KR20220114010A - Laminates and optical laminates - Google Patents

Abstract

A laminate comprising a first base layer, a first liquid crystal cured layer, an adhesive layer, a second liquid crystal cured layer, and a second base layer in this order, wherein the first liquid crystal cured layer and the second liquid crystal cured layer are all, A layer comprising a cured product of a polymerizable liquid crystal compound and an alignment layer, wherein the first liquid crystal cured layer and the second liquid crystal cured layer each form a film forming the layer in a square with a central portion of 30 mm×30 mm. Using a measurement sample joined to a paste-applied earth cut by cutting, a needle having a tip diameter of 1 mm φ 0.5R is punctured perpendicularly to the surface of the film at a speed of 0.33 cm / sec. When the amount of displacement due to bending in the piercing direction of the film is the deformation amount S (mm) and the stress applied to the film is F (g), Equation (1): piercing elastic modulus (g/mm) = F (g)/ The puncture modulus calculated by S (mm) (1) is 50 g/mm or less, and the first base material layer and the second base material layer can be peeled from the first liquid crystal cured layer and the second liquid crystal cured layer, respectively. And, among the first base layer and the second base layer, when the base layer to be peeled first is the first release layer, and the base layer to be peeled off later is the second release layer, when the first release layer is peeled off The peeling force is greater than the peeling force when peeling the second peeling layer, and the thickness of the alignment layer included in the first liquid crystal cured layer is smaller than the thickness of the alignment layer included in the second liquid crystal cured layer, The tensile elasticity modulus of the optical laminated body obtained by peeling a 1st base material layer and a 2nd base material layer from the said laminated body is 1,000 N/mm<2> or less, the laminated body.

Description

Laminates and optical laminates

The present invention relates to laminates and optical laminates.

In recent years, an image display device typified by an organic electroluminescence (hereinafter also referred to as organic EL) display device is rapidly spreading. The optical laminated body in which the circularly-polarizing plate provided with a polarizer and retardation film, and another optical function layer was further laminated|stacked is mounted on organic electroluminescent display apparatus.

As a retardation film for image display apparatuses, such as an organic electroluminescent display, the film which extended|stretched the conventional resin film, and the film formed using the liquid crystal compound as a material are examined. And as the demand for thickness reduction of an image display apparatus becomes strong, thickness reduction is calculated|required also about retardation film and the optical laminated body provided with the same (for example, refer patent document 1).

Japanese Patent Laid-Open No. 2017-102286

In the conventionally known optical laminate including the retardation film, cracks may occur from the retardation film as a starting point due to expansion and contraction due to a change in temperature. Such cracks are particularly likely to occur when a sudden temperature change (thermal shock) is given. When the said crack is easy to generate|occur|produce, in addition to durability of an optical laminated body falling, the visibility in an image display apparatus may also fall.

Further, for example, an optical laminate in which two or more liquid crystal cured layers such as a retardation layer are laminated is manufactured in a manufacturing process by bonding a substrate layer to both surfaces of the optical laminate, and the substrate on both surfaces of the laminate is manufactured. Although it is manufactured through the process of peeling a layer in many cases, in the said peeling process, when an external force is applied between the laminated|stacked two or more liquid crystal hardened layers, some peeling may arise between liquid crystal hardened layers. Also by such peeling, when an optical laminated body is incorporated in an image display apparatus, visibility may fall.

Accordingly, it is an object of the present invention to provide an optical laminate in which the occurrence of cracks due to rapid temperature change is suppressed. Moreover, this invention makes it a subject to provide the optical laminated body and laminated body in which peeling between the laminated|stacked liquid crystal hardened layers does not produce easily by the external force by peeling etc. of the base material layer laminated|stacked on the optical laminated body.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors examined the structure of the liquid crystal hardened layer in an optical laminated body, and an optical laminated body. As a result, when the film which forms a liquid crystal cured layer has a predetermined|prescribed puncture elastic modulus, and an optical laminated body has a predetermined|prescribed tensile elasticity modulus, it discovered that the said subject was achieved, and came to complete this invention.

That is, the present invention includes the following suitable aspects.

[1] A laminate comprising a first base layer, a first liquid crystal cured layer, an adhesive layer, a second liquid crystal cured layer and a second base layer in this order,

Both the first liquid crystal cured layer and the second liquid crystal cured layer include a layer including a cured product of a polymerizable liquid crystal compound and an alignment layer,

Each of the first liquid crystal cured layer and the second liquid crystal cured layer is a measurement sample in which the film forming the layer is bonded to a paste board cut into a square with a central portion of 30 mm × 30 mm, and the tip diameter is 1 A needle of mmφ 0.5R is pierced perpendicularly to the surface of the film at a speed of 0.33 cm / sec, and the amount of displacement due to bending in the piercing direction of the film measured when fracture occurs is the deformation amount S (mm), When the stress applied to the film is F(g), Equation (1):

Sting modulus (g/mm)=F(g)/S(mm) (1)

The stab elastic modulus calculated by is 50 g / mm or less,

The first base layer and the second base layer may be peeled from the first liquid crystal cured layer and the second liquid crystal cured layer, respectively, and among the first base layer and the second base layer, the base layer to be peeled off first When the first peeling layer is used and the base layer to be peeled thereafter is used as the second peeling layer, the peeling force at the time of peeling the first peeling layer is greater than the peeling force at the time of peeling the second peeling layer;

The thickness of the alignment layer included in the first liquid crystal cured layer is smaller than the thickness of the alignment layer included in the second liquid crystal cured layer,

The tensile elasticity modulus of the optical laminated body obtained by peeling a 1st base material layer and a 2nd base material layer from the said laminated body is 1,000 N/mm<2> or less, the laminated body.

[2] The above-mentioned [1], wherein the peeling force when peeling the first peeling layer is 0.15 N/25 mm or less, and the peeling force when peeling the second peeling layer is 0.05 N/25 mm or more. laminate.

[3] The thickness of the alignment layer included in the first liquid crystal aligning layer is 1/3 or less of the thickness of the alignment layer included in the second liquid crystal aligning layer, according to any one of [1] or [2]. laminate.

[4] The thickness of the alignment layer included in the first liquid crystal hardening layer is 10 nm to 500 nm, and the thickness of the alignment layer included in the second liquid crystal alignment layer is 1 μm to 3.5 μm, the above [1] to The laminate according to any one of [3].

[5] The first liquid crystal cured layer and the second liquid crystal cured layer are a layer imparting a phase difference of λ/4 and a positive C layer, or a layer imparting a phase difference of λ/4 and a phase difference of λ/2 The laminate according to any one of [1] to [4], which is a layer that provides

[6] The laminate according to any one of [1] to [5], wherein the adhesive layer is an adhesive layer.

[7] An optical laminate comprising a first liquid crystal cured layer, an adhesive layer, and a second liquid crystal cured layer in this order, wherein the first liquid crystal cured layer and the second liquid crystal cured layer are A layer comprising a cargo and an alignment layer,

Each of the first liquid crystal cured layer and the second liquid crystal cured layer is a measurement sample in which the film forming the layer is bonded to a paste board cut into a square with a central portion of 30 mm × 30 mm, and the tip diameter is 1 A needle of mmφ 0.5R is pierced perpendicularly to the surface of the film at a speed of 0.33 cm / sec, and the amount of displacement due to bending in the piercing direction of the film measured when fracture occurs is the deformation amount S (mm), When the stress applied to the film is F(g), Equation (1):

Sting modulus (g/mm)=F(g)/S(mm) (1)

The stab elastic modulus calculated by is 50 g / mm or less,

The thickness of the alignment layer included in the first liquid crystal cured layer is smaller than the thickness of the alignment layer included in the second liquid crystal cured layer,

The optical laminate having a tensile modulus of elasticity of 1,000 N/mm 2 or less.

[8] The optical laminate according to [7], wherein the thickness of the alignment layer included in the first liquid crystal cured layer is 1/3 or less of the thickness of the alignment layer included in the second liquid crystal alignment layer.

[9] The thickness of the alignment layer included in the first liquid crystal hardening layer is 10 nm to 500 nm, and the thickness of the alignment layer included in the second liquid crystal alignment layer is 1 μm to 3.5 μm, in the above [7] or The laminate according to [8].

ADVANTAGE OF THE INVENTION According to this invention, generation|occurrence|production of the crack by a sudden temperature change is suppressed, and it can provide the optical laminated body which peeling between the laminated|stacked liquid crystal hardened layers is hard to produce.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the laminated body of this invention.
Fig. 2 is a schematic diagram of a paste-covered paper (hereinafter, sometimes referred to as "grass-coated paper") having voids used for measurement of the measurement of the puncture elastic modulus when viewed from the top.
Fig.3 (a) is a schematic perspective view which shows the important part at the time of bonding a measurement film to a paste-coated board, (b) is a figure which shows typically the upper part after bonding a measurement film to a paste-coated board.
Fig. 4 is a diagram schematically showing a cross section when a needle is pierced into a sample after bonding a measurement film to a paste-coated sheet (hereinafter, sometimes referred to as a “sheet with a measurement film”).
5 is a diagram schematically showing a cross section at the time of measuring the puncture elastic modulus, and (a) and (b) show a state in which deformation occurs in the film by piercing the needle into the film.
It is a figure for demonstrating the measurement sample used for the measurement of the tensile elasticity modulus of an optical laminated body.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. In addition, the scope of the present invention is not limited to the embodiments described herein, and various changes can be made without departing from the spirit of the present invention.

<Laminate and Optical Laminate>

The optical laminate of the present invention includes a first liquid crystal cured layer, an adhesive adhesive layer and a second liquid crystal cured layer in this order, and the laminate of the present invention includes a first base material layer, a first liquid crystal cured layer, an adhesive layer, A second liquid crystal cured layer and a second base layer are included in this order. The optical laminated body and laminated body of this invention may contain the additional layer other than the above, as long as the said layer is included in the said order. The optical laminate and the first liquid crystal cured layer and the second liquid crystal cured layer included in the laminate all have a layer and an alignment layer containing a cured product of a polymerizable liquid crystal compound.

The first liquid crystal cured layer and the second liquid crystal cured layer included in the laminate and the optical laminate of the present invention are layers in which an alignment layer and a layer containing a cured product of a polymerizable liquid crystal compound are laminated. A polymerizable liquid crystal compound is a compound which has a polymeric group, Comprising: It is a compound which can become a liquid crystal state. When the polymerizable groups of the polymerizable liquid crystal compound react and the polymerizable liquid crystal compound polymerizes, the polymerizable liquid crystal compound hardens and each liquid crystal cured layer is formed. In addition, the hardened|cured material which the polymerizable liquid crystal compound superposed|polymerized does not need to show liquid crystallinity.

The first liquid crystal cured layer and the second liquid crystal cured layer are preferably a retardation layer, and more preferably each independently a layer imparting a retardation of λ/4, a layer imparting a retardation of λ/2, and a positive C layer. It is a layer selected from the group consisting of. The first liquid crystal cured layer and the second liquid crystal cured layer are a combination of a layer imparting a phase difference of λ/4 and a positive C layer, or a layer imparting a phase difference of λ/4 and a layer imparting a phase difference of λ/2 It is preferable that a combination of

Each of the first liquid crystal cured layer and the second liquid crystal cured layer uses a measurement sample in which a film forming the layer is bonded to a paste-covered base cut into a square with a central portion of 30 mm × 30 mm, and the tip diameter is 1 mm. A needle having a φ 0.5R is pierced perpendicularly to the surface of the film at a speed of 0.33 cm/sec, and the amount of displacement due to bending in the piercing direction of the film measured when fracture occurs is the deformation amount S (mm), When the stress applied to the film is F(g), Equation (1):

Sting modulus (g/mm)=F(g)/S(mm) (1)

The stab elastic modulus calculated by is 50 g/mm or less. In addition, in this specification, a 1st liquid crystal hardened layer and a 2nd liquid crystal hardened layer are also simply called "liquid crystal hardened layer." When the puncture elastic modulus computed by said Formula (1) of each liquid crystal hardened layer is 50 g/mm or less, generation|occurrence|production of the crack by a sudden temperature change can be suppressed. In the laminate and the optical laminate, when the puncture elastic modulus of the liquid crystal cured layer exceeds 50 g/mm, it is difficult to suppress the occurrence of cracks due to abrupt temperature change in the layer, and such an optical laminate is used in an image display device. When incorporating, the durability of the optical laminate is not sufficient, and visibility may be impaired.

The puncture modulus of the liquid crystal cured layer is preferably 40 g/mm or less, more preferably 35 g/mm or less, and still more preferably from the viewpoint of easily suppressing the occurrence of cracks due to rapid temperature change in the optical laminate. preferably 30 g/mm or less. Moreover, from a viewpoint of improving the peelability at the time of peeling a base material layer, and a viewpoint which is easy to raise the intensity|strength of an optical laminated body, Preferably it is 5 g/mm or more, More preferably, it is 10 g/mm or more, More preferably, 15 g/mm or more.

In the present specification, the puncture elastic modulus uses a measurement sample in which the film is joined to a paste-covered earth cut into a square with a central portion of 30 mm × 30 mm, and a needle with a tip diameter of 1 mmφ 0.5R is used at a speed of 0.33 cm/sec. So, the amount of displacement due to bending in the piercing direction of the film, measured when the film is pierced perpendicularly to the surface of the film, when fracture occurs, is the deformation amount S (mm), and the stress applied to the film is F (g). When, as the proportional constant between stress F and strain S (stress F/strain S), Equation (1):

Sting modulus (g/mm)=F(g)/S(mm) (1)

It is a physical property value calculated by . The measurement of the puncture elastic modulus can be performed using a compression tester equipped with a load cell, and examples of the compression tester include a puncture tester "NDG5" manufactured by Katotech Co., Ltd., a handy compression tester "KES-G5", Inc. Shimadzu Corporation's small tabletop tester "EZ Test" etc. are mentioned. From the stress-strain curve obtained by using such a compression tester, the stress applied to the film at the time of fracture and the amount of strain generated in the film can be measured so far. In addition, the fracture|rupture which arises in a film at the time of pressing a stabbing jig|tool includes the case where a through-hole arises in a film by the tip of a jig|tool. The measurement of the puncture modulus is specifically, as described in the Examples, using a measurement sample in which the film is bonded to a paste-coated base having a void portion cut into a square with a central portion of 30 mm × 30 mm, the film in the void portion A needle having a tip diameter of 1 mmφ 0.5R in the approximately center of the film is pierced at a speed of 0.33 cm/sec, approximately perpendicular to the surface of the film, and the amount of displacement due to bending in the piercing direction of the film measured when fracture occurs From the phosphorus deformation amount S (mm) and the stress F (g) applied to the film, it is calculated by the above formula (1).

An important part is demonstrated about the measuring means of the stab elastic modulus at the time of using the stabbing tester "NDG5" manufactured by Kato Tech Co., Ltd. with reference to drawings.

Fig. 2 is a schematic diagram of a paste-coated paper (grass-applied paper 7) having voids for obtaining the puncture modulus of the liquid crystal cured layer as viewed from above. The glued base 7 was cut out in a square of 30 mm x 30 mm to become a part for bonding the film (liquid crystal cured layer, hereinafter, also referred to as "measurement film 12") to be used for measurement in the central part. part (void portion 6 ).

3 is a schematic diagram showing an important part when the measurement film 12 is bonded to the grass-applied sheet 7, (a) is a perspective view when bonding the measurement film 12 to the grass-applied sheet 7, It is a schematic diagram seen from the upper part (direction A of Fig.3 (a)) of the board|substrate 1 with a measurement film after bonding the measurement film 12 to the paste|sticker board 7. As shown in FIG. The dotted line indicates the outer periphery 8 of the void portion 6 . The position M at which the needle N is pierced, which is located at the approximately central portion of the cavity 6, connects the points R and R' opposite to the inclination direction of the outer periphery 8 of the cavity 6 It is the intersection of two straight lines. Fig. 4 schematically shows a cross-sectional view taken along I-I' (before the needle N is pierced) in the sheet 1 to which the measurement film is attached.

The needle N is punctured at approximately the center of the measurement film 12 of Embodiment 1. In such stabbing, the correlation between the stress F(g) applied to the needle N and the deformation amount S(mm) due to the bending in the stabbing direction of the film is obtained, and the stress F(g) and the amount of deformation when the film breaks From S (mm), the puncture modulus is obtained according to the above formula (1). When calculating the puncture modulus, when fracture occurs in a deformed state in the film (when fracture occurs in the state of FIG. b)), the puncture modulus in the present invention is obtained from the applied stress in the puncture tester and the deformation amount S, and the deformation amount S is shown in Fig. 5(a) S may be used when fracture occurs in the state, or S when fracture occurs in the state of FIG. 5B may be used. Moreover, since the applied stress changes from an upward tendency to a downward tendency when a fracture|rupture arises in a film, it can be understood that a fracture|rupture arose at this change point.

In addition, the preparation means of the board|substrate 1 with a measurement film is not specifically limited. After bonding the liquid crystal cured film having a base material having a specific dimension to the voids 6 of the glued base 7, the base material is peeled from the liquid crystal cured film having the bonded base material, and the substrate 1 with a measurement film attached thereto. may be created, or before bonding to the glued base 7, the substrate may be peeled from the liquid crystal cured film having the substrate, and the liquid crystal cured film after peeling may be bonded.

In the paste-coated base 7, the glue for fixing the measurement film is not particularly limited as long as it can prevent the measurement film from peeling off even if it is partially from the plate to which the measurement film is attached during the measurement of the puncture elastic modulus. You may conduct an appropriate preliminary experiment for finding the glue of the glued earth|ground 7 used for stabbing elastic modulus measurement.

Although the thickness of a 1st liquid crystal hardened layer and a 2nd liquid crystal hardened layer is not specifically limited, From a viewpoint of being easy to fully improve durability of a laminated body and an optical laminated body, respectively, Preferably it is 0.5 micrometer or more, More preferably, it is 1.0 micrometer, respectively. or more, more preferably 2.0 µm or more. Further, the thickness is preferably 10 µm or less, more preferably 5 µm or less, and still more preferably 3.5 µm or less from the viewpoint of easily thinning the laminate and the optical laminate and improving visibility. In addition, the above-mentioned upper limit and lower limit can be combined arbitrarily. In addition, the thickness of a liquid crystal hardening layer can be measured using a laser microscope.

In the liquid crystal cured layer such as the first liquid crystal cured layer and the second liquid crystal cured layer, as will be described later, for example, a composition containing a polymerizable liquid crystal compound is applied on a suitable substrate, and a coating layer containing the polymerizable liquid crystal compound is applied. It can be formed by forming on a base material, and polymerizing the polymerizable liquid crystal compound contained in the application layer. A liquid crystal hardened layer of a desired thickness can be manufactured by the thickness control means of an application layer according to the application means of such a liquid crystal hardened layer. In order to calculate|require the correlation between the thickness of an application layer, and the thickness of the liquid crystal hardened layer obtained, you may perform an appropriate preliminary experiment.

In the laminate of the present invention, the first substrate layer and the second substrate layer are detachable from the first liquid crystal cured layer and the second liquid crystal cured layer, respectively, and the first substrate layer and the second substrate are separated from the laminate. The tensile modulus of elasticity of the optical laminated body obtained by peeling a layer is 1,000 N/mm<2> or less. When the tensile modulus of elasticity of the optical laminate exceeds 1,000 N/mm 2 , peeling between the laminated liquid crystal cured layers caused by external force such as peeling of the base layer laminated on the optical laminate cannot be sufficiently suppressed. The tensile modulus of elasticity of the optical laminate is preferably 980 N/mm 2 or less, more preferably 900 N/mm 2 or less, from the viewpoint of easily preventing peeling between the liquid crystal cured layers. In addition, the tensile modulus of elasticity of the optical laminate is preferably 400 N/mm 2 or more, more preferably 500 N/mm 2 or more, from the viewpoint of easy to prevent peeling between the liquid crystal cured layers, especially when the adhesive layer is an adhesive layer. More preferably, it is 600 N/mm<2> or more, More preferably, it is 700 N/mm<2> or more, Especially preferably, it is 800 N/mm<2> or more.

In the laminate of the present invention, among the first base layer and the second base layer, when the base layer to be peeled off first is the first release layer, and the base layer to be peeled off later is the second release layer, the first The peeling force at the time of peeling a peeling layer becomes like this from a viewpoint of being easy to prevent peeling between liquid crystal cured layers, Preferably it is 0.15 N/25 mm or less, More preferably, it is 0.13 N/25 mm or less, More preferably, it is 0.10. It is N/25 mm or less, and the peeling force at the time of peeling a 2nd peeling layer is from a viewpoint of being easy to prevent peeling between liquid crystal hardened layers, Preferably it is 0.05 N/25 mm or more, More preferably, it is 0.07. N/25 mm or more. The peel force can be measured using a tensile tester, for example, can be measured by the method described in Examples.

The optical laminated body of this invention is a laminated body obtained after preferably peeling a 1st base material layer and a 2nd base material layer from the laminated body of this invention.

There exists a tendency for generation|occurrence|production of the crack by the rapid temperature change in an optical laminated body to produce easily, when a liquid crystal hardened layer contains an orientation layer. According to the laminated body and optical laminated body of this invention, even in the said case, it is possible to suppress generation|occurrence|production of the crack by a sudden temperature change.

In addition, in the peeling between the laminated liquid crystal cured layers, among the first base layer and the second base layer in the laminate, the base layer to be peeled off first is the first peeling layer, and the base layer to be peeled off afterwards is removed. When it is set as 2 peeling layers, when the peeling force at the time of peeling a 1st peeling layer is larger than the peeling force at the time of peeling a 2nd peeling layer, it is easy to produce when a liquid crystal cured layer is bonded through an adhesive layer. According to the present invention, even in the above case, it is possible to suppress peeling between the laminated liquid crystal cured layers.

In the laminate of the present invention, when the base material layer to be peeled off first is the first release layer, and the base material layer to be peeled off later is the second release layer, the peel force at the time of peeling the first release layer is the second It is larger than the peeling force at the time of peeling a peeling layer. Even in this case, in the laminated body of this invention, the effect of suppressing peeling between the laminated|stacked liquid crystal hardened layers is acquired.

The thickness of the laminate of the present invention is preferably 80 µm or more, and more preferably 140 µm or more, from the viewpoint of a decrease in strength and poor workability when too thin. Moreover, when the said thickness is elongate, when it is too thick, the weight becomes heavy and handling becomes difficult, Preferably it is 170 micrometers or less, More preferably, it is 160 micrometers or less.

The thickness of the optical laminate of the present invention is preferably 3 µm or more, more preferably 5 µm or more, and still more preferably 6 µm or more from the viewpoint of easily thinning the optical laminate and improving visibility. Moreover, the said thickness becomes like this. Preferably it is 30 micrometers or less, More preferably, it is 25 micrometers or less, More preferably, it is 15 micrometers or less.

<Liquid crystal cured layer>

The first liquid crystal cured layer and the second liquid crystal cured layer included in the laminate and the optical laminate of the present invention are layers in which an alignment layer and a layer containing a cured product of a polymerizable liquid crystal compound are laminated.

(Polymerizable liquid crystal cured material-containing layer)

The first liquid crystal cured layer and the second liquid crystal cured layer included in the laminate and the optical laminate of the present invention include at least a layer containing a cured product of a polymerizable liquid crystal compound (also referred to as a “polymerizable liquid crystal cured product-containing layer”). include The kind of the polymerizable liquid crystal compound is not particularly limited, and may be either a rod-shaped type (a rod-shaped liquid crystal compound) or a disk-shaped type (a disk-shaped liquid crystal compound or a discotic liquid crystal compound) if classified according to its shape. In addition, in each classification, any of a low molecular type and a high molecular type may be sufficient. In addition, in this specification, polymer|macromolecule shows that the polymerization degree is 100 or more. The polymerizable liquid crystal compound contained in the liquid crystal cured layer as a cured product may be one, or a mixture of two or more (for example, a mixture of two or more rod-shaped liquid crystal compounds, a mixture of two or more disc-shaped liquid crystal compounds, or a rod-shaped liquid crystal compound) and a disk-shaped liquid crystal compound) may be used.

As a rod-shaped liquid crystal compound, for example, the compound of Claim 1 of Unexamined-Japanese-Patent No. Hei 11-513019 can be used suitably. As the discoid liquid crystal compound, for example, those described in paragraphs [0020] to [0067] of JP-A-2007-108732 or paragraphs [0013] to [0108] of JP-A-2010-244038 are suitable. can be used readily.

The number of polymerizable liquid crystal compounds may be one, and although two or more types may be used together, it is preferable that at least 1 type of polymerizable liquid crystal compound has two or more polymeric groups in a molecule|numerator.

The polymerizable group of the polymerizable liquid crystal compound is not particularly limited, but is preferably a functional group capable of addition polymerization reaction, more preferably an ethylenically unsaturated group and a ring polymerizable group, and still more preferably an ethylenically unsaturated group. As an ethylenically unsaturated group, a (meth)acryloyl group, a vinyl group, a styryl group, an allyl group, etc. are mentioned, for example. The polymerizable group is preferably a (meth)acryloyl group from the viewpoint of easy handling and easy production. In addition, a (meth)acryloyl group is a concept containing both a methacryloyl group and an acryloyl group.

A liquid crystal hardened layer is formed by, for example, forming an alignment layer on the base material layer mentioned later, and apply|coating the composition containing a polymeric liquid crystal compound on the alignment layer. Although a base material layer is normally used by peeling from a liquid crystal cured layer, when peeling, peeling arises between the said orientation layer and a base material layer, and an orientation layer is contained in an optical laminated body. Therefore, a 1st liquid crystal hardened layer and a 2nd liquid crystal hardened layer contain the layer containing the hardened|cured material of a polymeric liquid crystal compound, and an orientation layer. In this case, the alignment layer included in the first liquid crystal cured layer and the second liquid crystal cured layer is a transfer type alignment layer that does not peel off together with the base material.

Although the thickness of the layer containing the cured product of the polymerizable liquid crystal compound is not particularly limited, from the viewpoint of sufficiently increasing the durability of the laminate and the optical laminate, preferably 0.5 µm or more, more preferably 1 µm or more, More preferably, it is 2 micrometers or more. Further, the thickness is preferably 10 µm or less, more preferably 5 µm or less, and still more preferably 4 µm or less from the viewpoint of easily thinning the laminate and the optical laminate and improving visibility. In addition, the above-mentioned upper limit and lower limit can be combined arbitrarily. In addition, the thickness of the layer containing the hardened|cured material of a polymeric liquid crystal compound can be measured using a laser microscope. When the liquid crystal cured layer is a layer selected from the group consisting of a layer imparting a retardation of λ/4, a layer imparting a retardation of λ/2, and a positive C layer, the thickness of the layer containing the cured product of the polymerizable liquid crystal compound is , you may adjust so that the desired in-plane retardation value and the retardation value in the thickness direction may be obtained.

(Orientation layer)

The alignment layer is a layer having the ability to regulate the direction of the molecular axis of the polymerizable liquid crystal compound forming the liquid crystal cured layer so as to have a desired retardation characteristic. The layer (liquid crystal hardened layer) which the polymerizable liquid crystal compound hardened|cured is formed on the base material through an orientation layer. Examples of the alignment layer include an alignment layer containing an alignment polymer, a photo alignment film, and a groove alignment layer in which an uneven pattern or a plurality of grooves are formed on the surface to orientate.

After forming a liquid crystal hardening layer on an orientation layer, when peeling a base material layer from the laminated body containing a liquid crystal hardened layer, an orientation layer peels and removes with a base material layer, or remains in a liquid crystal hardened layer. In the present invention, in order to include the alignment layer in the liquid crystal cured layer, the substrate layer is peeled off while the alignment layer remains in the liquid crystal cured layer. Thus, by leaving an orientation layer in a liquid crystal hardened layer, it is easy to adjust the puncture elastic modulus of a liquid crystal hardened layer to the said desired range, and it is easy to improve the peelability at the time of peeling a base material layer. Therefore, from the same viewpoint, it is preferable that the first liquid crystal cured layer and the second liquid crystal cured layer are layers in which an alignment layer and a layer containing a cured product of a polymerizable liquid crystal compound are laminated.

The alignment layer is a monofunctional or bifunctional (meth)acrylate-based monomer from the viewpoint that the alignment layer is not peeled off together with the base layer and is easy to remain in the liquid crystal cured layer and the puncture elastic modulus is easily adjusted to a desired range; It is preferable to include a resin such as a cured product obtained by curing an imide-based monomer or a vinyl ether-based monomer, and more preferably include a cured product obtained by curing a monofunctional or bifunctional (meth)acrylate-based monomer. When an alignment layer does not peel off together with a base material layer and a liquid crystal cured layer contains an alignment layer, there also exists an advantage of being easy to maintain the intensity|strength of an optical laminated body.

In the laminate or optical laminate of the present invention in which the liquid crystal cured layer includes an alignment layer, preferred monofunctional (meth)acrylate monomers include, for example, alkyl (meth)acrylates having 4 to 16 carbon atoms and 2 carbon atoms. β-carboxyalkyl (meth) acrylate of ∼14, alkylated phenyl (meth) acrylate of 2 to 14 carbon atoms, methoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate and isobornyl (meth) ) acrylates and the like. Examples of the bifunctional (meth)acrylate-based monomer include 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, and ethylene glycol. Di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di Acrylate, bis(acryloyloxyethyl)ether of bisphenol A, ethoxylated bisphenol A-di(meth)acrylate, propoxylated neopentylglycol di(meth)acrylate, ethoxylated neopentylglycoldi(meth) acrylate and 3-methylpentanediol di(meth)acrylate. Examples of the imide-based resin obtained by curing the imide-based monomer include polyamide and polyimide. In addition, these 1 type may be sufficient as imide-type resin, and 2 or more types of mixture may be sufficient as them.

The resin contained in the alignment layer may contain structural units derived from monomers other than monofunctional or bifunctional (meth)acrylate-based monomers, imide-based monomers and vinyl ether-based monomers. , monofunctional or bifunctional (meth)acrylate-based monomers, imide-based monomers and the content ratio of structural units derived from vinyl ether-based monomers, based on all the structural units, preferably 50 mol% or more, more preferably Preferably at least 55 mol%, more preferably at least 60 mol%.

The thickness of the alignment layer is preferably 10 nm or more, more preferably 100 nm or more, still more preferably 500 nm or more, still more preferably 1,000 nm or more, particularly preferably 2,000 nm or more. Moreover, the thickness of an orientation layer becomes like this. Preferably it is 10,000 nm or less, More preferably, it is 7,000 nm or less, More preferably, it is 5,000 nm or less. In particular, when the alignment layer is included in the liquid crystal cured layer, if the thickness of the alignment layer is within the above range, it is easy to adjust the puncture modulus of the liquid crystal cured layer to the above preferred range.

As described above, when the base material layer to be peeled off first is the first release layer, and the base layer to be peeled off later is the second release layer, the peeling force when the first release layer is peeled is the second release layer. Even when it is larger than the peeling force at the time of peeling, in order to express the effect of suppressing peeling between the laminated|stacked liquid crystal hardened layers, the thickness of the orientation layer respectively contained in a 1st liquid crystal hardened layer and a 2nd liquid crystal hardened layer is different. It is effective to do Specifically, when the first liquid crystal cured layer and the first release layer, and the second liquid crystal cured layer and the second release layer are laminated, the thickness of the alignment layer included in the first liquid crystal cured layer is the second liquid crystal alignment layer. It is smaller than the thickness of the alignment layer included in the . In this way, while increasing the peel strength of the first peeling layer to be peeled off first, by reducing the thickness of the alignment layer included in the first liquid crystal cured layer laminated on the first peeling layer, it has appropriate peelability and thermal shock. The reason why the effect of being able to suppress the crack generation by this is expressed is not necessarily clear, but it is an achievement based on the knowledge of this inventor.

As described above, the thickness of the alignment layer (hereinafter also referred to as "first alignment layer") contained in the first liquid crystal cured layer is preferably 10 nm to 500 nm, more preferably 50 nm to 200 nm. do. It is preferable that they are 1 micrometer - 3.5 micrometers, and, as for the thickness of the orientation layer (henceforth "2nd orientation layer") contained in a 2nd liquid crystal hardening layer, it is more preferable that they are 1.5 micrometers - 3.0 micrometers. This combination of the thickness of the alignment layer is effective for improving peelability (that is, peeling the base layer while suppressing peeling between the laminated liquid crystal cured layers) while preventing the occurrence of cracks due to rapid temperature change. do. Making the thickness of the alignment layer included in the first liquid crystal cured layer within the above range is effective for preventing cracks from occurring. On the other hand, since a 2nd base material layer peels after than a 1st base material layer, the rigidity of the orientation layer contained in the 2nd liquid crystal cured layer on a 2nd base material layer is easy to give an influence on peelability. Making the thickness of the orientation layer contained in a 2nd liquid crystal hardened layer into the said range leads to improving the rigidity of an orientation layer, and is effective in the improvement of peelability. The thickness of the 1st alignment layer and the 2nd alignment layer is the thickness of the coating film at the time of forming an alignment layer on the base material by apply|coating on the base material the liquid composition called the orientation layer forming composition which can form these orientation layers. By adjusting the thickness, it can be adjusted to a desired range. Application|coating of an orientation layer formation composition may be performed, for example by die coating means, and the thickness of the orientation layer to be formed is determined by the thickness of the apply|coated coating film. Therefore, in order to make the thickness of the first alignment layer smaller than the thickness of the second alignment layer, the error of the application means to be used must be taken into account, since the thickness of the alignment layer usually includes an error due to the thickness error of the application means used. do. When such an error must be taken into consideration, when measuring the thickness of the alignment layer, the thickness of the alignment layer is measured at at least 3 points or more, more preferably at 5 points or more, and the average value of the results obtained is used as the thickness of the alignment layer. It is preferable to do In order to enjoy the effects of the present invention more, the thickness of the first alignment layer is preferably 1/3 or less of the thickness of the second alignment layer, more preferably 1/5 or less, and particularly preferably 1/10 or less. .

The alignment layer may be a vertical alignment layer for vertically aligning the molecular axis of the polymerizable liquid crystal compound, an alignment layer for horizontally aligning the molecular axis of the polymerizable liquid crystal compound, or an alignment layer for tilting the molecular axis of the polymerizable liquid crystal compound . The alignment layer preferably has solvent resistance that does not dissolve by coating of a composition containing a polymerizable liquid crystal compound described later, and has heat resistance in heat treatment for removal of the solvent or alignment of the liquid crystal compound. Examples of the alignment layer include an alignment layer containing an alignment polymer, a photo alignment film, and a groove alignment layer in which an uneven pattern or a plurality of grooves are formed on the surface to orientate.

The alignment layer is preferably composed of a resin obtained from a monomer in which the ratio of the number of hydroxyl groups per monomer molecule to the molecular weight of the monomer is less than 0.4% from the viewpoint of easy adjustment of the puncture modulus of the liquid crystal cured layer to the above preferred range. do. In addition, when the resin constituting the alignment layer is a resin obtained by polymerizing two or more monomers, the ratio of the number of hydroxyl groups per monomer molecule to the molecular weight of the monomer is calculated for each monomer, and from the ratio and the mixing ratio of each monomer A weighted average value may be calculated to calculate the ratio of the number of hydroxyl groups. The ratio of the number of hydroxyl groups per molecule to the molecular weight of the monomer is preferably less than 0.4%, more preferably 0.35% or less, still more preferably 0.30% or less, and may be 0%.

(Layer and alignment layer containing cured product of polymerizable liquid crystal compound)

As described above, the liquid crystal cured layer of the present invention includes an alignment layer and a layer containing a cured product of a polymerizable liquid crystal compound, and preferably a layer containing an alignment layer and a cured product of a polymerizable liquid crystal compound is laminated. layer that has been In the liquid crystal cured layer of the present invention, from the viewpoint of easy adjustment of the puncture elastic modulus of the liquid crystal cured layer to the above-mentioned preferred range, the liquid crystal cured layer has the following formula (A):

It is preferable that N calculated by is 0.67 or less. From a viewpoint of being easy to adjust the puncture elastic modulus of a liquid crystal hardened layer to the said preferable range, said N becomes like this. More preferably, it is 0.64 or less, More preferably, it is 0.50 or less. In addition, from the viewpoint of maintaining durability in a high-temperature environment, N is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably 0.15 or more.

Here, each symbol in said Formula (A) is demonstrated.

AL represents the number of kinds of structural units derived from the polymerizable compound constituting the resin constituting the alignment layer. In addition, when a liquid crystal hardening layer does not contain an orientation layer, AL=0.

C _wi represents the content (mass %) of the structural units derived from the polymerizable compound i on the basis of all the structural units derived from the polymerizable compound in the resin constituting the alignment layer, and M _i is the orientation The molecular weight of the polymerizable compound i constituting the layer is shown, and N _i represents the number of polymerizable groups in the polymerizable compound i constituting the alignment layer.

LC represents the number of types of structural units derived from the polymerizable liquid crystal compound constituting the layer with respect to a layer containing a cured product of the polymerizable liquid crystal compound.

C _wj is the content (mass %) of the structural units derived from the polymerizable liquid crystal compound j based on the total structural units derived from the polymerizable liquid crystal compound in the layer containing the cured product of the polymerizable liquid crystal compound , M _j represents the molecular weight of the polymerizable liquid crystal compound j constituting the layer, and N _j represents the number of polymerizable groups in the polymerizable liquid crystal compound j constituting the layer.

L _AL represents the thickness (μm) of the alignment layer, and L _LC represents the thickness (μm) of the layer including the cured product of the polymerizable liquid crystal compound. L _total represents the sum of L _AL and L _LC .

<Base layer>

The laminate of this invention contains a 1st base material layer and a 2nd base material layer. The 1st base material layer and the 2nd base material layer are laminated|stacked so that peeling is possible from a 1st liquid crystal hardened layer and a 2nd liquid crystal hardened layer, respectively, respectively, These base materials function as a release support body, The liquid crystal hardened layer for transcription|transfer (preferably) It is possible to support a phase difference layer) and an alignment layer. As the base material, a light-transmitting (preferably optically transparent) thermoplastic resin such as a polyolefin-based resin such as a chain polyolefin-based resin (polypropylene-based resin, etc.) and a cyclic polyolefin-based resin (norbornene-based resin, etc.); Cellulose-based resins such as triacetyl cellulose and diacetyl cellulose; polyester-based resins such as polyethylene terephthalate and polybutylene terephthalate; polycarbonate-based resin; (meth)acrylic-based resins such as methyl methacrylate-based resins; polystyrene-based resin; polyvinyl chloride-based resin; acrylonitrile-butadiene-styrene resin; acrylonitrile-styrene-based resin; polyvinyl acetate-based resin; polyvinylidene chloride-based resin; polyamide-based resin; polyacetal-based resin; modified polyphenylene ether-based resin; polysulfone-based resin; polyether sulfone-based resin; polyarylate-based resins; polyamideimide-based resins; polyimide-based resin; A film containing a maleimide-type resin etc. is mentioned.

Although the thickness of a base material layer is not specifically limited, Preferably it is 20 micrometers or more, More preferably, it is 35 micrometers or more, Preferably it is 200 micrometers or less, More preferably, it is 105 micrometers or less. When the thickness of a base material is more than the said lower limit and it is easy to provide intensity|strength to a laminated body, and it is below the said upper limit, when a laminated body is lengthened, it will be easy to handle. The thickness of the substrate can be measured, for example, by a contact type thickness meter (manufactured by MH-15M Nikon).

Various blocking prevention processes may be given to a base material layer. Examples of the blocking prevention treatment include a treatment for easy adhesion, a treatment for kneading a filler or the like, an embossing treatment (knurling treatment), and the like. By performing this anti-blocking treatment on the substrate, adhesion between the substrates when the substrate is wound, so-called blocking, can be effectively prevented, and it becomes possible to efficiently manufacture the laminate and the optical laminate, improving productivity easy to do

<Adhesive layer>

The laminate and the optical laminate of the present invention include an adhesive layer between the first liquid crystal cured layer and the second liquid crystal cured layer. The adhesive layer may be either an adhesive layer formed of an adhesive or an adhesive layer formed of an adhesive. In addition, in this specification, an adhesion layer is a layer which has viscosity even after bonding, and is not normally solid. A contact bonding layer is a layer which becomes solid by hardening etc. after bonding. Usually, when a liquid crystal hardened layer is laminated|stacked through an adhesive layer, there exists a tendency for generation|occurrence|production of a crack by a sudden temperature change, and peeling at the time of peeling a base material layer being easy to produce. However, according to the laminate and the optical laminate of the present invention, even when the first liquid crystal cured layer and the second liquid crystal cured layer are laminated with the adhesive layer interposed therebetween, the occurrence of cracks and peeling as described above can be sufficiently suppressed. . In particular, peeling at the time of peeling a base material layer tends to occur when these layers are laminated|stacked through an adhesive layer, but according to the laminated body and optical laminated body of this invention, a 1st liquid crystal cured layer and a 2nd liquid crystal cured layer are Even when it laminates|stacks through an adhesive layer, generation|occurrence|production of the above peeling can fully be suppressed.

From the viewpoint of being easy to adjust the tensile modulus of elasticity of the optical laminate, the tensile modulus of elasticity of the adhesive layer is preferably 2200 N/mm 2 or less, more preferably 1900 N/mm 2 or less, still more preferably 1500 N/mm 2 or less, more More preferably, it is 1300 N/mm<2> or less.

The tensile modulus of elasticity of the pressure-sensitive adhesive layer is measured by the method described in Examples to be described later.

(adhesive layer)

The adhesive layer contains, as a main component, a resin such as a (meth)acrylic resin, a rubber resin, a urethane resin, an ester resin, a silicone resin, or a polyvinyl ether resin. Among the above resins, (meth)acrylic resins are preferred from the viewpoint of excellent transparency, weather resistance, heat resistance, and the like. In this specification, the composition for forming an adhesive layer is also called an adhesive composition. The composition of an active energy ray hardening type or a thermosetting type may be sufficient as an adhesive composition.

The thickness of the pressure-sensitive adhesive layer is preferably 3 to 30 µm, more preferably 3 to 25 µm.

As the (meth)acrylic resin (base polymer) contained in the adhesive layer, for example, (meth) butyl acrylate, (meth) ethyl acrylate, (meth) acrylate isooctyl, (meth) acrylate 2-ethylhexyl The polymer or copolymer which uses 1 type(s) or 2 or more types of acrylic acid ester as a monomer is mentioned. Among the above base polymers, it is preferable to copolymerize a polar monomer. As the polar monomer, for example, (meth)acrylic acid, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid hydroxyethyl, (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, glycy Monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, and the like, like dil (meth)acrylate.

Although the adhesive composition may contain only the said base polymer, normally, it further contains a crosslinking agent. As a crosslinking agent, it is a divalent or more metal ion, Comprising: What forms a carboxylate metal salt between a carboxyl group; A polyamine compound that forms an amide bond between a carboxyl group; It is a polyepoxy compound or a polyol, Comprising: What forms an ester bond between a carboxyl group; As a polyisocyanate compound, one which forms an amide bond between a carboxyl group is illustrated. Especially, a polyisocyanate compound is preferable.

(adhesive layer)

Examples of the adhesive for forming the adhesive layer include a water-based adhesive, or a curable adhesive that can be cured by an active energy ray or heat. As an active energy ray, an ultraviolet-ray, a visible light, an electron beam, X-ray, etc. are mentioned. In addition, when the adhesive layer is formed using a curable adhesive, the cured product of these curable adhesives constitutes the adhesive layer. Among the above adhesives, since the drying step of removing the solvent by heating can be omitted, a curable adhesive that can be cured by an active energy ray or heat is preferable, and an active energy ray-curable adhesive is more preferable.

Examples of the water-based adhesive include a composition obtained by dissolving a polyvinyl alcohol-based resin or a urethane resin in water or dispersing it in water as a main component. You may make it further contain a curable component and a crosslinking agent like oxal and a water-soluble epoxy resin.

A curable adhesive agent contains a curable compound as a main component normally. The curable adhesive is classified according to its curing mode, and is a cationically polymerizable adhesive containing a cationically polymerizable compound as the curable compound, a radical polymerizable adhesive containing a radical polymerizable compound as the curable compound, a cationically polymerizable compound and a radical hybrid-type curable adhesives containing both polymerizable compounds; and the like. As a specific example of a cationically polymerizable compound, the epoxy compound which has one or more epoxy groups in a molecule|numerator, the oxetane compound which has one or more oxetane rings in a molecule|numerator, and a vinyl compound are mentioned. Moreover, as a specific example of a radically polymerizable compound, the (meth)acrylic-type compound and vinyl compound which have 1 or more (meth)acryloyl group in a molecule|numerator are mentioned. The curable adhesive may contain one or two or more cationically polymerizable compounds and/or may contain one or two or more radically polymerizable compounds.

The cationic polymerizable compound, which is the main component of the cationic polymerization adhesive, refers to a compound or oligomer that is cured by a cationic polymerization reaction proceeding by irradiation or heating of active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays, and epoxy compounds, jade A cetane compound, a vinyl compound, etc. can be illustrated. Especially, a preferable cationically polymerizable compound is an epoxy compound.

An epoxy compound is one or more in a molecule|numerator, Preferably it is a compound which has two or more epoxy groups. An epoxy compound may be used individually by 1 type, and may use 2 or more types together. As an epoxy compound, an alicyclic epoxy compound, an aromatic epoxy compound, a hydrogenated epoxy compound, an aliphatic epoxy compound, etc. are mentioned. Especially, from a viewpoint of weather resistance, a curing rate, and adhesiveness, an epoxy compound, Preferably an alicyclic epoxy compound and/or an aliphatic epoxy compound are contained, More preferably, an alicyclic epoxy compound is contained.

An alicyclic epoxy compound is a compound which has one or more epoxy groups couple|bonded with the alicyclic ring in a molecule|numerator. "The epoxy group couple|bonded with the alicyclic ring" means the oxygen atom -O- of bridge|crosslinking in the structure shown by following formula (I). In following formula (I), m is an integer of 2-5.

The compound in which the group of the form in which one or several hydrogen atoms were removed in (CH2) _m in the said Formula (I) is _couple |bonded with the other chemical structure can become an alicyclic epoxy compound. (CH ₂ ) One or more hydrogen atoms in _m may be suitably substituted with a linear alkyl group such as a methyl group or an ethyl group. As a compound represented by Formula (I), the compound which has an epoxycyclopentane structure of m=3, and the compound which has an epoxycyclohexane structure of m=4 are preferable.

Specific examples of the alicyclic epoxy compound include the following: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy -6-Methylcyclohexanecarboxylate, ethylenebis(3,4-epoxycyclohexanecarboxylate), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methyl) Cyclohexylmethyl) adipate, diethylene glycol bis (3,4-epoxycyclohexyl methyl ether), ethylene glycol bis (3,4-epoxycyclohexyl methyl ether), 2,3,14,15-diepoxy-7 ,11,18,21-tetraoxatrispiro[5.2.2.5.2.2]henicosan, 3-(3,4-epoxycyclohexyl)-8,9-epoxy-1,5-dioxaspiro[5.5] Undecane, 4-vinylcyclohexenedioxide, limonene dioxide, bis(2,3-epoxycyclopentyl)ether, dicyclopentadienedioxide.

An aromatic epoxy compound is a compound which has an aromatic ring and an epoxy group in a molecule|numerator. As the specific example, Bisphenol-type epoxy compounds, such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S, or its oligomer; novolak-type epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, and hydroxybenzaldehyde phenol novolac epoxy resins; Polyfunctional epoxy compounds such as glycidyl ether of 2,2',4,4'-tetrahydroxydiphenylmethane and glycidyl ether of 2,2',4,4'-tetrahydroxybenzophenone ; and polyfunctional epoxy resins such as epoxidized polyvinyl phenol.

The hydrogenated epoxy compound is a glycidyl ether of a polyol having an alicyclic ring, and a nuclear hydrogenated polyhydroxy compound obtained by selectively hydrogenating an aromatic polyol to an aromatic ring under pressure in the presence of a catalyst is glycidyl ether it may be angry As a specific example of an aromatic polyol, For example, bisphenol-type compounds, such as bisphenol A, bisphenol F, and bisphenol S; novolak-type resins such as phenol novolak resin, cresol novolak resin, and hydroxybenzaldehyde phenol novolak resin; and polyfunctional compounds such as tetrahydroxydiphenylmethane, tetrahydroxybenzophenone and polyvinylphenol. It can be set as glycidyl ether by making epichlorohydrin react with the alicyclic polyol obtained by performing a hydrogenation reaction on the aromatic ring of an aromatic polyol. As a preferable thing among a hydrogenation epoxy compound, the diglycidyl ether of hydrogenated bisphenol A is mentioned.

An aliphatic epoxy compound is a compound which has at least 1 oxirane ring (3-membered cyclic ether) couple|bonded with an aliphatic carbon atom in a molecule|numerator. For example, monofunctional epoxy compounds, such as butyl glycidyl ether and 2-ethylhexyl glycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, etc. epoxy compounds; trifunctional or more than trifunctional epoxy compounds such as trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether; There are epoxy compounds having one epoxy group directly bonded to an alicyclic ring and an oxirane ring bonded to an aliphatic carbon atom, such as 4-vinylcyclohexene dioxide and limonene dioxide. Among them, a bifunctional epoxy compound (also referred to as an aliphatic diepoxy-compound) having two oxirane rings bonded to an aliphatic carbon atom in the molecule from the viewpoint of adhesiveness between the polarizing film and the protective film is preferable. Such suitable aliphatic diepoxy-compounds are, for example, of the formula (II):

[In formula (II), Y represents an alkylene group having 2 to 9 carbon atoms, an alkylene group having 4 to 9 total carbon atoms interposed by an ether bond, or a divalent hydrocarbon having 6 to 18 carbon atoms having an alicyclic structure]

is a compound represented by Specifically, the aliphatic diepoxy-compound represented by the formula (II) is a diglycidyl ether of an alkanediol, a diglycidyl ether of an oligoalkylene glycol up to a repetition number of about 4, or a diglycidyl ether of an alicyclic diol. and glycidyl ether.

Specific examples of the diol (glycol) capable of forming the aliphatic diepoxy-compound represented by the formula (II) are given below. Examples of the alkanediol include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neo pentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8- octanediol, 1,9-nonanediol, and the like.

Examples of the oligoalkylene glycol include diethylene glycol, triethylene glycol, tetraethylene glycol, and dipropylene glycol. Examples of the alicyclic diol include cyclohexanediol such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, and 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, and 1,3-cyclohexanediol. and cyclohexanedimethanol such as methanol and 1,4-cyclohexanedimethanol.

The oxetane compound which is one of the cationically polymerizable compounds is a compound containing one or more oxetane rings (oxetanyl group) in a molecule|numerator, The specific example is 3-ethyl-3-hydroxymethyloxetane (oxetane) Alcohol), 2-ethylhexyloxetane, 1,4-bis[{(3-ethyloxetan-3-yl)methoxy}methyl]benzene (also called xylylenebisoxetane), 3-ethyl -3[{(3-ethyloxetan-3-yl)methoxy}methyl]oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-(cyclohexyloxy)methyl-3-ethyl Contains oxetane. An oxetane compound may be used as a main component of a cationically polymerizable compound, and may be used together with an epoxy compound. By using an oxetane compound together, a curing rate and adhesiveness may be improved.

Examples of the vinyl compound that can be a cationically polymerizable compound include an aliphatic or alicyclic vinyl ether compound, and specific examples include, for example, n-amyl vinyl ether, i-amyl vinyl ether, n-hexyl vinyl ether, and n- vinyl ethers of alkyl or alkenyl alcohols having 5 to 20 carbon atoms, such as octyl vinyl ether, 2-ethylhexyl vinyl ether, n-dodecyl vinyl ether, stearyl vinyl ether, and oleyl vinyl ether; hydroxyl group-containing vinyl ethers such as 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, and 4-hydroxybutyl vinyl ether; vinyl ethers of monoalcohols having an aliphatic ring or an aromatic ring, such as cyclohexyl vinyl ether, 2-methylcyclohexyl vinyl ether, cyclohexylmethyl vinyl ether, and benzyl vinyl ether; Glycerol monovinyl ether, 1,4-butanediol monovinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, neopentyl glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol Tetravinyl ether, trimethylolpropane divinyl ether, trimethylol propane trivinyl ether, 1,4-dihydroxycyclohexane monovinyl ether, 1,4-dihydroxycyclohexane divinyl ether, 1,4-dihydro mono-polyvinyl ethers of polyhydric alcohols such as hydroxymethylcyclohexane monovinyl ether and 1,4-dihydroxymethylcyclohexanedivinyl ether; polyalkylene glycol mono to divinyl ethers such as diethylene glycol divinyl ether, triethylene glycol divinyl ether, and diethylene glycol monobutyl monovinyl ether; and other vinyl ethers such as glycidyl vinyl ether and ethylene glycol vinyl ether methacrylate. A vinyl compound may be used as a main component of a cationically polymerizable compound, and may be used together with an epoxy compound or an epoxy compound and an oxetane compound. By using a vinyl compound together, a cure rate and viscosity-lowering of an adhesive agent can be improved in some cases.

The cationic polymerizable adhesive may further contain other cationic polymerizable compounds other than the above, such as a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, and a spiroorthoester compound.

From the viewpoint of easily improving adhesiveness, when the total amount of the curable compound contained in the cationically polymerizable adhesive (including the case of a hybrid curable adhesive) is 100% by weight, the content of the cationically polymerizable compound (cationically polymerizable adhesive) It is content of all the cationically polymerizable compounds contained in an adhesive agent, and when 2 or more types of cationically polymerizable compounds are contained, these total content), Preferably it is 50 weight% or more, More preferably, it is 60 weight% or more, More It is preferably 70% by weight or more. Moreover, as mentioned above, the cationic polymerization adhesive may further contain the polymer component (thermoplastic resin etc.).

Although the cation polymerization adhesive may be active energy ray-curable or thermosetting, it is possible to omit the heating process, and from a viewpoint of being easy to prevent deformation|transformation by heating of a laminated body, etc., Preferably it is active energy ray-curable. When providing active energy ray sclerosis|hardenability to the cation polymerization type adhesive agent containing a cationically polymerizable compound, it is preferable to mix|blend a photocationic polymerization initiator with the adhesive agent. A photocationic polymerization initiator generates a cationic species or a Lewis acid by irradiation of an active energy ray like a visible ray, an ultraviolet-ray, an X-ray, or an electron beam, and initiates the polymerization reaction of a cation-curable compound. Since a photocationic polymerization initiator acts catalytically with light, even if it mixes with a photocationic sclerosing|hardenable compound, it is excellent in storage stability and workability|operativity. Examples of the compound that generates cationic species or Lewis acid upon irradiation with active energy rays include onium salts such as aromatic iodonium salts and aromatic sulfonium salts, aromatic diazonium salts, and iron-arene complexes.

The aromatic iodonium salt is a compound having a diaryliodonium cation, and examples of the cation include a diphenyliodonium cation typically.

An aromatic sulfonium salt is a compound having a triarylsulfonium cation, and examples of the cation include a triphenylsulfonium cation and a 4,4'-bis(diphenylsulfonio)diphenylsulfide cation. have. An aromatic diazonium salt is a compound which has a diazonium cation, and a benzenediazonium cation is typically mentioned as the cation. In addition, the iron-arene complex is typically a cyclopentadienyl iron(II) arene cation complex salt.

The cation shown above is paired with an anion (anion) to constitute a photocationic polymerization initiator. Examples of anions constituting the photocationic polymerization initiator include a special phosphorus anion ([(Rf) _n PF _6-n ] ^- ), hexafluorophosphate anion (PF ₆ ^- ), hexafluoroantimonate anion (SbF ^6- ), pentafluorohydroxyantimonate anion (SbF ₅ (OH) ^- ), hexafluoroacetate anion (AsF ₆ ^- ), tetrafluoroborate anion (BF ₄ ^- ), tetrakis (pentafluoro rophenyl)borate anion (B(C ₆ F ₅ ) ₄ ); Especially, it is preferable that they are a special phosphorus type anion [(Rf) _n PF _6-n ] ^- , and a hexafluorophosphate anion PF ₆ ^- from a viewpoint of the sclerosis|hardenability of a cationically polymerizable compound and the safety|security of the adhesive bond layer obtained.

A photocationic polymerization initiator may be used individually by 1 type, and may use 2 or more types together. Among them, aromatic sulfonium salts are preferably used because they have ultraviolet absorption characteristics even in a wavelength region of around 300 nm, and therefore are excellent in curability and can provide a cured product having good mechanical strength and adhesive strength.

The compounding quantity of a photocationic polymerization initiator is 0.5-10 weight part normally with respect to 100 weight part of cationically polymerizable compounds, Preferably it is 6 weight part or less. By mix|blending 0.5 weight part or more of a photocationic polymerization initiator, a cationically polymerizable compound can fully be hardened, and high mechanical strength and adhesive strength can be provided to the polarizing plate obtained. On the other hand, when the quantity increases excessively, the hygroscopicity of hardened|cured material may become high by the ionic substance in hardened|cured material increases, and the durability of a polarizing plate may fall.

As above-mentioned, it can also be set as a hybrid-type curable adhesive agent by making a cationically polymerizable adhesive contain a radically polymerizable compound in addition to a cationically polymerizable compound. By using a radically polymerizable compound together, the effect which raises the hardness and mechanical strength of an adhesive bond layer can be anticipated, Furthermore, it becomes possible to perform adjustment of the viscosity, curing rate, etc. of a curable adhesive agent further easily.

The radically polymerizable compound, which is the main component of the radical polymerization adhesive, refers to a compound or oligomer that is cured by a radical polymerization reaction proceeding by irradiation or heating of active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays, specifically, ethylene and compounds having a sexually unsaturated bond. As the compound having an ethylenically unsaturated bond, in addition to the (meth)acrylic compound having one or more (meth)acryloyl group in the molecule, styrene, styrenesulfonic acid, vinyl acetate, vinyl propionate, N-vinyl-2-pyrrolidone and The same vinyl compound etc. are mentioned. Especially, a preferable radically polymerizable compound is a (meth)acrylic-type compound.

As the (meth)acrylic compound, it is obtained by reacting two or more types of a (meth)acrylate monomer having at least one (meth)acryloyloxy group in the molecule, a (meth)acrylamide monomer and a functional group-containing compound, and at least in the molecule (meth)acryloyl group containing compounds, such as a (meth)acryl oligomer which has two (meth)acryloyl groups, are mentioned. The (meth)acryl oligomer is preferably a (meth)acrylate oligomer having at least two (meth)acryloyloxy groups in the molecule. A (meth)acrylic-type compound may be used individually by 1 type, and may use 2 or more types together.

As a (meth)acrylate monomer, the monofunctional (meth)acrylate monomer which has one (meth)acryloyloxy group in a molecule|numerator, and bifunctional (meth)acrylate which has two (meth)acryloyloxy groups in a molecule|numerator Monomers and polyfunctional (meth)acrylate monomers having three or more (meth)acryloyloxy groups in the molecule are exemplified.

An example of a monofunctional (meth)acrylate monomer is an alkyl (meth)acrylate. Alkyl (meth)acrylate WHEREIN: As long as the alkyl group has 3 or more carbon atoms, linear or branched may be sufficient as it. If specific examples of alkyl (meth) acrylate are given, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t -Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. are mentioned. In addition, aralkyl (meth) acrylates such as benzyl (meth) acrylate; (meth)acrylates of terpene alcohols such as isobornyl (meth)acrylate; (meth)acrylates having a tetrahydrofurfuryl structure such as tetrahydrofurfuryl (meth)acrylate; A cycloalkyl group at the alkyl group site such as cyclohexyl (meth) acrylate, cyclohexylmethyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl (meth) acrylate, 1,4-cyclohexanedimethanol monoacrylate (meth)acrylate having; aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate; 2-phenoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate having an ether bond in the alkyl moiety (meth)acrylate can also be used as a monofunctional (meth)acrylate monomer.

Moreover, monofunctional (meth)acrylate which has a hydroxyl group in an alkyl part, and monofunctional (meth)acrylate which has a carboxyl group in an alkyl part can also be used. Specific examples of the monofunctional (meth)acrylate having a hydroxyl group in the alkyl moiety include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. ) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, and pentaerythritol mono (meth) acrylate. Specific examples of the monofunctional (meth)acrylate having a carboxyl group in the alkyl moiety include 2-carboxyethyl (meth)acrylate, ω-carboxy-polycaprolactone (n≒2)mono(meth)acrylate, 1-[ 2-(meth)acryloyloxyethyl]phthalic acid, 1-[2-(meth)acryloyloxyethyl]hexahydrophthalic acid, 1-[2-(meth)acryloyloxyethyl]succinic acid, 4-[ 2-(meth)acryloyloxyethyl]trimellitic acid, N-(meth)acryloyloxy-N',N'-dicarboxymethyl-p-phenylenediamine.

The (meth)acrylamide monomer is preferably (meth)acrylamide having a substituent on the N-position, and a typical example of the substituent on the N-position is an alkyl group, but forms a ring together with the nitrogen atom of (meth)acrylamide In addition to the carbon atom and the nitrogen atom of (meth)acrylamide, this ring may have an oxygen atom as a ring member. Further, a substituent such as alkyl or oxo (=O) may be bonded to the carbon atom constituting the ring.

Specific examples of the N-substituted (meth)acrylamide include N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-alkyl(meth)acrylamides such as N-t-butyl(meth)acrylamide and N-hexyl(meth)acrylamide; N,N-dialkyl(meth)acrylamide, such as N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide. In addition, the N-substituent group may be an alkyl group having a hydroxyl group, and examples thereof include N-hydroxymethyl (meth)acrylamide, N-(2-hydroxyethyl) (meth)acrylamide, N-(2-hydroxyl). propyl) (meth)acrylamide. In addition, specific examples of the N-substituted (meth)acrylamide forming the above-described 5-membered ring or 6-membered ring include N-acryloylpyrrolidine, 3-acryloyl-2-oxazolidinone, and 4-acryloylamide. Ilmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, and the like.

Examples of the bifunctional (meth)acrylate monomer include alkylene glycol di(meth)acrylate, polyoxyalkylene glycol di(meth)acrylate, halogen-substituted alkylene glycol di(meth)acrylate, and di(meth) aliphatic polyol. ) acrylates, di(meth)acrylates of hydrogenated dicyclopentadiene or tricyclodecanedialkanol, di(meth)acrylates of dioxane glycol or dioxane dialkanol, alkylene oxide adducts of bisphenol A or bisphenol F Epoxy di(meth)acrylate of di(meth)acrylate, bisphenol A, or bisphenol F, etc. are mentioned.

More specific examples of the bifunctional (meth)acrylate monomer include ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1, 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) ) acrylate, ditrimethylolpropane di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di ( Meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, silicone di(meth)acrylate, neopentyl glycol hydroxypivalate Ester di(meth)acrylate, 2,2-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxyethoxy Toxycyclohexyl]propane, hydrogenated dicyclopentadienyldi(meth)acrylate, tricyclodecanedimethanoldi(meth)acrylate, 1,3-dioxane-2,5-diyldi(meth)acrylate [alias : dioxane glycol di(meth)acrylate], an acetal compound of hydroxypivalaldehyde and trimethylolpropane [Chemical name: 2-(2-hydroxy-1,1-dimethylethyl)-5-ethyl-5-hydroxy methyl-1,3-dioxane-], di(meth)acrylate, tris(hydroxyethyl)isocyanurate di(meth)acrylate, and 1,4-cyclohexanedimethanol diacrylate.

Examples of the trifunctional or higher polyfunctional (meth)acrylate monomer include glycerin tri(meth)acrylate, alkoxylated glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and ditrimethylolpropane tri(meth)acryl. rate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Poly(meth)acrylates of trifunctional or higher aliphatic polyols such as meth)acrylate and dipentaerythritol hexa(meth)acrylate are typical examples, and in addition, poly(meth)acrylates of trifunctional or higher halogen-substituted polyols, Tri(meth)acrylate of an alkylene oxide adduct of glycerin, tri(meth)acrylate of an alkylene oxide adduct of trimethylolpropane, 1,1,1-tris[(meth)acryloyloxyethoxyethoxy] Propane, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, etc. are mentioned.

On the other hand, the (meth)acryl oligomer includes a urethane (meth)acryl oligomer, a polyester (meth)acryl oligomer, and an epoxy (meth)acryl oligomer.

A urethane (meth)acryl oligomer is a compound which has a urethane bond (-NHCOO-) and at least two (meth)acryloyl groups in a molecule|numerator. Specifically, a urethanation reaction product of a hydroxyl group-containing (meth)acrylic monomer and polyisocyanate each having at least one (meth)acryloyl group and at least one hydroxyl group in the molecule, or a terminal isoform obtained by reacting a polyol with a polyisocyanate. It may be a urethanation reaction product of a cyanato group-containing urethane compound and a (meth)acrylic monomer each having at least one (meth)acryloyl group and at least one hydroxyl group in the molecule.

The hydroxyl group-containing (meth)acrylic monomer used in the urethanization reaction may be, for example, a hydroxyl group-containing (meth)acrylate monomer, and specific examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate , pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Specific examples other than the hydroxyl group-containing (meth)acrylate monomer include N-hydroxyalkyl (meth)acrylamide monomers such as N-hydroxyethyl (meth)acrylamide and N-methylol (meth)acrylamide. .

Examples of the polyisocyanate used for the urethanation reaction with the hydroxyl group-containing (meth)acrylic monomer include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and these Diisocyanates obtained by hydrogenating aromatic isocyanates among diisocyanates (eg, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, etc.), triphenylmethane triisocyanate, di- or tri- such as dibenzylbenzene triisocyanate Polyisocyanate obtained by multiplying isocyanate and the said diisocyanate, etc. are mentioned.

Moreover, as a polyol used in order to set it as the urethane compound containing a terminal isocyanato group by reaction with polyisocyanate, besides an aromatic, aliphatic or alicyclic polyol, a polyester polyol, a polyether polyol, etc. can be used. Examples of the aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, ditrimethylol. propane, pentaerythritol, dipentaerythritol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutanoic acid, glycerin, hydrogenated bisphenol A, and the like.

A polyester polyol is obtained by the dehydration-condensation reaction of an above-mentioned polyol, polybasic carboxylic acid, or its anhydride. Examples of polybasic carboxylic acids or their anhydrides are expressed by adding "(anhydride)" to what may be anhydride, (anhydride) succinic acid, adipic acid, (anhydride) maleic acid, (anhydride) itaconic acid, (anhydride) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, hexahydro (anhydrous) phthalic acid, and the like.

The polyether polyol may be a polyoxyalkylene-modified polyol obtained by reaction of the above-described polyol or dihydroxybenzene with an alkylene oxide other than polyalkylene glycol.

A polyester (meth)acryl oligomer is a compound which has an ester bond and at least two (meth)acryloyl groups (typically a (meth)acryloyloxy group) in a molecule|numerator. Specifically, it can be obtained by a dehydration condensation reaction using (meth)acrylic acid, a polybasic carboxylic acid or an anhydride thereof, and a polyol. An example of a polybasic carboxylic acid or anhydride thereof used in the dehydration condensation reaction is expressed by adding “(anhydride)” to an anhydride that may be anhydride, (anhydride) succinic acid, adipic acid, (anhydride) maleic acid, (anhydride) Itaconic acid, (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, hexahydro (anhydrous) phthalic acid, (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, and the like. Examples of the polyol used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, and ditrimethylolpropane, pentaerythritol, dipentaerythritol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutanoic acid, glycerin, and hydrogenated bisphenol A.

The epoxy (meth)acryl oligomer can be obtained, for example, by addition reaction of polyglycidyl ether and (meth)acrylic acid, and has at least two (meth)acryloyloxy groups in the molecule. Examples of the polyglycidyl ether used in the addition reaction include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol. A diglycidyl ether etc. are mentioned.

Although active energy ray sclerosis|hardenability may be sufficient as a radical polymerization type adhesive agent, and thermosetting may be sufficient as it, Preferably it is active energy ray sclerosis|hardenability. When providing active energy ray sclerosis|hardenability to the radical polymerization type adhesive agent containing a radically polymerizable compound, it is preferable to mix|blend a photoradical polymerization initiator with the adhesive agent. A photoradical polymerization initiator initiates the polymerization reaction of a radically curable compound by irradiation of an active energy ray like a visible ray, an ultraviolet-ray, X-ray, or an electron beam. A photoradical polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

Specific examples of the photoradical polymerization initiator include acetophenone, 3-methylacetophenone, benzyldimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-methyl- acetophenone-based initiators such as 1-[4-(methylthio)phenyl-2-morpholinopropan-1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzophenone-based initiators such as benzophenone, 4-chlorobenzophenone, and 4,4'-diaminobenzophenone; benzoin ether-based initiators such as benzoin propyl ether and benzoin ethyl ether; thioxanthone-based initiators such as 4-isopropylthioxanthone; In addition, xanthone, fluorenone, campaquinone, benzaldehyde, anthraquinone are included.

The compounding quantity of a photoradical polymerization initiator is 0.5-20 weight part normally with respect to 100 weight part of radically polymerizable compounds, Preferably it is 1-6 weight part. By mix|blending 0.5 weight part or more of photoradical polymerization initiators, a radically polymerizable compound can fully be hardened and high mechanical strength and adhesive strength can be provided to the laminated body and optical laminated body obtained. On the other hand, when the quantity increases excessively, durability of a laminated body and an optical laminated body may fall.

(additive)

The pressure-sensitive adhesive layer, the pressure-sensitive adhesive and the adhesive for forming the layer, if necessary, may include other additives. Specific examples of the additive include ion trapping agents, antioxidants, chain transfer agents, polymerization accelerators (polyols, etc.), sensitizers, sensitizers, light stabilizers, tackifiers, thermoplastic resins, fillers, flow regulators, plasticizers, defoamers, leveling agents. , a silane coupling agent, a dye, an antistatic agent, an ultraviolet absorber, and a thermal polymerization initiator. In addition, a thermal polymerization initiator is used instead of a photoinitiator, when preparing a thermosetting adhesive agent. A photoinitiator and a thermal polymerization initiator can also be used together. Examples of the ion trapping agent include powdered inorganic compounds such as bismuth, antimony, magnesium, aluminum, calcium, titanium, and mixtures thereof. Examples of the antioxidant include hindered phenolic antioxidants. have.

<Method for producing laminated body>

Taking the laminate shown in FIG. 1 as an example, the manufacturing method of the laminated body of this invention is demonstrated. In addition, FIG. 1 is a schematic diagram for demonstrating the layer structure of a laminated body, and the thickness of each layer shown in FIG. 1 does not show the preferable relationship of the thickness of each layer. The laminated body 100 shown in FIG. 1 is a 1st base material layer 111 / 1st liquid crystal hardened layer 121 (1st alignment layer 131 and 1st polymeric liquid crystal hardened|cured material containing layer 141) / point It has a structure provided with the adhesive layer 15/2nd liquid crystal hardened layer 122 (2nd polymeric liquid crystal hardened|cured material containing layer 142 and 2nd alignment layer 132)/2nd base material layer 112. In addition, in the laminated body in one Embodiment of this invention shown in FIG. 1, when peeling the 1st base material layer 111, the 1st orientation layer 131 does not peel together. Therefore, the first liquid crystal cured layer 121 is composed of the first alignment layer 131 and the first polymerizable liquid crystal cured product-containing layer 141 . In addition, when peeling the 2nd base material layer 112, the 2nd alignment layer 132 does not peel together. Therefore, the second liquid crystal cured layer 122 is composed of the second alignment layer 132 and the second polymerizable liquid crystal cured material-containing layer 142 .

The laminated body of this invention can be manufactured by the manufacturing method containing at least an orientation layer formation process, a liquid crystal hardened layer formation process, and a bonding process normally. Specifically, first, in the alignment layer forming step, the composition for forming the alignment layer is coated on the substrate. As a coating method, well-known methods, such as a coating method, such as a spin coating method, the extrusion method, the gravure coating method, the die-coating method, the bar coating method, the applicator method, and the printing method, such as a flexographic method, are mentioned. When the laminate of the present invention is manufactured by a roll-to-roll continuous method, the coating method is preferably a gravure coating method, a die coating method, or a printing method such as a flexographic method. By apply|coating the composition for alignment layer formation on a base material using the said method, a 1st coating film is formed on the base material. An orientation layer is formed by hardening|curing as needed to a 1st coating film, and providing an orientation regulating force by normal methods, such as photo-alignment and a rubbing process. Here, before forming the alignment layer, the substrate may be subjected to an easy adhesion treatment such as saponification treatment, corona discharge treatment, plasma treatment, flame treatment, primer treatment, and anchor coating treatment. By performing such a treatment, the adhesiveness between the substrate and the alignment layer is weakened, and when the substrate is peeled from the laminate, the alignment layer is not peeled off together with the substrate, but remains in the liquid crystal cured layer.

Next, a composition including a polymerizable liquid crystal compound is coated on the alignment layer. As a coating method, you may use the coating method described about the said composition for orientation layer formation. Then, in the state which orientated the polymeric liquid crystal compound, a polymeric liquid crystal hardened|cured material containing layer is formed by heat-processing or irradiating an active energy ray to harden|cure a polymeric liquid crystal compound. The composition containing the polymerizable liquid crystal compound may contain components other than the polymerizable liquid crystal compound described above. For example, it is preferable that a polymerization initiator is contained in the said composition. The polymerization initiator used is, for example, a thermal polymerization initiator and a photoinitiator selected according to the type of polymerization reaction. Examples of the photopolymerization initiator include an α-carbonyl compound, an acyl ether, an α-hydrocarbon-substituted aromatic acyl compound, a polynuclear quinone compound, and a combination of a triarylimidazole dimer and p-aminophenyl ketone. . The amount of the polymerization initiator to be used is preferably 0.01 to 20 mass%, more preferably 0.5 to 5 mass%, based on the total solid content in the coating solution. In the present invention, "hardened" refers to a state in which even the formed layer alone can exist independently without deformation or flow, and the puncture elastic modulus of the formed layer is preferably 3 g/mm or more.

Moreover, the polymerizable monomer may be contained in the said composition from the point of the uniformity of a coating film, and the strength of a film|membrane. As a polymerizable monomer, a radically polymerizable or cationically polymerizable compound is mentioned. Especially, a polyfunctional radically polymerizable monomer is preferable. Moreover, as a polymerizable monomer, what can copolymerize with the polymeric liquid crystal compound mentioned above is preferable. It is preferable that it is 1-50 mass % with respect to the total mass of a polymerizable liquid crystal compound, and, as for the usage-amount of a polymerizable monomer, it is more preferable that it is 2-30 mass %.

Moreover, surfactant may be contained in the said composition from the point of the uniformity of a coating film, and the strength of a film|membrane. As surfactant, a conventionally well-known compound is mentioned. Among these, a fluorine-type compound is especially preferable.

Moreover, the solvent may be contained in the said composition, and an organic solvent is used preferably.

Examples of the organic solvent include amides (eg N,N-dimethylformamide), sulfoxides (eg dimethyl sulfoxide), heterocyclic compounds (eg pyridine), hydrocarbons (eg benzene, hexane), alkyl halides ( For example, chloroform, dichloromethane), esters (for example, methyl acetate, ethyl acetate, butyl acetate), ketones (for example, acetone, methyl ethyl ketone), ethers (for example, tetrahydrofuran, 1,2-dimethoxyethane) can be heard Among them, alkyl halides and ketones are preferable. Moreover, you may use together 2 or more types of organic solvents.

In addition, the composition contains various alignment agents called vertical alignment promoters such as a polarizer interface side vertical alignment agent and an air interface side vertical alignment agent, and a horizontal alignment accelerator such as a polarizer interface side horizontal alignment agent and an air interface side horizontal alignment agent. good to be Moreover, the adhesion improving agent, a plasticizer, a polymer, etc. may be contained in the said composition other than the said component.

The said active energy ray contains an ultraviolet-ray, a visible light, an electron beam, and X-ray, Preferably it is an ultraviolet-ray. Examples of the light source of the active energy ray include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, a wavelength range of 380 to 440 nm. LED light source that emits light, a chemical lamp, a black light lamp, a microwave excited mercury lamp, a metal halide lamp, etc. are mentioned.

The irradiation intensity of an ultraviolet-ray is 100 mW/cm<2> - 3,000 mW/cm<2> normally in the case of an ultraviolet-B wave (wavelength range 280-310 nm). Ultraviolet irradiation intensity|strength, Preferably it is intensity|strength in the wavelength range effective for activation of a cationic polymerization initiator or a radical polymerization initiator. The time period for irradiating the ultraviolet rays is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and still more preferably 0.1 second to 1 minute.

Ultraviolet rays can be irradiated once or divided into multiple times. Depending on the polymerization initiator to be used, the amount of accumulated light at a wavelength of 365 nm is preferably 700 mJ/cm 2 or more, more preferably 1,100 mJ/cm 2 or more, and still more preferably 1,300 mJ/cm 2 or more. . Setting it as the said integrated light amount is advantageous in raising the polymerization rate of the polymeric liquid crystal compound which comprises retardation film, and improving heat resistance. It is preferable to set it as 2,000 mJ/cm<2> or less, and, as for the amount of integrated light at a wavelength of 365 nm, it is more preferable to set it as 1,800 mJ/cm<2> or less. There exists a possibility of causing coloring of retardation film to set it as the said integrated light quantity. Moreover, you may provide a cooling process after irradiation of an ultraviolet-ray. The cooling temperature can be, for example, 20°C or lower, or 10°C or lower. The cooling time can be, for example, 10 seconds or longer, and can be 20 seconds or longer.

As described above, to prepare a first laminate including a first base layer and a first cured liquid crystal layer, and in the same manner to prepare a second laminate including a second base layer and a second cured liquid crystal layer do. The laminated body of this invention can be manufactured by bonding two obtained laminated bodies through an adhesive bonding layer. When a laminated body is elongate, you may join each member by roll-to-roll through an adhesive bonding layer (preferably a contact bonding layer).

Specifically, the pressure-sensitive adhesive composition or adhesive composition is coated on the first liquid crystal cured layer and/or the second liquid crystal cured layer, and these laminates are bonded through the coating film to dry the coating film, or by active energy ray or heat. By curing the composition, an adhesive layer can be formed. The pressure-sensitive adhesive and the adhesive may be coated using various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater, for example. In addition, while supplying continuously so that the bonding surface of a 1st laminated body and a 2nd laminated body may become inside, the method of casting an adhesive or an adhesive agent in the meantime may be employ|adopted.

<Manufacturing method of optical laminated body>

The optical laminated body of this invention can be manufactured by peeling a 1st base material layer and a 2nd base material layer from the laminated body manufactured as mentioned above.

<Use>

The optical laminate of the present invention can be used for various display devices. A display device is a device which has a display element, and contains a light emitting element or a light emitting device as a light emitting source. As the display device, for example, a liquid crystal display device, an organic EL display device, an inorganic electroluminescence (hereinafter also referred to as inorganic EL) display device, an electron emission display device (for example, a field emission display device (also referred to as FED), a surface field emission device) Display device (also called SED), display device using electronic paper (electronic ink or electrophoretic element), plasma display device, projection display device (eg, grating light valve (also called GLV) display device, digital micromirror device (DMD) (also referred to as a display device) and a piezoelectric ceramic display. The liquid crystal display device includes all of a transmissive liquid crystal display device, a transflective liquid crystal display device, and the like. These display devices may be a display device that displays a two-dimensional image or a stereoscopic display device that displays a three-dimensional image. The optical laminate can be used particularly effectively for an organic EL display device or an inorganic EL display device.

In addition, a flexible display device may be sufficient as a display device, and a flexible organic electroluminescent display device may be sufficient as it. A flexible organic electroluminescent display device contains the optical laminated body of this invention, and an organic electroluminescent display element. The optical laminated body of this invention is arrange|positioned on the visual recognition side with respect to an organic electroluminescent display element, and it is comprised so that bending is possible. Being bendable means being able to bend without generating cracks and fractures. When applying the optical laminated body of this invention to a flexible organic electroluminescent display apparatus, it is preferable that the optical laminated body is further laminated|stacked on at least one of a front plate and a touch sensor.

As a specific laminated body, the aspect laminated|stacked in this order of a front plate, a polarizing plate, retardation film, and a touch sensor from the viewing side, or an aspect laminated|stacked in this order of a front plate, a touch sensor, a polarizing plate, and retardation film from the viewing side is mentioned. When a polarizing plate exists on the visual recognition side of a touch sensor, since it becomes difficult to visually recognize the pattern of a touch sensor, and the visibility of a display image improves, it is preferable. Each member may be laminated using an adhesive, an adhesive, or the like. In addition, a light blocking pattern formed on at least one surface of any one of the front plate, the polarizing plate, the retardation film, and the touch sensor may be provided.

Example

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited by these examples. In Examples and Comparative Examples, "%" and "parts" are mass % and parts by mass, unless otherwise specified. In addition, the measurement of each physical property in the following example was performed by the following method.

(Measurement of puncture modulus)

The film for forming the liquid-crystal hardened layer which has a base material layer was cut out into the fragment|piece of 40 mm x 40 mm. In addition, a 40 mm x 40 mm pasted land was prepared. This glued site is cut into a square with a central part of 30 mm x 30 mm. The above-mentioned film was bonded to the pasted sheet so that the surface of the liquid crystal cured layer was in contact with the pasted sheet. The base material layer was peeled from the liquid crystal cured layer which has a base material layer, and the measurement sample of the puncture elastic modulus was produced.

The measurement of the puncture elastic modulus was performed as follows. The needle was attached to the Handy Compression Tester "NDG5 Puncture Tester, Needle Penetration Force Measurement Specification" manufactured by Katotech Co., Ltd.

The needle was punctured perpendicularly to the film surface of the measurement sample. Measurement sample The stress F(g) immediately before the sample for the puncture test and the amount of deformation S(mm) at that time are calculated, and the puncture elastic modulus (g/mm) is calculated from the formula of the stress F(g)/strain amount S(mm) did. This operation was performed with respect to each measurement sample of 5 sheets, and the average value was made into puncture elastic modulus. As the needle, one having a tip diameter of 1 mmφ and 0.5R was used. The needle piercing speed was set to 0.33 cm/sec. The measurement was performed in a room temperature environment with a temperature of 23°C and a humidity of 50%.

(Measurement of tensile modulus of optical laminate)

A method of preparing a measurement sample will be described with reference to FIG. 6 . The optical laminate having the double-sided base layer was cut into pieces of 60 mm x 200 mm. In addition, a 60 mm x 200 mm pasted base 17 was prepared. This glued base has a cut-out portion 18 cut into a rectangle of 10 mm x 140 mm in the center portion. The 1st base material layer was peeled from the optical laminated body which has a double-sided base material layer. The laminate was bonded to the pasted sheet so that the surface of the first liquid crystal cured layer was in contact with the pasted sheet. Then, the 2nd base material layer was peeled. In this way, a sample as shown in FIG. 6 is obtained. The optical laminated body 16 exists in the part of the cutout part 18, and in the other part, the paste|sticker board 17 and the optical laminated body 16 are bonded. Next, a 10 mm x 60 mm rectangular portion (the portion enclosed by the dotted line in Fig. 6) is cut to include the cut-out portion 18 of the glued base 17, and this is used as a measurement sample for the tensile modulus. did.

The measurement of the tensile modulus was performed according to JISK7161. The tensile test was performed by gripping the mount portions (slanted lines in FIG. 6 ) at both ends of the measurement sample and pulling them at a rate of 1 mm/min. The tensile test was performed in a room temperature environment with a temperature of 23°C and a humidity of 50%.

(Measurement of tensile modulus of adhesive layer)

The tensile modulus [N/mm 2 ] at a temperature of 30°C when an active energy ray-curable adhesive was used as the adhesive layer was calculated in the following procedure. An active energy ray-curable adhesive is coated on one side of a 50 µm-thick cyclic polyolefin-based resin film using a coating machine (bar coater, manufactured by Daiichi Rica Co., Ltd.), and the coated surface is further coated with a cyclic polyolefin having a thickness of 50 µm. A system resin film was laminated. Next, with "D Bulb" manufactured by Fusion UV Systems, an ultraviolet-ray was irradiated so that the accumulated light amount might be 1500 mJ/cm<2> (UVB), and the adhesive composition layer was hardened. One cyclic polyolefin resin film was peeled off, and the contact bonding layer which has a resin film was obtained. The adhesive layer having the resin film was cut into pieces of 60 mm x 200 mm.

In addition, a 60 mm x 200 mm pasted base 17 was prepared. This glued base has a cut-out portion 18 cut into a rectangle of 10 mm x 140 mm in the center portion. The adhesive layer with the said resin film was joined to the paste|pasted board|substrate so that the surface of the adhesive layer may contact|connect the paste of the paste|sticker board|substrate. Then, the other cyclic polyolefin resin film was peeled. In this way, a sample as shown in FIG. 6 is obtained. An adhesive layer exists in the part of the cut-out part 18, and in the other part, the paste|sticker base 17 and the adhesive layer are joined. Next, a 10 mm x 60 mm rectangular portion (the portion enclosed by the dotted line in Fig. 6) is cut to include the cut-out portion 18 of the glued base 17, and this is used as a measurement sample for the tensile modulus. did.

The measurement of the tensile modulus was performed according to JISK7161. The tensile test was performed by gripping the mount portions (slanted lines in FIG. 6 ) at both ends of the measurement sample and pulling them at a rate of 1 mm/min. The tensile test was performed in a room temperature environment with a temperature of 23°C and a humidity of 50%. In addition, even when an adhesive layer was used as an adhesive bonding layer, it evaluated with the sample of the same shape.

(Measurement of Peeling Force of Base Layer)

The pressure-sensitive adhesive layer 1 (manufactured by Lintech, Ltd., pressure-sensitive adhesive 25 µm thick) was bonded to the liquid crystal cured layer side of the obtained liquid crystal cured layer having a base layer, respectively. The laminate in which this adhesive layer 1 was formed was cut out, and the test piece of width 25mm x length about 150mm was produced. After bonding the pressure-sensitive adhesive layer surface of the test piece to the glass plate, a peeling tape (25 mm in width x about 180 mm in length) was attached to the surface (one side of 25 mm in width) on the base layer side of the test piece. One end of the peeling tape was held, the base layer was peeled using a tensile tester, and the peeling force was measured. The peeling test was performed in the atmosphere of the temperature of 23 degreeC, and 50% of relative humidity. The crosshead speed (gripper moving speed) was 300 mm/min. The peeling angle was 180 degrees. In addition, as described above, in this embodiment, the peel force of the base layer was performed using the liquid crystal cured layer having the base layer before bonding through the adhesive layer, but the peel force of the base layer was bonded through the adhesive layer. You may carry out using the laminated body after carrying out.

(Peelability test)

A 40 mm x 40 mm glued glass was prepared. The liquid crystal cured layer laminate having a double-sided base layer was bonded so that the surface of the second base layer was in contact with the glue in the glued glass. Then, the 1st base material layer was peeled. The peelability was evaluated on the basis of the following criteria.

Good peelability: there is no peeling between the first liquid crystal cured layer and the second liquid crystal cured layer and between the second liquid crystal cured layer and the second substrate layer, and the first liquid crystal cured layer is peeled off and does not remain on the first substrate layer .

The peelability is poor: there is peeling between the first liquid crystal cured layer and the second liquid crystal cured layer and/or between the second liquid crystal cured layer and the second substrate layer, or the first liquid crystal cured layer is peeled off to the first substrate layer left.

The same evaluation was performed with respect to 24 samples, and when the number of samples with good releasability was 24 to 17, it was evaluated as (double-circle), when it was 16 to 9, it was evaluated as ○, and when it was 8 to 0, it was evaluated as x. .

(thermal shock test)

Manufacture of polarizing plate

A polyvinyl alcohol film with a thickness of 20 µm (average degree of polymerization of about 2400, saponification degree of 99.9 mol% or more) is uniaxially stretched to about 4 times by dry stretching, and immersed in pure water at 40°C for 40 seconds while maintaining the tension state. After that, it was immersed in an aqueous solution having a weight ratio of iodine/potassium iodide/water of 0.052/5.7/100 at 28° C. for 30 seconds to perform dyeing treatment. Thereafter, it was immersed in an aqueous solution having a weight ratio of potassium iodide/boric acid/water of 11.0/6.2/100 at 70° C. for 120 seconds. Subsequently, after washing with pure water at 8° C. for 15 seconds, maintaining a tension of 300 N, drying at 60° C. for 50 seconds, and then drying at 75° C. for 20 seconds, iodine is adsorbed and oriented to the polyvinyl alcohol film A polarizer with a thickness of 8 μm was obtained.

A water-based adhesive containing a polyvinyl alcohol-based resin aqueous solution is applied to both surfaces of the obtained polarizer, and a cyclic olefin-based resin film (Nippon Zeon Co., Ltd., Zeonor ZF14) and a triacetyl cellulose (TAC) film (Fujifilm Co., Ltd.) Fujitag TJ25) manufactured by Shiki Co., Ltd. were respectively joined together. This elongate polarizing plate was cut out into a square of 8 cm x 8 cm, and the polarizing plate was obtained.

Preparation of samples for thermal shock testing

Two pressure-sensitive adhesive layers 2 (25 µm in thickness, P-3132, manufactured by Lintech, Ltd.) with separators on both sides were prepared. One separator was peeled from the adhesive layer 2 with a separator on both surfaces, and it bonded to the TAC film side surface of a polarizing plate. The 1st base material layer was peeled from the liquid crystal cured layer laminated body which has a double-sided base material layer, and the other separator was peeled from the polarizing plate which has an adhesive layer. Both were bonded together so that the surface of a 1st liquid crystal hardening layer might contact|connect the adhesive layer. Moreover, the 2nd base material layer was peeled, and one separator was peeled from the adhesive layer 2 with a separator on both surfaces of the other 1 sheet, and it bonded so that the surface of a 2nd liquid crystal hardened layer might contact|connect the adhesive layer. The other peeling film laminated|stacked on the adhesive layer 2 was peeled, and it bonded to the glass plate through the exposed adhesive layer. In this way, a polarizing plate / adhesive layer (2) / optical laminate (laminate of the first liquid crystal cured layer, the adhesive adhesive layer, and the second liquid crystal cured layer) / adhesive layer (2) / a sample for thermal shock test containing a glass plate was obtained. The obtained sample for thermal shock test was evaluated by the method shown below.

Assessment Methods

A starting point was formed by pressing the pen tip of an Eriksen pen (Model No. 318, manufactured by Eriksen) set to a load of 10 N against the sample for thermal shock test. The same starting points were prepared at equal intervals in two other places (3 places in total). Thereafter, three cycles of a thermal shock test with -20°C for 30 minutes and 60°C for 30 minutes as one cycle were performed. For the thermal shock test, TSA-303EL-W manufactured by SPEC Co., Ltd. was used. After the lapse of 3 cycles, the length of cracks generated from each starting point was measured.

The average value of the lengths of the cracks generated from the three starting points was taken as the crack length (mm).

Those having a crack length of less than 1 mm were evaluated as (double-circle), those having a crack length of 1 mm or more and less than 10 mm were evaluated as ○, and those having a crack length of 10 mm or more were evaluated as ×.

[Preparation of adhesive]

95.0 parts by mass of n-butyl acrylate, 4.0 parts by mass of acrylic acid, 1.0 parts by mass of 2-hydroxyethyl acrylate, 200 parts by mass of ethyl acetate and 2 , 0.08 parts by mass of 2'-azobisisobutyronitrile was put, and the air in the reaction vessel was substituted with nitrogen gas. While stirring in a nitrogen atmosphere, the reaction solution was heated to 60° C., reacted for 6 hours, and then cooled to room temperature. When the weight average molecular weight of a part of the obtained solution was measured, production|generation of the (meth)acrylic acid ester polymer with a weight average molecular weight of 1.8 million was confirmed.

100 parts by mass of the obtained (meth)acrylic acid ester polymer (in terms of solid content; the same applies below), 1.5 parts by mass of an isocyanate-based crosslinking agent, 0.30 parts by mass of a silane coupling agent, 7.5 parts by mass of an ultraviolet curable compound, and 0.5 parts by mass of a photopolymerization initiator shown below Wealth was mixed.

The solution was fully stirred and the coating solution of the adhesive composition was obtained by diluting with ethyl acetate.

· Isocyanate-based crosslinking agent: trimethylolpropane-modified tolylene diisocyanate (manufactured by Tosoh Corporation, Colonate L)

· Silane coupling agent: 3-glycidoxypropyl trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403)

・Ultraviolet curable compound: ethoxylated isocyanuric acid triacrylate (Shin-Nakamura Chemical Co., Ltd., A-9300)

-Photoinitiator: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (manufactured by BASF, Igacure 907)

The above-mentioned coating solution was coated with an applicator on the release-treated surface (releasable layer surface) of a separator (manufactured by Lintech Co., Ltd., SP-PLR382190) so that the thickness after drying might be 5 µm. The coating film was dried at 100 degreeC for 1 minute, and on it, one more separator (the Lintech Co., Ltd. make, SP-PLR381031) was bonded together. The pressure-sensitive adhesive layer was irradiated with ultraviolet rays (illuminance 500 mW/cm2, accumulated light quantity 500 mJ/cm2) through the separator using a belt conveyor unit ultraviolet irradiation device (manufactured by Fusion UV Systems, Inc., and the lamp used was a D-bulb), An adhesive layer was obtained. The tensile modulus of elasticity of the pressure-sensitive adhesive layer was 0.4 N/mm 2 .

[Preparation of Adhesive 1]

Cationic curable components a1 to a3 shown below and a cationic polymerization initiator were mixed. The cationic polymerization initiator and sensitizer shown below were further mixed with the obtained mixture. The obtained solution was degassed, and the photocurable adhesive agent (1) was obtained. In addition, the following compounding quantity is based on solid content.

-Cation curable component a1 (70 parts): 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, CEL2021P)

-Cation curable component a2 (20 parts): neopentyl glycol diglycidyl ether (manufactured by Nagase Chemtex Co., Ltd., EX-211)

-Cation curable component a3 (10 parts): 2-ethylhexyl glycidyl ether (manufactured by Nagase Chemtex Co., Ltd., EX-121)

Cationic polymerization initiator (2.25 parts (solid content)): 50% propylene carbonate solution of CPI-100 (manufactured by San Apro Corporation)

・Sensitizer (2 parts): 1,4-diethoxynaphthalene

The tensile modulus of elasticity of the adhesive layer obtained from Adhesive 1 was 1280.8 N/mm 2 .

[Preparation of adhesive 2]

Cationic curable components a1, a4 to a6 and a cationic polymerization initiator shown below were mixed.

The cationic polymerization initiator and sensitizer shown below were further mixed with the obtained mixture. The obtained solution was degassed, and the photocurable adhesive agent 2 was obtained. In addition, the following compounding quantity is based on solid content.

-Cation curable component a1 (7 parts): 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, CEL2021P)

·Cation curable component a4 (40 parts): fluorene type epoxy resin (Osaka Gas Chemicals Co., Ltd., OGSOL EG-200)

Cationic curable component a5 (33 parts): neopentyl glycol diglycidyl ether (EX-211L manufactured by Nagase Chemtex Co., Ltd.)

-Cation curable component a6 (20 parts): 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (Toagosei Co., Ltd., OXT-221)

Cationic polymerization initiator (2.25 parts (solid content)): Trade name: 50% propylene carbonate solution of CPI-100 (manufactured by San Apro Corporation)

・Sensitizer (2 parts): 1,4-diethoxy naphthalene

The tensile modulus of elasticity of the adhesive layer obtained from Adhesive 2 was 1756.3 N/mm 2 .

[Preparation of adhesive 3]

The cationic curable components a1, a6, a7 shown below and a cationic polymerization initiator were mixed.

The cationic polymerization initiator and sensitizer shown below were further mixed with the obtained mixture. The obtained solution was degassed, and the photocurable adhesive agent 3 was obtained. In addition, the following compounding quantity is based on solid content.

Cationic curable component a1 (32.5 parts): 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, CEL2021P)

-Cation curable component a6 (50 parts): 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (Toagosei Co., Ltd., OXT-221)

Cationic curable component a7 (17.5 parts): 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (manufactured by Daicel Corporation) , EHPE3150)

Cationic polymerization initiator (2.25 parts (solid content)): Trade name: 50% propylene carbonate solution of CPI-100 (manufactured by San Apro Corporation)

・Sensitizer (2 parts): 1,4-diethoxy naphthalene

The tensile modulus of elasticity of the adhesive layer obtained from the adhesive 3 was 2345.5 N/mm 2 .

[Preparation of the composition (1) for forming a photo-alignment layer]

The composition (1) for photo-alignment layer formation was obtained by mixing the following components and stirring the obtained mixture at the temperature of 80 degreeC for 1 hour.

·Light orientation material (5 parts):

· Solvent (95 parts): cyclopentanone

[Preparation of the composition (2) for forming an alignment layer]

As a composition for forming an alignment layer, 15 parts of diethylene glycol di(meth)acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-600) and 1,6-hexanediol di(meth)acrylate (Shin-Nakamura Chemical Co., Ltd.) 15 parts of Nakamura Chemical Co., Ltd., A-DCP) and 1.5 parts of Igacure 907 (manufactured by BASF) as a photoinitiator were dissolved in 70 parts of solvent methyl ethyl ketone to prepare a composition (2) for forming an alignment layer prepared.

[Preparation of the composition (3) for forming an alignment layer]

As a composition for forming an alignment layer, 5 parts of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH) and diethylene glycol di(meth)acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 parts of A-600 manufactured by Shiki Corporation, 10 parts of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMPT), 1,6-hexanediol di(meth)acrylate ( 10 parts of Shin-Nakamura Chemical Co., Ltd., A-DCP) and 1.5 parts of Igacure 907 (manufactured by BASF) as a photoinitiator were dissolved in 70 parts of solvent methyl ethyl ketone, composition for forming an alignment layer (3) was prepared.

[Preparation of the composition (4) for forming an alignment layer]

10 parts of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH) and diethylene glycol di(meth)acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-600) 5 parts and 10 parts of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMPT), and 10 parts of 1,6-hexanedioldi(meth)acrylate (Shin-Nakamura Chemical Co., Ltd.) Manufacture, A-DCP) 5 parts and 1.5 parts of Igacure 907 (made by BASF) as a photoinitiator were melt|dissolved in 70 parts of solvent methyl ethyl ketone, and the composition (4) for alignment layer formation was prepared.

[Preparation of the composition (A-1) for forming a liquid crystal cured layer]

The following components were mixed and the composition (A-1) for liquid crystal hardening layer formation was obtained by stirring the obtained mixture at 80 degreeC for 1 hour. Polymerizable liquid crystal compound A1 and polymerizable liquid crystal compound A2 were synthesize|combined by the method of Unexamined-Japanese-Patent No. 2010-31223.

-Polymerizable liquid crystal compound A1 (80 parts):

-Polymerizable liquid crystal compound A2 (20 parts):

-Polymerization initiator (6 parts): 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (manufactured by Chiba Specialty Chemicals, Igacure 369)

· Solvent (400 parts): cyclopentanone

[Preparation of the composition (B-1) for forming a liquid crystal cured layer]

After mixing the following components and stirring the obtained mixture at 80 degreeC for 1 hour, it cooled to room temperature and obtained the composition (B-1) for liquid crystal cured layer formation.

-Polymerizable liquid crystal compound LC242 (manufactured by BASF) (19.2%):

-Polymerization initiator (0.5%): Igacure 907 (manufactured by BASF)

·Reaction additive (1.1%): Laromer (registered trademark) LR-9000 (manufactured by BASF)

Solvent (79.1%): propylene glycol 1-monomethyl ether 2-acetate

[Preparation of the first liquid crystal cured layer (1-1) having a first base layer]

As the first substrate layer, a polyethylene terephthalate (PET) film having a thickness of 100 μm was prepared. The surface of the first base layer was corona-treated. The corona treatment was performed once under the conditions of an output of 0.3 kW and a processing speed of 3 m/min using a corona treatment apparatus (AGF-B10, manufactured by Kasuga Electric Co., Ltd.). The composition (1) for forming a photo-alignment layer was applied with a bar coater to the corona-treated surface. The coating film was dried at 80°C for 1 minute. The coating film was subjected to polarization UV exposure using a polarization UV irradiation apparatus (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.) at an accumulated light amount of 100 mJ/cm 2 to obtain a photo-alignment layer. The thickness of the obtained photo-alignment layer was measured with a laser microscope (LEXT, manufactured by Olympus Corporation), and was found to be 100 nm.

On the photo-alignment layer, the composition (A-1) for forming a liquid crystal cured layer was applied using a bar coater.

The coating film was dried at 120° C. for 1 minute. The coating film was irradiated with ultraviolet rays using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Denki Co., Ltd.). Ultraviolet irradiation was performed under nitrogen atmosphere. The wavelength of the ultraviolet rays was 365 nm, the irradiation intensity in the wavelength 365 nm was 10 mW/cm<2>, and the accumulated light quantity was 1000 mJ/cm<2>. In this way, the 1st liquid crystal hardened layer (layer A-1) as retardation layer was formed, and the 1st liquid crystal hardened layer (1-1) which has a 1st base material layer was obtained. It was 2 micrometers when the thickness of the 1st liquid crystal hardening layer (layer A-1) was measured with a laser microscope. The base material peeling force of the 1st liquid crystal cured layer (1-1) which has a 1st base material layer was 0.10 N/25 mm. The puncture modulus of the first liquid crystal cured layer 1-1 was 22.3 g/mm.

[Preparation of a second liquid crystal cured layer (2-1) having a second substrate layer]

As the second substrate layer, a polyethylene terephthalate (PET) film having a thickness of 38 μm was prepared. The surface of the second base layer was corona-treated. The corona treatment was performed once under the conditions of an output of 0.3 kW and a processing speed of 3 m/min using a corona treatment apparatus (AGF-B10, manufactured by Kasuga Electric Co., Ltd.). The composition (2) for forming an alignment layer was applied with a bar coater to the corona-treated surface. The coating film was dried at 90°C for 1 minute. Ultraviolet (UVB) was irradiated to the coating film so that the accumulated light amount might be 220 mJ/cm<2>, and the alignment layer was obtained. When the thickness of the obtained orientation layer was measured with a laser microscope, it was 2.8 micrometers.

On the alignment layer, the composition (B-1) for forming a liquid crystal cured layer was applied using a bar coater. The coating film was dried at 90°C for 1 minute. The coating film was irradiated with ultraviolet rays using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Denki Co., Ltd.). Ultraviolet irradiation was performed in nitrogen atmosphere. The wavelength of the ultraviolet rays was 365 nm, and the accumulated light quantity in the wavelength 365 nm was 500 mJ/cm<2>. In this way, the 2nd liquid crystal hardened layer (layer B-1) as retardation layer was formed, and the 2nd liquid crystal hardened layer (2-1) which has a 2nd base material layer was obtained. It was 0.6 micrometer when the thickness of the 2nd liquid-crystal hardening layer (layer B-1) was measured with a laser microscope. The base material peeling force of the 2nd liquid crystal cured layer (2-1) which has a 2nd base material layer was 0.07 N/25 mm. The puncture modulus of the second liquid crystal cured layer 2-1 was 20.3 g/mm.

(Preparation of a second liquid crystal cured layer (2-2) having a second base layer)

It manufactured similarly to manufacture of the 2nd liquid crystal hardened layer (2-1) except having used the composition (3) for alignment layer formation instead of the composition (2) for alignment layer formation. The orientation layer thickness, the base material peeling force, and the stab elastic modulus data are shown in Table 1.

(Preparation of a second liquid crystal cured layer (2-3) to (2-7) having a second substrate layer)

Except having changed the thickness of the orientation layer, it manufactured similarly to manufacture of the 2nd liquid crystal hardened layer (2-1).

The orientation layer thickness, the base material peeling force, and the stab elastic modulus data are shown in Table 1.

(Preparation of a second liquid crystal cured layer (2-8) having a second base layer)

It manufactured similarly to manufacture of the 2nd liquid crystal hardened layer (2-1) except having used the composition (4) for alignment layer formation instead of the composition (2) for alignment layer formation. The orientation layer thickness, the base material peeling force, and the stab elastic modulus data are shown in Table 1.

[Example 1]

Corona treatment (800 W, 10 m/min, bar width 700 mm, 1 pass) was performed on the surface of the liquid crystal cured layer side of the first liquid crystal cured layer (1-1) having the first base layer prepared above. One separator is peeled from the pressure-sensitive adhesive layer with separators on both sides prepared above, and a first liquid crystal cured layer (1-1) having a first base layer using a pasting device (“LPA3301” manufactured by Fuji Plastics Co., Ltd.) ) was bonded to the corona-treated surface to obtain a liquid crystal cured layer having an adhesive layer. Further, after corona-treating the surface on the side of the liquid crystal cured layer of the second liquid crystal cured layer (2-1) having the second base layer prepared above, the other separator of the liquid crystal cured layer having an adhesive layer is peeled off And it bonded similarly to the corona-treated surface of the 2nd liquid crystal cured layer (2-1) which has a 2nd base material layer, and the laminated body (I) was obtained. The obtained laminate (I) was left still overnight in an environment of a temperature of 23°C and a humidity of 50%. Table 1 shows the results of evaluation of the peelability and the tensile modulus of elasticity of the optical laminate obtained by peeling both substrates about the obtained liquid crystal cured layer laminate (I) which has a double-sided base material layer.

[Example 2]

Corona treatment (800 W, 10 m/min, bar width 700 mm, 1 pass) was performed on the surface of the liquid crystal cured layer side of the second liquid crystal cured layer (1-1) having the first base layer prepared above. The adhesive 1 prepared above was coated on the corona-treated surface using a coating machine (bar coater manufactured by Daiichi Rika Co., Ltd.). Next, the surface of the liquid crystal hardened layer side of the 2nd liquid crystal hardened layer (2-1) which has a 2nd base material layer prepared above was corona-treated under the conditions similar to the above. Through the adhesive 1, the 1st liquid crystal cured layer (1-1) which has a 1st base material layer, and the 2nd liquid crystal hardened layer (2-1) which has a 2nd base material layer are pasting apparatus (Fuji Plastics Co., Ltd. product "" LPA3301") was used. From the base layer side of the second liquid crystal cured layer 2-1 having the second base layer, ultraviolet rays are irradiated using an ultraviolet irradiation device having a belt conveyor (the lamp uses “H Bulb” manufactured by Fusion UV Systems Co., Ltd.) did. In the UVA region, the irradiation intensity is 390 mW/cm2, the accumulated light amount is 420 mJ/cm2, and in the UVB region, the irradiation intensity is 400 mW/cm2, and the accumulated light amount is 400 mJ/cm2 did. In this way, a laminate (II) was obtained. The thickness of the adhesive bond layer of the obtained laminated body (II) was 1.5 micrometers. The obtained layered product (II) was left still overnight in an environment of a temperature of 23°C and a humidity of 50%. About the obtained laminated body (II), Table 1 shows the result of evaluating peelability and the tensile modulus of the optical laminated body obtained by peeling both base materials.

[Examples 3-7, Comparative Examples 1-4]

A liquid crystal cured layer laminate (III to XI) having a double-sided substrate layer in the same procedure as in Example 2, except that the second liquid crystal cured layer and the adhesive having the second substrate layer used were changed as shown in Tables 1 and 2 got About the obtained liquid-crystal cured layer laminated body (III-XI) which has a double-sided base material layer, the result of having evaluated peelability and tensile modulus is shown in Table 1 and Table 2. In addition, with respect to bonding using the adhesive agent 2 or 3, bonding was performed under the same conditions as Example 2 using the adhesive agent 1. In addition, the thickness of an adhesive bond layer is 2.0 micrometers in laminated body (III), 1.5 micrometers in laminated body (IV), 2.0 micrometers in laminated body (V), 1.5 micrometers in laminated body (VI), laminated body It was 1.5 µm in (VII), 2.0 µm in the laminate (VIII), 1.5 µm in the laminate (IX), 1.5 µm in the laminate (X), and 1.5 µm in the laminate (XI).

In addition, the result of having computed N according to the said Formula (A) is shown in Table 3 about the liquid crystal hardened layer and orientation layer in the laminated body of an Example and a comparative example.

As shown in Table 1, in the optical laminates obtained in Examples 1 to 7, the peelability of the base layer is good, and in addition to the fact that peeling between the liquid crystal cured layers is difficult to occur, the occurrence of cracks due to rapid temperature change is suppression was confirmed. On the other hand, in the laminated body shown in the comparative example, when peeling a base material layer, peeling was easy to produce also between liquid crystal hardened layers, or a crack was easy to produce by a rapid temperature change.

1 sheet with measuring film
6 voids
7 Grassed Earth
8 Outsourcing
12 Measuring Film
N needle
M needle (N) piercing position
S deformation amount
100 Laminate
111 first base layer
121 first liquid crystal cured layer
131 first alignment layer
141 First polymerizable liquid crystal cured material-containing layer
15 adhesive layer
122 second liquid crystal cured layer
142 Second polymerizable liquid crystal cured material-containing layer
132 second alignment layer
112 second base layer

Claims (9)

A laminate comprising a first base layer, a first liquid crystal cured layer, an adhesive layer, a second liquid crystal cured layer and a second base layer in this order,
Both the first liquid crystal cured layer and the second liquid crystal cured layer include a layer including a cured product of a polymerizable liquid crystal compound and an alignment layer,
Each of the first liquid crystal cured layer and the second liquid crystal cured layer is a measurement sample in which the film forming the layer is bonded to a paste board cut into a square with a central portion of 30 mm × 30 mm, and the tip diameter is 1 A needle of mmφ 0.5R is pierced perpendicularly to the surface of the film at a speed of 0.33 cm / sec, and the amount of displacement due to bending in the piercing direction of the film measured when fracture occurs is the deformation amount S (mm), When the stress applied to the film is F(g), Equation (1):
Sting modulus (g/mm)=F(g)/S(mm) (1)
The stab elastic modulus calculated by is 50 g / mm or less,
The first base layer and the second base layer may be peeled from the first liquid crystal cured layer and the second liquid crystal cured layer, respectively, and among the first base layer and the second base layer, the base layer to be peeled off first When the first peeling layer is used and the substrate layer to be peeled thereafter is used as the second peeling layer, the peeling force when peeling the first peeling layer is greater than the peeling force when peeling the second peeling layer,
The thickness of the alignment layer included in the first liquid crystal cured layer is smaller than the thickness of the alignment layer included in the second liquid crystal cured layer,
The laminated body whose tensile elasticity modulus of the optical laminated body obtained by peeling a 1st base material layer and a 2nd base material layer from the said laminated body is 1,000 N/mm<2> or less. The laminate according to claim 1, wherein the peeling force when peeling the first peeling layer is 0.15 N/25 mm or less, and the peeling force when peeling the second peeling layer is 0.05 N/25 mm or more. The laminate according to claim 1 or 2, wherein the thickness of the alignment layer included in the first liquid crystal hardened layer is 1/3 or less of the thickness of the alignment layer included in the second liquid crystal alignment layer. The thickness of the alignment layer included in the second liquid crystal alignment layer according to any one of claims 1 to 3, wherein the thickness of the alignment layer included in the first liquid crystal hardening layer is 10 nm to 500 nm, and the thickness of the alignment layer included in the second liquid crystal alignment layer is 1 A laminate having a thickness of from mu m to 3.5 mu m. The method according to any one of claims 1 to 4, wherein the first liquid crystal cured layer and the second liquid crystal cured layer are a layer imparting a retardation of λ/4 and a positive C layer, or a retardation of λ/4. A laminate that is a layer that provides a layer and a layer that imparts a retardation of λ/2. The laminate according to any one of claims 1 to 5, wherein the adhesive layer is an adhesive layer. An optical laminate comprising a first liquid crystal cured layer, an adhesive layer, and a second liquid crystal cured layer in this order,
Both the first liquid crystal cured layer and the second liquid crystal cured layer include a layer including a cured product of a polymerizable liquid crystal compound and an alignment layer,
Each of the first liquid crystal cured layer and the second liquid crystal cured layer is a measurement sample in which the film forming the layer is bonded to a paste board cut into a square with a central portion of 30 mm × 30 mm, and the tip diameter is 1 A needle of mmφ 0.5R is pierced perpendicularly to the surface of the film at a speed of 0.33 cm / sec, and the amount of displacement due to bending in the piercing direction of the film measured when fracture occurs is the deformation amount S (mm), When the stress applied to the film is F(g), Equation (1):
Sting modulus (g/mm)=F(g)/S(mm) (1)
The stab elastic modulus calculated by is 50 g / mm or less,
The thickness of the alignment layer included in the first liquid crystal cured layer is smaller than the thickness of the alignment layer included in the second liquid crystal cured layer,
An optical laminate having a tensile modulus of elasticity of 1,000 N/mm 2 or less of the optical laminate. The optical laminate according to claim 7, wherein the thickness of the alignment layer included in the first liquid crystal cured layer is 1/3 or less of the thickness of the alignment layer included in the second liquid crystal alignment layer. The thickness of the alignment layer according to claim 7 or 8, wherein the alignment layer included in the first liquid crystal hardened layer has a thickness of 10 nm to 500 nm, and the thickness of the alignment layer included in the second liquid crystal alignment layer is 1 μm to 3.5 μm. phosphorus laminate.

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