KR20130089579A - Curable resin composition, laminate comprising same, and process for production of the laminate - Google Patents

Abstract

When laminating and integrating a face material through the resin layer which consists of hardened | cured material of curable resin composition, while being able to fully fix face materials, the curable resin composition which can reduce the stress by the shrinkage at the time of hardening of a resin layer to provide.
Curable resin composition containing following curable compound (II) and following noncurable oligomer (D), and content of this noncurable oligomer (D) is 10-90 mass%. Curable compound (II) consists of 1 or more types of curable compounds which harden-react at the time of hardening of curable resin composition, and at least 1 type of this curable compound has the hydroxyl group which does not react at the time of hardening of the said curable resin composition. . A non-curable oligomer (D) is an oligomer which does not harden-react with the said curable compound (II) at the time of hardening of curable resin composition, and has 0.8-3 hydroxyl groups per molecule.

Description

Curable resin composition and laminated body using the same, and its manufacturing method {CURABLE RESIN COMPOSITION, LAMINATE COMPRISING SAME, AND PROCESS FOR PRODUCTION OF THE LAMINATE}

This invention relates to the curable resin composition suitable for joining a face material, the laminated body which laminated | stacked the face material using this curable resin composition, and the manufacturing method of this laminated body.

In the display apparatus in which the protective plate was laminated | stacked on the display device via the bonding resin layer, when hardening a bonding resin layer, there exists a possibility that the stress generate | occur | produced by the shrinkage of the bonding resin layer may affect a display device. When stress is applied to the display device, the following problem may occur.

The display forming material (hereinafter referred to as a display material) in the display device is affected by the stress, and there is a possibility that the uniformity of the display may be impaired. For example, in the case of a liquid crystal display device, the array of liquid crystal enclosed in a display device may be disturbed by external stress, and may be visually recognized as a display nonuniformity.

When an optical film for improving display quality such as a viewing angle is formed on the surface of the substrate on the display surface side of the display device, the optical properties of the optical film may be locally changed by stress, which may impair the uniformity of the display. There is.

Moreover, since a bonding resin layer is formed in the visual recognition side of a display device, when a bubble exists in the bonding resin layer of hardening, the following problem may arise.

• The emitted light or the reflected light from the display device is disturbed by the bubbles, which may greatly impair the image quality of the display image.

When the display device does not display an image, bubbles remaining in the bonding resin layer are easily visually recognized through the protective plate, which may significantly impair the quality of the product.

The interfacial adhesion between the resin layer and the display device, or the interfacial adhesion between the resin layer and the protective plate is lowered.

The following method is known as a method of manufacturing the display apparatus which has a laminated structure by which the transparent face material was laminated | stacked on the display device.

(1) After inject | pouring a liquid raw material on the resin protective plate, and hardening | curing to form a bonding resin, or after laminating the roll sheet-shaped bonding resin on the resin protective plate in the degassing state, a liquid crystal cell is once The method of laminating | stacking in close contact in a degassing state, pressing from a press. As a raw material of bonding resin, silicone gel is used preferably (patent document 1).

(2) A method of laminating by injecting and curing a liquid resin material under reduced pressure into a space formed between the protective plate and the display panel after positioning and temporarily fixing the display panel to a predetermined position of the glass protective plate. As a liquid resin material, silicone resin is used preferably (patent document 2).

Japanese Laid-Open Patent Publication No. 7-209635 Japanese Laid-Open Patent Publication 2006-58753

According to the findings of the present inventors, the elasticity modulus of a junction resin layer can be reduced by making the polarity and molecular weight of resin which form a junction resin layer small. When the elasticity modulus of the bonding resin layer interposed between a display device and a transparent face material falls, the stress generate | occur | produced at the time of hardening shrinkage will become small, and the influence on display quality can be suppressed.

However, by simply lowering the elastic modulus of the bonding resin layer, the force for fixing the display device and the transparent face material may be insufficient. For example, when the display device is vertically installed and used, the display device is removed from the transparent face material. There is a risk of being shifted over time or falling off.

Moreover, although the method of lowering the elasticity modulus of a bonding resin layer can also be considered by using the high molecular weight hardening precursor compound as a raw material of a bonding resin layer as much as possible, and reducing the number of bonding sites of a curing reaction relatively, There exists a possibility that the viscosity of the composition at the time may become high too much, and injection or application will become difficult. Moreover, when the crosslinking density of the resin layer after hardening becomes too small by the decrease of the number of bonding site | parts, the force which fixes a display device and a transparent face material will become inadequate, for example, when using a display apparatus installed vertically, a transparent face material There is a possibility that the display device may be displaced or detached over time.

This invention is made | formed in view of the said situation, When laminating and integrating a face material through the resin layer which consists of hardened | cured material of a curable resin composition, it is possible to fully fix face materials, and to shrink | contract at the time of hardening of a resin layer. It aims at providing the laminated body which laminated | stacked the face material using the curable resin composition which can reduce the stress by this, and this curable resin composition.

Moreover, this invention can fully fix face materials when laminating and unifying a face material through the resin layer which consists of hardened | cured material of curable resin composition, and can reduce the stress by the shrinkage at the time of hardening of a resin layer, Moreover, it aims at providing the manufacturing method of a laminated body which can fully suppress generation | occurrence | production of the bubble in a resin layer.

The curable resin composition of this invention is a curable resin composition used for the laminated body formed by clamping and hardening an uncured curable resin composition between a pair of face materials, At least one face material is transparent, and the following curable compound (II) ) And the following non-curable oligomer (D), and the content of the non-curable oligomer (D) is 10 to 90 mass%.

Curable compound (II): It consists of 1 or more types of curable compounds which harden-cure at the time of hardening of curable resin composition, and at least 1 type of this curable compound has the hydroxyl group which does not react at the time of hardening of the said curable resin composition.

Non-curable oligomer (D): The oligomer which does not harden-react with the said curable compound (II) at the time of hardening of curable resin composition, and has 0.8-3 hydroxyl groups per molecule.

It is preferable that the said curable compound (II) has a curable group, and contains the monomer which has a hydroxyl group.

The curable compound (II) has a curable group, contains an oligomer (A ') having a molecular weight of 1000 to 100000, and a curable group and a monomer (B') having a molecular weight of 125 to 600, and the monomer (B ') It is preferable to contain the monomer (B3) which has a hydroxyl group.

It is preferable that the said non-curable oligomer (D) is a polyoxyalkylene polyol, and the said oligomer (A ') is a urethane oligomer synthesize | combined using polyoxyalkylene polyol and polyisocyanate as a raw material.

It is preferable that the said oligomer (A ') has an acryl group, and at least one part of the said monomer (B') has a methacryl group.

It is preferable that the said monomer (B3) contains the hydroxy methacrylate which has a hydroxyl number of 1-2 and a C3-C8 hydroxyalkyl group.

It is preferable that the said monomer (B ') contains the monomer (B4) chosen from the alkyl methacrylate which has a C8-C22 alkyl group.

It is preferable that it does not contain a chain transfer agent, or contains a chain transfer agent and its content is 1 mass part or less with respect to 100 mass parts of curable compound (II).

This invention provides the laminated body in which the pair of face materials in which at least one face material is transparent is integrated by lamination through the resin layer which consists of hardened | cured material of the curable resin composition of this invention.

It is preferable that one of said pair of face materials is a transparent face material, and the other is a display device.

As for the manufacturing method of the laminated body of this invention, any one of a 1st face material and a 2nd face material is a transparent face material, The laminated body which has a seal part enclosed around the resin layer and resin layer which were sandwiched between the 1st face material and the 2nd face material. As a method of manufacturing the above, the process includes the following steps (a) to (d).

(a) Process of apply | coating curable resin composition for liquid part formation of a liquid containing curable compound (I) and a polymerization initiator to the peripheral part of the surface of a 1st face material, and forming an unhardened seal part.

(b) Process of supplying curable resin composition for resin layer formation which consists of curable resin composition of this invention to the area | region enclosed by the uncured seal part.

(c) Under a reduced pressure atmosphere of 100 Pa or less, the second face member is superposed on the curable resin composition for resin layer formation, and the curable resin composition for resin layer formation is sealed with the first face member, the second face member and the uncured seal portion. Process of obtaining a laminated precursor.

(d) Process of hardening uncured seal part and curable resin composition for resin layer formation in the state which laminated | stacked precursor was placed in the pressure atmosphere of 50 Pa or more.

It is preferable that one of a said 1st face material and a 2nd face material is a transparent face material, and the other is a display device.

According to the curable resin composition of this invention, a pair of face materials can be fully fixed by clamping this between surface materials, and can harden the stress by the shrinkage at the time of hardening.

According to the laminated body of this invention, a face material and a face material are fully fixed through a resin layer, and the stress by the shrinkage at the time of hardening of the resin layer is reduced.

According to the manufacturing method of the laminated body of this invention, a pair of face material can fully be fixed through the resin layer which consists of hardened | cured material of curable resin composition of this invention, and the stress by the shrinkage | contraction at the time of hardening of the resin layer is A laminate can be manufactured while being able to reduce and fully suppress generation | occurrence | production of the bubble in a resin layer.

The laminated body of this invention is a display apparatus, for example, According to the manufacturing method of this invention, generation | occurrence | production of the bubble in the resin layer between a display device and a protective plate is fully suppressed, and a display device and a protective plate are interposed through the resin layer. And the display device can be sufficiently fixed, and the stress at the time of curing shrinkage can be reduced, and the display quality deteriorated by the stress can be prevented.

1: is sectional drawing which shows an example of the display apparatus with which a display device was protected by the transparent face material.
FIG. 2 is a plan view of the display device of FIG. 1.
3 is a plan view illustrating an example of a state of the step (a).
4 is a cross-sectional view showing an example of the state of the step (a).
5 is a plan view illustrating an example of a state of the step (b).
6 is a cross-sectional view showing an example of the state of the step (b).
7 is a cross-sectional view showing an example of the state of the step (c).
8 is a cross-sectional view showing an example of the state of the step (d).

In this invention, it defines as follows.

In a display apparatus, the transparent surface material used as the protective plate of a display device is called "surface material", and a display device is called "back surface material."

Surface material and back surface material are called generically "face material."

In the manufacturing method of this invention, the face material in which the sealing part is formed in the peripheral part and a liquid curable resin composition is supplied to the area | region enclosed by the seal part is called "1st face material" among the face materials, and it superimposes on this curable resin composition. The face material to be referred to as "second face material."

The face material which has light transmittance is called "transparent face material."

The transparent face material which consists of glass is called "glass plate."

Hereinafter, as a preferable embodiment of this invention, the laminated body in this invention is a display apparatus, a pair of face material is a surface material (transparent face material used as a protective plate) and a back surface material (display device), curable resin composition for sealing part formation, and Embodiments in which the curable resin composition for resin layer formation is a photocurable resin composition will be described.

<Display device>

1 is a cross-sectional view showing an example of the display device of the present embodiment, and FIG. 2 is a plan view.

The display device 1 includes a transparent face material 10 (second face material (or first face material)) that is a surface material, a display device 50 (first face material (or second face material)) that is a back face material, and a transparent face material ( 10) and the resin layer 40 sandwiched between the display device 50, the seal portion 42 surrounding the periphery of the resin layer 40, and the display device 50 connected to the display device 50. It has the flexible printed wiring board 54 (FPC) which mounted the drive IC, and the light shielding printing part 55 (light shielding part) formed in the peripheral part of the transparent face material 10. As shown in FIG.

In the display device 1, the light shielding printing portion 55 is formed at the periphery of the transparent face member 10, and the area of the light transmitting portion 56 surrounded by the light shielding printing portion 55 is surrounded by the seal portion 42. It becomes smaller than the area of the resin layer 40, the area of the transparent face material 10 becomes larger than the area of the display device 50, and the total area of the resin layer 40 and the seal part 42 is the transparent face material ( 10) and smaller than each area of the display device 50. As shown in FIG.

[Surface material]

The surface material is a transparent face material (protective plate) that transmits the display image of the display device.

As a transparent face material, a glass plate or a transparent resin plate is mentioned, As well as a point with high transparency with respect to the emission light or the reflected light from a display device, light resistance, low birefringence, high plane precision, surface scratch formation property, high Also from a point which has mechanical strength, a glass plate is the most preferable. A glass plate is preferable also at the point which transmits the light for hardening of a photocurable resin composition sufficiently.

Glass materials, such as soda-lime glass, are mentioned as a material of a glass plate, and iron powder is lower, and high permeability glass (white glass) of the blue group is more preferable. In order to improve safety, you may use tempered glass as a surface material.

As a material of the transparent resin plate, a resin material having high transparency (polycarbonate, polymethyl methacrylate, etc.) can be mentioned.

In order to improve the interface adhesive force with a resin layer, you may surface-treat a transparent face material. As a method of surface treatment, the method of processing the surface of a transparent face material with a silane coupling agent, the process of forming a thin film of silicon oxide through the oxide salt by a frame burner, etc. are mentioned.

In order to increase the contrast of a display image, you may provide an antireflection layer in the transparent surface material on the back surface of the bonding surface with a resin layer. An antireflection layer can be formed by the method of directly forming an inorganic thin film on the surface of a transparent face material, and the method of bonding together the transparent resin film which provided the antireflection layer to the transparent face material.

Moreover, according to the purpose of an image display, one part or all part of a transparent face material may be colored, scattering light in an opaque glass phase, or refracting or reflecting light at the time of transmission by fine unevenness | corrugation of surface, etc. It may be. Moreover, what bonded together to the transparent face material the optical film which performs optical modulation, such as an optical film and a polarizing film, etc. which show the above aspect can also be used as a transparent face material.

The thickness of a transparent face material is 0.5-25 mm normally in the case of a glass plate from a mechanical strength and transparency point. In the use of indoor television receivers, displays for PCs, etc., 0.7 to 6 mm is preferable in terms of weight reduction of the display device, and 3 to 20 mm is preferable in public display applications to be installed outdoors. You may use tempered glass as a transparent face material, and when a transparent face material is thin, chemically strengthened glass can be used. In the case of a transparent resin plate, 2-10 mm is preferable.

[Back side]

The backing material is a display device.

The display device 50 of the example of illustration shows the liquid crystal display device of the structure which bonded together the transparent face material 52 in which the color filter was formed, and the transparent face material 53 in which TFT was formed, and sandwiched this with a pair of polarizing plate 51. Although it is an example, the display device in this embodiment is not limited to the thing of an illustration example.

The display device clamps the display material by which an optical aspect changes with an external electrical signal at least one pair of electrodes which are transparent electrodes. According to the kind of display material, there exist a liquid crystal display device, an EL display device, a plasma display device, an electronic ink type display device, etc. Moreover, the display device has a structure which bonded at least one pair of face materials which are transparent face materials, and arrange | positions so that the transparent face material side may contact a resin layer. At this time, in some display devices, optical films, such as a polarizing plate and retardation plate, may be provided in the outermost layer side of the transparent face material of the side which contact | connects a resin layer. In this case, a resin layer becomes an aspect which bonds the optical film and surface material on a display device.

In order to improve the interface adhesive force with a seal part, you may surface-treat to the bonding surface with the resin layer of a display device. The surface treatment may be only a peripheral part or the whole surface of a face material may be sufficient as it. As a method of surface treatment, the method of processing with the primer for adhesion etc. which can be processed at low temperature, etc. are mentioned.

The thickness of a display device is 0.4-4 mm normally in the case of the liquid crystal display device operated by TFT, and is 0.2-3 mm normally in the case of an EL display device.

[Resin Layer]

A resin layer is a layer which hardens curable resin composition (henceforth the photocurable resin composition for resin layer formation) of this invention.

Curable resin composition (photocurable resin composition for resin layer formation of this embodiment) of this invention can reduce the elasticity modulus after hardening, and can reduce the stress which arises at the time of hardening. Therefore, the adverse effect on the display performance of a display device by such a stress can be suppressed. Moreover, since the viscosity at the time of unhardening of this curable resin composition is low, supplying of curable resin composition to a surface of a face material can be performed in a short time, and it is easy to prevent a bubble from remaining after laminating | stacking a surface material and a back surface material.

0.03-2 mm is preferable, as for the thickness of a resin layer, 0.1-0.8 mm is more preferable, 0.2-0.6 mm is especially preferable. When the thickness of the resin layer is 0.03 mm or more, the resin layer can effectively buffer the impact due to the external force from the transparent face member side and protect the display device. In particular, when the display device is sensitive to external force and the influence on the display quality is likely to occur, the thickness is preferably 0.2 mm or more. Moreover, in the manufacturing method of this embodiment, even if the foreign substance exceeding the thickness of a resin layer is mixed between a transparent face material and a display device, the thickness of a resin layer does not change significantly and there is little influence on light transmission performance. If the thickness of the resin layer is 2 mm or less, air bubbles hardly remain in the resin layer, and the thickness of the entire display device is not unnecessarily thick. When the elasticity modulus of a resin layer is small, it is preferable to set it as thickness of 0.6 mm or less, in order to suppress the shift | offset | difference of the bonding position over time, etc. of a display device.

As a method of adjusting the thickness of a resin layer, while adjusting the thickness of the seal part mentioned later, the method of adjusting the supply amount of the liquid resin layer formation photocurable resin composition supplied to a 1st face material is mentioned.

[Part of seal]

The seal portion is formed by applying and curing a liquid seal portion-forming photocurable resin composition to be described later. Since the outer area of the image display area of the display device is relatively narrow, the width of the seal portion is preferably narrowed. 0.5-2 mm is preferable and, as for the width | variety of a seal part, 0.8-1.6 mm is more preferable.

[Shading Printing Part]

As needed, a light-shielding printing part can be formed in the peripheral part of a transparent face material. The light-shielding printing unit hides the wiring member and the like connected to the display device by preventing the visual display area from the transparent face member side other than the image display area. A light shielding printing part can be provided in the bonding surface with the resin layer of a transparent face material, or its back surface, and is provided in the bonding surface with the resin layer of a transparent face material in the point which reduces the parallax of a light shielding printing part and an image display area | region. It is preferable. When the transparent face material is a glass plate, it is preferable to use a ceramic printing containing a black pigment in the light shielding printing part because of its high light shielding properties. A light shielding printed part can also be formed by bonding the transparent film which formed the light shielding printed part on the front surface or back surface to a transparent face material. You may use the transparent face material without a light-shielding printing part.

[shape]

The shape of a display apparatus is a rectangle normally.

Although the size of a display apparatus is not specifically limited, In the case of a PC monitor using a liquid crystal display device, since the manufacturing method of this embodiment is especially suitable for manufacture of the display apparatus of a comparatively large area, it is 0.3 m * 0.18 m, a television receiver. In the case of, 0.4 m × 0.3 m or more is suitable, and 0.7 m × 0.4 m or more is particularly preferred. The upper limit of the size of the display device is often determined by the size of the display device. In addition, an excessively large display device tends to be difficult to handle in installation or the like. The upper limit of the size of a display apparatus is about 2.5 m * 1.5 m normally from these restrictions. In the case of a small display, 0.14 m x 0.08 m or more is preferable.

Although the dimensions of the transparent face material used as a protective plate and a display device may be substantially the same, in many cases, a transparent face material becomes larger than a display device from relationship with the other case which accommodates a display apparatus. In addition, depending on the structure of another case, you may make a transparent face material slightly smaller than a display device.

<Method for Manufacturing Display Device>

The manufacturing method of the display apparatus of this embodiment is a method which has the following process (a)-(d).

(a) Apply the liquid photocurable resin composition for seal part formation containing a curable compound (I) and a photoinitiator (C1) to the periphery of the surface of a 1st face material (back surface material (or surface material)), and uncuring Process of forming a seal part (However, when a 1st face material is a display device, a seal part is formed in the surface of the image display side.).

(b) Process of supplying liquid photocurable resin composition for resin layer formation containing curable compound (II) and a photoinitiator (C2) to the area | region enclosed by the uncured seal part.

(c) A 2nd face material (surface material (or back surface material)) is superimposed on the photocurable resin composition for resin layer formation in the pressure-sensitive atmosphere of 100 Pa or less, and a resin layer by the 1st face material, a 2nd face material, and the uncured seal part. Process of obtaining the laminated precursor in which the photocurable resin composition for formation was sealed (However, when the antireflection film is formed in the surface of a 2nd surface material, the surface of the back surface side may contact the photocurable resin composition for resin layer formation. Moreover, when a 2nd face material is a display device, the image display side overlaps so that the photocurable resin composition for resin layer formation may be contact | connected.

(d) Process of irradiating and hardening uncured seal part and the photocurable resin composition for resin layer formation in the state which has laminated | stacked precursor in the pressure atmosphere of 50 Pa or more.

When the light shielding part is not formed in a transparent face material, light is irradiated to the sealing part and the photocurable resin composition for resin layer formation from the transparent face material side of a laminated precursor through a light transmission part.

When the light shielding part is formed in the peripheral part of a transparent face material, the area of the light transmission part surrounded by the light shielding part becomes smaller than the area of the resin layer surrounded by the seal | sticker part, and the photoinitiator contained in the said photocurable resin composition for resin layer formation (C2). ) Has an absorption wavelength range (λ2) that exists at a longer wavelength side than the absorption wavelength range (λ1) of the photopolymerization initiator (C1) contained in the seal portion-forming photocurable resin composition, and the laminated precursor in the step (d). The light irradiated from the side of is to include light of the wavelength in the absorption wavelength range λ1 and light of the wavelength in the absorption wavelength region λ2.

The manufacturing method of this embodiment encloses the liquid photocurable resin composition for resin layer formation between a 1st face material and a 2nd face material in a pressure-reduced atmosphere, and is for resin layer formation enclosed in high pressure atmosphere, such as atmospheric pressure atmosphere. It is a method (pressure reduction lamination method) which hardens a photocurable resin composition and forms a resin layer. Encapsulation of the photocurable resin composition for resin layer formation under reduced pressure is not a method of injecting the photocurable resin for resin layer formation into the narrow and wide space of the clearance gap of a 1st face material and a 2nd face material, but almost the whole of a 1st face material. It is a method of supplying the photocurable resin composition for resin layer formation to a surface, and then laminating | stacking a 2nd face material and encapsulating the photocurable resin composition for resin layer formation between a 1st face material and a 2nd face material.

An example of the manufacturing method of the transparent laminated body by sealing of the liquid photocurable resin composition for resin layer formation under reduced pressure, and hardening of the photocurable resin composition for resin layer formation under atmospheric pressure is known. For example, international publication 2008/81838 pamphlet and international publication 2009/16943 pamphlet describe the manufacturing method of a transparent laminated body, and the photocurable resin composition used for the manufacturing method, and are taken in in this specification.

[Step (a)]

First, an uncured seal portion is formed along the periphery of one surface of the first face member. It is arbitrary whether a back surface material or a surface material is used as a 1st surface material.

When the 1st face material is a transparent face material used as the protective plate of a display device, the surface which forms the unhardened seal part is arbitrary in any one of two surfaces. In the case where the properties of the two surfaces are different, the required one surface is selected. For example, when the surface treatment which improves the interface adhesive force with a resin layer is given to one surface, the unhardened seal part is formed in the surface. In addition, when the antireflection layer is formed on one surface, an uncured seal portion is formed on the rear surface.

When the 1st face material is a display device, the surface which forms the unhardened seal part is the surface of the side where an image is displayed.

In the step (c) described later, the uncured seal portion is a photocurable resin composition for forming a liquid resin layer from the interface between the uncured seal portion and the first face member and the interface between the uncured seal portion and the second face member. It is important to have an interfacial adhesive force of such a degree that it does not leak and hardness enough to maintain a shape. Therefore, it is preferable to apply | coat and form the uncured seal | sticker part by the printing, administration, etc. of the photocurable resin composition for seal part formation with high viscosity.

Moreover, in order to maintain the space | interval of a 1st face material and a 2nd face material, you may mix | blend the spacer particle of a predetermined particle diameter with the photocurable resin composition for sealing part formation.

Immediately after applying the photocurable resin composition for forming the seal portion, the shape of the seal portion can be maintained for a longer time by irradiating with light for curing the seal portion to partially semi-harden the seal portion.

[Photocurable Resin Composition for Seal Part Formation]

The photocurable resin composition for sealing part formation (henceforth a seal material) is a liquid composition containing a photocurable curable compound (I) and a photoinitiator (C1).

500-3000 Pa.s is preferable, as for the viscosity of the seal part formation photocurable resin composition, 800-2500 Pa.s is more preferable, 1000-2000 Pa.s is more preferable. When the viscosity is 500 Pa · s or more, the shape of the uncured seal portion can be maintained for a relatively long time, and the height of the seal portion can be sufficiently maintained. If the viscosity is 3000 Pa · s or less, the seal portion can be formed by a coating method.

The viscosity of the photocurable resin composition for sealing part formation is measured using an E-type viscometer at 25 ° C.

(Curable Compound (I))

Since it is easy to adjust the viscosity of the photocurable resin composition for seal part formation to the said range, curable compound (I) has a curable group, and the number average molecular weight is 10000 or more of the oligomer (A) of 30000-100000, It is preferable to have a curable group and to contain 1 or more types of monomers (B) whose molecular weight is 125-600.

Examples of the curable group of the oligomer (A) or the monomer (B) include an addition polymerizable unsaturated group (acryloyloxy group, methacryloyloxy group, etc.), a combination of an unsaturated group and a thiol group, and the like. And since the sealing part with high transparency is obtained, the group chosen from the group which consists of an acryloyloxy group and a methacryloyloxy group is preferable.

The curable group in an oligomer (A) and the curable group in a monomer (B) may mutually be same or different. Since the curability of a relatively high molecular weight oligomer (A) is less likely to be less reactive than that of a relatively low molecular weight monomer (B), curing of the monomer (B) proceeds first and the viscosity of the whole composition is rapidly increased. This increases and there is a fear that the curing reaction becomes heterogeneous. In order to make the difference of the reactivity of both curable groups small, and to obtain a homogeneous seal part, the curable group of an oligomer (A) is made into the highly reactive acryloyloxy group, and the curable group of the monomer (B) is relatively low in reactivity It is more preferable to set it as a loyloxy group.

The number average molecular weights of an oligomer (A) are 30000-100000, 40000-80000 are preferable and 50000-65000 are more preferable. If the number average molecular weight of an oligomer (A) is this range, it is easy to adjust the viscosity of the photocurable resin composition for seal part formation to the said range.

The number average molecular weight of an oligomer (A) is the number average molecular weight of polystyrene conversion obtained by GPC measurement. In addition, in the GPC measurement, when the peak of the unreacted low molecular weight component (monomer etc.) appears, the number average molecular weight is calculated | required except the peak.

The molecular weight of a monomer (B) is 125-600, 140-400 are preferable and 150-350 are more preferable. If the molecular weight of monomer (B) is 125 or more, volatilization of monomer (B) at the time of manufacturing a display apparatus by the pressure reduction lamination method mentioned later is suppressed. When the molecular weight of a monomer (B) is 600 or less, the solubility of the monomer (B) with respect to a high molecular weight oligomer (A) can be improved, and viscosity adjustment as a photocurable resin composition for sealing part formation can be performed preferably.

(Oligomer (A))

As an oligomer (A), it is preferable to have 1.8-4 average curable groups per molecule from the point of sclerosis | hardenability of the photocurable resin composition for seal part formation, and the mechanical characteristic of a seal | sticker part.

As an oligomer (A), the urethane oligomer which has a urethane bond, the poly (meth) acrylate of polyoxyalkylene polyol, the poly (meth) acrylate of polyester polyol, etc. are mentioned.

The urethane oligomer synthesized using polyol and polyisocyanate as a raw material is preferable at the point which can adjust the mechanical property of resin after hardening, adhesiveness with a face material, etc. widely by molecular design of a urethane chain, etc., The urethane oligomer mentioned later (A1) ) Is more preferred. The polyol is more preferably a polyoxyalkylene polyol.

(Urethane oligomer (A1))

Since the urethane oligomer (A1) whose number average molecular weight is the range of 30000-100000 becomes high viscosity, it is difficult to synthesize | combine by a conventional method and even if it can synthesize | combine, it is difficult to mix with monomer (B).

Therefore, after synthesize | combining a urethane oligomer (A1) by the synthesis method using a monomer (B) (following monomer (B1) and (B2)), the obtained product is used as a photocurable resin composition for sealing part formation as it is. Alternatively, the obtained product is also preferably diluted with a monomer (B) (the following monomer (B1), monomer (B3), etc.) and used as a seal portion-forming photocurable aqueous composition.

Monomer (B1): Monomer (B) which has a curable group and does not have a group which reacts with an isocyanate group.

Monomer (B2): Monomer (B) which has a curable group and has a group which reacts with an isocyanate group.

Monomer (B3): Monomer (B) which has a curable group and has a hydroxyl group.

Synthesis method of urethane oligomer (A1):

A method of reacting a polyol and a polyisocyanate in the presence of a monomer (B1) as a diluent to obtain a prepolymer having an isocyanate group, and then reacting the monomer (B2) with an isocyanate group of the prepolymer.

Examples of the polyols and polyisocyanates include known compounds, for example, polyols (i) and diisocyanates (ii) described as raw materials for the urethane oligomers (a) described in International Publication No. 2009/016943 pamphlet. It is accepted in this specification.

As a polyol, polyoxyalkylene polyol, such as polyoxyethylene glycol and polyoxypropylene diol, polyester polyol, polycarbonate polyol, etc. are mentioned. Among these, polyoxyalkylene polyols are preferable, and polyoxypropylene polyol is particularly preferable. Moreover, when a part of oxypropylene group of polyoxypropylene polyol is substituted by oxyethylene group, compatibility with the other component of the photocurable resin composition for resin layer formation can be improved, and it is still more preferable.

Herein, a part of the oxypropylene group may be substituted with an oxyethylene group means that a part of the oxypropylene structure constituting the polyoxypropylene polyol molecule is a molecular structure substituted with an oxyethylene structure. The same meaning is also shown about the same description after this. The oxyethylene structure may be present randomly or in blocks in the polyoxypropylene polyol molecule. In addition, the oxyethylene structure may be inside the polyoxypropylene polyol molecule or may be just before the terminal hydroxyl group. When the oxyethylene structure is just before the terminal hydroxyl group, it can be obtained by adding ethylene oxide to the polyoxypropylene polyol.

As diisocyanate (ii), the diisocyanate chosen from aliphatic diisocyanate, alicyclic diisocyanate, and non-yellowing aromatic diisocyanate is preferable. Among them, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, 2,4,4-trimethyl-hexamethylene diisocyanate, etc. are mentioned as an example of aliphatic polyisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate), and the like. Xylylene diisocyanate etc. are mentioned as a non-yellowing aromatic diisocyanate. These may be used individually by 1 type and may use two or more types together.

As a monomer (B1), the alkyl (meth) acrylate (n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, n-behenyl (meth) acrylate which has a C8-C22 alkyl group Etc.) (meth) acrylate (isobornyl (meth) acrylate, adamantyl (meth) acrylate, etc.) which has an alicyclic hydrocarbon group is mentioned.

As a monomer (B2), the monomer which has active hydrogen (hydroxyl group, an amino group, etc.) and a curable group is mentioned, Specifically, the hydroxyalkyl (meth) acrylate (2-hydroxy which has a C2-C6 hydroxyalkyl group) Hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc.); The hydroxyalkyl acrylate which has a hydroxyalkyl group of -4 is preferable.

(Monomer (B))

It is preferable that a monomer (B) has 1-3 curable groups per molecule from the point of sclerosis | hardenability of the photocurable resin composition for seal | sticker part formation, and the mechanical characteristic of a seal | sticker part.

The photocurable resin composition for sealing part formation may contain the monomer (B1) used as a diluent in the synthesis | combining method of the urethane oligomer (A1) mentioned above as a monomer (B). Moreover, as a monomer (B), you may contain the unreacted monomer (B2) used for the synthesis | combining method of the urethane oligomer (A1) mentioned above.

It is preferable that a monomer (B) contains the monomer (B3) which has a hydroxyl group from the adhesiveness of a face material and a seal part, and the solubility of the various additives mentioned later.

As a monomer (B3) which has a hydroxyl group, hydroxy methacrylate (2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate) which has a hydroxyl group of 1-2, a C3-C8 hydroxyalkyl group, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl methacrylate, glycerol monomethacrylate and the like) are preferred, and 2-hydroxybutyl methacrylate is particularly preferred.

The content rate of the monomer (B) in the seal | sticker part formation photocurable resin composition is the whole (100 mass%) of curable compound (I), ie, the sum total of an oligomer (A) and monomer (B) (100 mass%). 15-50 mass% is preferable in it, 20-45 mass% is more preferable, 25-40 mass% is further more preferable. If the ratio of a monomer (B) is 15 mass% or more, the hardenability of the photocurable resin composition for seal part formation, and adhesiveness of a face material and a seal part will become favorable. If the ratio of a monomer (B) is 50 mass% or less, it is easy to adjust the viscosity of the photocurable resin composition for seal part formation to 500 Pa.s or more.

In addition, in the synthesis | combination of a urethane oligomer (A1), since the monomer (B2) which reacted with the isocyanate group of a prepolymer exists as a part of oligomer (A), it is a monomer (B) in the photocurable resin composition for sealing part formation. It is not included in content of In addition, in the synthesis | combination of a urethane oligomer (A1), the monomer (B1) used as a diluent and the monomer (B) added after synthesize | combining a urethane oligomer (A1) are monomers in the photocurable resin composition for sealing part formation ( It is contained in content of B).

(Photoinitiator (C1))

Examples of the photopolymerization initiator (C1) contained in the seal portion-forming photocurable resin composition include acetophenone series, ketal series, benzoin or benzoin ether series, phosphine oxide series, benzophenone series, thioxanthone series, and quinone series. Photopolymerization initiators are mentioned, and acetophenone series, ketal series, and benzoin ether series photopolymerization initiators are preferable. When hardening by short wavelength visible light, a phosphine oxide type photoinitiator is more preferable from the viewpoint of an absorption wavelength range. By using together 2 or more types of photoinitiators (C1) from which an absorption wavelength range differs, hardening time can be made faster or surface hardenability in a sealing part can be improved. Moreover, when a light shielding printing part is formed in a transparent face material and hardens the uncured sealing part clamped by the light shielding printing part by light irradiation from the side surface of a face material, and the photocurable resin composition for resin layer formation, an uncured seal | sticker In the range which does not inhibit hardening of the photocurable resin composition for resin layer formation of the part adjacent to a part, you may use together the photoinitiator (C2) mentioned later. When using together, since the content rate of a polymerization initiator (C1) and a polymerization initiator (C2) can perform hardening efficiently and effectively, it is 50: 1-5: by mass ratio of (C1) :( C2). 1 is preferred. In order to harden | cure the photocurable resin composition for resin layer formation clamped by the light-shielding printing part in a short time by the light irradiated from the side surface of a face material through the uncured sealing material, the photocurable resin composition for seal part formation is a photoinitiator. It is preferable not to contain (C2).

Content of the photoinitiator (C1) in the seal part formation photocurable resin composition (when a photoinitiator (C2) is contained, the total amount of (C1) and (C2)) is the whole of curable compound (I), ie 0.01-10 mass parts is preferable with respect to a total of 100 mass parts of an oligomer (A) and a monomer (B), and 0.1-5 mass parts is more preferable.

(additive)

The photocurable resin composition for seal part formation may be a polymerization inhibitor, a photocuring accelerator, a chain transfer agent, a light stabilizer (such as an ultraviolet absorber or a radical trapping agent), an antioxidant, a flame retardant, or an adhesion improving agent (silane coupling agent, if necessary). Etc.), and various additives, such as a pigment and dye, may be included and it is preferable to contain a polymerization inhibitor and a light stabilizer. In particular, by containing a polymerization inhibitor in an amount smaller than a polymerization initiator, stability of the photocurable resin composition for sealing part formation can be improved, and the molecular weight of the resin layer after hardening can also be adjusted. When hardening a sealing material by the light irradiated from the side surface of a face material, a polymerization inhibitor, a chain transfer agent, an optical stabilizer, a pigment, a dye, etc. which have an effect which retards hardening reaction are not used as much as possible, or content is reduced. It is preferable to make it.

As a polymerization inhibitor, polymerization prohibitions, such as a hydroquinone type (2, 5- di-t- butyl hydroquinone etc.), a catechol type (pt-butyl catechol etc.), anthraquinone type, phenothiazine type | system | group, and a hydroxy toluene type, are prohibited. Can be mentioned.

As a light stabilizer, a ultraviolet absorber (benzotriazole type, a benzophenone type, a salicylate type etc.), a radical trapping agent (hindered amine type), etc. are mentioned.

Examples of the antioxidant include phosphorus and sulfur compounds.

10 mass parts or less are preferable with respect to the whole of curable compound (I), ie, 100 mass parts of total of an oligomer (A) and a monomer (B), and, as for the total amount of these additives, 5 mass parts or less are more preferable.

[Process (b)]

After the step (a), a liquid photocurable resin composition for forming a liquid resin layer is supplied to a region surrounded by an uncured seal portion.

The supply amount of the photocurable resin composition for resin layer formation is filled with the space formed by the seal portion, the first face member and the second face member by the photocurable resin composition for resin layer formation, and between the first face member and the second face member. Is set in advance in an amount equal to a predetermined interval (that is, the resin layer is a predetermined thickness). At this time, it is preferable to consider the volume reduction by hardening shrinkage of the photocurable resin composition for resin layer formation beforehand. Therefore, it is preferable that the quantity is such that the thickness of the photocurable resin composition for resin layer formation becomes slightly thicker than the predetermined thickness of the resin layer. When curing shrinkage is small, the predetermined thickness of a resin layer and the thickness of the photocurable resin composition for resin layer formation may be made substantially the same.

As a supply method, the method of placing a 1st face material horizontally and supplying in a point form, a line form, or a plane form by supply means, such as a dispenser and a die coater, is mentioned.

[Photocurable Resin Composition for Resin Layer Formation]

The photocurable resin composition for resin layer formation is a liquid composition containing a photocurable curable compound (II), a photoinitiator (C2), and a noncurable oligomer (D). A non-curable oligomer (D) is an oligomer which has 0.8-3 hydroxyl groups per molecule which does not harden-react with curable compound (II) in a composition at the time of hardening of the photocurable resin composition for resin layer formation.

0.05-50 Pa.s is preferable and, as for the viscosity of the photocurable resin composition for resin layer formation, 1-20 Pa.s is more preferable. If the viscosity is 0.05 Pa · s or more, the ratio of the monomer (B ') to be described later can be suppressed, and the decrease in the physical properties of the resin layer is suppressed. Moreover, since the component of low boiling point becomes small, it becomes suitable for the pressure reduction lamination method mentioned later. If the viscosity is 50 Pa · s or less, bubbles hardly remain in the resin layer.

The viscosity of the photocurable resin composition for resin layer formation is measured using an E-type viscosity meter at 25 degreeC.

(Curable Compound (II))

Curable compound (II) in the photocurable resin composition for resin layer formation consists of 1 or more types of curable compounds which harden-react at the time of hardening of the photocurable resin composition for resin layer formation, and at least 1 type of the curable compound And compound (IIa) having a hydroxyl group which does not react at the time of curing of the photocurable resin composition for resin layer formation.

When curable compound (II) contains such a compound (IIa), a hydroxyl group exists in the hardened | cured material which hardened and reacted curable compound (II) independently. The presence of such a hydroxyl group contributes to stabilization of the non-curable oligomer in the photocurable resin composition for resin layer formation.

Therefore, the compound (IIa) which has a hydroxyl group which does not react at the time of the said hardening should just be an unreacted hydroxyl group after a hardening reaction, for example, even if some hydroxyl groups of a compound (IIa) harden-react, other addition hardening is carried out. It is enough to remain unreacted without reacting.

Compound (IIa) which has a hydroxyl group which does not react at the time of such hardening may have a curable group which contributes to hardening reaction, and may have a hydroxyl group, may be a monomer, and may be an oligomer which has a repeating unit. In the point which makes it easy to adjust the viscosity of the photocurable composition at the time of uncuring, it is preferable to use the monomer which has a curable group and has a hydroxyl group as a compound (IIa). As a specific example of the compound (IIa) which is a monomer which has a hydroxyl group, Hydroxy (meth) acrylate (2-hydroxypropyl (meth) acrylate) which has a hydroxyl group of 1-2, a C3-C8 hydroxyalkyl group, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, glycerol mono (meth) acrylate, etc.) are preferable, and 2-hydroxy Butyl methacrylate is particularly preferred.

Curable compound (II) has one or more types of oligomer (A ') which has a curable group, and has a number average molecular weight of 1000-100000, and a curable group, and also one type of monomer (B') whose molecular weight is 125-600. It is preferable to contain the above. When such a curable compound (II) is used, it is easy to adjust the viscosity of the photocurable resin composition for resin layer formation to the said preferable range.

In this case, while having a curable group as at least a part of monomer (B '), it is preferable to use the monomer (B3) whose molecular weight is 125-600 which has a hydroxyl group.

Examples of the curable group of the oligomer (A ') or the monomer (B') include an addition polymerizable unsaturated group (acryloyloxy group, methacryloyloxy group, etc.), a combination of an unsaturated group and a thiol group, and the curing rate is high. Since a quick point and the resin layer with high transparency are obtained, the group chosen from the group which consists of an acryloyloxy group and a methacryloyloxy group is preferable.

The curable group in an oligomer (A ') and the curable group in a monomer (B') may mutually be same or different. Since the hardenable group in the relatively high molecular weight oligomer (A ') tends to have a lower reactivity than the hardenable group in the relatively low molecular weight monomer (B'), the curing of the monomer (B ') proceeds first and then the composition rapidly. Viscosity of the whole may become high and a hardening reaction may become heterogeneous. In order to make the difference of the reactivity of both curable groups small, and to obtain a homogeneous resin layer, the curable group of an oligomer (A ') is made into the highly reactive acryloyloxy group, and the curable group of the monomer (B') is relatively reactive. It is more preferable to set it as the low methacryloyloxy group.

(Oligomer (A '))

It is preferable that it is 1000-100000, and, as for the number average molecular weight of an oligomer (A '), it is more preferable that it is 10000-70000. It is easy to adjust the viscosity of the photocurable resin composition for resin layer formation to the said range that the number average molecular weight of an oligomer (A ') is this range.

The number average molecular weight of an oligomer (A ') is a number average molecular weight of polystyrene conversion obtained by GPC measurement. In addition, in the GPC measurement, when the peak of the unreacted low molecular weight component (monomer etc.) appears, the number average molecular weight is calculated | required except the peak.

As an oligomer (A '), it is preferable to have an average of 1.8-4 curable groups per molecule from the point of sclerosis | hardenability of the photocurable resin composition for resin layer formation, and the mechanical characteristic of a resin layer.

Examples of the oligomers (A ') include urethane oligomers having urethane bonds, poly (meth) acrylates of polyoxyalkylene polyols, poly (meth) acrylates of polyester polyols, and the like. Urethane oligomer (A2) is preferable at the point which can adjust the mechanical property of resin after hardening, adhesiveness with a face material, etc. widely.

After urethane oligomer (A2) reacts a polyol and polyisocyanate to obtain the prepolymer which has an isocyanate group, it is preferable to synthesize | combine by the method of making the said monomer (B2) react with the isocyanate group of this prepolymer.

Examples of the polyols and polyisocyanates include known compounds, for example, polyols (i) and diisocyanates (ii) described as raw materials for the urethane oligomers (a) described in International Publication No. 2009/016943 pamphlet. It is accepted in this specification.

As a urethane oligomer (A2), you may use a commercially available thing, for example, as reaction product of EB230 (made by Daicel Cytech Co., Ltd., functional group 2, polypropylene glycol / IPDI / 2-hydroxyethylhexyl acrylate) U-200AX (it is recognized by the reaction product of Shin-Nakamura Chemical Corporation, functional group number 2, aliphatic polyester polyol / aliphatic or alicyclic polyisocyanate / 2-hydroxyethylhexyl acrylate) is mentioned.

As for the content rate of an oligomer (A '), 20-90 mass% of all (100 mass%) of curable compound (II), ie, the sum total (100 mass%) of oligomer (A') and monomer (B '), Preferably, 30-80 mass% is more preferable. If the ratio of this oligomer (A ') is 20 mass% or more, the heat resistance of a resin layer will become favorable. When the ratio of this oligomer (A ') is 90 mass% or less, the hardenability of the photocurable resin composition for resin layer formation, and adhesiveness of a face material and a resin layer become favorable.

(Monomer (B '))

It is preferable that it is 125-600, and, as for the molecular weight of a monomer (B '), it is more preferable that it is 140-400. If the molecular weight of monomer (B ') is 125 or more, volatilization of the monomer at the time of manufacturing a display apparatus by the pressure reduction lamination method mentioned later is suppressed. If the molecular weight of a monomer (B ') is 600 or less, adhesiveness of a face material and a resin layer will become favorable.

It is preferable that a monomer (B ') has 1-3 curable groups per molecule from the point of sclerosis | hardenability of the photocurable resin composition for resin layer formation, and the mechanical characteristic of a resin layer.

10-80 mass% of content rates of a monomer (B ') is the whole (100 mass%) of curable compound (II), ie, the sum total (100 mass%) of an oligomer (A') and a monomer (B '). Preferably, 20-70 mass% is more preferable.

It is preferable that monomer (B ') has a curable group, and contains monomer (B3) which has a hydroxyl group. The monomer (B3) contributes to the stabilization of the non-curable oligomer (D). Moreover, when a monomer (B3) is contained, favorable adhesiveness of a face material and a resin layer will be easy to be obtained. Although the number of hydroxyl groups in one molecule of monomer (B3) can arbitrarily select the number which can stabilize a non-curable oligomer (D), It is preferable that it is 1-2 in 1 molecule from a viewpoint of availability.

As a monomer (B3) which has a hydroxyl group, the thing similar to the monomer (B3) in the photocurable resin composition for sealing part formation is mentioned, 2-hydroxybutyl methacrylate is especially preferable.

As for the content rate of a monomer (B3), 10-60 mass% is preferable in all (100 mass%) of curable compound (II), ie, the sum total (100 mass%) of an oligomer (A ') and a monomer (B'). And 20-50 mass% is more preferable. When the content rate of this monomer (B3) is 10 mass% or more, the effect of the stability improvement of the photocurable resin composition for resin layer formation, and the adhesiveness improvement of a face material and a resin layer will be easy to be acquired sufficiently. When the content rate of a monomer (B3) is 60 mass% or less, since the hardness of the hardened | cured material which consists of photocurable resin compositions for resin layer formation does not become high too much, it is preferable.

It is preferable that a monomer (B ') contains the following monomer (B4) from a viewpoint of the mechanical characteristic of a resin layer. Since monomer (B4) reduces the glass transition temperature (Tg) of the resin layer after hardening, it contributes to the fall of the elasticity modulus of the resin layer after hardening, and improves the flexibility of the resin layer.

However, there are cases where it is preferable that the content of the monomer (B4) is reduced or not contained, such as when the curability of the photocurable resin composition for resin layer formation is increased and the time required for curing is shortened.

Monomer (B4): 1 or more types chosen from the group which consists of an alkyl methacrylate which has a C8-C22 alkyl group. When carbon number is 8 or more, it is preferable at the point which can reduce the glass transition temperature of hardened | cured material, and when carbon number is 22 or less, it is preferable at the point which can obtain easily the alcohol of a raw material via natural product.

Examples of the monomer (B4) include n-dodecyl methacrylate, n-octadecyl methacrylate, n-behenyl methacrylate, and n-dodecyl methacrylate or n-octadecyl methacrylate. Is preferred.

As for the content rate of a monomer (B4), 5-50 mass% is preferable in all (100 mass%) of curable compound (II), ie, the sum total (100 mass%) of an oligomer (A ') and a monomer (B'). And, 15-40 mass% is more preferable. When the content ratio of the monomer (B4) is 5% by mass or more, a sufficient addition effect of the monomer (B4) is likely to be obtained.

(Photoinitiator (C2))

As a photoinitiator (C2) contained in the photocurable resin composition for resin layer formation, an acetophenone type, a ketal type, a benzoin or a benzoin ether type, a phosphine oxide type, a benzophenone type, a thioxanthone type, a quinone type etc. The photoinitiator is mentioned, A phosphine oxide type or a thioxanthone type photoinitiator is preferable, A phosphine oxide type is especially preferable at the point which suppresses coloring after a photoinitiation reaction.

Content of the photoinitiator (C2) in the photocurable resin composition for resin layer formation is 0.01-100 mass parts with respect to the whole of curable compound (II), ie, 100 mass parts in total of an oligomer (A ') and a monomer (B'). 10 mass parts is preferable, and 0.1-5 mass parts is more preferable.

When hardening a part of the photocurable resin composition for resin layer formation adjacent to a sealing material with the light irradiated from the side of a face material, the photoinitiator (C2) is the absorption wavelength range ((lambda) 1 of the said photoinitiator (C1)). It is preferable to have the absorption wavelength range ((lambda) 2) which exists in the long wavelength side rather than). The photoinitiator (C2) may have only an absorption wavelength range (λ2) or may have an absorption wavelength range (λ1 ') and an absorption wavelength range (λ2) overlapping with the absorption wavelength range (λ1).

(Non-curable oligomer (D))

Since the non-curable oligomer (D) is well compatible in the photocurable resin composition for resin layer formation and does not contribute to curing, the stress due to shrinkage during curing of the resin layer is reduced without impairing transparency and homogeneity. You can.

A non-curable oligomer (D) is an oligomer which has 0.8-3 hydroxyl groups per molecule which does not harden-react with curable compound (II) in a composition at the time of hardening of the photocurable resin composition for resin layer formation. As for the hydroxyl group per molecule, 2-3 pieces are more preferable. When the hydroxyl group per molecule is 0.8 or more, the non-curable oligomer can be stably maintained by the interaction of the hydroxyl period between the non-curable oligomers or between the non-curable oligomer and the cured product obtained from the curable compound (II). It is preferable that the non-curable oligomer can be conveniently compatible in the photocurable resin composition for resin layer formation that it is preferable that it is three or less hydroxyl groups per molecule.

As for the number average molecular weight (Mn) per hydroxyl group of a noncurable oligomer (D), 400-8000 are preferable. When the number average molecular weight per hydroxyl group is 400 or more, the polarity of a non-curable oligomer (D) does not become high too much, and favorable compatibility with curable compound (II) in the photocurable resin composition for resin layer formation is easy to be obtained. When the number average molecular weight per hydroxyl group is 8000 or less, the non-curable oligomer (D) is formed in the resin layer after curing by the interaction between the hydroxyl group derived from the curable compound (II) and the hydroxyl group of the non-curable oligomer (D). Stabilizing effect is easy to be obtained. It is presumed that hydrogen bonding is involved in this interaction.

Curable oligomer (D) may be used individually by 1 type, and may use two or more types together.

Examples of the non-curable oligomer (D) containing a hydroxyl group include high molecular weight polyols and the like, and polyoxyalkylene polyols, polyester polyols, or polycarbonate polyols are preferable.

As polyoxyalkylene polyol, polyoxyalkylene monool, polyoxyalkylenediol, or polyoxyalkylene triol which has a C2-C4 oxyalkylene repeating unit is mentioned. Specific examples thereof include polyoxypropylene monool, polyoxyethylene glycol, polyoxypropylene diol (hereinafter also referred to as polypropylene glycol), polyoxypropylene triol, polyoxytetramethylene glycol, and the like.

400-8000 are preferable and, as for the number average molecular weight (Mn) per hydroxyl group of polyoxyalkylene polyol, 600-5000 are more preferable.

As the polyester polyol, an aliphatic polyester having residues of aliphatic diols such as ethylene glycol, propylene glycol and 1,4-butanediol and residues of aliphatic dicarboxylic acids such as glutaric acid, adipic acid and sebacic acid Diols.

As polycarbonate polyol, aliphatic polycarbonate diol, such as aliphatic polycarbonate diol which has diol residues, such as 1, 6- hexanediol, and the ring-opening polymer of aliphatic cyclic carbonate, is mentioned.

400-8000 are preferable and, as for the number average molecular weight (Mn) per hydroxyl group of polyester polyol or polycarbonate polyol, 800-6000 are more preferable.

The number average molecular weight of the non-curable oligomer (D) in the present specification is a hydroxyl value measured based on JIS K 1557-1 (2007 edition) in one molecule of A (KOH mg / g) and non-curable oligomer (D). It is the value computed by following formula (1) from the number B of hydroxyl groups.

Molecular weight of non-curable oligomer (D) = 56.1 x B x 1000 / A (1)

Since the elastic modulus of the resin layer after hardening tends to become lower, it is preferable to use polyoxyalkylene polyol as a non-curable oligomer (D), and polyoxypropylene polyol is especially preferable. As described later, in order to adjust the polarity of the non-curable oligomer (D), a part of the oxypropylene group of the polyoxypropylene polyol may be substituted with an oxyethylene group. It is the same as that of description in said polyol which may replace a part of oxypropylene group by oxyethylene group.

For example, it is preferable from the viewpoint of compatibility that an oligomer (A ') is a urethane oligomer synthesize | combined using polyoxyalkylene polyol and polyisocyanate as a raw material, and a non-curable oligomer (D) is polyoxyalkylene polyol. .

In this invention, in order to stabilize the photocurable resin composition for resin layer formation at the time of uncuring, and to suppress that a noncurable oligomer (D) isolate | separates from the resin layer after hardening, an oligomer (A ') and a noncurable oligomer It is preferable that (D) has a molecular chain of the same structure or similar structure.

Specifically, while using the compound (henceforth a hydroxyl group containing compound) which has hydroxyl groups, such as a polyol, as a raw material at the time of synthesize | combining the oligomer (A ') in the photocurable resin composition for resin layer formation, It is preferable to use the same hydroxyl group containing compound as a non-curable oligomer (D).

For example, when an oligomer (A ') is a urethane oligomer synthesize | combined using polyoxyalkylene polyol and polyisocyanate as a raw material, it is preferable to use this polyoxyalkylene polyol as a nonhardening oligomer (D).

Or, when the hydroxyl group containing compound as a raw material of an oligomer (A ') and the hydroxyl group containing compound used as a non-curable oligomer (D) are not the same, both molecular chains have a common repeating unit, etc. partially It is desirable to have a common structure and to make both polarities the same. Examples of the method for adjusting the polarity include a method of increasing the polarity by introducing a polar group, a method of increasing the polarity by replacing a part of the oxypropylene group with an oxyethylene group, and a method of increasing the polarity by decreasing the molecular weight per hydroxyl group. have. These methods may be combined.

For example, when an oligomer (A ') is a urethane oligomer synthesize | combined using polyoxypropylene polyol (a') which substituted a part of oxypropylene group by oxyethylene group, and polyisocyanate as a raw material, the poly which does not have an oxyethylene group As an oxypropylene polyol, it is preferable to use the polyoxypropylene polyol whose molecular weight per hydroxyl group is smaller than the said polyol (a ') as a nonhardening oligomer (D).

As an example of the most preferable photocurable resin composition for resin layer formation, after reacting the polyoxypropylene diol which substituted a part of oxypropylene group with the oxyethylene group, and a polyisocyanate compound to obtain the prepolymer which has an isocyanate group, the said monomer (B2) A non-curable oligomer containing a urethane oligomer (A2) obtained by reacting with an oligomer (A '), wherein a part of the oxypropylene group, which is the same as the raw material of the urethane oligomer (A2), is substituted with an oxyethylene group. The composition containing as D) and containing the monomer (B3) which has a hydroxyl group as a monomer (B ') is mentioned.

As such, when the oligomer (A ') partially has the same molecular structure as the non-curable oligomer (D), the compatibility of the non-curable oligomer (D) in the composition is higher, and the monomer (B') has a hydroxyl group. It is thought that the noncurable oligomer (D) may exist stably in hardened | cured material by interaction of the hydroxyl group in the molecular structure after hardening of curable compound (II), and the hydroxyl group in the molecular structure of non-curable oligomer (D).

As another example, a urethane oligomer (A2) obtained by reacting a polyoxypropylene diol in which a part of an oxypropylene group is substituted with an oxyethylene group and a polyisocyanate compound to obtain a prepolymer having an isocyanate group, and then reacting with the monomer (B2) ) As an oligomer (A '), and a polyoxypropylene diol which is not substituted with an oxyethylene group, and contains as the non-curable oligomer (D) a molecular weight smaller than the polyoxypropylene diol of the raw material of the urethane oligomer (A2). Moreover, also in the composition containing the monomer (B3) which has a hydroxyl group as a monomer (B '), favorable compatibility of the noncurable oligomer (D) in a composition can be obtained, and a noncurable oligomer (D) is stable in hardened | cured material. Can be present.

10-90 mass% is preferable, and, as for content of the non-curable oligomer (D) in the photocurable resin composition for resin layer formation, 30-80 mass% is more preferable. When content of a noncurable oligomer is 10 mass% or more, the effect of reducing the stress which arises by shrinkage of resin at the time of hardening is easy to be acquired sufficiently. If it is 90 mass% or less, surface materials will be easy to fix sufficiently, and the position shift with time after a joining of a surface material and a back surface material can be prevented favorably.

It is preferable that the storage shear modulus in the dynamic-viscoelasticity measurement of the resin layer after hardening of the photocurable resin composition for resin layer formation is 5 * 10 <^2> -1 * 10 <^5> Pa, and it is 8 * 10 <^2> -5 * 10 <^4> Pa More preferably, 1 * 10 <^3> -5 * 10 <^4> Pa is more preferable. Moreover, it is preferable that loss tangent (tan-delta) is 1.4 or less, and 1.0 or less is more preferable. Although the lower limit of a loss tangent is not specifically limited, It can be set as the range which can be taken in manufacture, In the case of a comparatively flexible resin layer, it is normally 0.01 or more. The storage shear modulus and loss tangent are measured by applying light to the photocurable resin composition for forming an uncured resin layer using a dynamic viscoelasticity measuring device, and then irradiating the resin with dynamic light as described in detail below. It is performed by the method of hardening a composition.

If the shear modulus of elasticity after curing is 1 × 10 ⁵ Pa or less, the stress caused by the shrinkage of the resin during curing can be sufficiently reduced, and the influence on the display quality of the display panel can be suppressed. If the shear modulus is 5 × 10 ² Pa or more, a pair of face materials (display device and transparent face material) can be fixed well. If the loss tangent is 1.4 or less, the display device is sufficiently fixed to the transparent face member even when the display device is installed vertically, and the resin layer is deformed due to the weight of the display device. Position shifts are preferably prevented.

By incorporating the non-curable oligomer (D) in the photocurable resin composition for resin layer formation, the storage shear modulus can be reduced while suppressing the increase of the loss tangent (tanδ) of the resin layer after the curing, and thus, the dynamic viscoelasticity measurement Each preferable range of the storage shear modulus and the loss tangent (tan δ) can be achieved at the same time.

(additive)

The photocurable resin composition for resin layer formation may contain a polymerization inhibitor, a photocuring accelerator, a chain transfer agent, a light stabilizer (ultraviolet absorber, a radical trapping agent, etc.), an antioxidant, a flame retardant, and an adhesion improving agent (silane coupling agent, if necessary). Etc.), and various additives, such as a pigment and dye, may be included and it is preferable to contain a polymerization inhibitor and a light stabilizer. In particular, by containing a polymerization inhibitor in an amount less than a polymerization initiator, stability of the photocurable resin composition for resin layer formation can be improved, and the molecular weight of the resin layer after hardening can also be adjusted.

By containing a small amount of a chain transfer agent, although the molecular weight of the resin layer after hardening can be adjusted and the storage elastic modulus of a resin layer can be reduced, in many cases, a hardening rate becomes slow.

In the photocurable resin composition for resin layer formation containing a relatively large amount of the noncurable oligomer (D) of the present invention, the elastic modulus can be adjusted by the content of the oligomer (D), so that the content of the chain transfer agent is reduced or not contained. It is desirable to. Specifically, the addition amount of the chain transfer agent is preferably 1 parts by mass or less, and 0.5 parts by mass or less based on the total amount of the curable compound (II), that is, 100 parts by mass in total of the oligomer (A ') and the monomer (B'). More preferred.

[Step (c)]

After the step (b), the first face member to which the photocurable resin composition for resin layer formation was supplied is placed in a decompression device, and the first face member is placed horizontally so that the surface of the curable resin composition is on the fixed support plate in the decompression device. .

The upper part in a decompression device is provided with the movable support mechanism which can move to an up-down direction, and the 2nd face material is attached to the movable support mechanism. When the second face member is a display device, the surface on the side displaying the image is faced downward. When the antireflection layer is formed on the surface of the second face member, the surface on the side where the antireflection layer is not formed is faced downward.

The second face member is placed at a position above the first face member and not in contact with the photocurable resin composition for resin layer formation. That is, the photocurable resin composition for resin layer formation on a 1st face material and a 2nd face material are made to oppose, without contacting.

Moreover, you may provide the movable support mechanism which can move to an up-down direction in the lower part in a decompression device, and may provide the 1st surface material in which curable resin composition was supplied on the movable support mechanism. In this case, a 2nd face material is attached to the fixed support board formed in the upper part in a decompression device, and opposes a 1st face material and a 2nd face material.

Moreover, you may support both the 1st face material and the 2nd face material by the movement support mechanism provided in the up and down inside a decompression device.

After arrange | positioning a 1st face material and a 2nd face material to a predetermined position, the inside of a decompression device is pressure-reduced and it is set as a predetermined pressure-reduced atmosphere. If possible, the first face member and the second face member may be positioned at a predetermined position in the decompression device during the decompression operation or after the predetermined pressure reduction atmosphere.

After the inside of the decompression device becomes a predetermined decompression atmosphere, the second face member supported by the moving support mechanism is moved downward, and the second face member is superposed on the photocurable resin composition for resin layer formation on the first face member.

By superposition, the surface of the first face material (the surface of the image display side in the case of the display device), the surface of the second face material (the surface of the image display side in the case of the display device), and the uncured seal portion In the enclosed space, the photocurable resin composition for resin layer formation is sealed.

At the time of superposition, the photocurable resin composition for resin layer formation spreads by the self weight of the 2nd face material, the pressure from a movement support mechanism, etc., and the photocurable resin composition for resin layer formation fills in the said space, and thereafter, a process In (d), when exposed to high pressure atmosphere, the layer of the photocurable resin composition for resin layer formation with little or no bubble is formed.

The pressure reduction atmosphere at the time of superposition is 100 Pa or less, and 10 Pa or more is preferable. When the pressure-reduced atmosphere is too low, there is a possibility that the components (curable compound, photopolymerization initiator, polymerization inhibitor, light stabilizer, etc.) contained in the photocurable resin composition for resin layer formation are adversely affected. For example, when the pressure-reduced atmosphere is too low, each component may be vaporized, and it may take time to provide a pressure-reduced atmosphere. As for the pressure of a pressure reduction atmosphere, 15-40 Pa is more preferable.

The time from the time when the first face material and the second face material are overlapped is not particularly limited, and after sealing the photocurable resin composition for resin layer formation, the pressure sensitive atmosphere may be immediately released, and the resin layer After sealing of the photocurable resin composition for formation, you may hold | maintain a pressure reduction state for a predetermined time. By maintaining the pressure-reduced state for a predetermined time, the resin layer-forming photocurable resin composition flows in the sealed space, so that the interval between the first face member and the second face member becomes uniform, and the sealing state is easily maintained even if the atmospheric pressure is increased. Although the long time of several hours or more may be sufficient as time to maintain a reduced pressure state, from a viewpoint of productive efficiency, less than 1 hour is preferable and less than 10 minutes are more preferable.

In the manufacturing method of this embodiment, when the photocurable resin composition for seal part formation with a high viscosity is apply | coated and the uncured seal part is formed, the photocurable resin for resin layer formation in the laminated precursor obtained by process (c). The thickness of the composition can be made relatively thick at 10 µm to 3 mm.

[Process (d)]

After releasing a reduced pressure atmosphere in the step (c), the laminated precursor is placed in a pressure atmosphere having an atmospheric pressure of 50 Pa or more.

When the laminated precursor is placed in a pressure atmosphere of 50 Pa or more, the pressure is increased in the direction in which the first face material and the second face material are brought into close contact by the elevated pressure. The resin composition flows, and the entire sealed space is uniformly filled with the photocurable resin composition for resin layer formation.

The pressure atmosphere is 80 kPa-120 kPa normally. The pressure atmosphere may be an atmospheric pressure atmosphere or a higher pressure. Atmospheric pressure atmosphere is most preferable at the point which can perform operation, such as hardening of the photocurable resin composition for resin layer formation, without requiring a special installation.

The time (hereinafter referred to as high pressure holding time) from the time when the laminated precursor is placed in a pressure atmosphere of 50 Pa or more until the curing of the photocurable resin composition for resin layer formation is started is not particularly limited. When taking out a laminated precursor from a pressure reduction apparatus, it moves to a hardening apparatus, and performs the process until it starts hardening in atmospheric pressure atmosphere, the time required for the process becomes a high pressure holding time. Therefore, when the bubble is not already present in the sealed space of the laminated precursor at the time when it is placed in the atmospheric pressure atmosphere, or when the bubble is lost during the process, the photocurable resin composition for resin layer formation can be immediately cured. In the case where time is required until the bubbles disappear, the laminated precursor is maintained in an atmosphere of a pressure of 50 Pa or more until the bubbles disappear. Moreover, since a normal trouble does not arise even if a high pressure holding time becomes long, you may lengthen a high pressure holding time from another necessity on a process. Although the high pressure holding time may be a long time more than 1 day, in terms of production efficiency, less than 6 hours is preferable, less than 1 hour is more preferable, and less than 10 minutes is especially preferable at the point which further increases productive efficiency.

Next, by hardening the photocurable resin composition for resin layer formation in the state which set the laminated precursor in the pressure atmosphere of 50 Pa or more, the resin layer which bonds a display device and a protective plate is formed, and a display apparatus is manufactured.

The photocurable resin composition for resin layer formation and the photocurable resin composition for seal | sticker part formation irradiate and harden light. For example, visible light of ultraviolet rays or short wavelengths is irradiated from a light source (ultraviolet lamp, high pressure mercury lamp, black light, chemical lamp, UV-LED, etc.) to cure the photocurable resin composition.

At this time, the uncured seal portion formed from the photocurable resin composition for seal portion formation may be cured simultaneously with the curing of the photocurable resin composition for resin layer formation, and before curing of the photocurable resin composition for resin layer formation. You may harden. Moreover, when a light shielding printing part is formed in a part of a transparent face material, and is clamped by a light shielding printing part, and a seal part is formed, it is used for the light which passes through the light transmission part of a transparent face material used for hardening of the photocurable resin composition for resin layer formation. Since it is difficult to harden a seal part by this, you may harden a seal part after hardening of the photocurable resin composition for resin layer formation.

For example, light is irradiated to the photocurable resin composition for resin layer formation from the side which has a light transmittance among the 1st face material and the 2nd face material of a laminated precursor, and the light shielded part and the display device were inserted in the side of a laminated precursor. Light is irradiated to the sealing part of hardening and the photocurable resin composition for resin layer formation.

Among the first and second face members, the display device does not have light transmittance in a state where it is not operated, and thus, light is irradiated through the light transmitting portion from the transparent face member side serving as a protective plate.

Moreover, when the light shielding printing part is formed in the periphery of a transparent face material, and an uncured sealing part and the photocurable resin composition for resin layer formation exist in the area | region clamped by a light shielding printing part and a display device, Light alone cannot fully cure. Therefore, light is irradiated from the side of a display device.

As light, ultraviolet-ray or 450 nm or less visible light is preferable. In particular, when the antireflection layer is formed on the transparent face material, and the antireflection layer or the transparent resin film having the antireflection layer formed thereon, or the adhesive layer formed between the antireflection film and the transparent face material does not transmit ultraviolet rays, curing by visible light is prevented. It becomes necessary.

As a light source for light irradiation from the side, a light source used for light irradiation from the transparent face member side may be used. However, the use of LEDs emitting ultraviolet light or visible light of 450 nm or less may be applied to the arrangement space or a specific point of the light source. It is preferable at the point suitable for efficient light irradiation.

As a step of light irradiation, although it may irradiate light from the side after light irradiation from the transparent face material side, and vice versa or light irradiation at the same time, the uncured seal part and light-curable resin for resin layer formation in a light-shielding printing part In order to further accelerate photocuring of the composition, it is preferable to irradiate light from the side first or to irradiate light from the transparent face member side simultaneously with the side. Moreover, when time needs for hardening of a photocurable resin composition, such as hardening of the photocurable resin composition for resin layer formation progresses over time after light irradiation, hardening of the photocurable resin composition for resin layer formation After almost completion, the seal portion may be cured by light irradiation from the side.

[Example]

In the manufacturing method of this embodiment, it is arbitrary whether a back surface material or a surface material is used as a 1st face material. Therefore, the display apparatus can be manufactured by the following two types of methods, respectively according to the selection of a 1st face material.

(α-1) A method of using a display device (back surface material) as the first face material and using a transparent face material (surface material) that serves as a protective plate as the second face material.

(α-2) A method of using a transparent face material (surface material) serving as a protective plate as a first face material and a display device (back face material) as a second face material.

Hereinafter, the method of manufacturing the display device of FIG. 1 will be described in detail with reference to the case of the method (α-1) as an example.

(Step (a))

As shown to FIG. 3 and FIG. 4, the photocurable resin composition for seal | sticker part formation is apply | coated with a dispenser (illustration roughly) etc. along the periphery of the display device 50 (1st surface material), and the uncured seal | sticker part 12 is shown. To form.

Wiring members, such as an FPC, which transmit an electric signal for operating a display device, may be provided in the outer peripheral part of a display device. In the manufacturing method of this embodiment, when holding each face material, it is preferable to arrange | position a display device below as a 1st face material from the point which facilitates arrangement | positioning of a wiring member.

(Step (b))

Next, as shown in FIG. 5 and FIG. 6, the photocurable resin composition 14 for forming a resin layer is supplied to the rectangular region 13 surrounded by the uncured seal portion 12 of the display device 50. As for the supply amount of the photocurable resin composition 14 for resin layer formation, the space sealed by the uncured seal part 12, the display device 50, and the transparent face material 10 (refer FIG. 7) is for resin layer formation. The amount is set in advance as long as it is filled by the photocurable resin composition 14.

As shown in FIG. 5 and FIG. 6, supply of the photocurable resin composition 14 for resin layer formation places the display device 50 in the lower platen 18 horizontally, and the dispenser 20 which moves to a horizontal direction is carried out. Is performed by supplying the photocurable resin composition 14 for resin layer formation in linear form, strip form, or point shape.

The dispenser 20 is horizontally moved in the entire range of the region 13 by a known horizontal moving mechanism composed of a pair of feed screws 22 and a feed screw 24 orthogonal to the feed screws 22. It is possible. In addition, a die coater may be used instead of the dispenser 20.

(Step (c))

Next, as shown in FIG. 7, the display device 50 and the transparent face material 10 (2nd face material) are carried in in the pressure reduction apparatus 26. Then, as shown in FIG. An upper plate 30 having a plurality of suction pads 32 is disposed at an upper portion of the decompression device 26, and a lower plate 31 is formed at a lower portion thereof. The upper surface plate 30 is movable in the vertical direction by the air cylinder 34.

The transparent face material 10 is attached to the suction pad 32. The display device 50 is fixed on the lower platen 31 with the surface to which the photocurable resin composition 14 for resin layer formation was supplied facing up.

Next, the air in the decompression device 26 is sucked by the vacuum pump 28. After the atmospheric pressure in the pressure reduction apparatus 26 reaches the pressure reduction atmosphere of 15-40 Pa, for example, in the state which adsorbed and held the transparent face material 10 by the adsorption pad 32 of the upper surface plate 30, The air cylinder 34 is operated and lowered toward the display device 50 waiting for the air. And the display device 50 and the transparent face material 10 are overlapped through the uncured sealing part 12, and a laminated precursor is comprised and a laminated precursor is hold | maintained for a predetermined time in reduced pressure atmosphere.

In addition, the mounting position of the display device 50 with respect to the lower surface plate 31, the number of adsorption pads 32, the mounting position of the transparent face material 10 with respect to the upper surface plate 30, etc. are the display device 50 and It adjusts suitably according to the size, shape, etc. of the transparent face material 10. At this time, by using the electrostatic chuck as the adsorption pad and adopting the electrostatic chuck holding method described in the specification (accepted herein) attached to Japanese Patent Application No. 2008-206124, the glass substrate can be stably held in a reduced pressure atmosphere. have.

(Step (d))

Subsequently, after making the inside of the pressure reduction apparatus 26 into atmospheric pressure, for example, the laminated precursor is taken out from the pressure reduction apparatus 26. When the laminated precursor is placed in an atmospheric pressure atmosphere, the surface on the display device 50 side of the laminated precursor and the surface on the transparent face material 10 side are pressed by atmospheric pressure, and the photocurable resin composition 14 for forming a resin layer in the sealed space is It is pressed by the display device 50 and the transparent face material 10. By this pressure, the photocurable resin composition 14 for resin layer formation in a sealed space flows, and the whole sealed space is uniformly filled with the photocurable resin composition 14 for resin layer formation.

Next, when a light shielding printing part is formed in a transparent face material and the uncured sealing part clamped by the light shielding printing part and the photocurable resin composition for resin layer formation are first hardened | cured, as shown in FIG. Light (ultraviolet light or visible light of 450 nm or less) is applied to the uncured seal portion 12 and the resin layer-forming photocurable resin composition 14 sandwiched between the light shielding printing portion 55 and the display device 50. Irradiating to the periphery, and irradiating light (ultraviolet rays or visible light of 450 nm or less) to the photocurable resin composition 14 for resin layer formation through the light transmission part 56 from the side of the transparent face material 10, and inside a laminated precursor The display device 1 is manufactured by hardening the uncured sealing part 12 and the photocurable resin composition 14 for resin layer formation.

When there is no light-shielding printing part in a transparent face material, light is irradiated to the whole surface of a laminated precursor from the side of the transparent face material 10, and the uncured sealing part 12 and the photocurable resin composition for resin layer formation inside a laminated precursor are found. By hardening | curing 14, the display apparatus 1 is manufactured.

As mentioned above, although the manufacturing method of the display apparatus of this embodiment was demonstrated concretely, taking the case of the method ((alpha) -1) as an example, the display apparatus can be manufactured similarly also in the other method ((alpha) -2).

[Operational effect: manufacturing method of the display device]

According to the manufacturing method of the display apparatus of this embodiment demonstrated above, the display apparatus of a comparatively large area can be manufactured without generating an air bubble in a resin layer. Even if bubbles remain in the photocurable resin composition for resin layer formation sealed under reduced pressure, the pressure is also applied to the sealed resin layer formation photocurable resin composition under a high pressure atmosphere before curing, and the volume of the bubble decreases, Bubbles are easily lost. For example, it is thought that the volume of the gas in the bubble in the photocurable resin composition for resin layer formation sealed under 100 Pa will be 1/1000 under 100 Pa. Since a base may be melt | dissolved in the photocurable resin composition for resin layer formation, the gas in a microvolume of bubble rapidly melt | dissolves and disappears in the photocurable resin composition for resin layer formation.

Moreover, even if pressure, such as atmospheric pressure, is applied to the photocurable resin composition for resin layer formation after sealing, since the liquid photocurable resin composition for resin layer formation is a fluid composition, the pressure is distributed uniformly on the surface of a display device. And no more stress is applied to a part of the surface of the display device which contact | connected the photocurable resin composition for resin layer formation, and there is little possibility of damaging a display device.

Moreover, the interface adhesive force of the resin layer by hardening of the photocurable resin composition for resin layer formation, a display device, and a transparent face material is higher than the interface adhesive force by heat fusion. In addition, since the photocurable resin composition for fluid resin layer formation is pressurized to adhere to the surface of a display device or a transparent face material, and it hardens | cures in that state, a higher interface adhesive force is obtained, and the surface of a display device or a transparent face material is obtained. Uniform adhesion is obtained with respect to, and the interfacial adhesion is less likely to be partially lowered.

Therefore, there is little possibility that peeling will generate | occur | produce on the surface of a resin layer, and there exists also a little possibility that moisture and a corrosive gas invade in the part with insufficient interface adhesive force.

Moreover, compared with the method (injection method) of inject | pouring a fluid resin layer formation photocurable resin composition into the space of a narrow and large area between two surface materials, the generation | occurrence | production of a bubble is small and the photocurability for resin layer formation in a short time. The resin composition can be filled. Moreover, there are few restrictions of the viscosity of the photocurable resin composition for resin layer formation, and can easily fill the high viscosity photocurable resin composition for resin layer formation. Therefore, the photocurable resin composition for resin layer formation of the high viscosity containing the comparatively high molecular weight curable compound which can raise the intensity | strength of a resin layer can be used.

Moreover, as a photoinitiator (C2) of the photocurable resin composition for resin layer formation, photopolymerization which has the absorption wavelength range ((lambda) 2) which exists in the longer wavelength side rather than the absorption wavelength range ((lambda) 1) of the photoinitiator (C1) of the uncured seal part. Uncured seal | sticker by using an initiator (C2) and using both the light of the wavelength in the absorption wavelength range ((lambda) 1), and the light of the wavelength in the absorption wavelength range ((lambda) 2) as light irradiated from the side of a laminated precursor. The light of the wavelength in the absorption wavelength range ((lambda) 2) which is not absorbed by the negative photoinitiator (C1) reaches | attains the photocurable resin composition for resin layer formation enough to fit in the display device in a light shielding part, and absorbs the absorption wavelength range ((lambda) 2). By the photoinitiator (C2) which has the thing, hardening of the photocurable resin composition for resin layer formation can fully be performed.

[Effects: Curable Resin Composition]

In the bonding of the display device and the transparent face material, by reducing the shrinkage ratio at the time of curing of the curable resin composition or reducing the elastic modulus of the resin layer after curing, it is possible to reduce the stress on the display device and to damage display quality such as display irregularities. Can be effectively prevented.

By the way, in order to reduce the shrinkage at the time of hardening, when the molecular weight per hardening site | part of a curable compound is made large, the viscosity of a curable compound will become large, the uniform supply of curable resin composition to a face material surface will become difficult, or the hardening reaction at the time of hardening There is a risk of unevenness.

Moreover, in order to reduce the elasticity modulus of the resin layer after hardening, if it contains the nonhardening component which does not contribute to hardening, the compatibility in curable resin composition will fall at the time of uncuring, and the transparency of the resin composition after hardening will be impaired, The adhesiveness of the resin layer and hardening surface after hardening may fall, and a surface material and a back surface material may peel over time.

On the other hand, the curable resin composition of this invention is a non-curable component which does not harden-react with curable compound (II) in the photocurable resin composition for resin layer formation at the time of hardening, and is especially noncurable which has 0.8-3 hydroxyl groups per molecule. By containing 10-90 mass% of oligomers and having the hydroxyl group which does not react at the time of hardening in curable compound (II), stability of the photocurable resin composition for resin layer formation at the time of uncuring is favorable, Viscosity can be made low, the uniformity of hardening reaction at the time of hardening is favorable, shrinkage at the time of hardening can be reduced, and the elasticity modulus of resin after hardening can be reduced.

When the shrinkage at the time of curing is reduced and the elastic modulus of the resin after curing is reduced, the stress due to the curing shrinkage of the resin layer is reduced. If the stability of the photocurable resin composition for resin layer formation at the time of uncuring is favorable, and the uniformity of the hardening reaction at the time of hardening is favorable, a resin layer with favorable transparency will be easy to be obtained. When the viscosity of the photocurable resin composition for resin layer formation at the time of uncuring is low, generation | occurrence | production of a bubble is easy to be suppressed sufficiently, and favorable interface bonding force of a face material and a resin layer is easy to be obtained.

In particular, when the display device is a liquid crystal display device and a TN (Twisted Nematic) type liquid crystal display device in which an IPS (In-plane Switching) type or an optical film for visual improvement is bonded to the display surface, the display device is applied to the display device. Since the bearing stress tends to adversely affect the display quality, it is preferable that the bonding resin layer has a low modulus of elasticity.

Therefore, as a display device in the display apparatus which applies the curable resin composition of this invention, a liquid crystal display device is preferable and a liquid crystal display device of an IPS type or a TN type liquid crystal display device is more preferable.

In addition, the curable resin composition of this invention is not limited to a display apparatus, It can apply to the laminated body which laminated | stacked a pair of face material through the resin layer, and the same effect is acquired.

Moreover, thermosetting resin composition may be sufficient as curable resin composition of this invention, and in this case, a well-known thermosetting group is used as a curable group of a curable compound. Moreover, a well-known thermal polymerization initiator is contained as needed. In the said embodiment, when curable resin composition for resin layer formation is thermosetting, it is preferable to make curable resin composition for seal part formation also thermosetting.

In particular, since the photocurable resin composition does not require high temperature at the time of hardening, it is preferable at the point that there is little possibility of the bad influence on the surface material etc. by high temperature.

A photopolymerization initiator and a thermal polymerization initiator may be used together, and photocuring and thermosetting may be performed simultaneously or separately, and curability may be improved.

Moreover, the method of manufacturing a laminated body using the curable resin composition of this invention is not limited to the said embodiment method, A well-known method can be used suitably.

Example

Below, the example implemented in order to confirm the effectiveness of this invention is shown. Examples 1-5, 9, and 10 are Examples, and Examples 6-8 are comparative examples.

(Measurement of Storage Shear Modulus and Its Loss Tangent)

The storage shear modulus and the loss tangent (tanδ) of the resin layer after curing were determined by using a rheometer (Anton Farr Corporation, Physica MCR301), using a non-cured photocurable resin composition for forming a resin layer and a stage made of soda-lime glass. On the black light (Nippon Electric Co., FL15BL) which was sandwiched by a 0.4 mm gap between the measuring spindle (Anton Parr, D-PP20 / AL / S07) and installed at the lower part of the stage at 35 ° C under a nitrogen atmosphere. 1% dynamic shear deformation was applied while irradiating light at 2 mW / cm 2 for 30 minutes, thereby curing the photocurable resin composition for resin layer formation and measuring the result. At the time of hardening of the photocurable resin composition for resin layer formation, the position of a spindle was automatically adjusted so that a stress might not arise in the normal direction of a spindle.

Irradiation intensity was measured on the stage in which the photocurable resin composition for resin layer formation is installed using the illuminometer (Ushio Electric Co., Ltd., ultraviolet intensity meter unimeter UIT-101).

(Number average molecular weight)

The number average molecular weight of the oligomer was calculated | required using the GPC apparatus (HLC-8020 by TOSOH company).

(Viscosity)

The viscosity of the photocurable resin composition was measured with the E-type viscosity meter (Toki Sangyo make, RE-85U).

(Haizuchi)

Haze value was calculated | required by the measurement based on ASTMD1003 using Hazeguard II by Toyo Seiki Co., Ltd. product.

[Example 1]

(Display device)

A liquid crystal display device was taken out from a commercially available 17 type liquid crystal monitor (V137b, manufactured by Acer). The display mode of the liquid crystal display device was TN (Twisted Nematic) type, and the size of the display part was 338 mm in length and 270 mm in width. Polarizing plates are bonded to both sides of the liquid crystal display device, six FPCs for driving are bonded to one side of the long side, and three FPCs to one side of the short side, and a printed wiring board is bonded to the end of the FPC on the long side. there was. This liquid crystal display device was referred to as display device A.

(Glass)

Soda-lime glass of length 355mm, width 290mm, and thickness 2.8mm was made into the glass plate B used as a protective plate.

(Photocurable resin composition for seal part formation)

Bifunctional polypropylene glycol having 2 hydroxyl groups in 1 molecule which added ethylene oxide to a molecule terminal (number average molecular weight computed from hydroxyl value: 4000, ethylene oxide content 24 mass% in polypropylene glycol molecules), and hexa Methylene diisocyanate is mixed in a molar ratio of 6 to 7, and then diluted with isobornyl acrylate (IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and then reacted at a prepolymer obtained by reacting at 70 ° C in the presence of a catalyst of a tin compound. And 30 mass by adding 2-hydroxyethyl acrylate in a molar ratio of almost 1 to 2, adding 0.03 parts by mass of 2,5-di-t-butylhydroquinone (polymerization inhibitor) and reacting at 70 ° C. A urethane acrylate oligomer (hereinafter referred to as UC-1) solution diluted with% isobornyl acrylate was obtained. The number of curable groups of UC-1 was 2, and the number average molecular weight was about 55000. The viscosity at 60 degrees C of UC-1 solution was about 580 Pa.s.

90 mass parts of UC-1 solution and 10 mass parts of 2-hydroxybutyl methacrylate (The Kyester Co., Ltd. product, Lightester HOB) were mixed uniformly, and the mixture was obtained. 100 mass parts of this mixture, 3 mass parts of 1-hydroxy cyclohexyl phenyl- ketone (photoinitiator, the Chiba Specialty Chemicals make, IRGACURE 184) are mixed uniformly, and the photocurable resin composition for sealing part formation C was obtained.

The defoaming process was performed by installing in the pressure reduction apparatus in the open state, putting the seal part formation photocurable resin composition C in the container, and depressurizing the inside of a decompression device to about 20 kPa for 10 minutes. It was about 1300 Pa.s when the viscosity at 25 degrees C of the photocurable resin composition C for sealing part formation was measured.

(Photocurable resin composition for resin layer formation)

Bifunctional polypropylene glycol (number average molecular weight 4000 computed from hydroxyl value, ethylene oxide content 24 mass% in polypropylene glycol molecule) which has two hydroxyl groups in 1 molecule which added ethylene oxide to a molecule terminal, and isophorone Diisocyanate is mixed in a molar ratio of 4 to 5, 2-hydroxyethyl acrylate is added to a prepolymer obtained by reacting at 70 ° C in the presence of a catalyst of a tin compound in a molar ratio of almost 1 to 2, 2 The urethane acrylate oligomer (it describes as UA-2 hereafter) was obtained by adding 0.03 mass part of, 5-di-t-butylhydroquinone (polymerization inhibitor), and making it react at 70 degreeC. The number of curable groups of UA-2 was 2, the number average molecular weight was about 24000, and the viscosity in 25 degreeC was about 830 Pa.s.

40 parts by mass of UA-2, 30 parts by mass of 2-hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., Light Ester HOB), and 30 parts by mass of n-dodecyl methacrylate are uniformly mixed, and the mixture thereof. 0.5 mass parts of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (photoinitiator, Chiba Specialty Chemicals, IRGACURE 819) was uniformly dissolved in 100 parts by mass of the resin layer for forming a resin layer. Photocurable resin composition PD was obtained.

Next, the bifunctional polypropylene glycol (calculated from hydroxyl value) which has two hydroxyl groups in 40 mass parts of PD and one molecule which added ethylene oxide to the molecular terminal similar to the one used at the time of the synthesis | combination of UA-2. The number average molecular weight 4000 and 60 mass parts of ethylene oxide content 24 mass%) in a polypropylene glycol molecule were melt | dissolved uniformly, and the photocurable resin composition D for resin layer formation was obtained.

The defoaming process was performed by installing in the container the photocurable resin composition D for resin layer formation in the pressure reduction apparatus in the open state, depressurizing the inside of the pressure reduction apparatus to about 20 kPa, and holding it for 10 minutes. It was 1.3 Pa.s when the viscosity at 25 degrees C of the photocurable resin composition D for resin layer formation was measured.

In addition, the photoinitiator used for the photocurable resin composition D for resin layer formation (the said IRGACURE 819) is the absorption wavelength range (about 380 nm or less) of the photoinitiator used for the photocurable resin composition C for seal part formation (the said IRGACURE 184). The longer wavelength side also has an absorption wavelength range (about 440 nm or less).

Next, the viscoelastic property after photocuring of the photocurable resin composition D for resin layer formation was measured using the rheometer. As a result, the storage shear modulus was 3.7x10 <^3> Pa and the loss tangent (tan-delta) was 0.61.

(Step (a))

The photocurable resin composition C for seal part formation is apply | coated with a dispenser so that it may become width about 1 mm and application | coating thickness about 0.6 mm over the full perimeter of the position of about 3 mm outside of the image display area of the display device A, and uncured The seal portion of was formed.

(Step (b))

The photocurable resin composition D for resin layer formation was supplied to the several area | region so that gross mass may be 38 g using the dispenser to the inner area | region of the uncured seal part apply | coated to the outer periphery of the image display area of the display device A using a dispenser.

While supplying the photocurable resin composition D for resin layer formation, the shape of the uncured seal part was maintained.

(Step (c))

The display device A was placed horizontally so that the surface of the photocurable resin composition D for resin layer formation turned up on the upper surface of the lower surface plate in the decompression device in which the pair of lifting devices of the surface plate are provided.

The light-transmitting part without the light-shielding printing portion of the glass plate B when the glass plate B is viewed from the upper surface by using an electrostatic chuck on the lower surface of the upper and lower surfaces of the lifting device in the decompression device so that the surface on the side where the light-shielding printing portion is formed faces the display device A. In the vertical direction, the distance from the display device A was kept to be 30 mm so that the image display area of the display device A was in the same position with a margin of about 1 mm.

The pressure reduction device was sealed and exhausted until the pressure in the pressure reduction device was about 10 kPa. The upper and lower surface plates were brought close to the elevating device in the decompression device, and the display device A and the glass plate B were pressed at a pressure of 2 kPa through the photocurable resin composition D for resin layer formation, and held for 1 minute. The static electricity electrostatic chuck was separated, and the glass plate B was separated from the top plate, and the inside of the decompression device was returned to atmospheric pressure in about 15 seconds, and the photocurable resin composition D for resin layer formation was sealed with the display device A, the glass plate B, and the uncured seal part. Laminated precursor E was obtained.

In the laminated precursor E, the shape of the uncured seal portion was maintained in an almost initial state.

(Step (d))

The resin layer is formed by irradiating 30 minutes of ultraviolet-ray from a black light and visible light of 450 nm or less uniformly from the surface of the glass plate B side of laminated precursor E, and hardening the photocurable resin composition D for resin layer formation, and displaying The device F was obtained. Although the display apparatus F did not need the bubble removal process required at the time of manufacture by the conventional injection method, defects, such as a bubble which remain | survives in a resin layer, were not recognized. Moreover, defects, such as leaking of the photocurable resin composition for resin layer formation from the seal part, were not confirmed. Moreover, the thickness of the resin layer was made into the target thickness (about 0.4 mm).

The transparent laminated body was produced similarly using the glass plate of substantially the same size instead of the display device A, and the haze value in the part without a printing light shielding part was measured, and was 1% or less, and the transparency was favorable.

After returning the display apparatus F to the case of the liquid crystal monitor which took out the liquid crystal display device, and reconnecting wiring, the liquid crystal monitor was installed so that the display device A bonded by the glass plate B might become vertical. After stopping still for 5 days, the power was turned on, and when connected to a computer to display an image, a homogeneous and good display image was obtained over the entire surface of the display screen, and the display contrast was high from the beginning. Even if the image display surface was strongly pressed with a finger, the image did not become disturbed, and the glass plate B effectively protected the display device A.

Subsequently, in the same manner, the display device F was installed, and after one month, the bonding position of the display device was confirmed.

[Example 2]

(Photocurable resin composition for resin layer formation)

30 mass parts of the photocurable resin composition PD for resin layer formation used in Example 1, and bifunctional polypropylene glycol (number average molecular weight 2000 computed from hydroxyl value, EO in polypropylene glycol) which has two hydroxyl groups in 1 molecule Content 0 mass%) 70 mass parts was melt | dissolved uniformly, and the photocurable resin composition D2 for resin layer formation was obtained.

The defoaming process was performed by installing in the pressure reduction apparatus in the open state, putting resin layer formation photocurable resin composition D2 in the container, and depressurizing the inside of a pressure reduction apparatus to about 20 kPa for 10 minutes. It was 0.6 Pa.s when the viscosity at 25 degrees C of the photocurable resin composition D2 for resin layer formation was measured.

Next, using a rheometer and measuring the viscoelastic property after photocuring of the photocurable resin composition D2 for resin layer formation, the storage shear modulus was 9x10 <^2> Pa and the loss tangent (tan-delta) was 0.84.

A display device F2 was obtained in the same manner as in Example 1 except that the composition C was used as the seal portion-forming photocurable resin composition and the composition D2 was used as the resin layer-forming photocurable resin composition. After returning display apparatus F2 to the case of the liquid crystal monitor which took out the liquid crystal display device, and reconnecting wiring, the liquid crystal monitor was installed so that the display device A bonded by the glass plate B might become vertical. After stopping still for 5 days, the power was turned on, and when connected to a computer to display an image, a homogeneous and good display image was obtained over the entire surface of the display screen, and the display contrast was high from the beginning. Even if the image display surface was strongly pressed with a finger, the image did not become disturbed, and the glass plate B effectively protected the display device A.

Subsequently, in the same manner, the display device F2 was provided, and the bonding position of the display device was confirmed after one month.

[Example 3]

(Photocurable resin composition for resin layer formation)

40 parts by mass of UA-2 used in Example 1, 30 parts by mass of 2-hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., Light Ester HOB) and 30 parts by mass of n-dodecyl methacrylate are uniformly mixed. Then, 0.5 parts by mass of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (photopolymerization initiator, Chiba Specialty Chemicals, IRGACURE 819) and 100 parts by mass of the mixture were n-dodecyl. 0.5 mass part of mercaptan (chain transfer agent, the Chao Corporation make, thiocarcol 20) was melt | dissolved uniformly, and the photocurable resin composition PG for resin layer formation was obtained.

Next, the bifunctional polypropylene glycol (calculated from hydroxyl value) which has two hydroxyl groups in 60 mass parts of PG and one molecule which added ethylene oxide to the molecular terminal similar to the one used at the time of the synthesis | combination of UA-2. 40 mass parts of number average molecular weight: 4000 and 24 mass% of ethylene oxide content in a polypropylene glycol molecule were melt | dissolved uniformly, and the photocurable resin composition G for resin layer formation was obtained.

The defoaming process was performed by installing in the pressure reduction apparatus in the open state, putting the photocurable resin composition G for resin layer formation in the container, and depressurizing the inside of the pressure reduction apparatus to about 20 kPa for 10 minutes. It was 1.7 Pa.s when the viscosity at 25 degrees C of the photocurable resin composition G for resin layer formation was measured.

Next, using a rheometer and measuring the viscoelastic property after photocuring of the photocurable resin composition G for resin layer formation, the storage shear modulus was 1.0x10 <^4> Pa and the loss tangent (tan-delta) was 0.83.

A display device H was obtained in the same manner as in Example 1 except that the composition C was used as the sealant-forming photocurable resin composition and the composition G was used as the resin layer-forming photocurable resin composition.

After returning the display apparatus H to the case of the liquid crystal monitor which took out the liquid crystal display device, and reconnecting wiring, the liquid crystal monitor was installed so that the display device A bonded by the glass plate B might become vertical. After stopping still for 5 days, the power was turned on, and when connected to a computer to display an image, a homogeneous and good display image was obtained over the entire surface of the display screen, and the display contrast was high from the beginning. Even if the image display surface was strongly pressed with a finger, the image did not become disturbed, and the glass plate B effectively protected the display device A.

Subsequently, in the same manner, the display device H was installed, and after 1 month, the bonding position of the display device was confirmed.

[Example 4]

(Photocurable resin composition for resin layer formation)

Bifunctional polypropylene glycol having 2 hydroxyl groups in 1 molecule which added ethylene oxide to a molecule terminal (number average molecular weight computed from hydroxyl value: 4000, ethylene oxide content 24 mass% in polypropylene glycol molecules), and iso Porondiisocyanate is mixed in a molar ratio of 3 to 4, 2-hydroxyethyl acrylate is added in a molar ratio of almost 1 to 2 to a prepolymer obtained by reacting at 70 ° C in the presence of a catalyst of a tin compound, The urethane acrylate oligomer (it describes as UA-3 hereafter) was obtained by adding 0.03 mass part of 2, 5- di- t-butyl hydroquinone (polymerization inhibitor), and making it react at 70 degreeC. The number of curable groups of UA-3 was 2, the number average molecular weight was about 21000, and the viscosity in 25 degreeC was about 350 Pa.s.

80 parts by mass of UA-3 and 20 parts by mass of 2-hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., Light Ester HOB) were mixed with 100 parts by mass of bis (2,4,6). 0.5 mass parts of -trimethylbenzoyl) -phenylphosphine oxide (photoinitiator, the Chiba Specialty Chemicals make, IRGACURE 819) was melt | dissolved uniformly, and the photocurable resin composition PI was obtained.

Next, 70 mass parts of 30 mass parts of PI and bifunctional polypropylene glycol (The number average molecular weight 2000 computed from hydroxyl value, 0 mass% of EO content in polypropylene glycol) which have two hydroxyl groups in 1 molecule. It melt | dissolved uniformly and obtained the photocurable resin composition I for resin layer formation.

The defoaming process was performed by installing the resin layer forming photocurable resin composition I in the container in the open state in the open state, depressurizing the inside of a decompression device to about 20 kPa, and holding it for 10 minutes. It was 2.0 Pa.s when the viscosity at 25 degrees C of the photocurable resin composition I for resin layer formation was measured.

Next, using a rheometer and measuring the viscoelastic property after photocuring of the photocurable resin composition I for resin layer formation, the storage shear modulus was 2.5x10 <^4> Pa and the loss tangent (tan-delta) was 0.06.

A display device J was obtained in the same manner as in Example 1 except that the composition C was used as the sealant-forming photocurable resin composition and the composition I was used as the resin layer-forming photocurable resin composition.

After returning the display apparatus J to the case of the liquid crystal monitor which took out the liquid crystal display device, and reconnecting wiring, the liquid crystal monitor was installed so that the display device A bonded by the glass plate B might become vertical. As a result of turning on the power after stopping still for 5 days, a homogeneous and favorable display image was obtained over the whole surface of the display screen, and the display contrast was high from the beginning. Even if the image display surface was strongly pressed with a finger, the image did not become disturbed, and the glass plate B effectively protected the display device A.

Subsequently, in the same manner, the display device J was provided, and after one month, the bonding position of the display device was confirmed.

[Example 5]

(Photocurable resin composition for resin layer formation)

80 mass parts of 20 mass parts of PI used by Example 4, and 80 mass of bifunctional polypropylene glycol (number average molecular weight 2000 computed from hydroxyl value, 0 mass% of EO content in polypropylene glycol) which have two hydroxyl groups in 1 molecule. The part was melt | dissolved uniformly and the photocurable resin composition I2 for resin layer formation was obtained.

The defoaming process was performed by installing in the pressure reduction apparatus in the open state, putting the resin layer forming photocurable resin composition I2 in the container, and depressurizing the inside of a decompression device to about 20 kPa for 10 minutes. It was 1.0 Pa.s when the viscosity at 25 degrees C of the photocurable resin composition I2 for resin layer formation was measured.

Next, using a rheometer and measuring the viscoelastic property after photocuring of the photocurable resin composition I2 for resin layer formation, the storage shear modulus was 4.0x10 <^3> Pa and the loss tangent (tan-delta) was 0.07.

A display device J2 was obtained in the same manner as in Example 1 except that the composition C was used as the sealant-forming photocurable resin composition and the composition I2 was used as the resin layer-forming photocurable resin composition.

After returning the display apparatus J2 to the case of the liquid crystal monitor which took out the liquid crystal display device, and reconnecting wiring, the liquid crystal monitor was installed so that the display device A bonded by the glass plate B might become vertical. As a result of turning on the power after stopping still for 5 days, a homogeneous and favorable display image was obtained over the whole surface of the display screen, and the display contrast was high from the beginning. Even if the image display surface was strongly pressed with a finger, the image did not become disturbed, and the glass plate B effectively protected the display device A.

Subsequently, in the same manner, the display device J2 was provided, and after one month, the bonding position of the display device was confirmed. There was no positional shift or the like, and the glass plate was satisfactorily held.

[Example 6]

(Photocurable resin composition for resin layer formation)

The photocurable resin composition K for resin layer formation was obtained, without adding a noncurable oligomer to resin composition PD used in Example 1.

Defoaming process was performed by installing in the pressure reduction apparatus in the open state, putting the photocurable resin composition K for resin layer formation in the container, and depressurizing the inside of the decompression apparatus to about 20 kPa for 10 minutes. It was 2.2 Pa.s when the viscosity at 25 degrees C of the photocurable resin composition K for resin layer formation was measured.

Next, using a rheometer and measuring the viscoelastic property after photocuring of the photocurable resin composition K for resin layer formation, the storage shear modulus was 3.1x10 <^5> Pa and the loss tangent (tan-delta) was 0.32.

A display device L was obtained in the same manner as in Example 1 except that the composition C was used as the photocurable resin composition for forming a seal portion and the composition K was used as the photocurable resin composition for forming a resin layer.

After returning the display apparatus L to the case of the liquid crystal monitor which took out the liquid crystal display device, and reconnecting wiring, the liquid crystal monitor was installed so that the display device A bonded by the glass plate B might become vertical. After stopping for 5 days, the power was turned on, and when connected to a computer to display an image, display irregularities were generated in the picture frame at the periphery of the display screen, and the visual recognition was particularly remarkable in halftone display. In the part without display unevenness, the image of contrast higher than the initial stage was obtained.

Subsequently, in the same manner, the display device L was provided, and after one month, the bonding position of the display device was confirmed, but there was no positional shift or the like, and the glass plate was well maintained.

[Example 7]

(Photocurable resin composition for resin layer formation)

The photocurable resin composition M for resin layer formation was obtained, without adding a noncurable oligomer to resin composition PG used in Example 3.

The defoaming process was performed by installing in the pressure reduction apparatus in the open state, putting the resin layer M photocurable resin composition M in the container, and depressurizing the inside of the pressure reduction apparatus to about 20 kPa for 10 minutes. It was 2.1 Pa.s when the viscosity at 25 degrees C of the photocurable resin composition M for resin layer formation was measured.

Next, using a rheometer and measuring the viscoelastic property after photocuring of the photocurable resin composition M for resin layer formation, the storage shear modulus was 1.6x10 <^5> Pa and the loss tangent (tan-delta) was 0.46.

A display device N was obtained in the same manner as in Example 1 except that the composition C was used as the photocurable resin composition for forming a seal portion and the composition M was used as the photocurable resin composition for forming a resin layer.

After returning the display apparatus N to the case of the liquid crystal monitor which took out the liquid crystal display device, and reconnecting wiring, the liquid crystal monitor was installed so that the display device A bonded by the glass plate B might become vertical. After stopping for 5 days, the power was turned on, and when connected to a computer to display an image, display irregularities were generated in the picture frame at the periphery of the display screen, and the visual recognition was particularly remarkable in halftone display. In the part without display unevenness, the image of contrast higher than the initial stage was obtained.

Subsequently, in the same manner, the display device N was installed, and after 1 month, the bonding position of the display device was confirmed.

[Example 8]

(Photocurable resin composition for resin layer formation)

40 parts by mass of UA-2 used in Example 1, 20 parts by mass of 2-hydroxybutyl methacrylate (Kyosei Chemical Co., Ltd., Light Ester HOB) and 40 parts by mass of n-dodecyl methacrylate are mixed uniformly. And 0.3 parts by mass of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (photopolymerization initiator, Chiba Specialty Chemicals, IRGACURE 819) and 100 parts by mass of the mixture, n-dodecyl 1.5 mass parts of mercaptan (chain transfer agent, the Chao Corporation make, thiocarcol 20) was melt | dissolved uniformly, and the photocurable resin composition O for resin layer formation was obtained.

The defoaming process was performed by installing in the pressure reduction apparatus in the open state, putting the photocurable resin composition O for resin layer formation in the container, and depressurizing the inside of a pressure reduction apparatus to about 20 kPa for 10 minutes. It was 1.9 Pa.s when the viscosity at 25 degrees C of the photocurable resin composition O for resin layer formation was measured.

Next, using a rheometer and measuring the viscoelastic property after photocuring of the photocurable resin composition O for resin layer formation, the storage shear modulus was 7.5x10 <^3> Pa and the loss tangent (tan-delta) was 1.8.

A display device P was obtained in the same manner as in Example 1 except that the composition C was used as the photocurable resin composition for forming a seal portion and the composition O was used as the photocurable resin composition for forming a resin layer.

The display apparatus P was returned to the case of the liquid crystal monitor which took out the liquid crystal display device, and after reconnecting wiring, the liquid crystal monitor was installed so that the display device A bonded by the glass plate B might become vertical. As a result of confirming the bonding position of a display device after about 1 hour, it shifted away from the glass plate about several mm, and the display device was not able to hold | maintain favorably on a glass plate.

Therefore, when the display device P bonded to the glass plate B is horizontal, the display device P is installed horizontally, and the power supply is turned on after stopping for 5 days. As a result, there is no change in the deviation of the display device. A display image was obtained, and the display contrast was high from the beginning. Even if the image display surface was strongly pressed with a finger, the image did not become disturbed, and the glass plate B effectively protected the display device A.

[Example 9]

Bifunctional polypropylene glycol (number average molecular weight 5500 calculated by hydroxyl value) which has two hydroxyl groups in 1 molecule which does not add ethylene oxide to a molecule terminal, and 2,2,4-trimethyl- hexamethylene diisocyanate Urethane acrylate oligomer (UA-4) was synthesized in the same manner as in Example 1 except that a mixture containing about the same amount of 2,4,4-trimethyl-hexamethylene diisocyanate was mixed in a molar ratio of 1: 2. It was. The number of curable groups of UA-4 was 2, the number average molecular weight was about 16000, and the viscosity in 25 degreeC was about 39 Pa.s.

In Example 1, UA-4 is used instead of UA-2, and the photocurable resin composition PQ for resin layer formation is obtained similarly to Example 1. Bifunctional polypropylene glycol (number average calculated by hydroxyl value) which has two hydroxyl groups in 40 mass parts of PQ and one molecule which does not add ethylene oxide to the molecular terminal which is the same as what was used for the synthesis | combination of UA-4. Molecular weight 5500) to obtain a photocurable resin composition Q for forming a resin layer. The viscosity at 25 degrees C of the photocurable resin composition Q for resin layer formation was 0.8 Pa.s.

As for the viscoelastic characteristic after the photocuring of the photocurable resin composition Q for resin layer formation by a rheometer, the storage shear modulus was 2.4 * 10 <^4> Pa and the loss tangent (tan-delta) was 0.13.

A display device R was obtained in the same manner as in Example 1 except that the composition C was used as the sealant-forming photocurable resin composition and the composition Q was used as the resin layer-forming photocurable resin composition.

After returning the display apparatus R to the case of the liquid crystal monitor which took out the liquid crystal display device, and reconnecting wiring, the liquid crystal monitor was installed so that the display device A bonded by the glass plate B might become vertical. As a result of turning on the power after stopping still for 5 days, a homogeneous and favorable display image was obtained over the whole surface of the display screen, and the display contrast was high from the beginning. Even if the image display surface was strongly pressed with a finger, the image did not become disturbed, and the glass plate B effectively protected the display device A.

Subsequently, in the same manner, the display device R was installed, and after 1 month, the bonding position of the display device was confirmed. There was no positional shift or the like, and the glass plate was satisfactorily held.

[Example 10]

The bifunctional polypropylene glycol (number average molecular weight 2000 computed by hydroxyl value) and two isophorone diisocyanate which have two hydroxyl groups in 1 molecule which does not add ethylene oxide to a molecule terminal are molar ratio of 5: 6. A urethane acrylate oligomer (UA-5) was synthesize | combined similarly to Example 1 except having mixed. The number of curable groups of UA-5 was 2, the number average molecular weight was about 18000, and the viscosity in 25 degreeC was about 620 Pa.s.

In Example 1, UA-5 is used instead of UA-2, and the photocurable resin composition PS for resin layer formation is obtained like Example 1. Bifunctional polypropylene glycol (number average calculated by hydroxyl value) having two hydroxyl groups in 40 parts by mass of PS and the same molecule used for the synthesis of UA-5, without adding ethylene oxide to the molecular terminal. Bifunctional polypropylene glycol (with hydroxyl value) which has two hydroxyl groups in 30 mass parts of molecular weight 2000) and one molecule which does not add ethylene oxide to the molecular terminal whose molecular weight is larger than what was used for the synthesis | combination of UA-5. The photocurable resin composition S for resin layer formation is obtained using 30 mass parts of computed number average molecular weight 5500). The viscosity at 25 degrees C of the photocurable resin composition S for resin layer formation was 0.9 Pa.s.

As for the viscoelastic characteristic after the photocuring of the photocurable resin composition Q for resin layer formation by a rheometer, the storage shear modulus was 2.0 * 10 <^4> Pa and the loss tangent (tan-delta) was 0.15.

A display device T was obtained in the same manner as in Example 1 except that the composition C was used as the sealant-forming photocurable resin composition and the composition S was used as the resin layer-forming photocurable resin composition.

After returning the display apparatus T to the case of the liquid crystal monitor which took out the liquid crystal display device, and reconnecting wiring, the liquid crystal monitor was installed so that the display device A bonded by the glass plate B might become vertical. As a result of turning on the power after stopping still for 5 days, a homogeneous and favorable display image was obtained over the whole surface of the display screen, and the display contrast was high from the beginning. Even if the image display surface was strongly pressed with a finger, the image did not become disturbed, and the glass plate B effectively protected the display device A.

Subsequently, in the same manner, the display device T was provided, and after 1 month, the bonding position of the display device was confirmed.

Examples 1-5, 9, and 10 whose curable compound (II) and non-curable oligomer (D) of this invention are contained, and content of the said (D) are 10-90 mass% in curable resin composition are resin layers. It can be seen that the stress due to shrinkage at the time of curing can be reduced, and a homogeneous and good display image can be obtained over the entire surface of the liquid crystal display screen.

Examples 6 and 7 which contain the curable compound (II) of the present invention but do not contain the non-curable oligomer (D) have display irregularities occurring at the periphery of the liquid crystal display screen, and are particularly visually recognized in the display of the halftone. It became. Moreover, especially Example 8 which contains a chain transfer agent exceeding 1.5 mass parts with respect to 100 mass parts of curable compounds (II) was not able to hold | maintain a display device favorably on a glass plate.

Industrial availability

Curable resin composition of this invention is useful for manufacture of the laminated body used for a display apparatus.

In addition, all the content of the JP Patent application 2010-137532, a claim, drawing, and the abstract for which it applied on June 16, 2010 is referred here, and it takes in as an indication of the specification of this invention.

1: Display device
10: transparent face material
12: part of uncured seal
13: area
14 photocurable resin composition for resin layer formation
40: resin layer
42: seal part
50: display device
55: light shielding printing unit (shielding unit)
56: floodlight

Claims (12)

A curable resin composition used for a laminate formed by sandwiching and curing an uncured curable resin composition between a pair of face materials, wherein at least one face material is transparent, and the following curable compound (II) and the following non-curable oligomer (D ), And content of this non-curable oligomer (D) is 10-90 mass%, Curable resin composition characterized by the above-mentioned.
Curable compound (II): It consists of 1 or more types of curable compounds which harden-cure at the time of hardening of curable resin composition, and at least 1 type of this curable compound has the hydroxyl group which does not react at the time of hardening of the said curable resin composition.
Non-curable oligomer (D): The oligomer which does not harden-react with the said curable compound (II) at the time of hardening of curable resin composition, and has 0.8-3 hydroxyl groups per molecule. The method of claim 1,
Curable resin composition in which the said curable compound (II) has a curable group and contains the monomer which has a hydroxyl group. 3. The method of claim 2,
The curable compound (II) has a curable group, contains an oligomer (A ') having a molecular weight of 1000 to 100000, and a curable group and a monomer (B') having a molecular weight of 125 to 600, and the monomer (B ') Curable resin composition containing the monomer (B3) which has a hydroxyl group. The method of claim 3, wherein
Curable resin composition whose said non-curable oligomer (D) is a polyoxyalkylene polyol, and the said oligomer (A ') is a urethane oligomer synthesize | combined using polyoxyalkylene polyol and polyisocyanate as a raw material. The method according to claim 3 or 4,
Curable resin composition in which the said oligomer (A ') has an acryl group, and at least one part of the said monomer (B') has a methacryl group. 6. The method according to any one of claims 3 to 5,
Curable resin composition in which the said monomer (B3) contains the hydroxy methacrylate which has a hydroxyl number of 1-2 and a C3-C8 hydroxyalkyl group. 7. The method according to any one of claims 3 to 6,
Curable resin composition in which the said monomer (B ') contains the monomer (B4) chosen from the alkyl methacrylate which has a C8-C22 alkyl group. The method according to any one of claims 1 to 7,
Curable resin composition which does not contain a chain transfer agent or contains a chain transfer agent and whose content is 1 mass part or less with respect to 100 mass parts of curable compound (II). The laminated body in which one pair of face materials which are at least one transparent face material are laminated integrally via the resin layer which consists of hardened | cured material of the curable resin composition in any one of Claims 1-8. The method of claim 9,
The laminated body in which one side of said pair of face materials is a transparent face material, and the other is a display device. One of the first and second face members is a transparent face member, and includes a laminate having a first face member and a second face member, a resin layer sandwiched between the first face member and the second face member, and a seal portion surrounding the resin layer. The manufacturing method of the laminated body which has the following process (a)-(d) as a manufacturing method.
(a) Process of apply | coating curable resin composition for liquid part formation of a liquid containing curable compound (I) and a polymerization initiator to the peripheral part of the surface of a 1st face material, and forming an unhardened seal part.
(b) Process of supplying curable resin composition for resin layer formation which consists of curable resin composition of any one of Claims 1-8 to the area | region enclosed by the uncured seal part.
(c) Under a reduced pressure atmosphere of 100 Pa or less, the second face member is superposed on the curable resin composition for resin layer formation, and the curable resin composition for resin layer formation is sealed with the first face member, the second face member and the uncured seal portion. Process of obtaining a laminated precursor.
(d) Process of hardening uncured seal part and curable resin composition for resin layer formation in the state which laminated | stacked precursor was placed in the pressure atmosphere of 50 Pa or more. The method of claim 11,
The manufacturing method of the laminated body of which the said 1st face material and the 2nd face material are transparent face materials, and the other is a display device.

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