spinel, titanium oxide or talc, or a bead formed by spheroidizing the same.

The weight ratio of various additives in the photocurable transparent adhesive composition It is preferably 0.01 to 3% by weight, more preferably 0.01 to 1% by weight, still more preferably 0.02 to 0.5% by weight.

The curable resin composition of the present invention can be obtained by mixing and dissolving each of the above components at a normal temperature to 80 ° C, and optionally removing the inclusions by filtration or the like. The resin composition for subsequent use of the present invention preferably has a viscosity of 25 to 15000 mPa at 25 ° C in consideration of coatability. The range of s is appropriately adjusted to the blending ratio of the ingredients.

The cured shrinkage ratio of the cured product of the curable resin composition of the present invention is preferably 3.0% or less, and particularly preferably 2.0% or less. Thereby, when the curable resin composition is cured, the internal stress accumulated in the cured resin can be lowered, and strain at the interface between the substrate and the layer composed of the cured product of the curable resin composition can be effectively prevented.

In the case where the substrate such as glass is thin, since the warpage at the time of curing is large when the curing shrinkage ratio is large, the display performance is greatly adversely affected. It is also preferred that the hardening shrinkage rate is small.

The light transmittance of the cured product of the curable resin composition of the present invention at 400 nm to 800 nm is preferably 90% or more. When the light transmittance is less than 90%, light is not easily transmitted, and the visibility is lowered when used in a display device.

Further, when the light transmittance of the cured product at 400 to 450 nm is high, the improvement of the visibility can be further expected. Therefore, the light transmittance at 400 to 450 nm is preferably 90% or more.

The first curable resin composition 11 or the second curable resin composition 12 of the present invention preferably contains (I) (meth)acrylic acid amide or (meth)acrylic acid having a polyisoprene skeleton. An ester, a (II) (meth) acrylate monomer, and a photopolymerization initiator.

In addition, it is preferable to use a resin composition containing the components (I) and (II) as the first curable resin composition 11 and the second curable resin composition 12 to obtain an image display device.

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 terpene-based resin (especially a solid terpene-based resin) is preferably used.

Regarding the curable resin composition containing the (meth) acrylate (A) and the photopolymerization initiator (B) used in the production method of the present invention, several preferred aspects are described below. The "% by weight" in 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 (6), wherein the (meth) acrylate (A) is selected from the group consisting of (meth)acrylic acid amide and a polyisoprene skeleton (methyl). At least one (meth) acrylate of the group consisting of acrylate and (meth) acrylate monomers.

(A2)

The curable resin composition according to the above (6) or (A1), wherein the (meth) acrylate (A) contains (i) (meth) acrylate or has polyisoprene At least one of a (meth) acrylate of a diene skeleton, and (ii) a (meth) acrylate monomer

Both.

(A3)

The curable resin composition according to the above (6) or (A1), which comprises the (meth) acrylate (A), (i) an amine (meth) acrylate obtained by a reaction of a poly C2-C4 alkylene glycol, a diisocyanate and a hydroxy C2-C4 alkyl (meth) acrylate, and (ii) (methyl) Acrylate monomer

Both.

(A4)

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

(A5)

A curable resin composition containing a fluorenylphosphine oxide compound as a photopolymerization initiator (B) in a curable resin composition containing a (meth) acrylate (A) and a photopolymerization initiator (B), Or a curable resin composition as described in any one of the above (A1) to (A4), which contains a fluorenylphosphine oxide compound 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, 2,4,6- Trimethyl benzhydryl phenyl ethoxy phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide and bis(2,6-dimethoxybenzamide) At least one compound of the group consisting of -2,4,4-trimethyl-pentylphosphine oxide.

(A7)

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

(A8)

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

(A9)

The curable resin composition as described in the above (A8), wherein the (meth) acrylate (A) contains 20 to 80% by weight of (i) (meth) acrylate or polyisoprene. At least one of an olefinic (meth) acrylate and 5 to 70% by weight of (ii) a (meth) acrylate monomer, 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)

A curable resin composition containing a (meth) acrylate (A) and a photopolymerization initiator (B), or a curable resin composition as described in any one of the above (A1) to (A10), The hardening shrinkage of the cured product is 3% or less.

(A12)

A curable resin composition containing the (meth) acrylate (A) and the photopolymerization initiator (B), or the curable resin composition as described in any one of the above (A1) to (A11), The sheet of the cured product of the curable resin composition having a thickness of 200 μm has an average light transmittance of at least 90% in a wavelength region of 400 to 450 nm, and an average light transmittance of at least 90 in a wavelength region 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 C-III].

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, at least one of the plurality of optical substrates used is preferably an optical substrate having a light shielding portion.

The position of the light shielding portion on the optical substrate having the light shielding portion is not particularly limited. In a preferred embodiment, a strip-shaped light-blocking portion having a width of 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 applying a coating or printing.

As the material of the optical substrate used in the present invention, various materials can be used. Specific examples thereof include resins such as PET, PC, PMMA, a combination of PC and PMMA, glass, COC, COP, and plastic (acrylic resin). As the optical substrate used in the present invention, for example, a transparent plate or a sheet, a sheet obtained by laminating a film or a sheet such as a plurality of polarizing plates, a transparent plate, an unlaminated sheet or a transparent plate, and Transparent plate made of inorganic glass (inorganic glass plate and processed products thereof, such as lens, enamel, ITO glass).

Further, the optical substrate used in the present invention includes a touch panel (touch panel input sensor) or a display panel composed of a plurality of functional boards or sheets in addition to the polarizing plate or the like. Body (hereinafter also referred to as "functional laminate").

Examples of the sheet which can be used as the optical substrate used in the present invention include an icon sheet, a decorative sheet, and a protective sheet. As an optical member that can be used in the present invention The board (transparent board) of a manufacturing method is a decorative board and a protection board. As the material of the sheet or the sheet, it can be applied as a material of the transparent sheet.

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 substrate such as a transparent plate or a sheet is not particularly limited, and is usually from about 5 μm to about 5 cm, preferably from about 10 μm to about 10 mm, more preferably from about 50 μm to about 3 mm.

A preferred optical member obtained by the production method of the present invention is a plate-like or sheet-like transparent optical substrate having a light-shielding portion and a functional laminated body by using a cured product of the curable resin composition of the present invention. Combined optical components.

Further, in the manufacturing method of the present invention, by using a display module such as a liquid crystal display device as one of optical substrates and using an optical functional material as another optical substrate, a display body assembly with an optical functional material can be manufactured (hereinafter Also known as the display panel). Examples of the display module 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 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 using as an adhesive material for bonding an optical substrate, in order to improve the visibility, the refractive index of the cured product is further improved from 1.45 to 1.55, 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 diffuse reflection of light can be suppressed to reduce the light loss.

A preferred state of the optical member obtained by the manufacturing method of the present invention The following (i) to (vii) can be cited.

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

(ii) The optical member according to the above (i), wherein the optical substrate having the light-shielding portion is selected from a transparent glass substrate having a light-shielding portion, a transparent resin substrate having a light-shielding portion, and a light-shielding and transparent layer. An optical substrate in a group consisting of glass substrates of electrodes, and the functional laminate is a display body component 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 (or a touch panel input sensor) for bonding a plate-like or sheet-shaped optical substrate having a light-shielding portion to a touch using the cured product of the curable resin composition of the present invention The surface of the touch surface of the panel is formed.

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

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

The optical member, the touch panel, or the display panel of any one of the above-mentioned (A1) to (vi), wherein the curable resin composition is any one of the above (A1) to (A12). The curable resin composition described in the above.

By using the curable resin composition of the present invention and bonding a plurality of optical substrates selected from the above respective optical substrates by the methods described in the above steps A to C-III, the optical of the present invention can be obtained. member. In the above step B, the curable resin composition may be applied only to One of the opposing surfaces of the two optical substrates to which the cured optical layer is bonded may be applied to both surfaces.

For example, when the functional laminated body is the optical member described in the above (ii) of the touch panel or the display body assembly, in the step A, the resin composition can be applied only to the protection having the light shielding portion. Any of the surfaces of the board, preferably applied to 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 body assembly may be applied to both of them.

Further, in the case of the optical member of the above (vi) in which the protective sheet or the touch panel for protecting the display screen of the display unit assembly is bonded to the display unit assembly, the resin may be composed in the step A. The object may be applied to only one of the surface of the protective plate on which the light shielding portion is provided, the substrate surface opposite to the touch surface of the touch panel, and the display surface of the display body assembly.

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

[Examples]

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)

16 parts by weight of a reagent of acrylamide (hydrogenated polybutadiene diol (molecular weight 3000), isophorone diisocyanate, 2-hydroxyethyl acrylate (mole ratio 1: 1.2:2)) GI-2000 (two-terminal hydroxyhydrogenated polybutadiene, manufactured by Japan Soda Co., Ltd.) 18 parts by weight, Nippon Polybutene LV-100 (liquid polybutene, JX Nikko Nisseki Energy (share)) 13 parts, Clearon (trade name) M105 (aromatically modified hydrogenated terpene resin, manufactured by Yasuhara 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 parts, Speedcure (trade name) TPO (2,4,6-trimethylbenzhydryldiphenylphosphine oxide) 0.5 parts by weight of Irgacure (trade name) 184D (manufactured by BASF Corporation) was prepared by heating and mixing. The viscosity at 25 ° C is 4000 mPa. s.

(Preparation of the first curable resin composition B)

9 parts by weight of a reaction product of acrylamide (hydrogenated polybutadiene diol (molecular weight 3000), isophorone diisocyanate, 2-hydroxyethyl acrylate (mole ratio 1: 1.2:2)) GI-2000 (two-terminal hydroxyhydrogenated polybutadiene, manufactured by Nippon Soda Co., Ltd.) 55 parts by weight, Nippon Polybutene LV-100 (liquid polybutene, manufactured by JX Nikko Nisseki Energy Co., Ltd.) 13 parts, 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 parts were prepared by heating and mixing. The viscosity at 25 ° C is 3500 mPa. s.

(Preparation of the first curable resin composition C)

80 parts by weight of a reagent of acrylamide (hydrogenated polybutadiene diol (molecular weight 3000), isophorone diisocyanate, 2-hydroxyethyl acrylate (mole ratio 1:1.5:2)) , IBXA (isodecyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Speedcure (trade name) TPO (2,4,6-trimethylbenzhydryldiphenylphosphine oxide, manufactured by LAMBSON) ) 1 part by weight, Irgacure (trade name) 184D (manufactured by BASF Corporation), 3 parts were prepared by heating and mixing. 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 (23 parts of Acetone Chemical Co., Ltd.) 0.5 parts by weight of TPO (2,4,6-trimethylbenzimidyldiphenylphosphine oxide, manufactured by LAMBSON Co., Ltd.) and Irgacure (trade name) 184D (manufactured by BASF Corporation) were mixed and prepared 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), the first curable resin composition A is applied to the protective layer having the light-shielding portion 4 so as to have a thickness of 200 μm so that the first curable resin composition A is laminated on the light-shielding portion. The surface of the plate 2 is formed with the surface of the light shielding portion 4. Thereafter, an electrodeless ultraviolet lamp (D valve manufactured by Heraeus Noblelight Fusion UV Co., Ltd.) was used, and ultraviolet rays 5 having a cumulative light amount of 100 mJ/cm ^{2 were} irradiated from the atmosphere side to perform temporary hardening. Next, in the form in which the liquid crystal display unit 1 and the protective sheet 2 are formed with the first curable resin composition A, as shown in FIG. 1(b), the liquid crystal display unit 1 and the light-shielding portion are protected. Plate 2 fits. Then, an electrodeless ultraviolet lamp (manufactured by Heraeus Noblelight Fusion UV Co., Ltd., D valve) was used to irradiate the ultraviolet rays 5 having a cumulative light amount of 2000 mJ/cm ² from the side of the protective plate, thereby performing main hardening.

Then, as shown in FIG. 1(c), the second curable resin composition a is applied to the protective sheet 2 to the outer peripheral side surface portion of the sealing body 23 so as to connect the liquid crystal display unit 1 and the protective sheet. . Then, as shown in Fig. 1 (d), an electrodeless ultraviolet lamp (manufactured by Heraeus Noblelight Fusion UV Co., Ltd., D valve) was used for the second curable resin composition a, and the cumulative light amount was 2000 mJ/cm ² from the protective plate side. The ultraviolet ray 5 is thereby hardened to form the second cured layer 14, whereby the optical member shown in Fig. 7 is produced.

Example 2

The optically cured material layer was cured in the same manner except that the first curable resin composition applied to the protective sheet was changed to B, and the optical member shown in Fig. 7 was produced.

Example 3

The optically cured material layer was cured in the same manner except that the first curable resin composition applied to the protective sheet was changed to C, and the optical member shown in Fig. 7 was produced.

Example 4

As shown in Fig. 4 (a), the first curable resin composition A is applied to the protective layer having the light-shielding portion 4 at a thickness of 200 μm so that the first curable resin composition A is laminated on the light-shielding portion. The surface of the plate 2 is formed with the surface of the light shielding portion 4. Thereafter, an electrodeless ultraviolet lamp (D valve manufactured by Heraeus Noblelight Fusion UV Co., Ltd.) was used, and ultraviolet rays 5 having a cumulative light amount of 100 mJ/cm ^{2 were} irradiated from the atmosphere side to perform temporary hardening. Next, in the form in which the liquid crystal display unit 1 and the protective sheet 2 are formed with the first curable resin composition A, as shown in FIG. 4(b), the liquid crystal display unit 1 and the light-shielding portion are protected. Plate 2 fits. Thereafter, the second curable resin composition a is applied to the protective sheet 2 to the outer peripheral side surface portion of the sealing body 23 so as to connect the liquid crystal display unit 1 to the protective sheet. Then, as shown in FIG. 4(c), an electrodeless ultraviolet lamp (manufactured by Heraeus Noblelight Fusion UV Co., Ltd., D valve) is used for the first curable resin composition A and the second curable resin composition a. The optical member shown in FIG. 7 was produced by irradiating the ultraviolet light 5 having an integrated light amount of 2000 mJ/cm ^{2 on} the plate side to form the second cured material layer 14 by curing.

Example 5

As shown in Fig. 5 (a), the first curable resin composition A is applied to the light-shielding portion 4 with a thickness of 200 μm so that the first curable resin composition A is laminated on the light-shielding portion. The surface of the plate 2 is formed with the surface of the light shielding portion 4. Thereafter, an electrodeless ultraviolet lamp (D valve manufactured by Heraeus Noblelight Fusion UV Co., Ltd.) was used, and ultraviolet rays 5 having a cumulative light amount of 100 mJ/cm ^{2 were} irradiated from the atmosphere side to perform temporary hardening. Next, in the form in which the liquid crystal display unit 1 and the protective sheet 2 are formed with the first curable resin composition A, as shown in FIG. 5(b), the liquid crystal display unit 1 and the light-shielding portion are protected. Plate 2 fits. Thereafter, the second curable resin composition a is applied to the protective sheet 2 to the outer peripheral side surface portion of the sealing body 23 so as to connect the liquid crystal display unit 1 to the protective sheet. In the second curable resin composition a, an electrodeless ultraviolet lamp (D valve manufactured by Heraeus Noblelight Fusion UV Co., Ltd.) was used, and ultraviolet rays 5 having an integrated light amount of 2000 mJ/cm ^{2 were} irradiated from the protective plate side to be cured. The second cured layer 14 is. As shown in Fig. 5 (d), an electrodeless ultraviolet lamp (manufactured by Heraeus Noblelight Fusion UV Co., Ltd., D valve) was used for the first curable resin composition A, and ultraviolet rays having an integrated light amount of 2000 mJ/cm ^{2 were} irradiated from the protective plate side. 5, whereby the second cured layer 14 is formed by hardening, whereby the optical member shown in Fig. 7 is produced.

Comparative example 1

The first curable resin composition A is applied to the surface of the protective sheet 2 having the light shielding portion 4 and having the light shielding portion 4 so as to have a thickness of 200 μm so that the first curable resin composition A is laminated on the light shielding portion. The surface. Thereafter, an electrodeless ultraviolet lamp (D valve manufactured by Heraeus Noblelight Fusion UV Co., Ltd.) was used, and ultraviolet rays 5 having a cumulative light amount of 100 mJ/cm ^{2 were} irradiated from the atmosphere side to perform temporary hardening. Next, the second curable resin composition a is applied to the polarizing plate in the liquid crystal display unit 1. Next, in the form in which the liquid crystal display unit 1 and the protective sheet 2 are formed with the first curable resin composition A, as shown in FIG. 1(b), the liquid crystal display unit 1 and the light-shielding portion are protected. Plate 2 fits. Then, an electrodeless ultraviolet lamp (manufactured by Heraeus Noblelight Fusion UV Co., Ltd., D valve) was used to irradiate the ultraviolet light 5 having a cumulative light amount of 2000 mJ/cm ² from the protective plate side, thereby performing the first curable resin composition A and the second curability. The resin composition a is formally hardened to produce the optical member shown in Fig. 7.

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

(hardenability)

Two glass slides each having a thickness of 1 mm were prepared, and one of the cured glass compositions obtained was applied to a film thickness of 200 μm. Another slide was attached to its coated side. The resin composition was irradiated with ultraviolet rays having a cumulative light amount of 2000 mJ/cm ² by means of a high-pressure mercury lamp (80 W/cm, no ozone) through a glass. The hardened state of the hardened material was confirmed, and as a result, it was completely hardened.

(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 cured release resin composition was applied to one of the release agent-coated surfaces to have a film thickness of 200 μm. Thereafter, the 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 glass slides were peeled off to prepare a cured product for measuring a specific gravity of the film. The specific gravity (DS) of the cured product was measured in accordance with JIS K7112B. Further, the liquid specific gravity (DL) of the resin composition was measured at 25 °C. The hardening shrinkage ratio was calculated from the measurement results of DS and DL according to the following formula, and the result was less than 2.5%.

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 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 resin composition was cured to prepare a sample for adhesion evaluation. It was allowed to stand at 85 ° C, 85% RH for 250 hours. For the sample for evaluation, the slide of the slide glass or the acrylic plate from the cured resin was visually confirmed, and as a result, it was not peeled off.

(softness)

The curable resin composition obtained was sufficiently cured, and the hardness was evaluated by measuring the hardness of the durometer E using a durometer (type E) according to the method of JIS K7215. More specifically, the curable resin composition was cast 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 using a durometer (type E). As a result, the measured value was less than 10, and the flexibility was excellent.

(transparency)

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

The above test results are summarized in the table below.

Regarding the rigidity modulus of the first curable composition C, since the difference between the values of the storage rigidity modulus and the loss elastic modulus becomes large, the device can be measured outside the range.

The present invention has been described in detail with reference to the specific embodiments thereof. It is understood that various changes and modifications may be made without departing from the spirit and scope of the invention.

Furthermore, this application is based on a Japanese patent application filed on January 19, 2015. (2015-007810), which is incorporated herein by reference in its entirety. Again, all references cited herein are incorporated as a whole.

[Industrial availability]

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

1‧‧‧LCD components

3‧‧‧Transparent substrate

4‧‧‧Lighting Department

5‧‧‧ UV

11‧‧‧1st hardening resin composition

12‧‧‧2nd hardening resin composition

Claims (12)

A method of manufacturing an image display device, comprising: a liquid crystal display unit; a liquid crystal display unit; a polarizing plate disposed on the liquid crystal display unit; and a sealing body surrounding the polarizing plate and covering the liquid crystal display unit Or a housing for fixing the liquid crystal display unit by surrounding a peripheral wall portion of the liquid crystal display unit, the manufacturing method comprising the following steps (A) and (B): (A) a coating step, the liquid crystal display unit and the above At least one of the protective sheets is coated with a first curable resin composition having fluidity when not cured, and (B) a bonding step is performed by interposing the liquid crystal display unit and the protective sheet from the first curable resin composition. After the step (B), the step (CI) to (C-III) is followed by the step of: (CI) the first curable resin composition curing step, and the first curable resin composition (C-II) applying a coating step of applying a second curable resin composition to the liquid crystal display unit and the protective sheet, and bonding the liquid crystal display unit and the protective sheet to the outside of the protective sheet a step of applying a second curable resin composition to the side surface portion, an outer peripheral side surface portion of the sealing body covering the liquid crystal display unit, or an outer peripheral side surface portion of the casing for fixing the liquid crystal display unit, and (C-III) providing a cured layer; After the step (C-II), the second curable resin composition is cured, and the outer peripheral side surface portion of the protective sheet is covered with the outer peripheral side surface portion of the sealing body covering the liquid crystal display unit or the housing of the liquid crystal display unit is fixed. A hardened layer is provided on the outer peripheral side portion. The method of manufacturing the image display device according to the first aspect of the invention, wherein the step (A) is performed by applying the first curable resin composition onto the surface of the protective sheet to form a cured or uncured coating film. (B) the step of bonding the protective sheet on which the coating film is formed to the liquid crystal display unit, and the step (C-II) is applied to the outer peripheral side portion of the sealing body of the liquid crystal display unit or the housing of the liquid crystal display unit. The second curable composition is applied to the outer peripheral side surface portion to form a cured or uncured coating film. The method of producing a video display device according to the first or second aspect of the invention, wherein the average thickness of the coating film of the first curable resin composition is the average thickness of the coating film of the second curable resin composition. the following. The method of manufacturing the image display device according to any one of the first to third aspects, wherein the protective plate is composed of one or more selected from the group consisting of a substrate having a light shielding portion. A transparent glass substrate, a transparent resin substrate having a light shielding portion, a glass substrate on which a light shielding portion and a transparent electrode are formed, and a glass substrate in which a transparent electrode is formed on a transparent substrate having a light shielding portion or a substrate on which a film is bonded. The method of manufacturing an image display device according to any one of claims 1 to 4, wherein the protective plate is a touch panel. The first curable resin composition or the second curable resin composition in the method for producing an image display device according to any one of claims 1 to 5, further comprising a curable resin composition, comprising the first curable resin composition or the second curable resin composition (Meth) acrylate (A) and photopolymerization initiator (B). The curable resin composition of claim 6, wherein the (meth) acrylate (A) is selected from the group consisting of urethane (meth) acrylate, One or more of the group consisting of a (meth) acrylate of a polyisoprene skeleton, a (meth) acrylate having a polybutadiene skeleton, and a (meth) acrylate monomer. The curable resin composition of claim 6 or 7, wherein the photo-polymerization initiator (B) has a molar absorption coefficient of 300 ml/(at 302 nm or 313 nm). G.cm) or more is 100 ml/(g.cm) or less at 365 nm. The curable resin composition according to any one of claims 6 to 8, wherein the first curable resin composition has a storage rigidity at 25 ° C with respect to a resin layer having a curing rate of 80% when irradiated with ultraviolet rays. Modulus, a resin composition having a storage modulus of 3 to 20 times that of the resin layer at a curing rate of 98% when irradiated with ultraviolet rays, and a storage rigidity modulus (25 ° C) at a hardening rate of 80% is 1 × 10 ² Pa ~1×10 ⁵ Pa. A touch panel obtained by the method of manufacturing an image display device according to any one of claims 1 to 5. An image display device comprising a liquid crystal display unit, a liquid crystal display unit, a polarizing plate disposed on the liquid crystal display unit, and a sealing body surrounding the polarizing plate and covering the liquid crystal display unit Or a case in which the liquid crystal display unit is fixed by surrounding a peripheral wall portion of the liquid crystal display unit; the image display device has a first cured layer and a second cured layer as follows: the first cured layer is formed The first curable resin composition is cured on the polarizing plate, and the second cured layer is attached to the outer peripheral side surface portion of the protective plate, the outer peripheral side surface portion of the sealing body covering the liquid crystal display unit, or the fixed liquid crystal display member. The outer peripheral side surface portion of the case hardens the second curable resin composition that connects the liquid crystal display element and the protective plate obtain. The image display device according to claim 11, wherein the first curable resin composition and the second curable resin composition contain a (meth) acrylate compound and a photopolymerization initiator. a resin composition selected from the group consisting of an (meth)acrylic acid amine ester compound, a polyisoprene skeleton (meth)acrylate compound, and a polybutadiene skeleton (methyl) At least one of the group consisting of acrylate compounds.