TWI721964B - Polarizing film with adhesive layer attached on both sides, its manufacturing method and image display device - Google Patents

Abstract

The present invention provides a polarizing film with an adhesive layer attached on both sides, which is provided in an image display device with an adhesive layer on both sides of the polarizing film closest to the viewing side, and has good yield and can meet the level difference Absorptive.

The polarizing film with a double-sided adhesive layer of the present invention has a polarizing film disposed on the side closest to the viewing side of the polarizing film used in an image display device, and an adhesive layer A and an adhesive layer disposed on the viewing side of the polarizing film. The adhesive layer B is arranged on the opposite side of the adhesive layer A, and the adhesive layer A is provided with a separation film SA ₁ and the adhesive layer B is provided with a separation film SB, and the adhesive layer A is The storage elastic modulus at 23°C is 0.02~0.3MPa, and the curl amount of the polarizing film with the adhesive layer is -10mm~+60mm.

Description

Polarizing film with adhesive layer attached on both sides, its manufacturing method and image display device

The present invention relates to a polarizing film with an adhesive layer on both sides of the polarizing film closest to the viewing side of the polarizing film used in an image display device and a manufacturing method thereof. In addition, the present invention relates to an image display device in which the polarizing film with the above-mentioned double-sided adhesive layer is arranged on the viewing side. As an image display device, a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), electronic paper, etc. can be cited.

The polarizing film with a double-sided adhesive layer of the present invention has an adhesive layer on both sides of the polarizing film. The adhesive layer on the visual recognition side can be preferably applied to touch panels applied on the visual recognition side of image display devices, etc. Input devices, cover glass, plastic covers and other transparent substrates and other components. On the other hand, the adhesive layer on the side opposite to the visible side can be applied to the display portion of the above-mentioned image display device. As the above-mentioned touch panel, it can be suitably used for touch panels of an optical system, an ultrasonic system, an electrostatic capacitance system, a resistive film system, etc. In particular, it can be preferably used for touch panels of electrostatic capacitance type. The aforementioned touch panel is not particularly limited, and can be used for mobile phones, tablet computers, portable information terminals, etc., for example.

In liquid crystal display devices and the like, it is essential to arrange polarizing elements on both sides of the liquid crystal cell due to the image formation method, and polarizing films are generally attached. When attaching the said polarizing film to the display part side of a liquid crystal cell etc., an adhesive agent is usually used. In this case, it has advantages such as not requiring a drying step for fixing the polarizing film. Therefore, a polarizing film with an adhesive layer preliminarily provided on one side of the polarizing film in the form of an adhesive layer is generally used. As the above-mentioned polarizing film with an adhesive layer, various proposals have been proposed (Patent Documents 1 and 2). Such The adhesive layer side of the polarizing film with the adhesive layer is applied to the display part of the liquid crystal cell and the like.

On the other hand, input devices such as touch panels, transparent substrates such as cover glass and plastic covers are provided on the viewing side of the polarizing film. The above-mentioned members are generally bonded by an adhesive layer (Patent Document 3).

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-170907

[Patent Document 2] Japanese Patent Laid-Open No. 2006-053531

[Patent Document 3] Japanese Patent Laid-Open No. 2002-348150

As shown in the above-mentioned Patent Documents 1 and 2, regarding the polarizing film with the adhesive layer provided closest to the visible side of the polarizing film used in the image display device, the adhesive layer of the polarizing film with the adhesive layer is pasted Fit in the display section. On the other hand, when a transparent substrate and other members are provided on the viewing side of the polarizing film with the adhesive layer (installed on the side closest to the viewing side), the polarizing film with the adhesive layer is separately described in Patent Document 3. It shows the preparation of an adhesive sheet for interlayer film, which is used as an adhesive layer for bonding, and then a transparent substrate and other components are bonded on the adhesive layer. In this way, multiple steps are required for bonding members such as a transparent substrate to the polarizing film closest to the viewing side among the polarizing films used in the image display device.

In Patent Documents 1 and 2, as the above-mentioned polarizing film with adhesive layer, it is disclosed that there is an adhesive layer on both sides of the polarizing film (Full Lamination: Polarizing film with adhesive layer on both sides) . However, when the polarizing film with the above-mentioned double-sided adhesive layer is attached to the adherend (a transparent substrate on the visible side, and a display on the opposite side), it is easy to attach to the end of the attached surface Mixing of bubbles occurs, so the workability is insufficient and the yield is insufficient. Therefore, for the polarizing film with the adhesive layer on both sides, it is required to simplify the steps, improve the workability and increase the yield.

In addition, the surface of the transparent substrate, such as the cover glass, has a level difference due to printing ink. Therefore, when using the adhesive layer to attach the above-mentioned member with a stepped surface to other members, the adhesive layer is required to absorb the step so that the adhesive layer follows the above-mentioned step so that no voids are generated between the members. As an index of the adhesive layer related to the above level difference, it can be listed in the level difference absorption (%) represented by the level difference (μm) and the thickness of the adhesive layer (μm): (level difference/thickness of the adhesive layer) The value of )×100 satisfies the followability. As the above-mentioned level difference absorbency, about 20% is required. In recent years, the above-mentioned level difference absorption requirement is as high as 30%. Generally, in order to absorb the above-mentioned level difference, it is considered to reduce the elastic modulus of the adhesive layer to make it soft. However, if the adhesive layer is made soft, the workability is poor, a large amount of paste contamination is generated, and the workability is poor.

On the other hand, if the adhesive layer of the polarizing film with the above-mentioned double-sided adhesive layer (the side where the transparent substrate and other members are attached) becomes hard, the full bonding will reduce the absorption of the above-mentioned level difference, and further Reliability makes it easy to generate foaming.

Therefore, the object of the present invention is to provide a double-sided adhesive layer-attached polarizing film and a manufacturing method thereof. The double-sided adhesive layer-attached polarizing film is arranged in the polarizing film used in the image display device and is located closest to the viewing area. The polarizing film on the side has an adhesive layer on both sides, and the yield is good, and it can meet the level difference absorption.

In addition, an object of the present invention is to provide an image display device having a polarizing film with the above-mentioned double-sided adhesive layer attached.

The inventors of the present invention have repeatedly studied hard to solve the above-mentioned problems, and as a result, found the following polarizing film with an adhesive layer on both sides, and completed the present invention.

That is, the present invention relates to a polarizing film with a double-sided adhesive layer, which is characterized in that it has a polarizing film disposed on the side closest to the viewing side among the polarizing films used in image display devices, and a polarizing film disposed on the polarizing film. The adhesive layer A on the visible side of the film and the adhesive layer B arranged on the opposite side of the adhesive layer A, and the adhesive layer A is provided with a release film SA ₁ and the adhesive layer B is provided with a release film SB, and the storage elastic modulus of the adhesive layer A at 23°C is 0.02~0.3MPa, the amount of curl of the polarizing film of the double-sided adhesive layer (wherein, the side of the separator SB will be the lower side The amount of curl measured by placing it on a horizontal surface is expressed as +, and the amount of curl measured by placing it on the horizontal surface so that _{the side of the isolation film SA 1} becomes the lower side is expressed as -) is -10mm~+60mm, The amount of curl is obtained by cutting 300mm along the absorption axis direction of the polarizing film and 250mm along the perpendicular direction of the absorption axis to a rectangular object, and placing it on a horizontal surface so that the curled convex surface becomes the lower side. And determined.

In the polarizing film with an adhesive layer on both sides, it is preferable that the curl amount is +2 mm to +30 mm.

In the polarizing film with the double-sided adhesive layer, it is preferable that _{the thickness of the separator SA 1} is 50 μm or more, and the thickness of the separator SB is 30 μm to 55 μm.

In the polarizing film with a double-sided adhesive layer, it is preferable that the peeling force a _{1 of the separator SA 1} is higher than the peeling force b of the separator SB.

In addition, the present invention relates to a method for manufacturing a polarizing film with a double-sided adhesive layer, characterized in that it is a method for manufacturing the above-mentioned polarizing film with a double-sided adhesive layer, and includes attaching the adhesive layer B on one side The polarizing film and the adhesive layer A of the single-sided isolation film are such that the adhesive layer A of the adhesive layer A of the single-sided isolation film is arranged in the polarizing film of the single-sided adhesive layer B. An adhesive layer is provided Step (1) of roll-to-roll bonding on the polarizing film on the opposite side of the one side of B. The polarizing film of the above-mentioned one-side adhesive layer B has the polarizing film used in the image display device and is arranged closest to The polarizing film and the adhesive layer B on the visible side, and the separator SB is provided on the adhesive layer B, and the adhesive layer A with the separator on one side has a storage elastic modulus of 23°C _{on the separator SA 1} Adhesive layer A of 0.02~0.3MPa.

b之關係。 In the manufacturing method of the polarizing film with the above-mentioned double-sided adhesive layer, it is preferable that the above-mentioned single-side adhesive layer A has the above-mentioned separation film SA ₁ on one side of the adhesive layer A, and the other one side having a step (a) is attached on both sides of the insulating film SA insulating film ₂ a layer of adhesive release agent SA insulating film ₂ and the winner of the peel force of the separator SA ₁ a _1, SA ₂ of said insulating film The peeling force a ₂ , the peeling force b of the above-mentioned isolation film SB satisfies a ₁ > a ₂

b's relationship.

1.5b之關係。 A method for producing a polarizing film of the double-sided adhesive layers are attached, said insulating film is preferably of _a peel force of a SA _1, SA said insulating film ₂ of a peel force of _2, SB peel force of said insulating film satisfies a b ₁ >1.5a ₂

1.5b relationship.

In the manufacturing method of the polarizing film with the double-sided adhesive layer, it is preferable to combine the tension T1 of the adhesive layer A with the single-sided release film in the step (1) of the roll-to-roll bonding. The ratio of tension T2 (T1/T2) of the polarizing film with the adhesive layer B attached to one side is controlled to be 0.8 or more.

The manufacturing method of the polarizing film with the above-mentioned double-sided adhesive layer may further include the following steps: _{the step (b) of peeling the separator SA 1} from the obtained polarizing film with the double-sided adhesive layer, and the step (b) of peeling off the separator SA ₁ is attached on both sides of the adhesive layer of the adhesive layer A polarizing film roll to roll laminating with a separator curl adjustment SA 'of step ₁ (2).

In the manufacturing method of the above-mentioned double-sided adhesive layer-attached polarizing film, it is preferable that in the above-mentioned roll-to-roll bonding step (2), _{the tension T3 of the curl-adjusting separator SA 1} ′ is separated from the separation The ratio of tension T4 (T3/T4) of the polarizing film of the double-sided adhesive layer behind the film SA _{1 is controlled to be 0.8 or more.}

The manufacturing method of the polarizing film with the above-mentioned double-sided adhesive layer may further include the steps of: cutting the obtained polarizing film with the double-sided adhesive layer into any size (c), and the step (d) of cutting the ends of the cut polarizing film with the adhesive layer on both sides.

In addition, the present invention relates to an image display device, which is characterized in that it has at least one polarizing film with an adhesive layer attached on both sides, and the polarizing film used in the image display device is arranged on the side closest to the visibility The polarizing film of the double-sided adhesive layer is the polarizing film of the above-mentioned double-sided adhesive layer, the separator SA ₁ and the separator SB are removed from the polarizing film of the double-sided adhesive layer, and the adhesive layer of the polarizing film of the above-mentioned double-sided adhesive layer It is arranged so that A becomes the visible side and the adhesive layer B becomes the display part side.

In an image display device, members such as transparent substrates such as cover glass may be placed closer to the viewing side than the polarizing film on the viewing side. Previously an adhesive layer was laminated on the visible side of the polarizing film, and then the above-mentioned components were laminated, but the polarizing film with the adhesive layer of the present invention has an adhesive layer attached to a transparent substrate and other components on one side of the polarizing film , A polarizing film with a double-sided adhesive layer with an adhesive layer attached to the display on the opposite side, and an adhesive layer on the visible side of the polarizing film, so it can be used in the manufacture of image display devices. Simplify. In addition, according to a polarizing film with an adhesive layer provided on both sides in advance, by processing it into a specific size, productivity and quality can be improved.

In addition, in the polarizing film with a double-sided adhesive layer of the present invention, a separation film SA ₁ and a separation film SB are respectively provided on the double-sided adhesive layer A and the adhesive layer B, and the separation film SA ₁ and the separation film For the film SB, etc., the amount of curl is controlled to a specific amount. By controlling the amount of curl in this way, when the polarizing film with the double-sided adhesive layer is attached to the display part, and then when the transparent substrate and other members are attached, it is possible to prevent air bubbles from being mixed in the end of the attachment surface, thereby improving Workability, improve yield.

In addition, in the polarizing film with double-sided adhesive layer of the present invention, since the adhesive layer A (adhesive for bonding transparent substrates such as cover glass) is arranged on the visible side of the polarizing film The storage elastic modulus of the layer) is controlled to a specific range, so there is no problem such as paste contamination, and the operability is good. In addition, according to the adhesive layer that controls the storage elastic modulus to a specific range, it is possible to suppress the decrease in step absorbency due to full bonding, and to control durability related to reliability (suppression of foaming).

In addition, when the adhesive layer A is formed by a multilayer adhesive layer having at least two adhesive layers, even when a member such as a transparent substrate is a member with a step on its surface, the step can be followed The bonding is performed without gaps. This multilayer adhesive layer can follow the above-mentioned level difference even when a member such as a transparent substrate is a member having a level difference on the surface thereof, and can be bonded without voids.

The double-sided adhesive layer-attached polarizing film of the present invention can be used, for example, by combining the adhesive layer A with the adhesive layer A on one side with the separating film adhesive layer A and the separating film SB with the single side adhesive layer B attached to the polarizing film. Roll-to-roll lamination step is manufactured. Through the roll-to-roll lamination step, the operability can be improved, the paste contamination can be suppressed, and the processing of the obtained polarizing film with the double-sided adhesive layer can be improved. Sex.

In addition, in the roll-to-roll lamination step, by controlling the respective tensions of the adhesive layer A with the one-sided isolation film and the polarizing film with the adhesive layer B on the one-side, the obtained The curling amount of the polarizing film with the double-sided adhesive layer is controlled to a specific amount. In addition, even by replacing the separator SA ₁ in the polarizing film to which the double-sided adhesive layer is attached, the curling amount of the polarizing film of the double-sided adhesive layer can be controlled to a specific amount.

1‧‧‧Polarizing film

2‧‧‧Adhesive layer (Adhesive layer B)

3‧‧‧Transparent conductive layer (antistatic layer)

4‧‧‧Glass substrate

5‧‧‧Liquid crystal layer

6‧‧‧Drive electrode

7‧‧‧Antistatic layer and sensor layer

8‧‧‧Drive electrode and sensor layer

9‧‧‧Sensor layer

10.10'‧‧‧Polarizing film with adhesive layer on both sides

11‧‧‧Adhesive layer A with isolation film on one side

12‧‧‧Polarizing film with adhesive layer B attached to one side

13‧‧‧The polarizing film with adhesive layer on both sides after peeling off the separator SA ₁

14‧‧‧Adhesive layer A with isolation film on both sides

a‧‧‧The first adhesive layer

A‧‧‧Adhesive layer A (visual recognition side)

b‧‧‧Second adhesive layer

B‧‧‧Adhesive layer B (the side opposite to the visual recognition side)

C‧‧‧Component (touch panel or transparent substrate)

D‧‧‧Display part (image display device)

h‧‧‧Curl amount

R1, R2, R4, R5‧‧‧Laminating roller

R11, R12, R13, R14‧‧‧roller

SA ₁ ‧‧‧Isolation film of adhesive layer A (visual recognition side)

SA ₁ '‧‧‧ adhesive A (visible side) of the curl adjusting layer insulating film

SA ₂ ‧‧‧Isolation film for adhesive layer A (visual recognition side)

SB‧‧‧Isolation film of adhesive layer B (opposite side of visual recognition side)

T1, T2, T3, T4‧‧‧ Tension

Fig. 1a is a cross-sectional view schematically showing an embodiment of the polarizing film with a double-sided adhesive layer of the present invention.

Fig. 1b is a cross-sectional view schematically showing an embodiment of a polarizing film with a double-sided adhesive layer of the present invention.

Fig. 2a is a cross-sectional view schematically showing the amount of curl of the polarizing film with the double-sided adhesive layer of the present invention.

2b is a cross-sectional view schematically showing the amount of curl of the polarizing film with the double-sided adhesive layer of the present invention.

Fig. 3 is a conceptual diagram schematically showing a state in which the image display device is bonded to a transparent substrate and other members through the polarizing film with the double-sided adhesive layer of the present invention.

Fig. 4a is a cross-sectional view schematically showing an embodiment of the image display device.

Fig. 4b is a cross-sectional view schematically showing an embodiment of the image display device.

Fig. 4c is a cross-sectional view schematically showing an embodiment of the image display device.

Fig. 5 is a cross-sectional view schematically showing an embodiment of an adhesive layer A with isolation films on both sides.

Fig. 6 is a cross-sectional view schematically showing one embodiment of the step (1) of roll-to-roll bonding in the method of manufacturing a polarizing film with a double-sided adhesive layer of the present invention.

7 is a cross-sectional view schematically showing one embodiment of the roll-to-roll bonding step (2) of the roll-to-roll lamination step (2) using the release film for curl adjustment in the manufacturing method of the double-sided adhesive layer-attached polarizing film of the present invention.

Hereinafter, the embodiment of the polarizing film with a double-sided adhesive layer of the present invention, etc., will be described in detail using drawings. However, the present invention is not limited to the illustrated embodiment.

As shown in FIG. 1a and FIG. 1b, the polarizing film 10 (10') with a double-sided adhesive layer of the present invention has a polarizing film 1, and an adhesive layer A and an adhesive layer B on both sides of the polarizing film 1. . In addition, the polarizing film 10 (10') with a double-sided adhesive layer of the present invention is provided with a separation film SA ₁ on the adhesive layer A and a separation film SB on the adhesive layer B. In addition, as the separator SA _{1 , the separator SA 1} ′ for curl adjustment described later can be used.

In Figure 1a, the case where the adhesive layer A is one layer is illustrated, but the above-mentioned adhesive layer A can be set to have the first adhesive layer (a) and the second adhesive in order from the outermost side (visible side) The multi-layer adhesive layer of the agent layer (b). Fig. 1b illustrates the case where the adhesive layer A is a multilayer of the first adhesive layer (a) and the second adhesive layer (b). The layer of the multi-layer adhesive layer of the above-mentioned adhesive layer A The number is not particularly limited, and it can usually be installed up to about 5 layers. The number of layers of the multi-layer adhesive layer is preferably 2 to 4 layers, and more preferably 2 to 3 layers. In the above-mentioned multi-layer adhesive layer, each layer is directly adhered and provided.

Among the above-mentioned multi-layer adhesive layers, adjacent adhesive layers may use adhesive layers of different composition, but non-adjacent adhesive layers may use adhesive layers of the same composition. In Figure 1b, the first adhesive layer (a) and the second adhesive layer (b) have different compositions. When using the first adhesive layer (a), the second adhesive layer (b), and the third adhesive layer (c) as the adhesive layer A from the outermost side (visible side), the first adhesive The agent layer (a) and the second adhesive layer (b) have different compositions, and the second adhesive layer (b) and the third adhesive layer (c) have different compositions. The first adhesive layer (a), the second adhesive layer (b), and the third adhesive layer (c) may have different compositions, but the first adhesive layer (a) and the third adhesive layer (c) ) Can be the same composition.

2a and 2b are cross-sectional views schematically showing the amount of curling of the polarizing film 10 (10') with a double-sided adhesive layer of the present invention. The amount of curl is measured by cutting the polarizing film 10 (10') with the adhesive layer on both sides by 300 mm along the absorption axis direction of the polarizing film 1, and 250 mm along the direction orthogonal to the absorption axis. As shown in Figure 2a and Figure 2b, the amount of curl is measured by placing it on a horizontal surface so that the surface of the curl protrusion becomes the lower side. In addition, for the measurement of the amount of curl, the amount of curl is measured by placing it on a horizontal surface such that the side of the separator SB of the polarizing film 10 (10') with a double-sided adhesive layer is placed on the lower side as shown in FIG. 2a (h) is expressed as "+", shown in Figure 2b will cause said insulating film SA ₁ (SA ₁ ') of the side is the lower side of the curl amount is placed on a horizontal plane of the measured (h) is represented by "- ". The amount of curl (h) is the distance (mm) from the longest point to the horizontal plane among the four corners of the rectangular object.

In terms of workability and yield, the curl amount (h) is controlled to -10mm to +60mm. In terms of workability and yield, the curl amount (h) is preferably "+" as shown in Figure 2a, more preferably +2mm~+30mm, and more preferably +5mm~+20mm .

<Adhesive layer>

Hereinafter, the adhesive layer A and the adhesive layer B of the present invention will be described. Furthermore, both the adhesive layer A and the adhesive layer B are "transparent", which can be satisfied by the haze value measured at a thickness of 25 μm of 2% or less. The above-mentioned haze value is preferably 0 to 1.5%, and more preferably 0 to 1%.

<Thickness of Adhesive Layer>

In addition, the overall thickness of the adhesive layer A is preferably 5 μm to 1 mm. The overall thickness of the adhesive layer A can be appropriately designed according to the location where the adhesive layer A is applied. The overall thickness of the adhesive layer A is preferably 10 μm to 500 μm, and more preferably 20 μm to 300 μm.

In addition, when the adhesive layer A is a multilayer adhesive layer having a first adhesive layer (a) and a second adhesive layer (b), the thickness of each adhesive layer is preferably 3 μm to 200 μm, which is more It is preferably 5 μm to 150 μm, and more preferably 10 μm to 100 μm.

As shown in Figure 1b, when the adhesive layer A is composed of two layers of the first adhesive layer (a) and the second adhesive layer (b), the thickness of the first adhesive layer (a) is preferably 3 μm to 200 μm, more preferably 5 μm to 100 μm, and still more preferably 10 μm to 75 μm. The thickness of the second adhesive layer (b) is preferably 10 μm to 300 μm, more preferably 20 μm to 150 μm, and still more preferably 50 μm to 100 μm. In terms of step absorbency and processability, the difference between the thickness of the first adhesive layer (a) and the thickness of the second adhesive layer (b) is preferably 20 μm to 270 μm, and more preferably 30 μm ~200μm.

On the other hand, the thickness of the adhesive layer B is generally 1 μm to 500 μm, preferably 5 μm to 200 μm, and particularly preferably 10 μm to 100 μm.

<Storage Elastic Modulus of Adhesive Layer>

The storage elastic modulus of the adhesive layer A at 23°C is controlled to be 0.02~0.3MPa. By controlling the storage elastic modulus to the adhesive layer A in this range, paste contamination can be suppressed, and the workability of bonding on the transparent substrate can be improved, and the yield can be improved. The storage elastic modulus is preferably 0.02 to 0.4 MPa, more preferably 0.03 to 0.3 MPa, and still more preferably 0.05 to 0.1 MPa. The above-mentioned control of the storage elastic modulus of the adhesive layer A is also preferable in terms of satisfying the step absorbency.

<Peeling force of adhesive layer>

The adhesive layer A is provided with a separation film SA ₁ (SA ₁ ′), and the adhesive layer B is provided with a separation film SB. _{The peeling force a 1 of} the isolation film SA ₁ (SA ₁ ′) to the adhesive layer A is preferably 0.01-5N/50mm, more preferably 0.05-2N/50mm, and still more preferably 0.1-1N/50mm. In addition, the peeling force b of the separator SB to the adhesive layer B is preferably 0.01-5N/50mm, more preferably 0.05-2N/50mm, and still more preferably 0.1-1N/50mm.

In addition, in terms of bonding the display panel first, the peeling force a _{1 of the isolation film SA 1} (SA ₁ ′) is preferably adjusted to be higher than the peeling force b of the isolation film SB. In terms of preventing peeling failure, the difference _{between the peeling force a 1 of the isolation film SA 1} (SA ₁ ′) and the peeling force b of the isolation film SB is preferably 0.01~2N/50mm, and more preferably 0.02~ 1N/50mm.

The measurement of the storage elastic modulus and the peeling force are based on the description of the examples.

As shown in FIG. 3, the polarizing film of the present invention with a double-sided adhesive layer _{is applied to an image display device by removing the isolation film SA 1} (SA ₁ ′) and the above isolation film SB. The polarizing film of the polarizing film with a double-sided adhesive layer of the present invention is applied as a polarizing film disposed on the side closest to the viewing side among the polarizing films used in image display devices. The above-mentioned adhesive layer A of the polarizing film with a double-sided adhesive layer of the present invention is arranged on the visible side of the image display device, and is bonded to a member C such as a transparent substrate. The adhesive layer B is arranged on the opposite side of the adhesive layer A in the polarizing film 1 and is bonded to the display portion D.

As the member C, input devices such as a touch panel applied to the visibility side of an image display device, transparent substrates such as cover glass and plastic covers, and the like can be cited.

The display portion D and at least one polarizing film 1 form part of an image display device, and examples thereof include liquid crystal display devices, organic EL (electroluminescence) display devices, PDP (plasma display panels), electronic paper, and the like. As the display portion D, a liquid crystal display device having a liquid crystal layer 5 used with the polarizing film 1 can be preferably used. Schematic representation of the application of the adhesive of the present invention The cross-sectional views of the representative embodiment of the image display device (liquid crystal display device) of the polarizing film of the layer are shown in FIGS. 4a to 4c. In the image display device (liquid crystal display device) of FIGS. 4a to 4c, the upper polarizing film 1 is located closest to the visible side.

The image display device (liquid crystal display device) shown in Figure 4a has cover glass C/adhesive layer A/polarizing film 1 (visual recognition side)/adhesive layer 2(B)/antistatic layer 3/glass substrate 4/liquid crystal The composition of layer 5/driving electrode 6/glass substrate 4/adhesive layer 2/polarizing film 1. The antistatic layer 3 and the driving electrode 6 may be formed of a transparent conductive layer. Furthermore, the antistatic layer 3 can be arbitrarily formed.

The image display device (liquid crystal display device) shown in Figure 4b is a case where a transparent conductive layer is used as an electrode of a touch panel (in-cell touch panel), which has cover glass C/adhesive layer A/polarized light Film 1 (visual recognition side) / Adhesive layer 2 (B) / Antistatic layer and sensor layer 7 / Glass substrate 4 / Liquid crystal layer 5 / Drive electrode and sensor layer 8 / Glass substrate 4 / Adhesive layer 2 /The composition of the polarizing film 1. The antistatic layer and sensor layer 7 and the driving electrode and sensor layer 8 may be formed of a transparent conductive layer.

The image display device (liquid crystal display device) shown in FIG. 4c is a case where a transparent conductive layer is used as an electrode of a touch panel (out-cell type touch panel), which has cover glass C/adhesive layer A/polarized light Film 1/Adhesive layer 2(B)/Antistatic layer and sensor layer 7/Sensor layer 9/Glass substrate 4/Liquid crystal layer 5/Drive electrode 6/Glass substrate 4/Adhesive layer 2/Polarizing film 1 of the composition. The antistatic layer and sensor layer 7, the sensor layer 9, and the driving electrode 6 may be formed of a transparent conductive layer.

As a polarizing film, it is generally used for a polarizing element with a transparent protective film on one or both sides. The transparent protective film in the polarizing film can be provided with a functional layer such as a hard coat layer. In addition, optical films used in the formation of image display devices such as liquid crystal display devices and organic EL display devices can be suitably used in image display devices. In addition, as the optical film, for example, reflective plates, semi-reflective plates, retardation plates (including 1/2 or 1/4 wavelength plates), optical compensation films, visual compensation films, brightness enhancement films, etc. can be cited. It is sometimes used in the formation of optical layers of liquid crystal display devices. These can be used alone as an optical film, and can also be laminated on the above-mentioned polarizing film during actual use to use one layer or two or more layers.

Furthermore, in FIGS. 4a to 4c, an adhesive layer 2 for bonding with other components such as a liquid crystal cell (glass substrate) is disclosed. The adhesive layer 2 closer to the visible side (upper side) than the liquid crystal cell is used as the adhesive layer B. The adhesive layer 2 can be appropriately selected to use, for example, acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyether, fluorine or rubber, and other polymers as the base polymer. Various adhesives for things. Particularly preferred are those having excellent optical transparency like an acrylic adhesive, showing moderate wettability, cohesiveness, and adhesive properties of adhesion, and excellent weather resistance or heat resistance.

A liquid crystal display device is generally formed by appropriately assembling a liquid crystal cell (composition of a glass substrate/liquid crystal layer/glass substrate), a polarizing film arranged on both sides of the liquid crystal cell, and components such as an illumination system if necessary, and installing a driving circuit. Liquid crystal cells can use, for example, TN (Twisted Nematic, twisted nematic) type or STN (Super Twisted Nematic, super twisted nematic) type, π type, VA (Vertical Aligned, vertical alignment) type, IPS (In-Plane Switching, horizontal Any type such as electric field effect) type. In addition, it is possible to form an appropriate liquid crystal display device such as a backlight device or a reflector as a lighting system. Furthermore, when forming a liquid crystal display device, one or more than two layers of diffuser, anti-glare layer, anti-reflection film, protective plate, scallop array, lens array sheet, light diffuser, backlight device, etc. can be arranged at an appropriate position. Appropriate parts.

As the member C, a touch panel can be used. The touch panel C is an electrostatic capacitance type touch panel in which a transparent substrate, an adhesive layer 2, and a transparent conductive film are sequentially laminated. In addition, two or more layers of the transparent conductive film may be laminated. The transparent substrate may have a sensor layer. Furthermore, the transparent substrate can be used as a cover glass or a plastic cover, etc., to be individually applied to an image display device (liquid crystal display device). In addition, a hard coat film may be provided on the transparent conductive film on the opposite side of the touch panel C from the transparent substrate.

Furthermore, as the transparent substrate, a glass plate or a transparent acrylic plate (PMMA (polymethylmethacrylate) plate) can be cited. The so-called cover glass of the transparent base system can be used as a decorative panel. As a transparent conductive film, preferred A transparent conductive film is provided on a glass plate or a transparent plastic film (especially a PET (polyethylene terephthalate, polyethylene terephthalate) film). Examples of the transparent conductive film include thin films containing metals, metal oxides, or mixtures thereof, such as ITO (Indium Tin Oxide), ZnO, SnO, and CTO (Cadmium Tin Oxide) thin films. The thickness of the transparent conductive film is not particularly limited, and may be about 10 nm to 200 nm. As the above-mentioned transparent conductive film, a representative example is an ITO film in which an ITO film is provided on a PET film. The transparent conductive film can be provided via the primer coating layer. Furthermore, the primer coating layer can be provided with multiple layers. An oligomer transfer prevention layer can be provided between the transparent plastic film substrate and the adhesive layer. The hard coating film is preferably one that has been subjected to a hard coating treatment on a transparent plastic film such as a PET film.

The polarizing film 10 with a double-sided adhesive layer of the present invention can be manufactured by, for example, the following method: A single-sided adhesive layer having a polarizing film 1 and an adhesive layer B and a release film SB on the adhesive layer B B is polarized film 12, the insulating film in the SA ₁ having the adhesive layer A (. 11) attached to one side of the adhesive layer A of the insulating film, to one side attached to the adhesive layer of the polarizing composite film 12 B is provided with The polarizing film 1 on the opposite side of the adhesive layer B is attached with the adhesive layer A (11) of the adhesive layer A (11) of the above-mentioned one-sided isolation film attached to the polarizing film 1 on the side opposite to the side of the adhesive layer B. The above-mentioned manufacturing method is preferably performed by the step (1) of laminating roll-to-roll as shown in FIG. 6. In FIG. 6, the polarizing film 12 with the adhesive layer B on one side and the adhesive layer A (11) with the release film on one side conveyed from the delivery roller are laminated between a pair of laminating rollers R1 and R2. In step (1), a polarizing film 10 with a double-sided adhesive layer is obtained by a take-up roller.

In addition, the above-mentioned adhesive layer A (11) with an isolation film _{on one side can be because the adhesive layer A has an isolation film SA 1} on one side and an isolation film SA ₂ on the other side with an isolation film on both sides. Layer A (14) is obtained. The adhesive layer A (14) with isolation films on both sides can be represented by the composition of _{isolation film SA 1} /adhesive layer A / isolation film SA _{2 as shown in FIG. 5.} In Figure 6, the adhesive layer A (14) with the release film on both sides transported from the delivery roller is carried out by the release roller R3 to peel off the release film SA ₂ (a), and the one side with the release film is adhered The agent layer A (11) is supplied to the step (1) of bonding.

b之關係。進而，就提高作業性之方面而言，較佳為上述隔離膜SA₁之剝離力a₁、上述隔離膜SA₂之剝離力a₂、上述隔離膜SB之剝離力b滿足a₁>1.5a₂

1.5b之關係。 In the case of using the adhesive layer A (14) with isolation films on both sides, it is preferable in terms of the order of the product steps and the order of the laminating steps on liquid crystal panels, organic EL panels, etc. SA is a peel force of separator ₁ a _1, SA peel force of said insulating film ₂ of a _2, the release force of the separator SB of b satisfies a _1> a ₂

b's relationship. Further, in terms of improving workability aspect, the insulating film is preferably above ₁ SA peel strength of a _1, SA peel force of said insulating film ₂ of a _2, the release force of the separator SB of b satisfies a _1> 1.5a ₂

1.5b relationship.

The peeling force a ₁ of the separator SA _{1 and} the peeling force b of the aforementioned separator SB are as described above. The peeling force a _{2 of} the isolation film SA ₂ is preferably 0.01-5N/50mm, more preferably 0.05-2N/50mm, and still more preferably 0.05-1N/50mm. In respect to aspects of the step of bonding the polarizer attached on the workability of the peel force of the separator SA ₁ a ₁ and the peel force SA said insulating film ₂ of a ₂ difference is preferably 0.01 ~ 1N / 50mm, and further Preferably it is 0.03~0.5N/50mm.

In addition, in the above-mentioned roll-to-roll lamination step (1) of the polarizing film 10 with a double-sided adhesive layer of the present invention, it is preferable to adjust the tension T1 of the adhesive layer A (11) with the release film. The ratio (T1/T2) to the tension T2 of the polarizing film 12 of the above-mentioned one-side adhesive layer B is controlled to be 0.8 or more. In Fig. 6, the tension T1 and the tension T2 can be controlled by the rollers R11 and R12.

By controlling the tension ratio (T1/T2) to the above range, the amount of curl can be adjusted. The tension ratio (T1/T2) is preferably 0.9 or more, more preferably 1 or more, and still more preferably 3 or more. On the other hand, if the tension ratio (T1/T2) becomes too large, the amount of curl becomes too large, and the bonding accuracy in the bonding step on the panel is reduced. Therefore, the tension ratio (T1/T2) is preferably 10 or less, and further Preferably it is 6 or less, More preferably, it is 4 or less.

The aforementioned tension T1 is preferably 8 to 500 N/m, more preferably 50 to 300 N/m, and still more preferably 100 to 200 N/m.

The aforementioned tension T2 is preferably 10 to 400 N/m, more preferably 20 to 200 N/m, and still more preferably 40 to 100 N/m.

Furthermore, in the present invention, after the polarizing film 10 with the above-mentioned double-sided adhesive layer is manufactured, the separation film SA _{1 is} then peeled off from the adhesive layer A of the obtained polarizing film 10 with the double-sided adhesive layer, and thereafter After the separation film SA _{1 is} peeled off, the adhesive layer A of the polarizing film 13 with the double-sided adhesive layer is attached to the release film SA ₁ ′ for curl adjustment, whereby the polarizing film 10 ′ with the double-sided adhesive layer can be manufactured. By using the release film SA ₁ ′ for curl adjustment instead of the release film SA ₁ , the curl amount of the polarizing film 10 ′ with the adhesive layer on both sides can be adjusted. The above-mentioned manufacturing method is preferably performed by the step (2) of laminating roll-to-roll as shown in FIG. 7.

In FIG. 7, the double-sided adhesive layer-attached polarizing film 10 transported from the delivery roller is subjected to the step (b) of _{peeling the separator SA 1 by the peeling roller R6.} Then, a step (2) of bonding the conveyed polarizing film 13 with an adhesive layer on both sides and the release film SA _{1 for} curl adjustment between a pair of bonding rolls R4 and R5 is performed (2), and the winding rolls Obtain a polarizing film 10' with a double-sided adhesive layer.

'Peel force of a _1' above the curl adjustment SA separator ₁ is preferably _a peel force of the same range of a ₁ and the insulating film SA, and, on the relationship between the peel force of said insulating film b of SB, on the adjustment of crimp In terms of quantity, it is better to satisfy _{the relationship of a 1} ′>1.5b.

In addition, in the step (2) of the above-mentioned roll-to-roll bonding of the polarizing film 10' with a double-sided adhesive layer of the present invention, it is preferable to peel off the tension T3 of _{the curl-adjusting release film SA 1 '} after the _one-sided SA said insulating film adhesive attachment layer 13 of the polarizing film tension ratio of T4 (T3 / T4) is controlled to 0.8 or more. In Fig. 7, the tension T3 and the tension T4 can be controlled by the rollers R13 and R14.

By controlling the tension ratio (T3/T4) to the above range, the curl amount can be adjusted. The tension ratio (T3/T4) is preferably 0.9 or more, more preferably 1 or more, and still more preferably 3 or more. On the other hand, if the tension ratio (T3/T4) becomes too large, the amount of curl becomes too large, and the bonding accuracy is reduced in the bonding step on the panel. Therefore, the tension ratio (T3/T4) is preferably 10 or less, and further Preferably it is 6 or less, More preferably, it is 4 or less.

The aforementioned tension T3 is preferably 8 to 500 N/m, more preferably 50 to 300 N/m, and still more preferably 100 to 200 N/m.

The above-mentioned tension T4 is preferably 10~400N/m, and more preferably 20~200N/m. It is preferably 40-100 N/m.

Furthermore, the magnitude of the above-mentioned tension can be adjusted by the torque of the roller, and the method of applying it is not particularly limited. When the film is sent out by the roller, the tension can be applied along the conveying direction. In addition, the above-mentioned tension can be measured by, for example, a load cell type tension sensor roller that can be measured by the load applied to the conveyance roller. The above-mentioned tension was measured by the method described in the examples.

The obtained double-sided adhesive layer-attached polarizing film manufacturing method can then include the step (c) of cutting into any size, and the step of cutting the ends of the cut-out double-sided adhesive layer-attached polarizing film ( d). The step (d) of cutting may include a step of grinding.

<Material of Adhesive Layer>

In addition, as the material for forming the adhesive layer A and the adhesive layer B of the present invention, those containing various base polymers can be used. The type of base polymer is not particularly limited. Examples include rubber-based polymers, (meth)acrylic polymers, polysiloxane-based polymers, urethane-based polymers, and vinyl alkyl groups. Various polymers such as ether-based polymers, polyvinyl alcohol-based polymers, polyvinylpyrrolidone-based polymers, polyacrylamide-based polymers, and cellulose-based polymers.

Among these base polymers, those that are excellent in optical transparency, exhibit appropriate wettability, cohesiveness, and adhesive properties, and are excellent in weather resistance, heat resistance, and the like can be preferably used. As those exhibiting such characteristics, (meth)acrylic polymers can be preferably used. Hereinafter, the adhesive layer A and the adhesive layer B, which are forming materials, use (meth)acrylic polymer containing alkyl (meth)acrylate as the monomer unit as the base polymer of the acrylic adhesive will be described. .

The above-mentioned (meth)acrylic polymer is obtained by polymerizing a monomer component of an alkyl (meth)acrylate having an alkyl group having 4 to 24 carbon atoms at the end of the ester group. Furthermore, alkyl (meth)acrylate refers to alkyl acrylate and/or alkyl methacrylate, and (meth) in the present invention has the same meaning.

As the alkyl (meth)acrylate, one having a linear or branched alkyl group having 4 to 24 carbon atoms can be exemplified. The alkyl (meth)acrylate can be used alone or in combination of two or more.

As said (meth)acrylic acid alkyl ester, for example, the above-mentioned C4-C9 branched (meth)acrylic acid alkyl ester can be exemplified. The alkyl (meth)acrylate is preferable in that it is easy to achieve a balance of adhesive properties. Examples of alkyl (meth)acrylates include n-butyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, and isobutyl (meth)acrylate Ester, n-pentyl (meth)acrylate, isoamyl (meth)acrylate, isohexyl (meth)acrylate, isoheptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( Isooctyl meth)acrylate, isononyl (meth)acrylate and the like. In addition, in terms of storage elastic modulus control and step absorbency, it is preferable that the (meth)acrylic polymer of the adhesive layer A contains 2-ethylhexyl acrylate as the monomer with the largest content. unit. Furthermore, when the above-mentioned adhesive layer A is a multilayer adhesive layer having at least a first adhesive layer (a) and a second adhesive layer (b), it is used as a multilayer adhesive layer (as the total of each layer), Preferably, the (meth)acrylic polymer contains 2-ethylhexyl acrylate as the monomer unit with the largest content. On the other hand, in terms of storage elastic modulus control, processability, storage properties, and durability, it is preferable that the (meth)acrylic polymer of the adhesive layer B contains butyl acrylate as the most content Monomer unit.

In the present invention, the above-mentioned alkyl (meth)acrylate having an alkyl group with 4 to 24 carbon atoms at the end of the ester is 40 by weight relative to the total amount of the monofunctional monomer components forming the (meth)acrylic polymer % Or more, preferably 50% by weight or more, and more preferably 60% by weight or more. It is preferable to use 40% by weight or more in terms of easily achieving a balance of adhesive properties.

In the monomer component forming the (meth)acrylic polymer of the present invention, a comonomer other than the above-mentioned alkyl (meth)acrylate may be contained as a monofunctional monomer component. The comonomer can be used as the balance of the above-mentioned alkyl (meth)acrylate in the monomer component.

、乙烯基吡

、乙烯基吡咯、乙烯基咪唑、乙烯基

唑、乙烯基

啉等具有含氮雜環之乙烯基單體等。又，可列舉含有

啉環、哌啶環、吡咯啶環、哌

環等雜環之(甲基)丙烯酸系單體。具體而言，可列舉N-丙烯醯基

啉、N-丙烯醯基哌啶、N-甲基丙烯醯基哌啶、N-丙烯醯基吡咯啶等。上述環狀含氮單體中，就介電常數及凝聚性之方面而言，較佳為內醯胺系乙烯基單體。 As the comonomer, for example, a cyclic nitrogen-containing monomer may be contained. As the cyclic nitrogen-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and having a cyclic nitrogen structure can be used without particular limitation. The cyclic nitrogen structure is preferably one having a nitrogen atom in the cyclic structure. Examples of cyclic nitrogen-containing monomers include internal vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactone, and methyl vinylpyrrolidone; vinyl Pyridine, vinylpiperidone, vinylpyrimidine, vinylpiper

Vinylpyridine

, Vinyl pyrrole, vinyl imidazole, vinyl

Azole, vinyl

Vinyl monomers with nitrogen-containing heterocyclic ring, etc. In addition, it can be enumerated containing

Morpholine ring, piperidine ring, pyrrolidine ring, piper

Heterocyclic (meth)acrylic monomers such as rings. Specifically, N-acryloyl

Pyroline, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine, etc. Among the above-mentioned cyclic nitrogen-containing monomers, in terms of dielectric constant and cohesiveness, a lactam-based vinyl monomer is preferable.

In the present invention, the cyclic nitrogen-containing monomer is preferably 45% by weight or less relative to the total monomer components forming the (meth)acrylic polymer, more preferably 0.5-40% by weight, and still more preferably 0.5~ 30% by weight. In terms of surface resistance control, especially compatibility with ionic compounds when ionic compounds are used, and durability of antistatic function, it is preferable to use cyclic nitrogen-containing monomers within the above-mentioned range. body.

The monomer component forming the (meth)acrylic polymer of the present invention may contain, for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and a monomer having a cyclic ether group as a monofunctional monomer component.

As the hydroxyl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and having a hydroxyl group can be used without particular limitation. Examples of hydroxyl-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxyethyl (meth)acrylate Hydroxypropyl ester, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, (meth)acrylate Base) 12-hydroxylauryl acrylate, etc. (meth) hydroxyalkyl acrylate; (4-hydroxymethylcyclohexyl) methyl (meth)acrylate, etc. (meth)acrylic acid Hydroxyalkyl cycloalkyl ester. Moreover, hydroxyethyl (meth)acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, etc. are mentioned. These monomers can be used alone or in combination. Among them, hydroxyalkyl (meth)acrylate is preferred.

As the carboxyl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and a carboxyl group can be used without particular limitation. Examples of carboxyl group-containing monomers include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, Methacrylic acid, etc., these monomers can be used alone or in combination. Iconic acid and maleic acid can use these acid anhydrides. Among them, acrylic acid and methacrylic acid are preferred, and acrylic acid is particularly preferred. Furthermore, in the monomer component used in the production of the (meth)acrylic polymer of the present invention, a carboxyl group-containing monomer may be arbitrarily used, and on the other hand, a carboxyl group-containing monomer may not be used. Adhesives containing (meth)acrylic polymers obtained from monomer components that do not contain carboxyl group-containing monomers can form an adhesive layer that reduces metal corrosion caused by carboxyl groups.

As a monomer having a cyclic ether group, a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and an epoxy group or an oxetanyl group can be used without particular limitation. Those who are cyclic ether groups. Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether Wait. Examples of the oxetanyl-containing monomer include: 3-oxetanyl methyl (meth)acrylate, 3-methyl-oxetanyl methyl (meth)acrylate, 3-ethyl-oxetanyl methyl (meth)acrylate, 3-butyl-oxetanyl methyl (meth)acrylate, 3-hexyl-oxetanyl (meth)acrylate Butyl methyl ester and so on. These can be used alone or in combination.

In the present invention, the above-mentioned hydroxyl group-containing monomer, carboxyl group-containing monomer, and monomer having a cyclic ether group are preferably 30% by weight relative to the total amount of the monofunctional monomer components forming the (meth)acrylic polymer Below, it is more preferably 27% by weight or less, and more preferably 25% by weight or less under.

The monomer components forming the (meth)acrylic polymer of the present invention may include, for example, CH ₂ =C(R ¹ )COOR ² (the above R ¹ represents hydrogen or methyl, and R ² represents carbon number 1 to 3. (Meth)acrylate represented by unsubstituted alkyl, substituted alkyl, cyclic cycloalkyl) is used as a comonomer.

Here, the unsubstituted alkyl group or substituted alkyl group having 1 to 3 carbon atoms ^{as R 2 means a straight-chain or branched-chain alkyl group.} In the case of a substituted alkyl group, the substituent is preferably an aryl group having 3 to 8 carbons or an aryloxy group having 3 to 8 carbons. The aryl group is not particularly limited, but a phenyl group is preferred.

基酯等。該等可單獨使用或組合使用。 Examples of such monomers represented by CH ₂ =C(R ¹ )COOR ² include methyl (meth)acrylate, ethyl (meth)acrylate, phenoxyethyl (meth)acrylate, Benzyl (meth)acrylate, cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isopropyl (meth)acrylate

Base ester and so on. These can be used alone or in combination.

In the present invention, _{the (meth)acrylate represented by CH 2} =C(R ¹ )COOR ² may be 45% by weight or less relative to the total amount of the monofunctional monomer components forming the (meth)acrylic polymer Used, preferably 35% by weight or less. More preferably, it is 30% by weight or less.

啉、乙烯基醚單體等。又，作為共聚單體，可使用(甲基)丙烯酸萜烯酯、(甲基)丙烯酸二環戊酯等具有環狀結構之單體。 As other comonomers, vinyl acetate, vinyl propionate, styrene, α-methylstyrene; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxy Glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate and other glycol-based acrylate monomers; tetrahydrofurfuryl (meth)acrylate, fluoro(meth)acrylate, poly Silicone (meth)acrylate or 2-methoxyethyl acrylate and other acrylate monomers; amine group-containing monomers, amine group-containing monomers, amide group-containing monomers, N-acrylic acid group

Morpholine, vinyl ether monomers, etc. In addition, as a comonomer, monomers having a cyclic structure such as terpene (meth)acrylate and dicyclopentyl (meth)acrylate can be used.

Furthermore, silane-based monomers containing silicon atoms and the like can be cited. As the silane-based monomer, for example, 3-propenoxypropyltriethoxysilane, vinyl trimethoxysilane Alkyl, vinyl triethoxy silane, 4-vinyl butyl trimethoxy silane, 4-vinyl butyl triethoxy silane, 8-vinyl octyl trimethoxy silane, 8-vinyl octyl Triethoxysilane, 10-methacryloxydecyl trimethoxysilane, 10-methacryloxydecyl trimethoxysilane, 10-methacryloxydecyl triethoxysilane, 10-Propylene oxydecyl triethoxysilane, etc.

When forming the adhesive layer A and the adhesive layer B, the above-mentioned comonomer can be appropriately selected during the preparation of the (meth)acrylic polymer as the base polymer. As the above-mentioned comonomer, when the first adhesive layer (a) in the adhesive layer A and the adhesive layer B are formed from an acrylic adhesive, the cohesive force, the adhesive force is improved, the transparency, and the durability are improved. In terms of aspect, it is preferable to contain at least one of (meth)acrylic acid and nitrogen-containing monomer as a monomer unit in at least one of these.

In the monomer components forming the (meth)acrylic polymer of the present invention, in addition to the monofunctional monomers exemplified above, in order to adjust the cohesive force of the adhesive, a multifunctional monomer may be contained as needed.

A multifunctional single-system monomer having at least two (meth)acrylic acid groups or vinyl groups and other polymerizable functional groups with unsaturated double bonds, for example: (poly)ethylene glycol bis(methyl) Acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol Triacrylate, dipentaerythritol hexa(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-twelve The ester compound of polyol and (meth)acrylic acid such as alkanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, etc.; Allyl meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butylene glycol di(meth)acrylate, hexyl Diol di(meth)acrylate and the like. Among them, trimethylolpropane tri(meth)acrylate, hexanediol di(meth)acrylate, and dipentaerythritol hexa(meth)acrylate can be preferably used. A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.

The amount of the polyfunctional monomer used varies according to its molecular weight or number of functional groups. It is preferably 3 parts by weight or less, more preferably 2 parts by weight or less, with respect to 100 parts by weight of the total of monofunctional monomers. Preferably, it is 1 part by weight or less. Moreover, as a lower limit, it does not specifically limit, Preferably it is 0 weight part or more, More preferably, it is 0.001 weight part or more. By using the amount of the multifunctional monomer within the above range, the adhesive force can be improved.

For the production of such a (meth)acrylic polymer, known production methods such as radiation polymerization such as solution polymerization and ultraviolet polymerization, various radical polymerizations such as bulk polymerization, and emulsion polymerization can be appropriately selected. In addition, the obtained (meth)acrylic polymer may be any of random copolymers, block copolymers, graft copolymers, and the like.

The polymerization initiator, chain transfer agent, emulsifier, etc. used in radical polymerization are not particularly limited, and can be appropriately selected and used. Furthermore, the weight average molecular weight of the (meth)acrylic polymer can be controlled by the usage amount of the polymerization initiator and the chain transfer agent, and the reaction conditions, and the appropriate usage amount can be adjusted according to these types.

For example, in solution polymerization etc., as a polymerization solvent, ethyl acetate, toluene, etc. can be used, for example. As a specific example of solution polymerization, a polymerization initiator is added under a stream of inert gas such as nitrogen, and the reaction is usually carried out under reaction conditions of about 50°C to 70°C for about 5 hours to 30 hours.

As the thermal polymerization initiator used in solution polymerization, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'- Azobis(2-methylpropionic acid) dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis(2-amidine) Propane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis( 2-Methylpropionamidine) disulfate, 2,2'-azobis(N,N'-dimethylisobutylamidine), 2,2'-azobis(N-(2-carboxyl) Ethyl)-2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057) and other azo-based initiators; persulfates such as potassium persulfate and ammonium persulfate; bis(peroxydicarbonate) 2-ethylhexyl) ester, bis(4-tertiary butylcyclohexyl) peroxydicarbonate Ester, di-second butyl peroxydicarbonate, tertiary butyl peroxide neodecanoate, tertiary hexyl peroxide pivalate, tertiary butyl peroxide pivalate, dilaurin peroxide, peroxide Di-n-octyl alcohol, 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoic acid, bis(4-methylbenzyl) peroxide, dibenzyl peroxide, peroxide Peroxide-based initiators such as tert-butyl isobutyrate, 1,1-di(tertiary hexyl peroxide) cyclohexane, tertiary butyl hydroperoxide, hydrogen peroxide, etc.; persulfate and sulfurous acid The combination of sodium hydrogen, the combination of peroxide and sodium ascorbate, etc., the redox initiator of the combination of peroxide and reducing agent, etc., but it is not limited to these.

The above-mentioned polymerization initiator may be used singly or in combination of two or more. The content as a whole is preferably about 0.005 to 1 part by weight, and more preferably about 0.02 to 0.5 part by weight relative to 100 parts by weight of the monomer.

Furthermore, when 2,2'-azobisisobutyronitrile is used as a polymerization initiator to produce the above-mentioned weight average molecular weight (meth)acrylic polymer, the usage amount of the polymerization initiator is relative to the monomer The total amount of 100 parts by weight of the components is preferably about 0.06 to 0.2 parts by weight, and more preferably about 0.08 to 0.175 parts by weight.

As the chain transfer agent, for example, lauryl mercaptan, glycidyl mercaptan, thioglycolic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolic acid, 2,3-dimercapto -1-propanol and so on. The chain transfer agent may be used alone or in combination of two or more, and the content as a whole is about 0.1 parts by weight or less with respect to 100 parts by weight of the total amount of monomer components.

In addition, as emulsifiers used in emulsion polymerization, for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, polyoxyethylene alkyl ether ammonium sulfate, polyoxyethylene alkyl phenyl Anionic emulsifiers such as sodium ether sulfate, nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer, etc. . These emulsifiers may be used alone or in combination of two or more kinds.

Furthermore, in the reactive emulsifier, as freely introduced propenyl groups, allyl ether groups, etc. The emulsifier based on the polymerizable functional group, specifically, there are Aqualon HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (the above are all manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) , ADEKA REASOAP SE10N (made by ADEKA company), etc. The reactive emulsifier is incorporated into the polymer chain after polymerization, so the water resistance becomes good, so it is preferable. The use amount of the emulsifier is 0.3 to 5 parts by weight relative to 100 parts by weight of the total monomer components, and more preferably 0.5 to 1 part by weight in terms of polymerization stability or mechanical stability.

In addition, when the (meth)acrylic polymer is produced by active energy ray polymerization, it can be produced by irradiating active energy rays such as electron beams and ultraviolet rays to polymerize the above-mentioned monomer components. In the case of using electron beam to carry out the above-mentioned active energy ray polymerization, it is not particularly necessary for the monomer component to contain a photopolymerization initiator, but when the above-mentioned active energy ray polymerization is carried out by ultraviolet polymerization, the polymerization can be shortened in particular. In terms of time advantages, etc., a photopolymerization initiator can be contained in the monomer component. The photopolymerization initiator can be used alone or in combination of two or more. When the above-mentioned monomer components are irradiated with radiation, a part of the monomer components may be polymerized in advance to form a slurry.

系光聚合起始劑、醯基氧化膦系光聚合起始劑等。 There are no particular restrictions on the photopolymerization initiator, as long as it is one that initiates photopolymerization, there are no particular restrictions, and a photopolymerization initiator commonly used can be used. For example, benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, α-ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, and photoactive oxime-based photopolymerization initiators can be used. Polymerization initiator, benzoin-based photopolymerization initiator, benzophenone-based photopolymerization initiator, benzophenone-based photopolymerization initiator, ketal-based photopolymerization initiator, 9-oxysulfur

It is a photopolymerization initiator, an phosphine oxide-based photopolymerization initiator, etc.

Specifically, as the benzoin ether-based photopolymerization initiator, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1, 2-Diphenylethane-1-one [trade name: IRGACURE 651, manufactured by BASF Corporation], anisin methyl ether and the like. As an acetophenone-based photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone [trade name: IRGACURE 184, manufactured by BASF Corporation Manufacture], 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2- Methyl-1-propane-1-one [trade name: IRGACURE 2959, manufactured by BASF Corporation], 2-hydroxy-2-methyl-1-phenyl-propane-1-one [trade name: DAROCUR 1173, BASF Corporation Manufacturing], methoxyacetophenone, etc. As an α-ketol-based photopolymerization initiator, for example, 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-hydroxy-2-methyl Propane-1-one and so on. As an aromatic sulfonyl chloride-based photopolymerization initiator, for example, 2-naphthalenesulfonyl chloride and the like can be cited. As a photoactive oxime-type photopolymerization initiator, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime etc. are mentioned, for example.

系光聚合起始劑中例如包含9-氧硫

、2-氯-9-氧硫

、2-甲基-9-氧硫

、2,4-二甲基-9-氧硫

、異丙基-9-氧硫

、2,4-二氯-9-氧硫

、2,4-二乙基-9-氧硫

、異丙基-9-氧硫

、2,4-二異丙基-9-氧硫

、十二烷基-9-氧硫

等。 In addition, the benzoin-based photopolymerization initiator includes, for example, benzoin and the like. The benzyl-based photopolymerization initiator includes benzyl and the like, for example. The benzophenone-based photopolymerization initiator includes, for example, benzophenone, benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, and polyvinyl benzophenone. , Α-hydroxycyclohexyl phenyl ketone and so on. The ketal-based photopolymerization initiator includes, for example, benzil dimethyl ketal and the like. 9-oxysulfur

The photopolymerization initiator contains, for example, 9-oxysulfur

, 2-Chloro-9-oxysulfur

, 2-Methyl-9-oxysulfur

, 2,4-Dimethyl-9-oxysulfur

, Isopropyl-9-oxysulfur

, 2,4-Dichloro-9-oxysulfur

, 2,4-Diethyl-9-oxysulfur

, Isopropyl-9-oxysulfur

, 2,4-Diisopropyl-9-oxysulfur

, Dodecyl-9-oxysulfur

Wait.

As the phosphine oxide-based photopolymerization initiator, for example, bis(2,6-dimethoxybenzyl)phenyl phosphine oxide, bis(2,6-dimethoxybenzyl) )(2,4,4-Trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzyl)n-butylphosphine oxide, bis(2,6-dimethoxybenzyl) (2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzyl)-(1-methylpropane-1-yl)phosphine oxide, bis(2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzyl)-(1-methylpropan-1-yl)phosphine oxide, 2,6-Dimethoxybenzyl) tertiary butyl phosphine oxide, bis(2,6-dimethoxybenzyl) cyclohexyl phosphine oxide, bis(2,6-dimethoxy) Benzyl) octyl phosphine oxide, bis(2-methoxybenzyl) (2-methylpropan-1-yl) phosphine oxide, bis(2-methoxybenzyl) (1 -Methylpropane-1-yl)phosphine oxide, bis(2,6-diethoxybenzyl)(2-methylpropane-1-yl)phosphine oxide, bis(2,6-diethoxy) Benzyl) (1-methylpropane- 1-yl)phosphine oxide, bis(2,6-dibutoxybenzyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4-dimethoxybenzyl) )(2-methylpropane-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzyl)(2,4-dipentyloxyphenyl)phosphine oxide, bis(2, 6-Dimethoxybenzyl)benzyl phosphine oxide, bis(2,6-dimethoxybenzyl)-2-phenylpropyl phosphine oxide, bis(2,6-dimethoxy) Benzyl)-2-phenylethyl phosphine oxide, bis(2,6-dimethoxybenzyl) benzyl phosphine oxide, bis(2,6-dimethoxybenzyl) )-2-Phenylpropyl phosphine oxide, bis(2,6-dimethoxybenzyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzylbenzyl Butyl phosphine oxide, 2,6-dimethoxybenzyl benzyl octyl phosphine oxide, bis(2,4,6-trimethylbenzyl)-2,5-diisopropylbenzene Phosphine oxide, bis(2,4,6-trimethylbenzyl)-2-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)-4-methyl Phenyl phosphine oxide, bis(2,4,6-trimethylbenzyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzyl) )-2,3,5,6-tetramethylphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)-2,4-di-n-butoxyphenylphosphine oxide, 2 ,4,6-Trimethylbenzyldiphenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide, bis( 2,4,6-trimethylbenzyl) isobutyl phosphine oxide, 2,6-dimethoxybenzyl-2,4,6-trimethylbenzyl n-butyl oxidation Phosphine, bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, bis(2,4,6-trimethylbenzyl)-2,4-dibutoxyphenyl Phosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzyl)phosphine oxide]decane, tris(2-methylbenzyl)phosphine oxide, and the like.

The amount of the photopolymerization initiator used is not particularly limited. For example, it is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, and more preferably 0.05 to 1.5 parts by weight relative to 100 parts by weight of the above-mentioned monomer components. Preferably it is 0.1 to 1 part by weight.

If the used amount of the photopolymerization initiator is less than 0.01 parts by weight, the polymerization reaction may be insufficient. If the used amount of the photopolymerization initiator exceeds 5 parts by weight, the photopolymerization initiator absorbs ultraviolet rays, so there are cases where the ultraviolet rays cannot reach the inside of the adhesive layer. In this case, the polymerization rate decreases, or the molecular weight of the produced polymer decreases. Moreover, the cohesive force of the formed adhesive layer becomes low, and when the adhesive layer is peeled from the film, There are cases where part of the adhesive layer remains on the film and the film cannot be reused. In addition, the photopolymerization initiator can be used alone or in combination of two or more.

The weight average molecular weight of the (meth)acrylic polymer of the present invention is preferably 400,000 to 2.5 million, more preferably 600,000 to 2.2 million. By making the weight average molecular weight greater than 400,000, the durability of the adhesive layer can be satisfied or the cohesive force of the adhesive layer can be suppressed from becoming small, resulting in paste residue. On the other hand, if the weight average molecular weight is greater than 2.5 million, the adhesion and adhesion tend to decrease. Furthermore, there are cases where the viscosity of the adhesive is too high in the solution system, making it difficult to apply. In addition, the weight average molecular weight refers to a value calculated by GPC (gel permeation chromatography) and calculated by polystyrene conversion. In addition, it is difficult to measure the molecular weight of (meth)acrylic polymers obtained by radiation polymerization.

<Determination of weight average molecular weight>

The weight average molecular weight of the obtained (meth)acrylic polymer was measured by GPC (Gel Permeation Chromatography). Regarding the sample, the sample was dissolved in tetrahydrofuran to prepare a 0.1% by weight solution, and after leaving it to stand overnight, it was filtered with a 0.45 μm membrane filter, and the filtrate obtained by filtration was used.

‧Analysis device: manufactured by Tosoh Corporation, HLC-8120GPC

‧Column: manufactured by Tosoh Corporation, (meth)acrylic polymer: GM7000H _XL +GMH _XL +GMH _XL

Aromatic polymer: G3000HXL+2000HXL+G1000HXL

‧Column size: 7.8mmΦ×30cm each, 90cm in total

‧Eluent: Tetrahydrofuran (concentration 0.1% by weight)

‧Flow rate: 0.8mL/min

‧Inlet pressure: 1.6MPa

‧Detector: Differential Refractometer (RI)

‧Column temperature: 40℃

Injection volume: 100μl

Eluent: Tetrahydrofuran

Detector: Differential refractometer

Standard sample: Polystyrene

唑啉系交聯劑、氮丙啶系交聯劑、矽烷系交聯劑、烷基醚化三聚氰胺系交聯劑、金屬螯合物系交聯劑、過氧化物等交聯劑。交聯劑可單獨使用一種或組合兩種以上使用。作為上述交聯劑，可較佳地使用異氰酸酯系交聯劑、環氧系交聯劑。 The adhesive forming the adhesive layer A and the adhesive layer B of the present invention may contain a crosslinking agent. As crosslinking agents, including isocyanate-based crosslinking agents, epoxy-based crosslinking agents, silicone-based crosslinking agents,

Oxazoline-based cross-linking agents, aziridine-based cross-linking agents, silane-based cross-linking agents, alkyl etherified melamine-based cross-linking agents, metal chelate-based cross-linking agents, peroxides and other cross-linking agents. A crosslinking agent can be used individually by 1 type or in combination of 2 or more types. As the above-mentioned crosslinking agent, an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent can be preferably used.

The above-mentioned crosslinking agent may be used alone or in combination of two or more kinds. As a whole content, it is preferable to contain the said crosslinking agent in the range of 0.01-5 weight part with respect to 100 weight part of the said (meth)acrylic-type polymer. Regarding the content of the crosslinking agent, it is preferably 0.01 to 4 parts by weight, and more preferably 0.02 to 3 parts by weight.

The isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups in one molecule (including isocyanate regenerating functional groups after the isocyanate groups are temporarily protected by a blocking agent or multimerization).

Examples of the isocyanate-based crosslinking agent include aromatic isocyanates such as toluene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.

More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, and lipids such as cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, etc. Cyclic isocyanates, aromatic diisocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylol Trimethylolpropane/toluene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name Corona L), trimethylolpropane/hexamethylene diisocyanate trimer adduct (Nippon Polyurethane Industry Co., Ltd.) Coronate HL), isocyanurate compound of hexamethylene diisocyanate (manufactured by Japan Polyurethane Industry Co., Ltd., brand name Corona HX) and other isocyanate adducts, trihydroxyl of xylylene diisocyanate Methylpropane adduct (manufactured by Mitsui Chemicals, trade name D110N), trimethylolpropane adduct of hexamethylene diisocyanate (manufactured by Mitsui Chemicals, trade name D160N); polyether polyisocyanate, polyester Polyisocyanates, and their adducts with various polyols, are polyisocyanates formed by polyfunctionalization through isocyanurate bonds, biuret bonds, allophanate bonds, etc. Among them, the use of aliphatic isocyanates has a faster reaction speed, which is preferable.

The above-mentioned isocyanate-based crosslinking agent may be used singly or in combination of two or more. The total content is preferably 0.01 to 5 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer, and further Preferably, it contains 0.01 to 4 parts by weight, more preferably 0.02 to 3 parts by weight of the above-mentioned isocyanate-based crosslinking agent. It can be appropriately contained in consideration of cohesive force, prevention of peeling during durability test, etc.

Furthermore, in the aqueous dispersion of modified (meth)acrylic polymer made by emulsion polymerization, the isocyanate-based crosslinking agent may not be used, but if necessary, in order to easily react with water, it may also be used Blocked isocyanate-based crosslinking agent.

The above-mentioned epoxy-based crosslinking agent refers to a multifunctional epoxy compound having two or more epoxy groups in one molecule. As the epoxy-based crosslinking agent, for example, bisphenol A, epichlorohydrin type epoxy resin, N,N,N',N'-tetraglycidyl metaxylylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl Ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, glycerol diglycidyl ether, glycerin Triglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, tris(2 -Hydroxyethyl) triglycidyl isocyanurate, m-benzene Diphenol diglycidyl ether, bisphenol S diglycidyl ether, and epoxy resins with more than two epoxy groups in the molecule, etc. As the epoxy-based crosslinking agent, for example, commercially available products such as "TETRAD C" and "TETRAD X" manufactured by Mitsubishi Gas Chemical Co., Ltd. can be cited.

The epoxy-based crosslinking agent may be used singly or in combination of two or more. The content as a whole preferably contains 0.01 to 5 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer. It is more preferable to contain 0.01 to 4 parts by weight, and more preferably 0.02 to 3 parts by weight of the above-mentioned epoxy-based crosslinking agent. It can be appropriately contained in consideration of cohesive force, prevention of peeling during durability test, etc.

As the peroxide crosslinking agent, as long as it is one that crosslinks the base polymer of the adhesive by generating free radical active species by heating, it can be used appropriately. Considering workability and stability, it is preferably used with a one-minute half-life The peroxide temperature is 80°C~160°C, and it is better to use the peroxide temperature of the one-minute half-life temperature of 90°C~140°C.

Usable peroxides include, for example, bis(2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6°C), bis(4-tertiarybutylcyclohexyl) peroxydicarbonate Ester (1 minute half-life temperature: 92.1°C), di-second butyl peroxydicarbonate (1 minute half-life temperature: 92.4°C), tert-butyl peroxyneodecanoate (1 minute half-life temperature: 103.5°C), Tertiary hexyl pivalate oxide (1 minute half-life temperature: 109.1°C), tertiary pivalate peroxide (1 minute half-life temperature: 110.3°C), dilaurin peroxide (1 minute half-life temperature: 116.4°C) ), di-n-octyl peroxide (1 minute half-life temperature: 117.4°C), 2-ethylhexanoic acid 1,1,3,3-tetramethylbutyl peroxide (1 minute half-life temperature: 124.3°C), over Di(4-methylbenzyl oxide) (1 minute half-life temperature: 128.2°C), Dibenzyl peroxide (1 minute half-life temperature: 130.0°C), tert-butyl peroxide isobutyrate (1 minute half-life) Temperature: 136.1°C), 1,1-bis(third hexylperoxy) cyclohexane (1 minute half-life temperature: 149.2°C), etc. Among them, particularly in terms of excellent crosslinking reaction efficiency, bis(4-tertiarybutylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1°C), dilaurin peroxide ( 1 minute half-life temperature: 116.4℃), peroxide Dibenzamide (1 minute half-life temperature: 130.0°C) and the like.

Furthermore, the half-life of peroxide is an indicator of the decomposition rate of peroxide, which is the time for the residual amount of peroxide to reach half. Regarding the decomposition temperature used to obtain the half-life at any time or the half-life time at any temperature, it is recorded in the manufacturer's catalog, etc., for example, in the Nippon Oil & Fat Co., Ltd. "Organic Peroxide Catalog 9th Edition (May 2003) There are records in.

The above-mentioned peroxides can be used alone or in combination of two or more. The content as a whole is 0.02 to 2 parts by weight relative to 100 parts by weight of the above-mentioned (meth)acrylic polymer. Preferably, it contains 0.05 to 1 part by weight. In order to adjust processability, secondary processability, crosslinking stability, peelability, etc., it can be appropriately selected within this range.

In addition, as a method for measuring the amount of peroxide decomposition remaining after the reaction treatment, for example, it can be measured by HPLC (High Performance Liquid Chromatography).

More specifically, for example, about 0.2 g of the adhesive after the reaction treatment is taken each time, immersed in 10 ml of ethyl acetate, extracted with a shaker at 25°C and 120 rpm for 3 hours, and then left standing at room temperature for 3 hours. day. Then, add 10ml of acrylonitrile, shake at 120rpm for 30 minutes at 25°C, filter through a membrane filter (0.45μm), and inject about 10μl of the obtained extract into the HPLC for analysis. The amount of oxide.

Moreover, as a crosslinking agent, an organic crosslinking agent or a polyfunctional metal chelate compound can also be used together. The polyfunctional metal chelate is one in which a polyvalent metal and an organic compound are covalently bonded or coordinately bonded. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, etc. . Examples of the atoms in the organic compound to be covalently bonded or coordinately bonded include oxygen atoms and the like, and examples of the organic compounds include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, ketone compounds, and the like.

The adhesive forming the adhesive layer A and the adhesive layer B of the present invention may contain a multifunctional monomer as a crosslinking agent. The polyfunctional monomer is a monomer having at least two (meth)acrylic acid groups or polymerizable functional groups with unsaturated double bonds such as vinyl groups, and can be exemplified as a monomer for forming (meth)acrylic polymers. The exemplified body composition is the same.

The multifunctional monomer as the crosslinking agent may be used alone or in combination of two or more. The content as a whole preferably contains the crosslinking agent (polyfunctional monomer) in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the (meth)acrylic polymer. Regarding the content of the above-mentioned crosslinking agent (multifunctional monomer), 0.005 to 3 parts by weight is preferable, and 0.01 to 1 part by weight is more preferable.

A photopolymerization initiator is prepared in the adhesive prepared with the above-mentioned crosslinking agent (multifunctional monomer). As the photopolymerization initiator, the same ones as those used in the preparation of the (meth)acrylic polymer can be exemplified. The use amount of the photopolymerization initiator is usually 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, and more preferably 0.05 to 1.5 parts by weight relative to 100 parts by weight of the above-mentioned crosslinking agent (multifunctional monomer) , And more preferably 0.1 to 1 part by weight. The adhesive prepared with the above-mentioned crosslinking agent (multifunctional monomer) is cured by irradiation with active energy rays to form an adhesive layer (active energy ray curable adhesive layer).

In terms of forming a specific thickness and step absorbency, it is preferable that the multilayer adhesive layer of the above-mentioned adhesive layer A is at least one adhesive layer that is hardened by active energy rays formed by irradiation of active energy rays Type adhesive layer. In particular, it is preferable that the first adhesive layer (a) and/or the second adhesive layer (b) be an active energy ray-curable adhesive layer.

When forming the adhesive of the adhesive layer A and the adhesive layer B of the present invention, in order to improve the adhesive force, a (meth)acrylic oligomer may be contained. The (meth)acrylic oligomer preferably uses a polymer having a higher Tg than the (meth)acrylic polymer of the present invention and a weight average molecular weight smaller than the (meth)acrylic polymer of the present invention. The above-mentioned (meth)acrylic oligomer functions as an adhesion-imparting resin and has the advantage of increasing adhesive force without increasing the dielectric constant.

It is desirable that the Tg of the (meth)acrylic oligomer is about 0°C or higher and 300°C or lower, preferably about 20°C or higher and 300°C or lower, and more preferably about 40°C or higher and 300°C or lower. If the Tg is less than about 0°C, the cohesive force above room temperature of the adhesive layer may decrease, and the retention characteristics or adhesiveness at high temperature may decrease. In addition, the Tg of the (meth)acrylic oligomer is the theoretical value calculated based on the Fox formula similarly to the Tg of the (meth)acrylic polymer.

The weight average molecular weight of the (meth)acrylic oligomer is 1,000 or more and less than 30,000, preferably 1,500 or more and less than 20,000, and more preferably 2,000 or more and less than 10,000. If the weight average molecular weight is 30,000 or more, the effect of improving the adhesive force may not be sufficiently obtained. In addition, if it is less than 1000, the molecular weight is low, so adhesive force or retention characteristics may decrease. In the present invention, the measurement of the weight average molecular weight of the (meth)acrylic oligomer can be determined by the GPC method in terms of polystyrene. Specifically, in the HPLC8020 manufactured by Tosoh Co., Ltd., TSKgelGMH-H(20)×2 was used as a column, and a tetrahydrofuran solvent was used for measurement at a flow rate of about 0.5 ml/min.

基酯、(甲基)丙烯酸二環戊酯之類的(甲基)丙烯酸與脂環族醇之酯；(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯之類的(甲基)丙烯酸芳基酯；由萜烯化合 物衍生物醇獲得之(甲基)丙烯酸酯等。此種(甲基)丙烯酸酯可單獨使用或組合兩種以上使用。 Examples of the monomer constituting the (meth)acrylic oligomer include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate Propyl ester, butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, pentyl (meth)acrylate, (meth)acrylate Base) isoamyl acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate Ester, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, (meth) ) Alkyl (meth)acrylates such as dodecyl acrylate; cyclohexyl (meth)acrylate, isopropyl (meth)acrylate

(Meth)acrylic acid and alicyclic alcohol esters such as dicyclopentyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate and the like (meth) Aryl acrylate; (meth)acrylate obtained from terpene compound derivative alcohol, etc. Such (meth)acrylate can be used individually or in combination of 2 or more types.

基酯、(甲基)丙烯酸二環戊酯之類的(甲基)丙烯酸與脂環式醇之酯；(甲基)丙烯酸苯酯或(甲基)丙烯酸苄酯之類的(甲基)丙烯酸芳基酯等具有環狀結構之(甲基)丙烯酸酯為代表之具有較大體積之結構之丙烯酸系單體作為單體單元。藉由使(甲基)丙烯酸系低聚物具有此種大體積之結構，可進而提高黏著劑層之接著性。特別是就大體積之方面而言，具有環狀結構者之效果較高，含有複數個環者之效果更高。又，於(甲基)丙烯酸系低聚物之合成時或黏著劑層之製作時採用紫外線之情形時，就不易引起阻聚之方面而言，較佳為具有飽和鍵者，可較佳地使用烷基具有支鏈結構之(甲基)丙烯酸烷基酯或與脂環式醇之酯作為構成(甲基)丙烯酸系低聚物之單體。 The (meth)acrylic oligomer preferably contains alkyl (meth)acrylate having a branched structure with an alkyl group such as isobutyl (meth)acrylate or tert-butyl (meth)acrylate. Base ester; cyclohexyl (meth)acrylate or isopropyl (meth)acrylate

(Meth)acrylic acid and alicyclic alcohol esters such as dicyclopentyl (meth)acrylate; (meth)acrylates such as phenyl (meth)acrylate or benzyl (meth)acrylate The aryl acrylate and other (meth)acrylic acid esters with a cyclic structure are represented by acrylic monomers with a relatively bulky structure as monomer units. By making the (meth)acrylic oligomer have such a bulky structure, the adhesiveness of the adhesive layer can be further improved. Especially in terms of large volume, the effect of having a ring structure is higher, and the effect of having a plurality of rings is higher. In addition, when ultraviolet rays are used during the synthesis of the (meth)acrylic oligomer or the production of the adhesive layer, it is less likely to cause polymerization inhibition, preferably those with saturated bonds, which are more preferable As the monomer constituting the (meth)acrylic oligomer, an alkyl (meth)acrylate having a branched alkyl group structure or an ester with an alicyclic alcohol is used.

基酯(IBXMA)之共聚物、甲基丙烯酸環己酯(CHMA)與丙烯醯基

啉(ACMO)之共聚物、甲基丙烯酸環己酯(CHMA)與二乙基丙烯醯胺(DEAA)之共聚物、丙烯酸1-金剛烷基酯(ADA)與甲基丙烯酸甲酯(MMA)之共聚物、甲基丙烯酸二環戊酯(DCPMA)與甲基丙烯酸異

基酯(IBXMA)之共聚物、甲基丙烯酸環戊酯(DCPMA)與甲基丙烯酸甲酯(MMA)之共聚物、甲基丙烯酸二環戊酯(DCPMA)、甲基丙烯酸環己酯(CHMA)、甲基丙烯酸異

基酯(IBXMA)、丙烯酸異

基酯(IBXA)、丙烯酸二環戊酯(DCPA)、甲基丙烯酸1-金剛烷基酯(ADMA)、丙烯酸1-金剛烷基酯 (ADA)之各自之均聚物等。特別是，較佳為含有CHMA作為主成分之低聚物。 In this respect, as preferred (meth)acrylic oligomers, for example, a copolymer of cyclohexyl methacrylate (CHMA) and isobutyl methacrylate (IBMA), methacrylic acid ring Hexyl ester (CHMA) is different from methacrylic acid

Copolymer of IBXMA, cyclohexyl methacrylate (CHMA) and acrylic

Copolymer of ACMO, copolymer of cyclohexyl methacrylate (CHMA) and diethyl acrylamide (DEAA), 1-adamantyl acrylate (ADA) and methyl methacrylate (MMA) Copolymer, dicyclopentyl methacrylate (DCPMA) and methacrylic acid

IBXMA copolymer, cyclopentyl methacrylate (DCPMA) and methyl methacrylate (MMA) copolymer, dicyclopentyl methacrylate (DCPMA), cyclohexyl methacrylate (CHMA) ), methacrylic acid

Base ester (IBXMA), acrylic iso

Homopolymers of IBXA, dicyclopentyl acrylate (DCPA), 1-adamantyl methacrylate (ADMA), 1-adamantyl acrylate (ADA), etc. In particular, it is preferably an oligomer containing CHMA as a main component.

When the above-mentioned (meth)acrylic oligomer is used in the adhesive forming the adhesive layer A and the adhesive layer B of the present invention, its content is not particularly limited, and is relative to the (meth)acrylic polymer 100 parts by weight is preferably 70 parts by weight or less, more preferably 1 to 70 parts by weight, still more preferably 2 to 50 parts by weight, and still more preferably 3 to 40 parts by weight. If the addition amount of the (meth)acrylic oligomer exceeds 70 parts by weight, the modulus of elasticity becomes high and the adhesiveness at low temperature deteriorates. Furthermore, when 1 part by weight or more of (meth)acrylic oligomer is blended, it is effective in terms of the effect of improving the adhesive force.

Furthermore, in order to improve the water resistance at the interface when the adhesive layer is applied to a hydrophilic adherend such as glass, the adhesive forming the adhesive layer A and the adhesive layer B of the present invention may contain a silane coupling agent. The compounding amount of the silane coupling agent is preferably 1 part by weight or less relative to 100 parts by weight of the (meth)acrylic polymer, more preferably 0.01 to 1 part by weight, and still more preferably 0.02 to 0.6 part by weight. If the blending of the silane coupling agent is too much, the adhesion to the glass will increase and the re-peelability will be poor. If it is too little, the durability will decrease, which is not good.

As the silane coupling agent that can be preferably used, there can be mentioned: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyl Epoxy-containing silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2-( Aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-benzene -Γ-aminopropyltrimethoxysilane and other amino-containing silane coupling agents, 3-propenoxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. (Meth)acrylic silane coupling agent, 3-isocyanate propyl triethoxy silane and other isocyanate group-containing silane coupling agents, etc.

Furthermore, the adhesive forming the adhesive layer A and the adhesive layer B of the present invention may contain other well-known additives. For example, polypropylene glycol and other polyalkylene glycols may be appropriately added according to the intended use. Polyether compounds based on glycols, colorants, pigments, etc., powders, dyes, surfactants, plasticizers, adhesion imparting agents, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light Stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particles, foils, etc. In addition, within a controllable range, a redox system with a reducing agent can also be used.

The adhesive layer A and the adhesive layer B can be formed, for example, by applying the forming material (adhesive) to a member such as a transparent substrate and/or a polarizing film, and drying and removing the polymerization solvent and the like. When applying the above-mentioned forming materials, one or more solvents other than the polymerization solvent may be newly added as appropriate.

As the coating method of the above-mentioned forming material, various methods can be used. Specifically, for example, roll coating, touch roll coating, gravure coating, reverse coating, roll brush coating, spray coating, dip roll coating, bar coating, knife coating, air knife coating can be cited. Methods such as cloth, curtain coating, die lip coating, extrusion coating using die nozzle coater, etc.

The heating and drying temperature is preferably 40°C to 200°C, more preferably 50°C to 180°C, and particularly preferably 70°C to 170°C. By setting the heating temperature in the above range, the adhesive layer A or the adhesive layer B having excellent adhesive properties can be obtained. The drying time can be suitably used for an appropriate time. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.

In addition, regarding the formation of the adhesive layer A and the adhesive layer B, when the forming material (adhesive) is an active energy ray curable adhesive, polymerization can be performed by irradiating active energy rays such as ultraviolet rays. High-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, etc. can be used for ultraviolet irradiation.

In addition, the above-mentioned adhesive layer A and adhesive layer B may be formed on a support and transferred to a polarizing film or the like. As the above-mentioned support, for example, a release-treated sheet can be used. As the release-treated sheet, a silicone release liner can be preferably used. Furthermore, when the above-mentioned adhesive layer A is a multi-layer adhesive layer, the peeling process can be used to sequentially shape The first adhesive layer (a), the second adhesive layer (b), etc. are formed by bonding with the polarizing film, or the first adhesive layer (a) and the second adhesive layer may be formed separately (b) The first adhesive layer (a) is attached to the polarizing film in sequence so that the first adhesive layer (a) becomes the outermost surface.

The stripped sheet is (separation film), which can be used as the separation film SA ₁ of the adhesive layer A and the separation film SB of the adhesive layer B. In actual application, the above-mentioned peeling-treated sheet is peeled off.

As a constituent material of the separator, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and non-woven fabrics, meshes, and foamed sheets are mentioned. Appropriate sheets such as metal foils, laminates of these, etc., in terms of excellent surface smoothness, plastic films can be preferably used.

The plastic film is not particularly limited as long as it can protect the adhesive layer A or the adhesive layer B. Examples include polyethylene film, polypropylene film, polybutene film, and polybutadiene film. , Polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-acetic acid Vinyl ester copolymer film, etc.

For the above-mentioned isolation film, the above-mentioned plastic film can be used as a base film, and if necessary, a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, etc. can be used for release and Anti-fouling treatment, or antistatic treatment such as coating type, kneading type, vapor deposition type, etc. In particular, by appropriately performing peeling treatments such as silicone treatment, long-chain alkyl treatment, fluorine treatment, etc., on the surface of the isolation film, the releasability from the adhesive layer A or the adhesive layer B can be further improved.

As a silicone mold release layer, addition reaction type silicone resin is mentioned, for example. Examples include: KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-847T, TPR-6700, TPR-6710, TPR-6721 manufactured by Toshiba Organosilicon manufactured by Shin-Etsu Chemical Industry SD7220, SD7226, etc. manufactured by Toray Dow Corning. The coating amount (after drying) of the silicone-based mold release agent is preferably in the range of 0.01 to 2 g/m ² , preferably 0.01 to 1 g/m ² , and more preferably 0.01 to 0.5 g/m ² .

The release layer can be formed, for example, by applying the above-mentioned materials on the oligomer prevention layer by using a conventionally known coating method such as reverse gravure coating, bar coating, die nozzle coating, etc. It is usually hardened by heat treatment at about 120°C to 200°C. In addition, heat treatment and active energy ray irradiation such as ultraviolet irradiation may be used in combination as necessary.

The thickness of the isolation film (including the release layer) is usually about 5 μm to 200 μm. Since the thickness of the isolation film is related to its peeling force, it is preferable to use a thickness corresponding to that of the isolation film. From the standpoint of peeling force and in order to prevent dents, the thicknesses of the above-mentioned separation films SA ₁ , SA ₁ ′, and SA ₂ are all preferably 30 μm or more, more preferably 40 μm or more, and still more preferably 50 μm or more. In detail, _{the thickness of SA 1} , SA ₁ ′, and SA ₂ is preferably 40 μm to 130 μm, and more preferably 50 μm to 80 μm. In addition, the thickness of the aforementioned isolation film SB is preferably 10 μm to 80 μm, more preferably 20 μm to 50 μm, still more preferably 30 μm to 50 μm, and still more preferably 30 μm to 40 μm. In addition, in the structure of the polarizing film with the adhesive layer attached on both sides, the thickness of the isolation film, the viewpoint of peeling force and the aspect of preventing dents, it is particularly preferable to use the isolation film SA ₁ (SA ₁ ' The case where the thickness of) is 50μm or more is combined with the case where the thickness of the separator SB is 30μm~50μm.

In addition, when the adhesive layer A or the adhesive layer B is provided on the above-mentioned polarizing film, the surface of the polarizing film can be processed for easy adhesion. Examples of easy adhesion treatment include corona treatment, plasma treatment, excimer treatment, hard coating treatment, primer treatment, and the like. In addition, easy bonding treatment can also be performed on the surface of the adhesive layer. Regarding the polarizing film with the adhesive layer of the present invention, it is preferable to perform easy adhesion treatment on the surface of the polarizing film on which the adhesive layer A is laminated in terms of preventing peeling and foaming.

In addition, the polarizing film with adhesive layer of the present invention can be prepared in such a way that any part has an antistatic function. The antistatic function can be imparted to the polarizing film attached to the adhesive layer by, for example, containing an antistatic agent in the polarizing film or the adhesive layer, or providing an antistatic layer.

In the polarizing film with an adhesive layer of the present invention, the antistatic layer is arranged in the figure Among the polarizing films used in an image display device (for example, a liquid crystal display device), the polarizing film that is arranged closest to the viewing side is closer to the viewing side. Therefore, it is possible to greatly reduce problems such as the elimination of polarized light or the generation of bright spots caused by impurities that may occur when an antistatic layer (low surface resistance layer) is installed between the polarizing film on the viewing side and the liquid crystal panel. And it will not damage the reliability of the polarizing film placed closest to the viewing side. In this way, an antistatic function can be imparted without compromising the performance of the image display device.

Especially, it is effective when applied to liquid crystal display devices with built-in touch sensors such as built-in or external touch sensors. It can be used for liquid crystal displays with built-in touch sensors such as built-in or external touch sensors. The device is of high quality.

In order to impart an antistatic function to the adhesives forming the adhesive layer A and the adhesive layer B of the present invention, an ionic compound may be included as an antistatic agent in addition to the base polymer. As the ionic compound, an alkali metal salt and/or an organic cation-anion salt can be preferably used. As the alkali metal salt, organic salts and inorganic salts of alkali metals can be used. In addition, the "organic cation-anion salt" in the present invention refers to an organic salt whose cation portion is composed of an organic substance, and the anion portion may be an organic substance or an inorganic substance. "Organic cation-anion salt" can also be called ionic liquid or ionic solid.

In addition, as the ionic compound, in addition to the above-mentioned alkali metal salts and organic cation-anion salts, inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, iron chloride, and ammonium sulfate can be cited. The ionic compound can be used alone or in combination of plural kinds.

The ratio of the ionic compound in the adhesive forming the adhesive layer A and the adhesive layer B of the present invention is preferably 0.0001 to 5 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer. If the above-mentioned ionic compound is less than 0.0001 parts by weight, the effect of improving the antistatic performance may be insufficient. The ionic compound is preferably 0.01 part by weight or more, and more preferably 0.1 part by weight or more. On the other hand, if the ionic compound exceeds 5 parts by weight, the durability may be insufficient. The ionic compound is preferably 3 parts by weight or less, and more preferably 1 part by weight or less. The ratio of the above ionic compounds The above upper limit or lower limit can be used to set a better range.

[Example]

Hereinafter, the present invention will be specifically explained through examples, but the present invention is not limited to these examples. In addition, the parts and% in each example are based on weight. The evaluation items in the examples etc. were measured in the following manner.

<Production of Polarizing Film>

A polyvinyl alcohol film with a thickness of 80μm was stretched to 3 times while dyeing one side in a 0.3% concentration iodine solution between rollers with different speed ratios at 30°C. Afterwards, it was stretched to a total stretching ratio of 6 times while immersed in an aqueous solution containing 4% concentration of boric acid and 10% concentration of potassium iodide at 60°C for 0.5 minutes. Then, washing was performed by immersing in an aqueous solution containing 1.5% potassium iodide at 30°C for 10 seconds, and then drying at 50°C for 4 minutes to obtain a polarizing element with a thickness of 20 μm. A polyvinyl alcohol-based adhesive is used to bond a saponified triacetyl cellulose film with a thickness of 40 μm on one side of the polarizing element, and a polyethanol-based adhesive is used to bond an acrylic film with a thickness of 20 μm on the other side. Thus made a polarizing film. The surface of the polarizing film where the adhesive layer B is attached (the side of the triacetyl cellulose film) is appropriately corona treated.

<Separation film SA ₁ >

A release film provided with the following release layer on a polyethylene terephthalate film having a thickness of 38 μm, 50 μm, or 75 μm is used.

<Isolation film SA ₁ '>

A release film provided with the following release layer on a polyethylene terephthalate film having a thickness of 50 μm was used.

<Separation film SA ₂ >

A release film provided with the following release layer on a polyethylene terephthalate film having a thickness of 50 μm was used.

<Isolation film SB>

A release film provided with the following release layer on a polyethylene terephthalate film having a thickness of 38 μm, 50 μm, or 75 μm is used.

"Formation of the release layer"

The following release layer was formed on each of the above-mentioned isolation films.

Use methyl ethyl ketone/toluene mixed solvent (mixing ratio is 1:1) 350 parts by weight to dilute silicone resin (KS-847H: manufactured by Shin-Etsu Chemical): 20 parts by weight and hardener (PL-50T: manufactured by Shin-Etsu Chemical) ): 0.2 parts by weight, to prepare a solution of silicone-based release agent. The solution of the silicone-based release agent was coated on each of the above-mentioned polyethylene terephthalate films (substrate films) by a gravure coater so that the thickness after drying became 100 nm, and then on Drying is performed at 120° C. to form a release layer, thereby obtaining a release film having a base film/release layer composition.

Manufacturing example 1

<Preparation of Forming Material of Adhesive Layer A>

Put 70 parts of 2-ethylhexyl acrylate (2EHA), 15 parts of N-vinylpyrrolidone (NVP), and 4-hydroxybutyl acrylate into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a cooler. 15 parts of ester (4HBA), 0.05 parts of two photopolymerization initiators (trade name: Irgacure 184, manufactured by BASF Corporation), and 0.05 parts of photopolymerization initiator (trade name: Irgacure 651, manufactured by BASF Corporation) to prepare monomers mixture. Then, the monomer mixture is exposed to ultraviolet rays under a nitrogen atmosphere to partially photopolymerize, thereby obtaining a partial polymer (acrylic polymer slurry) with a polymerization rate of about 10%.

Then, 0.01 part of trimethylolpropane triacrylate (TMPTA) was added to 100 parts of the above-mentioned acrylic polymer slurry, and then these were uniformly mixed to prepare the adhesive layer A forming material (monomer component : A1).

Manufacturing example 2~5

In Production Example 1, except that the composition of each component used in the preparation of the monomer components was changed as shown in Table 1, the same operation as in Production Example 1 was performed to prepare the shape of the adhesive layer A Material (monomer components: A2 to A5).

In Table 1, 2EHA represents 2-ethylhexyl acrylate; NVP represents 2-vinylpyrrolidone; 4HBA represents 4-hydroxybutyl acrylate; TMPTA represents trimethylolpropane triacrylate.

<Production of adhesive layer A with isolation film on both sides>

_{The adhesive layer A forming material (monomer component) prepared in the above manufacturing example was applied to the release film SA 1} shown in Table 2 or Table 3 so that the final thickness became 50 μm, 100 μm, 200 μm or 300 μm. The surface is molded to form a coating layer. _{Then, the surface of the monomer component to be coated was covered with the separation film SA 2} shown in Table 2 or Table 3 so that the release treatment surface of the film became the coating layer side. Thereby, the coating layer of the monomer component blocks oxygen. Use a chemical lamp (manufactured by Toshiba Co., Ltd.) to irradiate the sheet with the coating layer thus obtained ^{with ultraviolet light with an illuminance of 5mW/cm 2} (measured by TOPCON UVR-T1 with the maximum sensitivity at about 350nm) for 360 seconds to coat The cloth layer is hardened to form an adhesive layer A, thereby forming an adhesive layer A with isolation films on both sides.

<Preparation of Adhesive Forming Adhesive Layer B>

Into a separable flask equipped with a thermometer, a stirrer, a reflux cooling tube, and a nitrogen introduction tube, 99 parts of butyl acrylate (BA) and 4-hydroxybutyl acrylate as the monomer component are added so that the solid content becomes 30% (4HBA) 1 part, 0.2 part of azobisisobutyronitrile as the polymerization initiator and ethyl acetate as the polymerization solvent. While mixing, perform nitrogen replacement for about 1 hour. After that, the flask was heated to 60°C and reacted for 7 hours to obtain an acrylic polymer with a weight average molecular weight (Mw) of 1.1 million. Add 0.1 part of trimethylolpropane toluene methyl diisocyanate ("Takenate D110N" manufactured by Mitsui Chemicals Co., Ltd.) and silane as an isocyanate-based crosslinking agent to the above-mentioned acrylic polymer solution (100 parts of solid content) 0.1 part of coupling agent ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.) to prepare an adhesive composition (solution).

<Production of Adhesive Layer B with Isolation Film>

The adhesive solution prepared above was applied to the release treatment surface of the release film SB shown in Table 2 or Table 3 so that the thickness after drying became 20μm, and heated and dried under normal pressure at 60°C for 3 minutes. The adhesive layer B was produced by heating and drying at 120°C for 3 minutes, and further aging at 23°C for 120 hours.

<Production of Polarizing Film with Adhesive Layer B on One Side>

Transfer the adhesive layer B of the release film SB to the surface of the polarizing film (the side of the triacetyl cellulose film) to produce a polarizing film with the adhesive layer B attached to one side.

Example 1

<Production of Polarizing Film with Adhesive Layer on Both Sides>

Use the device shown in Figure 6.

The adhesive layer A with the separation film on both sides is transported from the delivery roller, and the separation film SA _{2 is} peeled off by the peeling roller, and the adhesive layer A with the separation film SA ₁ is transported. On the other hand, on the polarizing film side (acrylic film side) of the polarizing film with the adhesive layer B on one side separately conveyed from the delivery roller, the adhesive layer A _{with the release film SA 1 is bonded using a pair of rollers.} Thus, the polarizing film with adhesive layer attached on both sides is made roll-to-roll. In addition, during the above bonding, as shown in Table 2, the tension T1 of the adhesive layer A with the one-side release film and the tension T2 of the polarizing film with the one-side adhesive layer B were controlled as shown in Table 2.

The production of the polarizing film is attached double-sided adhesive layers, the insulating film SA _1, SA ₂ separator, the separator thickness SB, SA separator peeling force of ₁ a _1, separator ₂ SA peel force of a ₂ , The peeling force b of the separator SB is shown in Table 1.

The surface of the adhesive layer B (the side of the triacetyl cellulose film) used for the above-mentioned polarizing film has been corona treated.

In addition, the thickness of the adhesive layer A is shown in Table 1.

<Measurement of Tension>

Measure the stress converted to 1m width using a detection roller equipped with a MB tension sensor manufactured by Nireco.

Examples 2~13, Comparative Examples 1~5

In Example 1, as shown in Table 1 SA changes separator _1, SA ₂ separator, the separator thickness SB, SA separator peeling force of ₁ a _1, SA ₂ film separator peel force of a _2, separator Peel force b of SB, thickness of adhesive layer A, storage elastic modulus of adhesive layer A (type of adhesive), whether there is corona treatment on the surface of adhesive layer A of polarizing film, single-side adhesion isolation Except for the tension T1 of the adhesive layer A of the film and the tension T2 of the polarizing film with the adhesive layer B on one side, the same operation as in Example 1 was performed to produce a polarizing film with an adhesive layer on both sides.

Furthermore, regarding Comparative Examples 1 and 2, instead of roll-to-roll, the polarizing film with the adhesive layer B on one side and _{the adhesive layer A with the isolation film SA 1} were prepared separately using a single sheet manufactured by Suntec. The film bonding device uses the absorption axis as the long side and performs bonding in an area of 500 mm×400 mm.

Example 14

<Production of Polarizing Film with Adhesive Layer on Both Sides>

Use the device shown in Figure 7.

The polarizing film with the double-sided adhesive layer obtained in Comparative Example 3 was transported from the delivery roller, and the separator SA _{1 was} peeled off by the peeling roller, and the polarized film with the double-sided adhesive layer after peeling off the separator SA _{1 was transported.}

_{On the other hand, the release film SA 1 for} curl adjustment that is separately transported from the delivery roller is attached to the adhesive layer A of the polarizing film with the above-mentioned double-sided adhesive layer using a pair of rollers, thereby making a double roll to roll. Polarized film with adhesive layer on the surface. In addition, during the above bonding, the tension T3 of the _{separator SA 1} ′ for curl adjustment and the tension T4 of the polarizing film of the double-sided adhesive layer after _{peeling off the separator SA 1 were controlled as shown in Table 3.} .

Attached to the double-sided adhesive layer of a polarizing film, the insulating film SA ₁ 'of the thickness of the insulating film SA _1' 'as described in Table 3. The peel force of a ₁ FIG.

Comparative example 6

In Example 14, as shown in Table 3, the double-sided adhesive layer-attached polarizing film transported from the delivery roller was changed (Comparative Example 3 was changed to Example 2), the tension T3 of the _{above-mentioned curl adjustment separator SA 1 '} SA and peeling the separator ₁ after the tension of the polarizing film attached to the double-sided adhesive layers T4, except that the same manner as in Example 14, making a double-sided adhesive layer of a polarizing film is attached.

The following evaluations were performed for the polarizing films with double-sided adhesive layers obtained in the above-mentioned production examples, examples, and comparative examples. The evaluation results are shown in Table 1.

<Measurement of Shear Storage Elastic Modulus>

The shear storage elastic modulus at 23°C is determined by dynamic viscoelasticity measurement. Using a dynamic viscoelasticity measuring device (device name "ARES", manufactured by TA Instrument), at a frequency of 1 Hz, in a temperature range of -20 ~ 100 ℃, 5 ℃ / min for the above measurement sample (adhesive layer A. Adhesive layer B) Measure and calculate the shear storage elastic modulus at 23°C.

<Measurement of the peeling force of the isolation film>

Cut the measurement sample with release film (release liner) (adhesive layer A with release film, adhesive layer B with release film) to a width of 50mm and a length of 100mm, and then use the tensile test The machine measures the peeling force (N/50mm) when the release film (release liner) is peeled from the sample under the conditions of a peeling angle of 180° and a peeling speed of 300mm/min.

<curl>

For the rectangular object obtained by cutting the polarizing film with the double-sided adhesive layer along the absorption axis direction of the polarizing film by 300 mm and 250 mm along the direction orthogonal to the absorption axis, place it so that the curly convex surface becomes the lower side. On a horizontal surface, measure the distance (mm) from the longest point on the horizontal plane among the four corners.

<Yield>

For the polarizing film with adhesive layer on both sides (size 70mm×100mm), after peeling off the separator SB, the side of the adhesive layer B is attached to an alkali-free glass (manufactured by Corning, 1737) with a thickness of 0.7mm. This operation was performed 10 times.

In addition, during the bonding operation, confirm whether the bonding operation can be completed without air bubbles being mixed in the ends. The ratio (success rate) of the cases where no air bubbles are mixed in the end is expressed by the following standard.

◎: The success rate is 100%.

○: The success rate is more than 80% and less than 100%.

△: The success rate is more than 50% and less than 80%.

×: The success rate is less than 50%.

<Evaluation method of level difference absorptivity>

Cut a sheet with a width of 50mm and a length of 100mm from the adhesive layer A with the release film on both sides. A release film was peeled off from the above-mentioned sheet, and the adhesive layer side of the sheet was attached to a COP (cyclic polyolefin) film (thickness: 100 μm) using a manual roller.

Next, the other release film is peeled off from the above-mentioned sheet sheet bonded to the COP film. The glass plate with print level difference is bonded under the following bonding conditions in such a way that the surface of the glass plate where the print level difference is applied is in contact with the adhesive layer on the above-mentioned COP film. Thereby, a sample for evaluation with a COP film/adhesive layer/glass plate with print level was obtained.

(Fitting conditions)

Surface pressure: 0.3MPa

Attaching speed: 25mm/s

Roller rubber hardness: 70°

Furthermore, the above-mentioned glass plate with printing level difference is used for the glass plate (manufactured by Songlang Glass Industry Co., Ltd., length 100mm, width 50mm, thickness 0.7mm) with the thickness of the printed part (the height of the printing level difference) It is a printed glass plate of 50μm or 80μm.

The (level difference/thickness of the adhesive layer)×100 (%), which is an indicator of the level difference absorbency, is 50% and 80%, respectively.

Next, the sample for evaluation was put into the autoclave, and the autoclave treatment was carried out for 15 minutes under the conditions of a pressure of 5 atm and a temperature of 50°C. After the autoclave treatment, the sample for evaluation was taken out, the adhesion state of the adhesive layer and the glass plate with print step was observed visually, and the step absorbency was evaluated according to the following evaluation criteria.

○: No air bubbles remain, and no swelling is generated between the adhesive layer and the glass plate with printing steps.

×: Air bubbles remain, and swelling occurs between the adhesive layer and the glass plate with a printing step.

<Durability>

The release film of the adhesive layer A (visible side) of the polarizing film with the adhesive layer obtained in each of the above examples was peeled off and attached to the alkali-free glass (1737 made by Corning) with a thickness of 0.7mm using a laminator. on. Then, autoclave treatment was performed at 50° C. and 0.5 MPa for 15 minutes, so that the polarizing film with the adhesive layer was completely in close contact with the alkali-free glass. Then, the vacuum bonding device manufactured by LANTECH was used to perform vacuum bonding under the conditions of a pressure of 0.2 MPa and a degree of vacuum of 30 Pa. Put them into a heating oven (heating) at 85°C and 95°C and a constant temperature and humidity machine (humidification) at 60°C/95%RH respectively, and evaluate them based on the following benchmarks Check whether the polarizing film peeled off after 500 hours.

⊚: Peeling is not observed at all.

○: Peeling to an extent that cannot be confirmed visually is observed.

△: Slight peeling that can be confirmed visually is observed.

×: Remarkable peeling (over 0.5 μm) is observed.

The result of the yield rate of Comparative Example 5 "Bubble" means that since the storage elastic modulus of the adhesive layer A is higher, after the cover glass is laminated, the ink level difference of the cover glass will not be completely filled and after the bonding Bubbles are generated immediately.

Comparative Example 6 is a case where the characteristics are reduced due to replacement of the attachment.

1‧‧‧Polarizing film

10.10'‧‧‧Polarizing film with adhesive layer on both sides

11‧‧‧Adhesive layer A with isolation film on one side

12‧‧‧Polarizing film with adhesive layer B attached to one side

13‧‧‧The polarizing film with adhesive layer on both sides after peeling off the separator SA ₁

a‧‧‧The first adhesive layer

A‧‧‧Adhesive layer A (visual recognition side)

b‧‧‧Second adhesive layer

B‧‧‧Adhesive layer B (the side opposite to the visual recognition side)

SA ₁ ‧‧‧Isolation film of adhesive layer A (visual recognition side)

SA ₁ '‧‧‧ adhesive A (visible side) of the curl adjusting layer insulating film

SB‧‧‧Isolation film of adhesive layer B (opposite side of visual recognition side)

Claims (11)

A polarizing film with a double-sided adhesive layer, which is characterized in that it has a polarizing film disposed on the side closest to the viewing side of the polarizing film used in an image display device, and an adhesive disposed on the viewing side of the polarizing film The adhesive layer (A) and the adhesive layer (B) arranged on the opposite side of the adhesive layer (A), and the adhesive layer (A) is provided with a separation film (SA ₁ ), and the adhesive layer ( B) with isolation film (SB), and the storage elastic modulus of the adhesive layer (A) at 23℃ is 0.02~0.3MPa, the peeling force a _{1 of the isolation film (SA 1} ) is higher than the isolation film (SB) peeling force b, the amount of curl of the polarizing film with the above-mentioned double-sided adhesive layer (wherein, the amount of curl measured when placed on a horizontal surface so that the side of the above-mentioned release film (SB) becomes the lower side is expressed Is +, the amount of curl measured is placed on a horizontal surface so that the side of the isolation film (SA ₁ ) becomes the lower side, and the amount of curl measured is expressed as -) is -10mm~+60mm, and the amount of curl is relative to the amount along the polarizing film A rectangular object cut by 300 mm in the direction of the absorption axis and 250 mm in the orthogonal direction of the absorption axis was measured by placing it on a horizontal surface so that the curled convex surface became the lower side. For example, the polarizing film with double-sided adhesive layer of claim 1, wherein the amount of curl is +2mm~+30mm. Such as the polarizing film with double-sided adhesive layer of claim 1, wherein _{the thickness of the separator (SA 1} ) is 50 μm or more, and the thickness of the separator (SB) is 30 to 55 μm. A method for manufacturing a polarizing film with a double-sided adhesive layer, characterized in that it is a method for manufacturing a polarizing film with a double-sided adhesive layer as claimed in any one of claims 1 to 3, and includes attaching one side The polarizing film of the adhesive layer (B) and the adhesive layer (A) with one side attached to the isolation film are opposite to the side where the adhesive layer (B) is provided in the above single side attached to the polarizing film of the adhesive layer (B) On the polarizing film on the side, the adhesive layer (A) of the adhesive layer (A) of the single-sided isolation film is arranged in the roll-to-roll method (1), and the single-sided adhesive layer (B) is attached The polarizing film has a polarizing film and an adhesive layer (B) that are arranged closest to the viewing side of the polarizing film used in an image display device, and a separator (SB) is provided on the adhesive layer (B), the above The adhesive layer (A) with the isolation film attached on one side has an adhesive layer (A) with a storage elastic modulus of 0.02~0.3MPa at 23°C _{on the isolation film (SA 1 ).} The manufacturing method of a polarizing film with a double-sided adhesive layer attached to claim 4, wherein the adhesive layer (A) with a separation film attached on one side is formed by having the separation film on one side of the adhesive layer (A) (SA ₁ ), on the other side with the isolation film (SA ₂ ) on both sides of the isolation film adhesive layer (A) to peel off the isolation film (SA ₂ ) step (a), the above isolation film ( SA ₁₎ of the peel force a _1, the release force of the release force separator (SA ₂₎ of said insulating film and a ₂ (SB) of b satisfies a _1> a ₂

b's relationship. The method for producing a polarizing film such as a request of the adhesive layers of double-side attachment 5, wherein the release force of the separator (SA ₁₎ of a _1, the release force of the separator (SA ₂₎ of said insulating film and a ₂ (SB ) The peeling force b satisfies a ₁ >1.5a ₂

1.5b relationship. The method for manufacturing a polarizing film with a double-sided adhesive layer according to claim 4, wherein in the above-mentioned roll-to-roll lamination step (1), the tension of the adhesive layer (A) with the single-sided release film The ratio (T1/T2) between T1 and the tension T2 of the polarizing film of the single-sided adhesive layer (B) is controlled to be 0.8 or more. For example, the method of manufacturing a polarizing film with a double-sided adhesive layer of claim 4, which is relayed to the method of manufacturing a polarizing film with a double-sided adhesive layer of claim 4, includes the following steps: from the obtained double-sided adhesive The step (b) of the polarizing film of the agent layer peeling off the separator (SA ₁ ), and the adhesive layer (A) of the polarizing film with the adhesive layer on both sides after peeling off the separator (SA _1). Step (2) of roll-bonding the release film for curl adjustment (SA _1'). Such as Claim 8 of the manufacturing method of a polarizing film with a double-sided adhesive layer, wherein in the above-mentioned roll-to-roll lamination step (2), the tension T3 of the _{release film for curl adjustment (SA 1') is combined with} The tension T4 ratio (T3/T4) of the polarizing film of the double-sided adhesive layer after the separation film (SA _{1) is peeled off is controlled to be 0.8 or more.} For example, the method for manufacturing a polarizing film with a double-sided adhesive layer of any one of claims 4 to 9 is relayed to the method for manufacturing a polarizing film with a double-sided adhesive layer of any one of claims 4 to 9, It includes the following steps: the step (c) of cutting the obtained polarizing film with the double-sided adhesive layer into any size, and the step (d) of cutting the ends of the cut-out polarizing film with the double-sided adhesive layer ). An image display device, characterized in that it is a polarizing film with at least one double-sided adhesive layer, and the double-sided adhesive is arranged on the side closest to the viewing side of the polarizing film used in the image display device The polarizing film of the layer is the polarizing film of any one of Claims 1 to 3 with the double-sided adhesive layer except the above-mentioned separator (SA ₁ ) and the above-mentioned separator (SB), and the above-mentioned double-sided adhesive layer The adhesive layer (A) of the polarizing film becomes the visible side and the adhesive layer (B) becomes the display side.

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