CN110275236A

CN110275236A - The manufacturing method of the optical laminate of the manufacturing method of optical laminate and subsidiary adhesive layer

Info

Publication number: CN110275236A
Application number: CN201910192606.2A
Authority: CN
Inventors: 名田敬之
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2018-03-15
Filing date: 2019-03-13
Publication date: 2019-09-24
Also published as: JP2019159198A; KR20190109269A

Abstract

A kind of manufacturing method for the optical laminate being sequentially laminated with optical film, the first adhesive layer, the first liquid crystal layer, bonding agent cured layer and the second liquid crystal layer, comprising: the second liquid crystal layer of the first liquid crystal layer of subsidiary substrate layer and subsidiary substrate layer is laminated with the second liquid crystal layer across the opposite mode of bonding agent cured layer with the first liquid crystal layer, thus the process for obtaining the liquid crystal layer laminates of subsidiary substrate layer；First base material layer is at least removed from the liquid crystal layer laminates of subsidiary substrate layer, thus the process for obtaining liquid crystal layer laminates；And expose surface side across the process of the first adhesive layer laminated optical film in first by removing the liquid crystal layer laminates that first base material layer exposes.

Description

The manufacture of the optical laminate of the manufacturing method of optical laminate and subsidiary adhesive layer Method

Technical field

The present invention relates to the manufacturing method of optical laminate and the manufacturing methods of the optical laminate of subsidiary adhesive layer.

Background technique

Use the organic EL display device of Organic Light Emitting Diode (OLED) compared with liquid crystal display device etc., it can not only It enough realizes lighting, slimming, and can be realized the high image quality such as large-scale visual angle, quick response speed, high contrast, Therefore it is used for the various fields such as smart phone, TV, digital camera.In addition, for organic EL display device, from slim and From the perspective of capable of being shown without using backlight, it is also proposed that the device shape as bending or batch.Organic In EL display device, it is known that in order to inhibit the reduction of the visibility caused by the reflection of ambient light and use circularly polarizing plate etc. To improve antireflection property.

For example, in patent document 1 and 2, as the film for the image display panel for being applied to organic EL display device etc., note The optical film with anti-reflective function is carried, and describe the optical film there is the phase difference formed using liquid crystal material Layer.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2015-230386 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2015-79256 bulletin

Summary of the invention

Subject to be solved by the invention

For optical film as described above, in order not to damage feature i.e. lighting/slimming of display device, and want Ask slimming, the bending of existing degree or more.In addition, above-mentioned optical film fit in optical display element come using, still, if Optical film generates the side being bonded with optical display element and is curled into concave so-called inverse curling, then there is following tendency: being easy Occur when being bonded with optical display element optical film due to bubble is mixed into or fold occurs by visuognosis for it is unequal not Good situation.Such unfavorable condition becomes the bad reason of image display panel, it is therefore desirable for inhibiting the inverse curling of optical film.

The object of the present invention is to provide the light that can manufacture the optical laminate for inhibiting inverse curling and subsidiary adhesive layer Learn the manufacturing method of laminated body.

Means for solving the problems

The present invention provides the system of the manufacturing method of optical laminate as shown below and the optical laminate of subsidiary adhesive layer Make method.

(1) a kind of manufacturing method of optical laminate is to be sequentially laminated with optical film, the first adhesive layer, the first liquid crystal The manufacturing method of the optical laminate of layer, bonding agent cured layer and the second liquid crystal layer,

The manufacturing method includes:

Prepare the process of the first liquid crystal layer of subsidiary substrate layer, the first liquid crystal layer of the subsidiary substrate layer has the first base Material layer and above-mentioned first liquid crystal layer for forming polymerizable liquid crystal compound polymerization on above-mentioned first base material layer；

Prepare the process of the second liquid crystal layer of subsidiary substrate layer, the second liquid crystal layer of the subsidiary substrate layer has the second base Material layer and above-mentioned second liquid crystal layer for forming polymerizable liquid crystal compound polymerization on above-mentioned second substrate layer；

By the second liquid crystal layer of the first liquid crystal layer of above-mentioned subsidiary substrate layer and above-mentioned subsidiary substrate layer with above-mentioned first liquid Crystal layer is laminated with above-mentioned second liquid crystal layer across the opposite mode of above-mentioned bonding agent cured layer, to obtain subsidiary substrate layer Liquid crystal layer laminates process；

Above-mentioned first base material layer is at least removed from the liquid crystal layer laminates of above-mentioned subsidiary substrate layer, to obtain liquid crystal layer by layer The process of stack；And

Expose surface side across upper in first by removing the above-mentioned liquid crystal layer laminates that above-mentioned first base material layer exposes The process for stating the first above-mentioned optical film of bonding layer stackup.

(2) manufacturing method of the optical laminate according to (1), wherein the process that above-mentioned optical film is laminated includes:

Above-mentioned first adhesive layer is formed on above-mentioned optical film, thus the process for obtaining the optical film of subsidiary adhesive layer；With And

By above-mentioned the of above-mentioned first adhesive layer and above-mentioned liquid crystal layer laminates in the optical film of above-mentioned subsidiary adhesive layer The process that one exposed surface is bonded.

(3) manufacturing method of the optical laminate according to (2), wherein the above-mentioned optical film for obtaining subsidiary adhesive layer Process include:

Prepare the process for being laminated with the first adhesive layer of the subsidiary peeling layer of above-mentioned first adhesive layer and the first peeling layer；With And

After above-mentioned first adhesive layer in first adhesive layer of above-mentioned subsidiary peeling layer is bonded with above-mentioned optical film, The process for removing above-mentioned first peeling layer.

(4) manufacturing method of the optical laminate according to (1), wherein the process that above-mentioned optical film is laminated includes:

Above-mentioned first adhesive layer is formed in above-mentioned first exposed surface of above-mentioned liquid crystal layer laminates, to obtain subsidiary the The process of the liquid crystal layer laminates of one adhesive layer；And

Above-mentioned first adhesive layer in the liquid crystal layer laminates of above-mentioned subsidiary first adhesive layer is carried out with above-mentioned optical film The process of fitting.

(5) manufacturing method of the optical laminate according to (4), wherein the above-mentioned liquid for obtaining subsidiary first adhesive layer The process of crystal layer laminated body includes:

By the upper of above-mentioned first adhesive layer and the above-mentioned liquid crystal layer laminates in the first adhesive layer of above-mentioned subsidiary peeling layer State the process for after the first exposed surface is bonded, removing above-mentioned first peeling layer.

(6) manufacturing method of the optical laminate according to any one of (1)~(5), wherein above-mentioned to obtain subsidiary base The process of the liquid crystal layer laminates of material layer includes:

Second of above-mentioned first liquid crystal layer and above-mentioned subsidiary substrate layer in the first liquid crystal layer of above-mentioned subsidiary substrate layer Above-mentioned second liquid crystal layer in liquid crystal layer at least one of on form the process of adhesive composite layer, the bonding agent group Closing nitride layer includes the adhesive composite for being used to form above-mentioned bonding agent cured layer；And

By the second liquid crystal layer of the first liquid crystal layer of above-mentioned subsidiary substrate layer and above-mentioned subsidiary substrate layer with above-mentioned first liquid After crystal layer and above-mentioned second liquid crystal layer are laminated across the opposite mode of above-mentioned adhesive composite layer, by above-mentioned bonding agent group Close the process that nitride layer is solidified to form above-mentioned bonding agent cured layer.

(7) manufacturing method of the optical laminate according to any one of (1)~(6), wherein above-mentioned optical film includes Polarization plates.

(8) manufacturing method of the optical laminate according to any one of (1)~(7), wherein above-mentioned optical film includes The polarization plates of the subsidiary protective film of protective film are laminated in at least single side of polarization plates.

(9) manufacturing method of the optical laminate according to any one of (1)~(8), wherein above-mentioned to obtain liquid crystal layer The process of laminated body is to remove above-mentioned first base material layer from the liquid crystal layer laminates of above-mentioned subsidiary substrate layer and do not remove above-mentioned the The process of two substrate layers,

It further include the process for removing above-mentioned second substrate layer after the process that above-mentioned optical film is laminated.

(10) manufacturing method of the optical laminate according to any one of (1)~(8), wherein obtain above-mentioned liquid crystal The process of layer laminates is to remove above-mentioned first base material layer and above-mentioned second base from the liquid crystal layer laminates of above-mentioned subsidiary substrate layer Material layer, thus the process for obtaining liquid crystal layer laminates.

(11) a kind of manufacturing method of the optical laminate of subsidiary adhesive layer is to be sequentially laminated with optical film, first viscous Close the optical laminate of the subsidiary adhesive layer of layer, the first liquid crystal layer, bonding agent cured layer, the second liquid crystal layer and the second adhesive layer Manufacturing method,

The manufacturing method includes:

Prepare the manufacturing method for utilizing optical laminate described in (9) or (10) and the process of optical laminate manufactured； And

It is above-mentioned to expose surface side stacking in second by removing the above-mentioned optical laminate that above-mentioned second substrate layer exposes The process of second adhesive layer.

(12) manufacturing method of the optical laminate of the subsidiary adhesive layer according to (11), wherein stacking above-mentioned second The process of adhesive layer includes:

Prepare the process for being laminated with the second adhesive layer of the subsidiary peeling layer of above-mentioned second adhesive layer and the second peeling layer；With And

By the above-mentioned of above-mentioned second adhesive layer and the above-mentioned optical laminate in the second adhesive layer of above-mentioned subsidiary peeling layer The process that second exposed surface is bonded.

(13) a kind of manufacturing method of the optical laminate of subsidiary adhesive layer is to be sequentially laminated with optical film, first viscous Close the optical laminate of the subsidiary adhesive layer of layer, the first liquid crystal layer, bonding agent cured layer, the second liquid crystal layer and the second adhesive layer Manufacturing method,

The manufacturing method includes:

Above-mentioned second substrate layer is at least removed from the liquid crystal layer laminates of above-mentioned subsidiary substrate layer, to obtain liquid crystal layer by layer The process of stack；

Expose in the stacking of surface side in second by removing the above-mentioned liquid crystal layer laminates that above-mentioned second substrate layer exposes The second adhesive layer is stated, thus the process for obtaining the liquid crystal layer laminates of subsidiary second adhesive layer；

From the liquid crystal layer laminates of above-mentioned subsidiary substrate layer or the liquid crystal layer laminates removing of above-mentioned subsidiary second adhesive layer The process of above-mentioned first base material layer；And

The of the liquid crystal layer laminates by removing above-mentioned subsidiary second adhesive layer that above-mentioned first base material layer exposes One exposes surface side across the process of the above-mentioned first bonding above-mentioned optical film of layer stackup.

(14) manufacturing method of the optical laminate of the subsidiary adhesive layer according to (13), wherein above-mentioned to be attached to The process of the liquid crystal layer laminates of second adhesive layer includes:

By the upper of above-mentioned second adhesive layer and the above-mentioned liquid crystal layer laminates in the second adhesive layer of above-mentioned subsidiary peeling layer State the process for after the second exposed surface is bonded, removing above-mentioned second peeling layer.

The effect of invention

According to the present invention it is possible to manufacture the optical laminate of the optical laminate for inhibiting inverse curling and subsidiary adhesive layer.

Detailed description of the invention

(a) of Fig. 1~(d) is the diagrammatic sectional view for schematically showing an example of manufacturing process of optical laminate of the invention Figure.

It (a) of Fig. 2 and (b) is to schematically show that the subsequent outline of the manufacturing process of optical laminate shown in Fig. 1 cuts open View.

(a) of Fig. 3~(c) is to schematically show that the subsequent outline of the manufacturing process of optical laminate shown in Fig. 2 cuts open View.

It (a) of Fig. 4 and (b) is to schematically show that the subsequent outline of the manufacturing process of optical laminate shown in Fig. 3 cuts open View.

(a) of Fig. 5 and (b) be schematically show subsidiary adhesive layer of the invention optical laminate manufacturing process one The schematic sectional view of example.

(a) of Fig. 6~(d) is the manufacturing process for schematically showing the optical laminate of other subsidiary adhesive layers of the invention An example schematic sectional view.

(a) of Fig. 7~(e) be schematically show the manufacturing process for the optical laminate being different from the present invention an example it is general Slightly cross-sectional view.

(a) of Fig. 8~(d) is to schematically show that the subsequent outline of the manufacturing process of optical laminate shown in Fig. 7 cuts open View.

Description of symbols

The first liquid crystal layer, 11,11p first base material layer, the first liquid crystal layer of 12,12p, 20,20p of 10,10p subsidiary substrate layers Incidentally the second liquid crystal layer of substrate layer, the second substrate layer of 21,21p, the second liquid crystal layer of 22,22p, 25 are attached to the second of composition layers Liquid crystal layer, the first adhesive layer of 31,31p, 32 bonding agent cured layers, 32a adhesive composite layer, the second ' adhesive layer of 32p, 33 Two adhesive layers, the liquid crystal layer laminates of 40 subsidiary substrate layers, 41,43 liquid crystal layer laminates, 45 subsidiary second adhesive layers liquid crystal The first adhesive layer, 51 first peeling layers, the second ' peeling layer of 52p, 53 second peeling layers, 58 of layer laminates, 50 subsidiary adhesive layers Incidentally optical film, 70, the 70p optical laminate, 71 of the second adhesive layer of peeling layer, 60,60p optical film, 61 subsidiary adhesive layers, 71p is attached to the optical laminate of the optical laminate (optical laminate) of substrate layer, 80,81 subsidiary adhesive layers.

Specific embodiment

Hereinafter, referring to attached drawing to the optical laminate of the manufacturing method of optical laminate of the invention and subsidiary adhesive layer The preferred embodiment of manufacturing method is illustrated.

[embodiment 1 (manufacturing method of optical laminate)]

FIG. 1 to FIG. 4 is the diagrammatic sectional view for schematically showing an example of the manufacturing process of optical laminate of present embodiment Figure.In figure, W indicates width direction.As shown in (b) of Fig. 4, using the manufacturing method of the optical laminate 70 of present embodiment The optical laminate 70 of manufacture is to be sequentially laminated with optical film 60, the first adhesive layer 31, the first liquid crystal layer 12, bonding agent cured layer 32 and second liquid crystal layer 22 optical laminate.

The manufacturing method of optical laminate 70 includes the first liquid crystal layer 10 for preparing subsidiary substrate layer shown in (a) of Fig. 1 The process of second liquid crystal layer 20 of subsidiary substrate layer shown in (b) with Fig. 1.First liquid crystal layer 10 of subsidiary substrate layer has the One substrate layer 11 and the first liquid crystal layer 12 for forming polymerizable liquid crystal compound polymerization on first base material layer 11, subsidiary base Second liquid crystal layer 20 of material layer have the second substrate layer 21 and on the second substrate layer 21 by polymerizable liquid crystal compound polymerize and The second liquid crystal layer 22 formed.

The process for preparing the first liquid crystal layer 10 of subsidiary substrate layer may include following process: apply on first base material layer 11 Cloth includes the liquid crystal layer formation composition of polymerizable liquid crystal compound, is dried, passes through and irradiate ultraviolet light isoreactivity energy Ray and polymerizable liquid crystal compound is polymerize and is allowed to solidify, formed the first liquid crystal layer 12.Similarly, prepare subsidiary substrate layer The process of the second liquid crystal layer 20 may include following process: coating includes polymerizable liquid crystal compound on the second substrate layer 21 Liquid crystal layer formed and use composition, be dried, by irradiation ultraviolet light isoreactivity energy-ray by polymerizable liquid crystal chemical combination Object polymerize and is allowed to solidify, and forms the second liquid crystal layer 22.

Then, the surface for carrying out 22 side of the second liquid crystal layer in the second liquid crystal layer 20 of subsidiary substrate layer forms bonding agent The process of composition layer 32a, the adhesive composite layer 32a include the bonding agent combination for being used to form bonding agent cured layer 32 Object.Using the process, the second liquid crystal layer 25 ((c) of Fig. 1) of available subsidiary composition layer.It is attached as shown in (c) of Fig. 1 The second liquid crystal layer 25 with composition layer is sequentially laminated with adhesive composite layer 32a, the second liquid crystal layer 22 and the second substrate layer 21.The process for forming adhesive composite layer 32a may include the second liquid crystal in the second liquid crystal layer 20 of subsidiary substrate layer The process of the surface coating adhesive composition of 22 side of layer.

By the adhesive composite layer 32a in the second liquid crystal layer 25 of resulting subsidiary composition layer and it is attached to substrate layer After the first liquid crystal layer 12 in first liquid crystal layer 10 is laminated ((d) of Fig. 1), adhesive composite layer 32a is solidified, is formed Bonding agent cured layer 32, to obtain the liquid crystal layer laminates 40 ((a) of Fig. 2) of subsidiary substrate layer.Make adhesive composite layer The cured method of 32a can suitably be selected according to type of adhesive composite etc., and it can be mentioned, for example active energy beams Irradiation, heat treatment, addition of curing agent etc..It is as described later about the type of adhesive composite or its curing method.Such as Shown in (a) of Fig. 2, the liquid crystal layer laminates 40 of subsidiary substrate layer are sequentially laminated with first base material layer 11, the first liquid crystal layer 12, glue Connect agent cured layer 32, the second liquid crystal layer 22 and the second substrate layer 21.Liquid crystal layer laminates 40 by being attached to substrate layer from this are shelled From first base material layer 11, and the second substrate layer 21 is not removed, thus obtain liquid crystal layer laminates 41 ((b) of Fig. 2).Such as Fig. 2 (b) shown in, liquid crystal layer laminates 41 are sequentially laminated with the first liquid crystal layer 12, bonding agent cured layer 32, the second liquid crystal layer 22 and the Two substrate layers 21.

Next, preparing the first adhesive layer for being formed with the subsidiary peeling layer of the first adhesive layer 31 on the first peeling layer 51 50 ((a) of Fig. 3).The process for preparing the first adhesive layer 50 of subsidiary adhesive layer may include being coated with to glue on the first peeling layer 51 Mixture composite is simultaneously allowed to process that is dry etc. and forming the first adhesive layer 31.Other are used furthermore it is possible to be set as desired Peeling layer covers the process with the face of 51 opposite side of the first peeling layer of the second adhesive layer 31.The subsidiary peeling layer that will be prepared The first adhesive layer 50 in the first adhesive layer 31 be bonded with optical film 60 ((b) of Fig. 3), remove the first peeling layer 51, Obtain the optical film 61 ((c) of Fig. 3) of subsidiary adhesive layer.As shown in (c) of Fig. 3, the optical film 61 of subsidiary adhesive layer is laminated with Optical film 60 and the first adhesive layer 31.

Later, reveal by the first adhesive layer 31 in the optical film 61 of subsidiary adhesive layer and by removing first base material layer 11 The first liquid crystal layer 12 (the first exposed surface) in liquid crystal layer laminates 41 out is bonded, and the optical layer of subsidiary substrate layer is obtained Stack 71 (optical laminate) ((a) of Fig. 4).As shown in (a) of Fig. 4, the optical laminate 71 of subsidiary substrate layer is stacked gradually There are optical film 60, the first adhesive layer 31, the first liquid crystal layer 12, bonding agent cured layer 32, the second liquid crystal layer 22 and the second substrate layer 21.Optical laminate 71 by being attached to substrate layer from this removes the second substrate layer 21, it is hereby achieved that optical laminate 70 ((b) of Fig. 4).

In the manufacturing method of above-mentioned optical laminate 70, use in first base material layer 11 or the second substrate layer 21 Polymerizable compound is polymerize on (the two is referred to as " substrate layer " sometimes below) and is allowed to subsidiary substrate layer made of solidification The first liquid crystal layer 10 or the second liquid crystal layer 20 of subsidiary substrate layer (the two is referred to as the " liquid of subsidiary substrate layer sometimes below Crystal layer ").In the liquid crystal layer of subsidiary substrate layer, coating includes the liquid crystal layer of polymerizable liquid crystal compound usually on substrate layer It is formed and uses composition, be dried, and polymerize polymerizable liquid crystal compound by irradiating ultraviolet light isoreactivity energy-ray And solidify, it is possible thereby to form the first liquid crystal layer 12 or the second liquid crystal layer 22 (the two is referred to as " liquid crystal layer " sometimes below). It can speculate: the liquid for remaining and being coated in by the above-mentioned liquid crystal layer for the processes such as being coated and dried, polymerizeing, solidify and formed The shrinkage stress generated when the drying of crystal layer formation composition or the associated solidification of the polymerization of polymerizable liquid crystal compound.In liquid Crystal layer is present in the state of the liquid crystal layer of the subsidiary substrate layer on substrate layer, and above-mentioned shrinkage stress is inhibited by substrate layer, But as described above, substrate layer is stripped in the process of manufacture optical laminate 70, it can thus be assumed that the contraction of liquid crystal layer is answered Power is released because of the removing of substrate layer.At this point, if liquid crystal layer is bonded with optical film, sometimes because of peeling base layer And discharge shrinkage stress and in the laminated body of optical film and liquid crystal layer occur be warped into using liquid crystal layer side as inside it is bowed Deformation (hereinafter sometimes referred to as " inverse curling ").

It is believed that: after by optical film 60 and liquid crystal layer stackup, peeling base layer and the shrinkage stress for discharging liquid crystal layer Number is more, then is more easy to happen such curling.For example, as shown in Figures 7 and 8, when stacking gradually liquid crystal on optical film Layer and in the case where manufacturing optical laminate, time of the shrinkage stress of liquid crystal layer will be discharged by existing after optical film and liquid crystal layer stackup Number becomes more tendencies.Fig. 7 and Fig. 8 is to schematically show the light different from the manufacturing process of optical laminate shown in FIG. 1 to FIG. 4 Learn the schematic sectional view of an example of the manufacturing process of laminated body.

In the manufacturing method of optical laminate 70p shown in (d) of Fig. 8, firstly, will have on first base material layer 11p There is first liquid crystal layer 10p (Fig. 7 of the subsidiary substrate layer for the first liquid crystal layer 12p that polymerizable liquid crystal compound is polymerize and is formed (b)) in the first side liquid crystal layer 12p fit in the subsidiary adhesive layer for being laminated with the optical film adhesive layer of 60p and the first ' 31p The first ' adhesive layer 31p ((c) of Fig. 7) in optical film 61p ((a) of Fig. 7).Later, removing first base material layer 11p (Fig. 7's (d)), by the first liquid crystal layer 12p exposed by the removing and the second ' adhesive layer being formed on the second ' peeling layer 52p 32p is bonded ((e) of Fig. 7), and the second ' peeling layer 52p ((a) of Fig. 8) is removed.Then, will have on the second substrate layer 21p There is second liquid crystal layer 20p (Fig. 8 of the subsidiary substrate layer for the second liquid crystal layer 22p that polymerizable liquid crystal compound is polymerize and is formed (b)) in the second side liquid crystal layer 22p fit in the second ' adhesive layer 32p, to obtain the optical laminate of subsidiary substrate layer 71p ((c) of Fig. 8).The second substrate layer 21p is removed from the optical laminate 71p for being attached to substrate layer, obtains optical laminate 70p ((d) of Fig. 8).

Like this, it in Fig. 7 and manufacturing process shown in Fig. 8, is laminated on optical film 60p across the first ' adhesive layer 31p After first liquid crystal layer 12p, first base material layer 11p is removed, across the second ' adhesive layer 32p stacking second on the first liquid crystal layer 12p After liquid crystal layer 22p, the second substrate layer 21p is removed.It can thus be assumed that: removing first base material layer 11p's and the second substrate layer 21p In each process, the shrinkage stress of the first liquid crystal layer 12p and the second liquid crystal layer 22p are discharged respectively, therefore, in optical laminate 70p In be easy to produce inverse curling.

In contrast, in the manufacturing method of the optical laminate 70 of the present embodiment shown in FIG. 1 to FIG. 4, firstly, will First liquid crystal layer 10 of subsidiary substrate layer and the second liquid crystal layer 20 of subsidiary substrate layer are laminated across bonding agent cured layer 32, Obtain the liquid crystal layer laminates 40 ((a) of Fig. 2) of subsidiary substrate layer.Later, first base material layer 11 is removed, has been released first The liquid crystal layer laminates 41 ((b) of Fig. 2) of the shrinkage stress of liquid crystal layer 12 carry out the liquid crystal layer laminates 41 with optical film 60 It is bonded ((a) of Fig. 4), and removes the second substrate layer 21 ((b) of Fig. 4).Therefore, according to the manufacturing method of optical laminate 70, The stripping process carried out after the first liquid crystal layer 12 and the second liquid crystal layer 22 are laminated in optical film 60 is only to remove the second substrate The process of layer 21 can be reduced and be discharged after liquid crystal layer is laminated in optical film compared with Fig. 7 and manufacturing process shown in Fig. 8 The number of the shrinkage stress of liquid crystal layer.Thus it is believed that: in the manufacturing method of optical laminate 70 shown in FIG. 1 to FIG. 4, with Optical laminate 70p is compared obtained from Fig. 7 and manufacturing process shown in Fig. 8, can reduce in optical laminate 70 The inverse curling generated.

In addition, in the optical laminate 71 of subsidiary substrate layer shown in (a) of Fig. 4, by the first liquid crystal layer 12 and second Liquid crystal layer 22 is laminated across bonding agent cured layer 32.On the other hand, the optics of the subsidiary substrate layer shown in (c) of Fig. 8 In laminated body 71p, the first liquid crystal layer 12p and the second liquid crystal layer 22p are laminated across the second ' adhesive layer 32p.If with Two ' adhesive layer 32p are compared, then the rigidity of bonding agent cured layer 32 is higher, less easily-deformable.Therefore can speculate: even if from Fig. 4's (a) optical laminate 71 of subsidiary substrate layer shown in removes the second substrate layer 21, is also easy to remain and is solidified using bonding agent Layer 32 inhibits the state of the shrinkage stress of the second liquid crystal layer 22.In contrast, it is believed that: it is subsidiary shown in (c) from Fig. 8 In the case that the optical laminate 71p of substrate layer removes the second substrate layer 21p, the shadow of the shrinkage stress by the second liquid crystal layer 22 It rings, the first ' adhesive layer 31p, the second ' adhesive layer 32p, optical film 60p are easily deformed, are easy to produce in optical laminate 70 inverse Curling.Therefore, in the manufacturing method of optical laminate 70 shown in FIG. 1 to FIG. 4, with utilization Fig. 7 and manufacture work shown in Fig. 8 Optical laminate 70p obtained from sequence is compared, and is easily reduced the inverse curling generated in optical laminate 70.

As described above, by reducing the inverse curling generated in optical laminate 70, thus the optics will be used to be laminated When the optical laminate (aftermentioned) for the subsidiary adhesive layer that body 70 obtains fits in optical display element, it can inhibit in subsidiary bonding Layer optical laminate and optical display element between be mixed into bubble, generate fold or generate be bonded fault as it is bad Situation.

In addition, as shown in (e) of Fig. 7, sometimes after by optical film 60p and the first liquid crystal layer 12p stacking, in the first liquid crystal The second ' adhesive layer 32p is set on layer 12p.In this case, it will be set on the second ' peeling layer 52p as described above sometimes The second ' adhesive layer 32p is layered on the first liquid crystal layer 12p together with the second ' peeling layer 52p, then removes the second ' peeling layer 52p.The process for removing the second ' peeling layer 52p may also become the reason of making to be easy to produce inverse curling in optical laminate 70p.

On the other hand, in the manufacturing method of the optical laminate 70 of the present embodiment shown in FIG. 1 to FIG. 4, by first Liquid crystal layer 12 is bonded with the second liquid crystal layer 22 across bonding agent cured layer 32, and liquid crystal layer stackup shown in (b) of Fig. 2 is obtained Body 41.Moreover, because the liquid crystal layer laminates 41 are laminated with optical film 60, therefore, in the optical laminate of present embodiment In 70 manufacturing method, if at least there is no removings compared with the manufacturing process of Fig. 7 and optical laminate 70p shown in Fig. 8 Therefore the process of second peeling layer 52p can reduce the quantity for the layer removed after being laminated in optical film 60.It therefore can Think: in the manufacturing method of optical laminate 70, compared with the manufacturing process of optical laminate 70p, being easy to inhibit in optics The inverse curling generated in laminated body 70.

For the inverse curling generated in optical laminate, it is believed that: optical film 60 contained in optical laminate Thickness or rigidity it is smaller, then the release of the easier shrinkage stress by liquid crystal layer is influenced.In addition, the thickness of substrate layer or Rigidity is bigger, then remaining shrinkage stress is bigger in the liquid crystal layer, therefore, easier by being discharged in peeling base layer The influence of shrinkage stress.Therefore, the manufacturing method of the optical laminate of present embodiment be suitable for optical film 60 with a thickness of 2 μm Above and 500 μm or less of situation.The thickness of optical film 60 can be 10 μm or more, furthermore it is possible to which 350 μm hereinafter, can also be with For 200 μm hereinafter, can also be 150 μm or less.

It is explained, the first liquid crystal of the subsidiary substrate layer used in the present embodiment in order to manufacture optical laminate First bonding of layer 10, the second liquid crystal layer 20 of subsidiary substrate layer, the second liquid crystal layer 25 of subsidiary composition layer, subsidiary peeling layer Layer 50, optical film 60, incidentally the membranoid substances such as optical film 61 of adhesive layer are both preferably the membranoid substance of strip, preferably on one side by them It continuously transports and carries out each process on one side.Width direction W is the direction orthogonal with the length direction of membranoid substance.

The manufacturing method of the optical laminate of present embodiment can variation as shown below change like that.Separately Outside, can also by above embodiment with it is following shown in variation arbitrarily combine.

(variation 1 of embodiment 1)

Above-mentioned enumerate is equipped with bonding agent group using 22 side of the second liquid crystal layer of the second liquid crystal layer 20 in subsidiary substrate layer The second liquid crystal layer 25 ((c) of Fig. 1) of the subsidiary composition layer of nitride layer 32a is closed, and on the upper layer adhesive composite layer 32a It is illustrated in case where the first liquid crystal layer 12 in first liquid crystal layer 10 of folded subsidiary substrate layer, still, as long as can It obtains the first liquid crystal layer 12 that will be attached in the first liquid crystal layer 10 of substrate layer and is attached in the second liquid crystal layer 20 of substrate layer The liquid crystal layer laminates 40 for the subsidiary substrate layer that second liquid crystal layer 22 is laminated across bonding agent cured layer 32 be (Fig. 2's (a)), then it's not limited to that.For example, can be arranged in 12 side of the first liquid crystal layer of the first liquid crystal layer 10 of subsidiary substrate layer viscous Agent composition layer 32a is met, and the second liquid for being attached to the second liquid crystal layer 20 of substrate layer is laminated on adhesive composite layer 32a After crystal layer 22, adhesive composite layer 32a is solidified to form bonding agent cured layer 32.Alternatively, it is also possible in subsidiary substrate layer The first liquid crystal layer 10 12 side of the first liquid crystal layer and subsidiary substrate layer the second liquid crystal layer 20 22 side of the second liquid crystal layer this two Side forms adhesive composite layer 32a.

(variation 2 of embodiment 1)

First adhesive layer 50 of subsidiary peeling layer shown in above-mentioned (a) enumerated using Fig. 3 is arranged on optical film 60 First adhesive layer 31 and the optical film 61 ((c) of Fig. 3) for obtaining subsidiary adhesive layer, and this is attached to the optical film 61 of adhesive layer In the first adhesive layer 31 be bonded with the first liquid crystal layer 12 in liquid crystal layer laminates 41 in case where be illustrated, But it as long as can be in exposed surface (the first liquid crystal layer for the liquid crystal layer laminates 41 exposed by removing first base material layer 11 12) across the first adhesive layer 31 and laminated optical film 60, then it's not limited to that.For example, can use attached shown in (a) of Fig. 3 The first adhesive layer 50 with peeling layer obtains viscous equipped with first in the exposed surface (the first liquid crystal layer 12) of liquid crystal layer laminates 41 Close the liquid crystal layer laminates of subsidiary first adhesive layer of layer 31, and the laminated optical film 60 on first adhesive layer 31.At this In the case of, as long as the liquid crystal layer laminates of subsidiary first adhesive layer successively have the first adhesive layer 31, the first liquid crystal layer 12, bonding Agent cured layer 32, the second liquid crystal layer 22 and the second substrate layer 21, can be in the first adhesive layer 31 and the first liquid crystal layer 12 There is the first peeling layer 51 on the face of opposite side.

(variation 3 of embodiment 1)

The liquid crystal layer laminates 40 of subsidiary substrate layer shown in above-mentioned (a) enumerated from Fig. 2 remove first base material layer 11 And it does not remove the second substrate layer 21 and obtains liquid crystal layer laminates 41 shown in (b) of Fig. 2, and by optical film 60 and liquid crystal layer Laminated body 41 across the first adhesive layer 31 be laminated after remove the second substrate layer 21 again in case where be illustrated, but simultaneously It is not limited to this.For example, can the liquid crystal layer laminates 40 of subsidiary substrate layer shown in (a) from Fig. 2 remove first base material layer 11 and second substrate layer 21 and obtain liquid crystal layer laminates, and by removing first base material layer 11 expose liquid crystal layer by layer The exposing surface side of stack across the first adhesive layer 31 and laminated optical film 60.It is removed from the liquid crystal layer laminates 40 of subsidiary substrate layer It is solid that liquid crystal layer laminates obtained from first base material layer 11 and the second substrate layer 21 are sequentially laminated with the first liquid crystal layer 12, bonding agent Change layer 32 and the second liquid crystal layer 22.

[embodiment 2 (manufacturing method of the optical laminate of subsidiary adhesive layer)]

It (a) of Fig. 5 and (b) is the manufacturing process for schematically showing the optical laminate of subsidiary adhesive layer of present embodiment An example schematic sectional view.In figure, W indicates width direction.As shown in (b) of Fig. 5, the subsidiary bonding of present embodiment is utilized The manufacturing method of the optical laminate 80 of layer and the optical laminate 80 of subsidiary adhesive layer manufactured be sequentially laminated with optical film 60, First adhesive layer 31, the first liquid crystal layer 12, bonding agent cured layer 32, the second liquid crystal layer 22 and the second adhesive layer 33.It can also be The side opposite with the second liquid crystal layer 22 of second adhesive layer 33 has the second peeling layer 53.

The manufacturing method of the optical laminate 80 of subsidiary adhesive layer includes: to prepare optical laminate 70 shown in (b) of Fig. 4 Process；And prepare the subsidiary peeling layer for being laminated with the second peeling layer 53 and the second adhesive layer 33 as shown in (a) of Fig. 5 The second adhesive layer 58 process.The process for preparing the second adhesive layer 58 of subsidiary peeling layer may include in the second peeling layer 53 Upper coating adhesive composition is simultaneously allowed to process that is dry etc. and forming the second adhesive layer 33.Alternatively, it is also possible to as needed The process with the face of 53 opposite side of the second peeling layer that the second adhesive layer 33 is covered with other peeling layers is set.

By the second adhesive layer 33 in the second adhesive layer 58 of the subsidiary peeling layer prepared and pass through the second substrate of removing Layer 21 and the second liquid crystal layer 22 (the second exposed surface) in the optical laminate 70 that exposes is bonded, obtain subsidiary adhesive layer Optical laminate 80 ((b) of Fig. 5).The optical laminate 80 of subsidiary adhesive layer resulting at this time has the second peeling layer 53.? In the case where optical laminate 80 and optical display element stacking that this is attached to adhesive layer, the second peeling layer 53 can be removed, And the second adhesive layer 33 is bonded with optical display element and image display panel is made.

The optical laminate 80 of subsidiary adhesive layer the second adhesive layer 33 can be fitted in optical display element come using.? In the manufacturing method of the optical laminate 80 of above-mentioned subsidiary adhesive layer, the inhibition illustrated in embodiment previous is used The optical laminate 70 of inverse curling, it can thus be assumed that be able to suppress the second adhesive layer of the optical laminate 80 of subsidiary adhesive layer 33 sides are curled into concave so-called inverse curling.As a result, the optical laminate 80 and optical display element that will be attached to adhesive layer into It when row fitting, can inhibit to be mixed into bubble between optical laminate and optical display element, generate and be bonded the bad feelings such as make mistakes Condition.

It is explained, the optics stacking used in the present embodiment in order to manufacture the optical laminate of subsidiary adhesive layer The equal membranoid substances of second adhesive layer 58 of body 70 or subsidiary peeling layer are preferably the membranoid substance of strip, preferably on one side by them continuously Transport carries out each process on one side.Width direction W is the direction orthogonal with the length direction of membranoid substance.

[embodiment 3 (manufacturing method of the optical laminate of subsidiary adhesive layer)]

(a) of Fig. 6~(d) is the manufacturing process for schematically showing the optical laminate of subsidiary adhesive layer of present embodiment An example schematic sectional view.In figure, W indicates width direction.Utilize the optical laminate of the subsidiary adhesive layer of present embodiment Manufacturing method and the optical laminate 81 of subsidiary adhesive layer manufactured and the subsidiary bonding illustrated in embodiment previous The optical laminate 80 ((b) of Fig. 5) of layer is identical, and the bonding of optical film 60, first is sequentially laminated with as shown in (d) of Fig. 6 The 31, first liquid crystal layer 12 of layer, bonding agent cured layer 32, the second liquid crystal layer 22 and the second adhesive layer 33.It can also be in the second bonding The side opposite with the second liquid crystal layer 22 of layer 33 has the second peeling layer 53.

In the manufacturing method of the optical laminate 81 of subsidiary adhesive layer, with the manufacturer illustrated in previous embodiment Method gets similarly the liquid crystal layer laminates 40 of subsidiary substrate layer shown in (a) of Fig. 2, and prepares subsidiary shown in (a) of Fig. 5 Second adhesive layer 58 of peeling layer.About the process for the liquid crystal layer laminates 40 for obtaining subsidiary substrate layer, such as implement previous (a) of (a)~(e) and Fig. 2 based on Fig. 1 in mode illustrate like that, about the second adhesive layer 58 for preparing subsidiary peeling layer Process, as in embodiment previous (a) based on Fig. 5 illustrate, therefore omit its description.

Then, the liquid crystal layer laminates 40 of subsidiary substrate layer shown in (a) from Fig. 2 are removed the second substrate layer 21 and are not shelled Liquid crystal layer laminates 43 ((a) of Fig. 6) is obtained from first base material layer 11.As shown in (a) of Fig. 6, liquid crystal layer laminates 43 according to It is secondary to be laminated with first base material layer 11, the first liquid crystal layer 12, bonding agent cured layer 32 and the second liquid crystal layer 22.Removing second will be passed through The second of substrate layer 21 and the second liquid crystal layer 22 (the second exposed surface) and subsidiary peeling layer in the liquid crystal layer laminates 43 of exposing The second adhesive layer 33 in adhesive layer 58 is bonded, obtain subsidiary second adhesive layer liquid crystal layer laminates 45 (Fig. 6's (b)).As shown in (b) of Fig. 6, the liquid crystal layer laminates 45 of subsidiary second adhesive layer are sequentially laminated with first base material layer 11, first Liquid crystal layer 12, bonding agent cured layer 32, the second liquid crystal layer 22, the second adhesive layer 33 and the second peeling layer 53.

Next, preparing the optical film 61 of subsidiary adhesive layer shown in (c) of Fig. 3.About the light for obtaining being attached to adhesive layer The process for learning film 61, as in embodiment previous (a) based on Fig. 3~(c) illustrate, therefore omission saying to it It is bright.Later, first base material layer 11 ((c) of Fig. 6) is removed from the liquid crystal layer laminates 45 of subsidiary second adhesive layer, and stripping will be passed through First in the optical film 61 of the first liquid crystal layer 12 (the first exposed surface) and subsidiary adhesive layer that expose from first base material layer 11 Adhesive layer 31 is bonded, and the optical laminate 81 ((d) of Fig. 6) of subsidiary adhesive layer is obtained.

In the manufacturing method of the optical laminate 81 of above-mentioned subsidiary adhesive layer, by the first liquid crystal layer 12 and the second liquid crystal layer 22 are laminated across bonding agent cured layer 32 and obtain liquid crystal layer laminates 43, then stacking second is viscous on the second liquid crystal layer 22 It closes layer 33 and obtains the liquid crystal layer laminates 45 of subsidiary second adhesive layer.And it is believed that: due to being attached to the second adhesive layer from this Liquid crystal layer laminates 45 remove first base material layer 11, and be laminated in optical film 61 across the first adhesive layer, therefore, based on The reasons why illustrating in embodiment previous same reason is able to suppress the optical laminate 81 of resulting subsidiary adhesive layer Inverse curling.Thereby, it is possible to inhibit when the optical laminate 81 for being attached to adhesive layer is fitted in optical display element in optics It is mixed into bubble between laminated body and optical display element, fold occurs, generates a problem that being bonded fault.

It is explained, the subsidiary substrate used in the present embodiment in order to manufacture the optical laminate of subsidiary adhesive layer First liquid crystal layer 10 of layer, the second liquid crystal layer 20 of subsidiary substrate layer, the first adhesive layer 50 of subsidiary peeling layer, subsidiary peeling layer The second adhesive layer 58, optical film 60, subsidiary adhesive layer the membranoid substances such as optical film 61 be both preferably the membranoid substance of strip, preferably Each process is carried out while continuously transporting them.Width direction W is the direction orthogonal with the length direction of membranoid substance.

(variation 1 of embodiment 3)

It is attached to the first adhesive layer 50 of peeling layer shown in above-mentioned (a) enumerated using Fig. 3 and obtains in optical film 60 It is equipped with the optical film 61 of the subsidiary adhesive layer of the first adhesive layer 31, and this is attached to first in the optical film 61 of adhesive layer Adhesive layer 31 is illustrated in case where being bonded with the first liquid crystal layer 12 of liquid crystal layer laminates 41, still, as long as It can be in the first exposed surface of the liquid crystal layer laminates 45 of subsidiary second adhesive layer exposed by removing first base material layer 11 (the first liquid crystal layer 12) across 31 laminated optical film 60 of the first adhesive layer, then it's not limited to that.It is, for example, possible to use Fig. 3's (a) liquid crystal layer of subsidiary second adhesive layer of the first adhesive layer 50 of subsidiary peeling layer shown in after removing first base material layer 11 First adhesive layer 31 is set in the first exposed surface (the first liquid crystal layer 12) of laminated body 45, and on 31 upper layer of the first adhesive layer Folded optical film 60.

(variation 2 of embodiment 3)

The liquid crystal layer laminates 40 of subsidiary substrate layer shown in above-mentioned (a) enumerated from Fig. 2 remove the second substrate layer 21 And do not remove first base material layer 11 and obtain liquid crystal layer laminates 43 shown in (a) of Fig. 6, and by liquid crystal layer laminates 43 with The case where the second adhesive layer 33 in second adhesive layer 58 of subsidiary peeling layer removes first base material layer 11 after being laminated again be Example is illustrated, and but not limited to this.For example, can subsidiary substrate layer shown in (a) from Fig. 2 liquid crystal layer laminates 40 removing first base material layers 11 and the second substrate layer 21 and obtain liquid crystal layer laminates, and by the second of the liquid crystal layer laminates Second adhesive layer 58 of liquid crystal layer side and subsidiary peeling layer, which is laminated, obtains the liquid crystal layer laminates of subsidiary second adhesive layer Afterwards, optics is laminated across the first adhesive layer 31 in 12 side of the first liquid crystal layer of the liquid crystal layer laminates of subsidiary second adhesive layer Film 60.In this case, liquid crystal layer laminates are sequentially laminated with the first liquid crystal layer 12, bonding agent cured layer 32 and the second liquid crystal layer 22, the liquid crystal layer laminates of subsidiary second adhesive layer are sequentially laminated with the first liquid crystal layer 12, bonding agent cured layer 32, the second liquid crystal The 22, second adhesive layer 33 of layer and the second peeling layer 53.

More than, embodiments of the present invention and its variation are illustrated, still, the present invention is not limited to these Embodiment and its variation, for example, it is also possible to by implementing again after the combination of each process of above embodiment and its variation.With Under, general each process in whole embodiment and its variation is described in detail.

(optical film)

Optical film can for polarizing film, polarizing film at least single side formed matcoveredn polarization plates, in polarization plates At least single side is laminated with the polarization plates of the subsidiary protective film of protective film, reflectance coating, Semitransmissive reflectance coating, brightness enhancement film, optics and mends Repay film, film with anti-dazzle function etc..Optical film can be 1 layer of structure, or the stacking light of 2 layers or more of multilayered structure Learn film.In the present specification, " polarizing film " refers to: with making to make when unpolarized light incidence have the vibration orthogonal with absorption axiss The layer of dynamic this property of the linear polarization light transmission in face.

(polarizing film)

It, can be using arbitrary appropriate polarizing film as polarizing film.In the present specification, " polarizing film " refers to: having Make to make the straight line with this property of the linear polarization light transmission of the vibration plane orthogonal with absorption axiss inclined when unpolarized light incidence Shake piece.For example, the resin film for forming polarizing film can be the resin film of single layer, or two layers or more of stacked film.Polarization Piece can be so that dichroism pigment is oriented in polymerizable liquid crystal compound, and make what polymerizable liquid crystal compound was polymerized to consolidate Change film.

It as the concrete example for the polarizing film being made of the resin film of single layer, can enumerate: (sometimes also simple below to polyvinyl alcohol Referred to as " PVA ") hydrophilies such as mesentery, part formalizing PVA mesentery, the partly-hydrolysed film of vinyl-vinyl acetate copolymer system Polymeric membrane implements polarizing film obtained by dyeing processing and stretch processing based on the dichroic substances such as iodine or dichroic dye； Polyenoid system alignment films such as the dehydration treatment of PVA or the dehydrochlorinated products of polyvinyl chloride etc..From the side for keeping optical characteristics excellent It sets out, it is preferable to use by PVA mesentery iodine staining and polarizing film obtained from being uniaxially stretched in face.

Polyvinyl alcohol resin can be manufactured by the way that polyvinyl acetate system resin to be saponified.In addition to vinyl acetate Except homopolymer, that is, polyvinyl acetate of ester, polyvinyl acetate system resin may be vinyl acetate and can be with acetic acid The copolymer of the other monomers of vinyl acetate copolymerization.As can be with the other monomers of vinyl acetate copolymerization, it can be mentioned, for example not Saturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class, acrylic amide with ammonium etc..

The saponification degree of polyvinyl alcohol resin is usually 85~100 moles of % or so, preferably 98 moles of % or more.Poly- second Enol system resin can be modified, such as also can be used by the modified polyvinyl formal of aldehydes or polyvinyl alcohol contracting second Aldehyde etc..The degree of polymerization of polyvinyl alcohol resin is usually 1,000~10,000 or so, preferably 1,500~5,000 or so.

Film made of such polyvinyl alcohol resin is used as the former material film of polarizing film.The film of polyvinyl alcohol resin Method is not particularly limited, and can be filmed with well known method.The film thickness of polyvinyl alcohol resin former material film is such as 10 ~100 μm or so, preferably 10~60 μm or so, more preferably 15~30 μm or so.

As the manufacturing method of other polarizing films, the method including following process can be enumerated: firstly, prepare base material film, The solution of the resins such as pva coating system resin on base material film carries out the drying etc. for removing solvent, forms tree on base material film Rouge layer.It is explained, prime coat can be pre-formed on the face of base material film to form resin layer.It, can be with as base material film Use the resin films such as PET.As the material of prime coat, can enumerate tree made of the crosslinking of hydrophilic resin used in polarizing film Rouge etc..

Then, base material film and resin layer are carried out uniaxial drawing later by the moisture equal solvent amount of adjustment resin layer as needed It stretches, then, the dichroism pigments such as resin layer iodine is dyed, make dichroism pigment gas absorption quantity in resin layer.Then, root According to needing to there is the resin layer of dichroism pigment to be handled with boric acid aqueous solution gas absorption quantity, then carry out washing away boric acid aqueous solution Cleaning process.Thus manufacture gas absorption quantity has the film of the resin layer of dichroism pigment, i.e. polarizing film.It can be adopted in each process With well known method.

Base material film and being uniaxially stretched for resin layer can carry out before dyeing, can also carry out in dyeing, can be with It carries out, can also be uniaxially stretched respectively in above multiple stages in boric acid processing after dyeing.Base material film and resin Layer can be uniaxially stretched along the direction MD (film carriage direction), in such a case it is possible to the different roller of peripheral speed it Between be uniaxially stretched, hot-rolling also can be used and be uniaxially stretched.In addition, base material film and resin layer can also be along the directions TD (direction vertical with film carriage direction) is uniaxially stretched, in such a case it is possible to use so-called tenter frame process.In addition, Base material film and stretching for resin layer can be the dry type stretching stretched in an atmosphere, or make resin using solvent The wet tensile stretched in the state of layer swelling.In order to embody the performance of polarizing film, stretching ratio is 4 times or more, preferably It is 5 times or more, particularly preferably 5.5 times or more.There is no particular restriction for the upper limit of stretching ratio, but from inhibit fracture etc. sight Point sets out, and preferably 8 times or less.

It can be obtained by the peeling base film after the aftermentioned protective layer of stacking using the polarizing film of above method production.Root According to this method, the further filming of polarizing film may be implemented.

As making dichroism pigment be oriented in polymerizable liquid crystal compound and polymerizable liquid crystal compound made to be polymerized Cured film, that is, polarizing film manufacturing method, can enumerate following methods: coating is comprising polymerizable liquid crystal compound on base material film And the polarizing film of dichroism pigment forms and uses composition, and polymerizable liquid crystal compound is carried out under conditions of keeping mesomorphic state Polymerization, and be allowed to be solidified to form polarizing film.The polarizing film obtained in this way is in the state being layered on base material film, can be used The polarizing film of subsidiary base material film is as optical film.Alternatively, can also be by the polarizing film of subsidiary base material film across the first adhesive layer 31 After being laminated in after liquid crystal layer laminates or being laminated in the first adhesive layer 50 of subsidiary peeling layer, peeling base film and use polarization Piece is as optical film.

Absorbance as dichroism pigment, absorbance and short-axis direction that the long axis direction of molecule can be used has not Connatural pigment preferably for example has the pigment for absorbing very big wavelength (λ max) in the range of 300~700nm.As in this way Dichroism pigment, it can be mentioned, for example acridine pigment, oxazines pigment, anthocyanidin, naphthalene pigment, azopigment, anthraquinone pigment etc., Wherein, preferred azopigment.As azopigment, monoazo pigment, bisazo pigment, trisazo- pigment, four azos can be enumerated Pigment, talan azopigment (stilbene azo dye) etc., more preferable bisazo pigment, trisazo- pigment.

Polarizing film formation may include the polymerization initiators such as solvent, Photoepolymerizationinitiater initiater, photosensitizer, polymerization inhibitor with composition Agent etc..The polymerizable liquid crystal compound contained in polarizing film formation composition, dichroism pigment, solvent, polymerization cause Agent, photosensitizer, polymerization inhibitor etc. can use well known substance, can be used such as Japanese Unexamined Patent Publication 2017-102479 bulletin, The substance illustrated in Japanese Unexamined Patent Publication 2017-83843 bulletin.In addition, polymerizable liquid crystal compound can be used with as in order to Obtain aftermentioned first liquid crystal layer and the second liquid crystal layer and the polymerizable liquid crystal compound that uses illustrated by compound it is same Polymerizable liquid crystal compound.About the method for using polarizing film formation composition and forming polarizing film, can also use above-mentioned Method illustrated by bulletin.

The thickness of polarizing film is preferably 2 μm or more, and more preferably 3 μm or more.In addition, above-mentioned polarizing film with a thickness of 25 μm Hereinafter, preferably 15 μm hereinafter, more preferably 13 μm hereinafter, further preferably 7 μm or less.It is explained, the above-mentioned upper limit Value and lower limit value can be combined arbitrarily.The thickness of polarizing film is thinner, then rigidity is smaller, easier by the first liquid crystal layer or the Therefore the influence of the shrinkage stress of two liquid crystal layers in the case where the polarizing film for using thickness small is as optical film, can be suitble to Ground uses the manufacturing method of the optical laminate of above embodiment and the manufacturing method of the optical laminate of subsidiary adhesive layer.

(polarization plates)

Polarization can be made across well known adhesive layer or bonding layer stackup protective layer in its single or double in polarizing film Plate.The polarization plates are so-called linear polarization plate.As the protective layer for the single or double that can be laminated in polarizing film, can make With for example by excellent thermoplastic resins such as the transparency, mechanical strength, thermal stability, moisture insulating, isotropism, draftabilitys The film of formation.It as the concrete example of such thermoplastic resin, can enumerate: the celluosic resins such as tri acetyl cellulose；Poly- pair The polyester resin such as ethylene terephthalate, polyethylene naphthalate；Polyethersulfone resin；Polysulfone resin；Polycarbonate resin Rouge；The polyamides such as nylon or aromatic polyamide；Polyimide resin；Polyethylene, polypropylene, ethylene-propylene copolymer Equal polyolefin resins；Cyclic polyolefin resin (also referred to as norbornene resin) with ring system and norbornene structure；(first Base) acrylic resin；Polyarylate resin；Polystyrene resin；Polyvinyl alcohol resin；And their mixture.It will protect Sheath be laminated in polarizing film it is two-sided in the case where, the resin composition of two protective layers may be the same or different.Above-mentioned reality Even if applying the manufacturing method of the manufacturing method of the optical laminate of mode and the optical laminate of subsidiary adhesive layer from slimming From the perspective of and using only can also press down in the case where the polarization plates of protective layer have been laminated as optical film in the single side of polarizing film The inverse curling of system, therefore be suitable.Be explained, in the present specification, " (methyl) acrylic acid " refer to can for acrylic acid or Any one of methacrylic acid." (methyl) " of (methyl) acrylate etc. is also same meaning.

In order to improve with the adaptation of the polarizing film comprising PVA system resin and dichroic substance, can be to by thermoplastic resin The film that rouge is formed implements surface treatment (such as sided corona treatment etc.), can also form the thin layers such as prime coat (also referred to as priming coat).

Moisture permeability of the protective layer at 40 DEG C of temperature, humidity 90%RH is preferably 1~1500g/m²·24hr.If protective layer Moisture permeability be more than 1500g/m²R for 24 hours is then easy to happen the curling by the time of polarization plates in hot and humid environment sometimes Variation.The moisture permeability of protective layer is lower, then is more easy to get the effect for being able to suppress the ongoing change of curling of polarization plates.Protection Moisture permeability of the layer at 40 DEG C of temperature, humidity 90%RH is more preferably 1000g/m²R is hereinafter, further preferably 100g/ for 24 hours m²R is hereinafter, be still more preferably 10g/m for 24 hours²R or less for 24 hours.Moisture permeability can be surveyed according to JIS Z 0208:1976 It is fixed.

Be explained, by protective layer be laminated in polarizing film it is two-sided in the case where, preferably make in optical laminate or subsidiary The moisture permeability of the outside protective layer that side is laminated of can the see when optical laminate of adhesive layer fits in optical display element with The moisture permeability for the inside protective layer that first adhesive layer side is laminated is mutually the same, or makes the moisture permeability of outside protective layer less than interior Side protective layer.When being especially applied with moisture in the preservation of polarization plates as a result, can keep FLAT (flat) shape or By making inside protective layer swelling and become state from polarization plates to just crimp side that crimp, be easily formed optical laminate or The state that the optical laminate of subsidiary adhesive layer is crimped to just crimp side.In addition, the moisture permeability of outside protective layer is more preferably 10g/m²R or less for 24 hours.Even only also can control volume in the polarization plates of the single side stacking matcoveredn of polarizing film as a result, Song can also inhibit by the time after the optical laminate of optical laminate or subsidiary adhesive layer fits in optical display element Change in size (deformation).

In turn, in order to further reduce the first liquid crystal layer or the second liquid crystal layer shrinkage stress influence and inhibit in light The just crimp generated in the optical laminate of laminated body or subsidiary adhesive layer is learned, preferably in the polarization plates used as optical film Improve the rigidity for being laminated in the protective layer of polarizing film.Here, rigidity is under the room temperature (23 DEG C) of film used in protective layer The form of the product that tensile modulus of elasticity (hereinafter sometimes referred to as " 23 DEG C of elasticity modulus ") is multiplied with film thickness defines.For example, using Using tri acetyl cellulose as 23 DEG C of elasticity modulus of the protective layer of the cellulose-based polymer of representative be preferably 3000~ The range of 5000MPa has used 23 DEG C of bullets using polymethyl methacrylate as the protective layer of the acrylic acid series polymeric compounds of representative Property modulus is preferably the range of 2000~4000MPa, has used the cyclic olefine polymer as with norbornene structure Protective layer 23 DEG C of elasticity modulus be preferably 2000~4000MPa range.On the outside in protective layer, from above-mentioned moisture permeability and From the perspective of rigidity, it is suitble to use acrylic acid series polymeric compounds or polyolefin polymer, it is particularly preferably poly- using cyclic olefine Close object.

Protective layer can be for example thermoplastic resin obtained by the above-mentioned thermoplastic resin of stretching, or be not stretched Thermoplastic resin (hereinafter sometimes referred to as " non-stretched resin ").As stretch processing, it can enumerate and be stretched uniaxially or biaxially.

Draw direction in stretch processing can be the length direction of non-stretched resin, or orthogonal to the longitudinal direction Direction, can also be direction with length direction oblique.In the case where being uniaxially stretched, as long as along appointing in these directions One direction stretches non-stretched resin.Biaxial stretch-formed can be to be drawn simultaneously along 2 draw directions in these directions It is biaxial stretch-formed while stretching, or to be drawn after being stretched along defined direction further along the gradually twin shaft that other directions stretch It stretches.

Stretch processing for example can be by using the niproll of 2 pairs or more of the peripheral speed for increasing downstream side along length Degree direction stretch or clamp the two side ends of non-stretched resin with fixture and along direction orthogonal to the longitudinal direction Stretch etc. come carry out.At this point, by adjusting the thickness or adjustment stretching ratio of the thermoplastic resin after stretching, so as to control Desired phase difference value and wavelength dispersion.

The thermoplastic resin stretched preferably satisfies following formula.

(1)80nm≤Re(590)≤180nm

(2) 0.5 < Rth (590)/Re (590)≤0.8

(3) 0.85≤Re (450)/Re (550) < 1.00

In formula, Re (590), Re (450), Re (550) are illustrated respectively in the face under measurement wavelength 590nm, 450nm, 550nm Interior phase difference value, Rth (590) indicate the thickness direction phase difference value in the case where measuring wavelength 590nm.In these faces phase difference value and Thickness direction phase difference value refers to the value measured in the environment of 23 DEG C of temperature, relative humidity 55%.

The refractive index of slow-axis direction is set as nx, by the (side orthogonal with slow-axis direction in face of fast axis direction in face in by face To) refractive index be set as ny, the refractive index of thickness direction be set as to nz, the thickness of the thermoplastic resin stretched is set as d when, Phase difference value Re, thickness direction phase difference value Rth are in face with following formula (S1), formula (S2) Lai Dingyi.

(S1) Re=(nx-ny) × d

(S2) Rth=[{ (nx+ny)/2 }-nz] × d

Above-mentioned outside protective layer preferably meets the thermoplastic resin after above-mentioned formula (1)~(3) are stretched.In addition, Above-mentioned outside protective layer preferably fits in polarization in a manner of having slow axis on the direction of the absorption axiss oblique with polarizing film Piece, preferably with for example make outside protective layer slow axis angle relative to the absorption axiss of polarizing film reach 45 ± 10 ° or 135 ± Outside protective layer is bonded by 10 ° of mode with polarizing film.By making the angle above range of slow axis, to make fast axle side Difference is generated between the phase of light in the phase and slow-axis direction of upward light, therefore, if by the optical layer of present embodiment Stack is applied to optical display element, then the light being emitted by optical laminate can be made to become circularly polarized light.Therefore, it incite somebody to action this It is watched even if the optical laminate of embodiment is applied to display device obtained by optical display element through polarized sunglasses Visibility is also excellent in the case where showing image etc..

The thickness of protective layer is preferably 3 μm or more, and more preferably 5 μm or more.In addition, the thickness of protective layer is preferably 50 μm Hereinafter, more preferably 30 μm or less.It is explained, above-mentioned upper limit value and lower limit value can be combined arbitrarily.The thickness of polarization plates Degree is thinner, then rigidity is smaller, and the easier shrinkage stress by the first liquid crystal layer or the second liquid crystal layer is influenced, and therefore, is made The polarization plates for using thickness small, can be compatibly using the system of the optical laminate of above embodiment as in the case where optical film Make the manufacturing method of the optical laminate of method and subsidiary adhesive layer.

Protective layer can have surface-treated layer with the surface of polarizing film opposite side, can have such as hard conating, Anti-reflection layer, antiblocking layers, anti-dazzle photosphere, diffusion layer etc..Surface-treated layer can be the other layers being layered on protective layer, The layer that can be formed to implement surface treatment to protective layer.

Hard conating is the layer for the purpose of preventing the damage on polarization plates surface etc., such as can use the surface to protective layer The excellent cured film such as the additional hardness obtained by the ultraviolet curing resin of acrylic acid series, silicone-based etc. or sliding properties Mode etc. formed.Anti-reflection layer is the layer for the purpose of the reflection for preventing the ambient light on polarization plates surface, can be passed through It is realized based on the formation of previous antireflection film etc..In addition, antiblocking layers are to prevent the layer with adjoining course for the purpose of closely sealed.

Anti-dazzle photosphere is the view to prevent from hindering the transmitted light of polarization plates because reflecting ambient light on the surface in polarization plates Feel the layer for the purpose of identification etc., for example, can by the way of roughened by based on sandblasting in the way of or in the way of embossing processing, it is saturating The modes such as the fit system of bright particle assign minute concave-convex structure to the surface of protective layer to be formed.As in order to protective layer Surface assigns minute concave-convex structure and the transparent particle that uses, it can be mentioned, for example: the titanium dioxide that average grain diameter is 0.5~50 μm It is micro- that silicon, aluminium oxide, titanium oxide, zirconium oxide, tin oxide, indium oxide, cadmium oxide, antimony oxide etc., which can have the inorganic of electric conductivity, Grain；The particles such as the organic systems particle such as crosslinking or uncrosslinked polymer.The content of transparent particle forms fine recessed relative to composition 100 mass parts of resin of the layer of male structure and usually 2~50 mass parts, preferably 5~25 mass parts.Anti-dazzle photosphere can be simultaneous The diffusion layer (visual angle expanded functionality etc.) for acting on the transmitted light of diffusion polarization plates and expanding visual angle etc..

In the case where surface-treated layer is other layers on the protective layer for being layered in polarization plates, the thickness of surface-treated layer Preferably 0.5 μm or more, more preferably 1 μm or more.Additionally, it is preferred that for 10 μm hereinafter, more preferably 8 μm or less.If thickness is not Then there is the tendency for being difficult to be effectively prevented polarization plates surface damage in 0.5 μm of foot.In addition, if thickness is more than 10 μm, sometimes because Cure shrinkage becomes larger etc. and becomes difficult to inhibit the inverse curling of polarization plates.

The manufacturing method of the optical laminate of the optical laminate of above embodiment and subsidiary adhesive layer is suitable for polarizing Plate with a thickness of 2 μm or more and 300 μm or less of situation.The thickness of polarization plates can be 10 μm or more, furthermore it is possible to be 150 μ M or less, or 120 μm hereinafter, can also be 80 μm or less.

For polarization plates, shelling from the polarization plates of subsidiary protective film for the method measurement recorded in aftermentioned embodiment is utilized Actual measurement MD crimp values and actual measurement TD crimp values from the polarization plates after protective film are separately preferably -40mm or more and 40mm Range below, more preferably -30mm or more and 35mm range below, further preferably -20mm or more and 30mm or less Range.If above-mentioned actual measurement MD crimp values and actual measurement TD crimp values are other than above-mentioned range, it is easy to form that there are polarization plates The tendency of tubular, and there is the tendency for being difficult to obtain curly form.In addition, if the actual measurement of the polarization plates of aftermentioned subsidiary protective film MD crimp values and actual measurement TD crimp values and polarization plates actual measurement MD crimp values and actual measurement TD crimp values be away from each other, then protective film with It generates and floats between polarization plates, or the tunneling effect (tunneling) for generating gap between protective film and polarization plates occurs, It is not preferable.

(polarization plates of subsidiary protective film)

Usually protective film is laminated in its single side in polarization plates, it is possible thereby to which the polarization plates of subsidiary protective film are made.Protective film packet Resin film containing protective film and the protective film adhesive layer being laminated thereon.The thickness of protective film can be such as 30~200 μm, Preferably 40~150 μm, more preferably 50~120 μm.

As constitute protective film resin film resin, it can be mentioned, for example: as polyethylene-based resin, polypropylene-based resin that The polyolefin-based resins of sample；Cyclic polyolefin hydrocarbon system resin；Such as polyethylene terephthalate or polyethylene naphthalate Such polyester based resin；Polycarbonate-based resin；(methyl) acrylic resin etc..Wherein, preferred poly terephthalic acid second The polyester based resins such as diol ester.Protective film resin film can be 1 layer of structure, it is possible to have 2 layers or more of multilayered structure.

As the adhesive for constituting protective film adhesive layer, can be used same as the adhesive for constituting aftermentioned adhesive layer Adhesive.In addition, pass through the coating adhesive composition in protective film resin film surface and form adhesive layer ands being allowed to dry etc., So as to obtain protective film.In order to improve adaptation, the adhesive coated face to protective film resin film can according to need Implement surface treatment (such as sided corona treatment etc.), the thin layers such as prime coat (also referred to as priming coat) can also be formed.Alternatively, it is also possible to Have and carried out with protective film with the surface of resin film side opposite side for covering protection film adhesive layer as needed The peeling layer of protection.The peeling layer can be removed the opportune moment when being bonded with polarization plates.

In the production process of the polarization plates for the subsidiary protective film that protective film is fitted in polarization plates, by assigning tension difference Or difference, just crimp can also be assigned to the length direction of the polarization plates of subsidiary protective film.Therefore, in above-mentioned embodiment party In the manufacturing method of the optical laminate of the manufacturing method of the optical laminate of formula and subsidiary adhesive layer, subsidiary protective film is being used Polarization plates as optical film in the case where, by the production process of the polarization plates of subsidiary protective film to subsidiary protective film Polarization plates assign just crimp, so as to expect more easily to inhibit the inverse of the optical laminate of optical laminate or subsidiary adhesive layer Curling.

For the polarization plates of subsidiary protective film, the subsidiary protective film for the method measurement recorded in aftermentioned embodiment is utilized Polarization plates actual measurement MD crimp values and actual measurement TD crimp values be separately preferably -40mm or more and 40mm model below It encloses, more preferably -30mm or more and 35mm range below, further preferably -20mm or more and 30mm range below.If Above-mentioned actual measurement MD crimp values and actual measurement TD crimp values are other than above-mentioned range, then the polarization plates that there is subsidiary protective film are easy shape At the tendency of tubular, and there is the tendency for being difficult to obtain curly form.Additionally, there are add by the polarization plates for being attached to protective film Work is difficult to suitably to be kept with attracting mechanism of laminating apparatus etc. at predetermined size and when being bonded with optical display element, The tendency such as bubble or generation fold is mixed into when fitting, it is not preferable.

The thickness of the polarization plates of subsidiary protective film is thinner, then rigidity is smaller, easier by the first liquid crystal layer or the second liquid Therefore the influence of the shrinkage stress of crystal layer in the case where the polarization plates for using thickness small are as optical film, can compatibly make With the manufacturing method of the optical laminate of the manufacturing method and subsidiary adhesive layer of the optical laminate of above embodiment.Above-mentioned In the case that the optical film 60 of embodiment is the polarization plates of subsidiary protective film, the optical laminate of above embodiment and subsidiary The manufacturing method of the optical laminate of adhesive layer be suitable for the polarization plates of subsidiary protective film with a thickness of 32 μm or more and 500 μm with Under situation.The thickness of the polarization plates of subsidiary protective film can be 40 μm or more, furthermore it is possible to be 350 μm or less, or 200 μm hereinafter, can also be 150 μm or less.

(adhesive layer)

First adhesive layer and the second adhesive layer (they are referred to as " adhesive layer " sometimes below) refer to be made of adhesive Layer.In the present specification, " adhesive " is soft rubber-like, by the way that its own is pasted on the quilts such as optical film or liquid crystal layer It glues object and embodies cementability, be referred to as so-called pressure sensitive bonding agent.In addition, aftermentioned active energy ray curable adhesive The degree of cross linking or bonding force can be adjusted by irradiation energy ray.

As adhesive, the excellent adhesive of known optical transparence can be used without particular limitation, such as The adhesive with base polymers such as acrylic acid series, polyurethane series, silicone-based, polyvingl ether systems can be used.In addition, It can be active energy ray curable adhesive, heat-curing type adhesive etc..Wherein, it is appropriate that with the transparency, bonding force, The excellent acrylic resins such as releasable (being also referred to as re-workability below), weatherability, heat resistance are as basic polymer Adhesive.Adhesive layer is preferably by the bonding comprising (methyl) acrylic resin (1), crosslinking agent (2), silane compound (3) The reaction product of agent composition is formed, and also may include other compositions (4).

((methyl) acrylic resin (1))

(methyl) acrylic resin (1) contained in adhesive composition is preferably to come from shown in following formula (I) The structural unit (below also referred to as " structural unit (I) ") of (methyl) alkyl acrylate is that principal component (such as includes 50 matter Measure the structural unit of % or more) polymer (below also referred to as " (methyl) acrylate polymer ").In the present specification, " coming from " refers to: since the compounds such as (methyl) alkyl acrylate polymerize, chemical structure changes.

[changing 1]

[in formula, R¹⁰Indicate hydrogen atom or methyl, R²⁰Indicate that the alkyl of carbon atom number 1~20, abovementioned alkyl can have The hydrogen atom of any structure in straight-chain, branched or ring-type, abovementioned alkyl can be taken by the alkoxy of carbon atom number 1~10 Generation.]

As (methyl) acrylate shown in formula (I), it can be mentioned, for example: (methyl) methyl acrylate, (methyl) propylene Acetoacetic ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid Isobutyl ester, (methyl) acrylic acid n-pentyl ester, (methyl) the just own ester of acrylic acid, (methyl) Isohexyl acrylate, (methyl) acrylic acid Positive heptyl ester, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) third The positive nonyl ester of olefin(e) acid, the different nonyl ester of (methyl) acrylic acid, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) third Olefin(e) acid n-dodecane base ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) stearyl acrylate, (methyl) tert-butyl acrylate etc..As the concrete example of the alkyl acrylate containing alkoxy, (methyl) acrylic acid 2- can be enumerated Methoxy acrylate, (methyl) ethioxy methyl esters etc..Wherein, (methyl) n-butyl acrylate or (methyl) third are preferably comprised Olefin(e) acid 2- ethylhexyl particularly preferably includes (methyl) n-butyl acrylate.

(methyl) acrylate polymer may include the structure list from other monomers other than structural unit (I) Member.Structural unit from other monomers can be a kind, or two or more.It can as (methyl) acrylate polymer With comprising other monomers, the monomer with polar functional group, the monomer with aromatic group, acrylamide list can be enumerated Body.

As the monomer with polar functional group, (methyl) acrylate with polar functional group can be enumerated.As pole Property functional group, can enumerate hydroxyl, carboxyl, substituted-amino, unsubstituted amino etc..As polar functional group, epoxy group can be also enumerated Equal heterocycles etc..

The content of the structural unit from the monomer with polar functional group in (methyl) acrylate polymer is opposite In 100 mass parts of entire infrastructure unit of (methyl) acrylate polymer be preferably 20 below the mass more preferably 0.1 matter Part or more and 20 below the mass is measured, more than further preferably 0.1 mass parts and 10 below the mass, particularly preferably 0.5 More than mass parts and 10 below the mass.

As the monomer with aromatic group, can enumerate has 1 (methyl) acryloyl group and 1 or more in the molecule Aromatic rings (such as phenyl ring, naphthalene nucleus etc.), and (methyl) acrylate with phenyl, Phenoxyethyl or benzyl.

The content of the structural unit from the monomer with aromatic group in (methyl) acrylate polymer is opposite In 100 mass parts of entire infrastructure unit of (methyl) acrylate polymer be preferably 50 below the mass more preferably 4 mass Part or more and 50 below the mass, more than further preferably 4 mass parts and 25 below the mass.

As acrylamide monomer, N- (methoxy) acrylamide, N- (ethoxyl methyl) acryloyl can be enumerated Amine, N- (propoxy methyl) acrylamide, N- (butoxymethyl) acrylamide, N- (2- methyl propoxy methyl) acrylamide Deng.By the inclusion of these structural units, the exudation of the additives such as aftermentioned antistatic agent can be inhibited.

It in turn, may include from benzene second as the structural unit from other monomers other than structural unit (I) The structural unit of alkene monomer, the structural unit from vinyl monomer come from the molecule with multiple (methyl) propylene The structural unit etc. of the monomer of acyl group.

The weight average molecular weight (hereinafter also referred to as " Mw ") of (methyl) acrylic resin (1) is preferably 500,000~2,500,000. If weight average molecular weight is 500,000 or more, the durability of the adhesive layer under high temperature, high humidity environment can be improved.If Weight-average molecular Amount is for 2,500,000 hereinafter, operability when then applying the coating liquid containing adhesive composition becomes good.With weight average molecular weight (Mw) molecular weight distribution (Mw/Mn) indicated with the ratio between number-average molecular weight (hereinafter also referred to as " Mn ") is usually 2~10.? In this specification, " weight average molecular weight " and " number-average molecular weight " is the polystyrene measured using gel permeation chromatography (GPC) method Scaled value.

For (methyl) acrylic resin (1), the solution of 20 mass % of concentration is made being dissolved in ethyl acetate When, the preferred 20Pas of viscosity at 25 DEG C is hereinafter, more preferably 0.1~15Pas.(if methyl) acrylic resin (1) It is then to facilitate re-workability etc. in above range in the viscosity at 25 DEG C.Above-mentioned viscosity can use Brookfield viscosity Meter is to measure.

From the viewpoint of taking into account adhesiveness and durability, the glass transition temperature of (methyl) acrylic resin (1) Preferably -10 DEG C~-60 DEG C.It is explained, glass transition temperature can use differential scanning calorimetry (DSC) (DSC) to measure.

(methyl) acrylic resin (1) may include (methyl) acrylate polymer of more than two kinds.As such (methyl) acrylate polymer, it can be mentioned, for example: with from above-mentioned (methyl) acrylate structural unit (I) based at Point and weight average molecular weight be 50,000~300,000 range etc lower (methyl) acrylate polymer of molecular weight.

(crosslinking agent (2))

The adhesive composition for forming adhesive layer preferably comprises crosslinking agent (2).As crosslinking agent (2), can enumerate usual Crosslinking agent (such as isocyanate compound, epoxide, aziridine cpd, metal chelate compound, peroxide etc.), Especially from the viewpoints such as the working life of adhesive composition, crosslinking rate, preferably isocyanates based compound.

It, can preferably in the molecule with the compound of at least two isocyanato (- NCO) as isocyanates based compound It enumerates such as aliphatic isocyanates based compound (such as hexamethylene diisocyanate), alicyclic isocyanate system chemical combination Object (such as isophorone diisocyanate), hydrogenation benzene dimethylene diisocyanate, hydrogenated diphenyl methane diisocyanate, Aromatic isocyanate based compound (such as toluene di-isocyanate(TDI), benzene dimethylene diisocyanate, diphenyl methane two are different Cyanate, naphthalene diisocyanate, triphenylmethane triisocyanate etc.) etc..In addition, crosslinking agent (2) can be above-mentioned isocyanic acid The addition product (adduct) of ester compounds obtained based on polyol compound is [such as based on glycerol, trimethylolpropane etc. The addition product arrived], it is isocyanuric acid carboxylate, biuret form compound, more with polyether polyol, polyester polyol, acrylic compounds Carbamate prepolymer type obtained from addition reaction occurs for first alcohol, polybutadiene polyol, polyisoprene polyol etc. The derivatives such as isocyanate compound.Crosslinking agent (2) can be used alone or two or more is applied in combination.Wherein, from durability From the perspective of, preferably toluene di-isocyanate(TDI), benzene dimethylene diisocyanate, hexamethylene diisocyanate and it Polyol compound or their isocyanurate compound.

The ratio of crosslinking agent (2) can be such as 0.01~10 relative to (1) 100 mass parts of (methyl) acrylic resin Mass parts, preferably 0.1~3 mass parts, further preferably 0.1~1 mass parts.It is if above-mentioned upper limit value hereinafter, then right In improving, durability is advantageous, more than above-mentioned lower limit value, then inhibits the generation of gas, advantageous for improving re-workability.

(silane compound (3))

Adhesive composition contains silane compound (3).By contain silane compound (3), can be improved adhesive layer with The adaptation for the layer being laminated.Also silane compound of more than two kinds (3) can be used.

As silane compound (3), it can be mentioned, for example vinyltrimethoxysilane, vinyltriethoxysilane, second Alkenyl three (2- methoxy ethoxy) silane, 3- glycidoxypropyltrime,hoxysilane, three second of 3- glycidoxypropyl group Oxysilane, 3- epoxy propoxy propyl methyl dimethoxysilane, 3- glycidoxypropyl group ethyoxyl dimethylsilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3- chloropropylmethyldimethoxysilane, 3- r-chloropropyl trimethoxyl silicon Alkane, 3- methacryloxypropyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane etc..

In addition, silane compound (3) may include the oligomer from above-mentioned silane compound (3).

The content of silane compound (3) in adhesive composition is relative to (1) 100 mass of (methyl) acrylic resin Part be usually 0.01~10 mass parts, preferably 0.03~5 mass parts, more preferably 0.05~2 mass parts, further preferably 0.1~1 mass parts.If the content of silane compound (3) is 0.01 mass parts or more, be easy to improve adhesive layer and optical film or The adaptation of the adherends such as liquid crystal layer.If content below the mass, can inhibit silane compound (3) to seep from adhesive layer for 10 Out.

(other compositions (4))

Formed in the adhesive composition of adhesive layer, as other compositions (4), may include it is individually a kind of or two or more Following substance: used the antistatic agent of ionic compound etc., solvent, crosslinking catalyst, tackifying resin (tackifier), increased Mould the additives such as agent, weathering stabilizers, softening agent, dyestuff, pigment, inorganic filler, resin in addition to acrylic resin.

(active energy ray curable adhesive)

Cooperate the ultra-violet solidified compounds such as polyfunctional acrylate in adhesive composition, forms adhesive layer Afterwards irradiation ultraviolet light solidify it and be made harder adhesive layer be also it is useful, can be used active energy ray curable glue Mixture." active energy ray curable adhesive " has the irradiation by energy-rays such as ultraviolet light or electron rays and solidifies Property.Active energy ray-curing adhesive has adhesiveness before energy-ray irradiation, therefore is with energy Enough irradiations closely sealed and using energy-ray with the adherends such as optical film or liquid crystal layer be allowed to solidify adjust closing force this The adhesive of property.

Active energy ray curable adhesive generally comprises acrylic adhesive and energy-ray polymerizable compound As principal component.Cooperate crosslinking agent, also usually alternatively, it is also possible to cooperate Photoepolymerizationinitiater initiater or photosensitizer as needed Deng.

The storage modulus of adhesive layer is preferably 0.10~10.0MPa, more preferably 0.15~5.0MPa at 23 DEG C.If A problem that storage modulus at 23 DEG C is 0.10MPa or more, then is able to suppress removing when temperature change occurs, so it is excellent Choosing.In addition, if the storage modulus at 23 DEG C be 10.0MPa hereinafter, if be not easy to cause it is durable caused by the reduction of bonding force Property reduce, so it is preferred that.It is explained, the storage modulus of adhesive layer can use commercially available determination of viscoelasticity device, such as The determination of viscoelasticity device " DYNAMIC ANALYZER RDA II " of REOMETRIC corporation measures.

The thickness of adhesive layer is preferably 3 μm or more, and more preferably 5 μm or more.In addition, the thickness of adhesive layer is preferably 40 μm Hereinafter, more preferably 30 μm or less.It is explained, above-mentioned upper limit value and lower limit value can be combined arbitrarily.

(bonding agent cured layer)

Bonding agent cured layer refers to the layer by being solidified to form the curability composition in adhesive composite.As with In the adhesive composite for forming bonding agent cured layer, can enumerate as the bonding other than pressure sensitive bonding agent (adhesive) Agent, such as water system bonding agent, active energy ray-curable bonding agent.As water system bonding agent, it can be mentioned, for example make polyethylene Alcohol system resin is dissolved or dispersed in bonding agent obtained from water.As active energy ray-curable bonding agent, it can be mentioned, for example The cured curability of irradiation comprising the active energy beam by ultraviolet light, visible light, electron ray, X-ray etc Close the no-solvent type active energy ray-curable bonding agent of object.It is bonded by using no-solvent type active energy ray-curable The adaptation of interlayer can be improved in agent.In contrast, if in active energy ray-curable bonding agent (especially comprising solvent It is organic solvent), even if then curability composition contained in bonding agent is identical, it is also unable to get sufficient adaptation, by light When laminated body cuts into predetermined size, a problem that its end is easy to happen removing.In addition, due to it is additional by solvent into The dry process of row, therefore application exists in optical laminate because of the shrinkage stress of the addition caused by heat or is attached to adhesive layer The risk of inverse curling is easy to happen in optical laminate.

Using the no-solvent type activity energy comprising the cured curability compound of irradiation by active energy beam In the case where measuring ray-curable bonding agent, indicate that the index of the hardness of the active energy ray-curable bonding agent after solidifying is Storage modulus is in the majority multiplied by the situation for the rigidity for being rigidly higher than the water system bonding agent after solidifying obtained from thickness.If setting is the The rigidity of bonding agent cured layer between one liquid crystal layer and the second liquid crystal layer is high, then contraction when can prevent from being removed by substrate is answered Curling aggravation caused by power, therefore it is preferable to use no-solvent type active energy ray-curable bonding agents.

As active energy ray-curable bonding agent, from display good bonding aspect, preferably comprise sun from Any one of the curability compound of sub- polymerism, free-radical polymerised curability compound or both.Active-energy is penetrated The cationic polymerization that line curability bonding agent can further include the curing reaction for causing above-mentioned curability compound draws Send out agent or radical polymerization initiator.

As the curability compound of cationically polymerizable, it can be mentioned, for example epoxy compounds (to have 1 in the molecule Or the compound of 2 or more epoxy groups), oxetanes based compound (in the molecule have 1 or 2 or more oxa- ring fourth The compound of ring) or their combination.

As free-radical polymerised curability compound, it can be mentioned, for example (methyl) acrylic compounds (in molecule Inside there is the compound of 1 or 2 or more (methyl) acryloxy), other vinyl with free-radical polymerised double bond Based compound or their combination.

Active energy ray curable bonding agent can according to need and contain sensitizer.By using sensitizer, thus Make reactive raising, and can be further improved the mechanical strength or adhesive strength of adhesive layer.It, can be appropriate as sensitizer Using well known sensitizer.In the case where cooperating sensitizer, use level is relative to active energy ray curable bonding agent 100 mass parts of total amount be preferably 0.1~20 mass parts range.

Active energy ray-curable bonding agent can according to need and contain ion trap agent, antioxidant, chain tra nsfer Agent, tackifier, thermoplastic resin, filler, flowing regulator, plasticizer, defoaming agent, antistatic agent, levelling agent, solvent etc. add Add agent.

By the way that adhesive composite to be coated on to the first liquid crystal layer of subsidiary substrate layer or the second liquid crystal of subsidiary substrate layer The joint surface of layer, so as to form adhesive composite layer.As coating method, as long as using die coating machine, comma has been used Coating machine, reverse roll coater, gravure coater, bar coater, bar coater, knife type coater, Kohler coater etc. lead to Normal coating technique.

To using drying means when water system bonding agent to be not particularly limited, can using for example using air drier or The method that infrared drier is dried.

Using active energy ray-curable bonding agent, ultraviolet light, visible light, electronics can be irradiated and penetrated The active energy beam of line, X-ray etc and make adhesive composite layer solidify, to form bonding agent cured layer.As work Low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, superelevation can be used as light source at this time in property energy-ray, preferably ultraviolet light Pressure mercury lamp, chemical lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp etc..

In the case where making the cured situation of adhesive composite layer using ultraviolet light irradiation, the photo-irradiation intensity of ultraviolet light is according to viscous The composition of agent composition is connect to determine, is not particularly limited, but preferably 10~1,000mW/cm², more preferably 100~ 600mW/cm².If to resin combination irradiation photo-irradiation intensity less than 10mW/cm², then the reaction time becomes too long, if being more than 1,000mW/cm², then there is the fever when polymerization of heat and adhesive composite from radiation of light source due to make gained bonding agent A possibility that xanthochromia, occurs for cured layer.In addition, can there is also generate further shrinkage stress due to the heat from radiation of light source It can property.Exposure intensity is the effective wavelength region for the activation of polymerization initiator, preferably light cationic polymerization initiator Intensity, the more preferably intensity in wavelength 400nm wavelength region below, further preferably 280~320nm's of wavelength The intensity of wavelength region.It is preferred that according to being irradiated 1 time with such photo-irradiation intensity or repeatedly its accumulated light being made to reach 10mJ/ cm²Above, preferably 100~1,000mJ/cm², more preferable 200~600mJ/cm²Mode set.If to adhesive composite The accumulated light of layer irradiation is less than 10mJ/cm², then the generation of the reactive species from polymerization initiator is insufficient, bonding agent combination The solidification of nitride layer is insufficient.If accumulated light is more than 1,000mJ/cm², then irradiation time becomes very long, produces for improving Rate is unfavorable.In addition, there is also generate further shrinkage stress due to the heat from radiation of light source.According to first base material Type, combination of ingredient in adhesive composite of layer, the second substrate layer, the first liquid crystal layer, the second liquid crystal layer etc. etc., and make Wavelength (UVA (320~390nm) or UVB (280~320nm) etc.) when light irradiates is different, the wavelength pair when irradiating with light Ying Di, required accumulated light also change.

As the viscosity of active energy ray curable bonding agent, as long as can be applied using arbitrary coating method Deposited mode is selected, and the viscosity at 25 DEG C of temperature is preferably the range of 10~1,000mPasec, more preferably 20~ The range of 500mPasec.If viscosity is too small, there is the tendency for the bonding agent cured layer for being not easy to be formed expectation thickness.It is another There is the active energy ray curable bonding agent in coating and be not easy to flow and be difficult to obtain invariably in aspect if viscosity is too big The tendency of equal homogeneous film.Viscosity said here be using E type viscosimeter after being 25 DEG C by the bonding agent temperature adjustment with The value of 10rps measurement.

From the viewpoint of as the durability of the polarization plates of optical film, the inverse curling of inhibition, bonding agent cured layer is in temperature Storage modulus at 30 DEG C is preferably 100MPa or more, further preferably 1000MPa or more, more preferably 1500MPa or more, Particularly preferably 2000MPa or more.On the other hand, if the storage modulus of bonding agent cured layer is excessive, bonding agent cured layer becomes Must be really up to the mark, whens carrying out for making the optical laminate of optical laminate or subsidiary adhesive layer become the Punching Technology etc. of prescribed level Processability reduce sometimes.Therefore, storage modulus of the bonding agent cured layer at 30 DEG C of temperature is preferably 10000MPa hereinafter, more Preferably 8000MPa is hereinafter, further preferably 5000MPa or less.

Storage modulus of the bonding agent cured layer at 30 DEG C of temperature can calculate according to the following steps.Use coating machine The above-mentioned active energy of single side coating of (bar coater, the first physical and chemical Co. Ltd. system) in 50 μm of thickness of cyclic polyolefin resin films Ray-curable bonding agent is measured, 50 μm of thickness of cyclic polyolefin resin film is further laminated in the applicator surface.Then, sharp 1500mJ/cm is reached with accumulated light with " the D Valve " of Fusion UV Systems corporation²(UVB) mode irradiates purple Outside line solidifies adhesive composite layer.The size for being cut into 5mm × 30mm removes a cyclic polyolefin hydrocarbon system resin Film obtains the bonding agent cured layer of subsidiary resin film.The measurement of dynamic viscoelasticity device of control Co. Ltd. system is measured using IT This is attached to the bonding agent cured layer of resin film in such a way that its long side becomes draw direction, between fixture by " DVA-220 " It is clamped every 2cm, the frequency for stretching and shrinking is set as 10Hz, speed is will heat up and is set as 10 DEG C/min and is gradually warmed up, ask Obtain the storage modulus at 30 DEG C of temperature.

The thickness of bonding agent cured layer be preferably 10 μm hereinafter, more preferably 5 μm hereinafter, further preferably 2 μm or less. Additionally, it is preferred that be 0.1 μm or more, more preferably 0.5 μm or more, further preferably 1 μm or more.By making bonding agent cured layer With a thickness of lower limit value more than, so that rigidity be made to get higher, and the light for inhibiting optical laminate or subsidiary adhesive layer can be improved Learn the effect of the curling in laminated body.On the other hand, by make bonding agent cured layer with a thickness of upper limit value within, so as to Prevent bubble the coating such as to bite bad.

(adhesive layer of subsidiary peeling layer)

They (are referred to as by the second adhesive layer of the first adhesive layer of subsidiary peeling layer and subsidiary peeling layer sometimes below " adhesive layer of subsidiary peeling layer ") it by the coating adhesive composition in the demoulding process face of peeling layer and can for example be allowed to It is dry etc. and form adhesive layer to obtain.The adhesive layer of subsidiary peeling layer can according to need and have for covering adhesive layer Other peeling layers protected with the surface of peeling layer side opposite side.Peeling layer and other peeling layers can be appropriate Opportunity removing.

(peeling layer)

First peeling layer and the second peeling layer (they are referred to as " peeling layer " sometimes below) can be removed from adhesive layer, It has the function of the adhesive layer that support is formed on peeling layer and protects adhesive layer.Well known removing can be used in peeling layer Film or peeling paper, such as can be the film implementation silicone coating etc. to being formed by the resin material illustrated as aftermentioned substrate layer Stripping film obtained by demoulding processing.About other peeling layers, material same as peeling layer also can be used.

Peeling layer can be removed from adhesive layer, and the size of the peeling force between peeling layer and adhesive layer needs to consider will removing The sequence of layer removing determines.About above-mentioned peeling force, the measurement test film on peeling layer with adhesive layer can be prepared (size of length 200mm, width 25mm), is bonded with appropriately sized glass, uses drawing automatically for Shimadzu Seisakusho Ltd. Figure instrument (AGS-50NX) clamps the peeling layer after being partially stripped in a manner of being formed and remove starting point and glass respectively, Peeling layer is removed in 180 ° of direction with 300mm/ minutes speed, the peel strength measured at this time is set as peeling force.Stripping Peeling force between absciss layer and adhesive layer is preferably 0.01~0.20N/25mm, more preferably 0.02~0.10N/25mm, into one Step is preferably 0.02~0.06N/25mm.If being lower than 0.01N/25mm, deposit during transport peeling layer and adhesive layer it Between generate the risk floated.In addition, if the adaptation of peeling layer and adhesive layer is high, and peeling layer is not easy more than 0.20N/25mm It is removed from adhesive layer, therefore, if removing peeling layer, there are following risks: bonding fault rupture and becomes the removing after removing Adhere to the state of some adhesive layer on layer, or occur between non-targeted layer removing (such as adhesive layer with removing The removing between layer and adhesive layer engaged in layer opposite side).

(liquid crystal layer)

First liquid crystal layer and the second liquid crystal layer (the two is referred to as " liquid crystal layer " sometimes below) are by making polymerism liquid The cured layer of brilliant compound polymerization and formation, can be phase separation layer.The optical characteristics of liquid crystal layer can use polymerizable liquid crystal The state of orientation of compound adjusts.

In the present specification, the case where optical axis of polymerizable liquid crystal compound being orientated relative to substrate layer planar water level land The case where being defined as being horizontally oriented, the optical axis of polymerizable liquid crystal compound is vertically oriented relative to substrate layer plane is defined as It is vertically oriented.Optical axis refers to: in the index ellipsoid body that the orientation by polymerizable liquid crystal compound is formed, with optical axis just The section of the direction cutting of friendship is that the refractive index in direction, i.e. 2 direction of circle reaches equal direction.

As polymerizable liquid crystal compound, rodlike polymerizable liquid crystal compound, discoid polymerizable liquid crystal can be enumerated Compound.In the case where rodlike polymerizable liquid crystal compound is relative to substrate layer horizontal alignment or vertical orientation, the polymerization The optical axis of property liquid-crystal compounds is consistent with the long axis direction of the polymerizable liquid crystal compound.In discoid polymerizable liquid crystal chemical combination In the case that object is orientated, the optical axis of the polymerizable liquid crystal compound is present in the disc face with the polymerizable liquid crystal compound Orthogonal direction.

In order to make the liquid crystal layer that polymerizable liquid crystal compound is polymerize and formed show phase difference in face, as long as making polymerism Liquid-crystal compounds is orientated to direction appropriate.In the case where polymerizable liquid crystal compound is rodlike, by making the polymerization Property liquid-crystal compounds optical axis be orientated relative to substrate layer planar water level land and show phase difference in face, in this case, optical axis Direction is consistent with slow-axis direction.In the case where polymerizable liquid crystal compound is discoid, by making the polymerizable liquid crystal chemical combination The optical axis of object is orientated to show phase difference in face relative to substrate layer planar water level land, and in this case, optical axis is orthogonal with slow axis. The state of orientation of polymerizable liquid crystal compound can use the combination of alignment films and polymerizable liquid crystal compound to adjust.

Polymerizable liquid crystal compound is that have polymerizable group and the compound with liquid crystal liquid crystal property.Polymerizable group refers to ginseng With the group of polymerization reaction, preferably polymerism group.Here, polymerism group refers to by being caused by aftermentioned photopolymerization Living radical or acid that agent generates etc. and the group of polymerization reaction can be participated in.As polymerizable group, can enumerate vinyl, Vinyl oxygroup, 1- chlorovinyl, isopropenyl, 4- ethenylphenyl, acryloxy, methacryloxy, epoxy second Base, oxetanylmethoxy etc..Wherein, preferably acryloxy, methacryloxy, vinyl oxygroup, epoxy ethyl and oxa- Cyclobutyl, more preferable acryloxy.The liquid crystal liquid crystal property possessed by polymerizable liquid crystal compound can be thermotropic liquid crystal, It may be lysotropic liquid crystal, can be nematic crystal, or smectic if thermotropic liquid crystal is classified by the degree of order Type liquid crystal.

As rodlike polymerizable liquid crystal compound or discoid polymerizable liquid crystal compound, can be used well known poly- Conjunction property liquid-crystal compounds, can be used such as Japanese Unexamined Patent Publication 2015-163937 bulletin, Japanese Unexamined Patent Publication 2016-42185 public affairs Polymerizable liquid crystal chemical combination illustrated by report, International Publication No. 2016/158940, Japanese Unexamined Patent Publication 2016-224128 bulletin Object.

Liquid crystal layer can be 1 layer of structure, or 2 layers or more of multilayered structure.In the multilayered structure with 2 layers or more In the case where, as long as state the liquid crystal layer of subsidiary substrate layer after preparation, 2 layers or more of multilayered structure is formed on substrate layer Liquid crystal layer.In the case where liquid crystal layer is 1 layer of structure, the thickness of liquid crystal layer is preferably 0.3 μm or more, or 1 μm More than, usually 10 μm hereinafter, preferably 5 μm or less.In the case where liquid crystal layer is 2 layers or more of multilayered structure, liquid crystal layer Thickness be preferably 0.5 μm or more, or 1 μm or more, usually 10 μm hereinafter, preferably 5 μm or less.It is inclined from facilitating The slimming of vibration plate entirety, from the perspective of effectively inhibiting issuable inverse curling, the thickness of liquid crystal layer be preferably 5 μm with Under.In addition, the degree that there is inverse curling is therefore slight tendency makes in the case where the thickness of liquid crystal layer is less than 0.3 μm With necessity of the manufacturing method of the optical laminate of the manufacturing method or subsidiary adhesive layer of the optical laminate of above embodiment Property is small.

(liquid crystal layer of subsidiary substrate layer)

The two (is referred to as by the second liquid crystal layer of the first liquid crystal layer of subsidiary substrate layer and subsidiary substrate layer sometimes below " liquid crystal layer of subsidiary substrate layer ") it can obtain in the following manner, that is, coating includes polymerizable liquid crystal chemical combination on substrate layer The liquid crystal layer of object, which is formed, uses composition, is dried, and polymerizable liquid crystal compound is made to polymerize and form cured layer, form liquid Crystal layer.In the case where being formed with aftermentioned oriented layer on substrate layer, liquid crystal layer formation only would be applied to oriented layer with composition It is upper, in the case where liquid crystal layer is 2 layers or more of multilayered structure, as long as using composition by the formation of successively coating liquid crystal layer Etc. forming multilayered structure.

Liquid crystal layer is formed in composition, and usual on the basis of comprising polymerizable liquid crystal compound also includes solvent.Liquid Crystal layer formation composition can also include polymerization initiator, reactive additive, polymerization inhibitor etc..Cause about solvent, polymerization Agent, reactive additive, polymerization inhibitor etc. can be used in Japanese Unexamined Patent Publication 2015-163937 bulletin, Japanese Unexamined Patent Publication 2016- No. 42185 bulletins, International Publication No. 2016/158940, in Japanese Unexamined Patent Publication 2016-224128 bulletin illustrated by substance.

The coating of liquid crystal layer formation composition can use for example spin-coating method, extrusion, gravure coating process, die coating method, Method well known to print processes such as the rubbing methods such as slot coated method, stick coating method, applicator method or soft version method etc. carries out.Carry out After liquid crystal layer forms the coating with composition, preferably it polymerize polymerizable liquid crystal compound contained in coating layer Under the conditions of remove solvent.As drying means, natural seasoning, aeration-drying method, heat drying, hypobaric drying method can be enumerated Deng.

The polymerization of the polymerizable liquid crystal compound carried out after the drying of coating layer, which can use, to be made with polymerism function The known method that polymerize of compound of group carries out.As polymerization, it can be mentioned, for example thermal polymerization or photopolymerization etc., from It polymerize from the perspective of easiness, preferably photopolymerization.In the case where polymerizeing polymerizable liquid crystal compound using photopolymerization, Preferably: the liquid crystal layer formation composition containing Photoepolymerizationinitiater initiater is used as liquid crystal layer formation composition, it will The liquid crystal layer formation is coated with composition, is dried, polymerizable liquid crystal compound contained in the dry coationg after making drying Liquid crystal aligning occurs, carries out photopolymerization under conditions of maintaining the liquid crystal aligning state.

Photopolymerization can be by irradiating activity to the polymerizable liquid crystal compound after the progress liquid crystal aligning in dry coationg Energy-ray carries out.As the active energy beam irradiated, can be polymerize according to possessed by polymerizable liquid crystal compound Property group type and its amount, the type of Photoepolymerizationinitiater initiater etc. suitably selected, it can be mentioned, for example be selected from luminous ray, purple The active energy beam of one or more of outside line, laser, X-ray, alpha ray, β ray and gamma-rays.Wherein, from being easy to control The progress of polymerization reaction is set out in terms of being able to use the device for being widely used in this field as photo-polymerization device, excellent Ultraviolet light is selected, preferably come selective polymerization liquid-crystal compounds or photopolymerization in the way of it can carry out photopolymerization using ultraviolet light The type of initiator.In photopolymerization, dry coationg is cooled down using cooling way appropriate on one side, irradiates active-energy on one side Thus ray also can control polymerization temperature.

(substrate layer)

First base material layer and the second substrate layer (the two is referred to as " substrate layer " sometimes below), which have to be used as, is supported on this The supporting layer of the aftermentioned first alignment layer and second orientation layer and the first liquid crystal layer and the second liquid crystal layer that are formed on a little substrate layers Function.Substrate layer is preferably the film formed by resin material.

As resin material, the excellent resin material such as use such as transparency, mechanical strength, thermal stability, draftability. Specifically, can enumerate: the polyolefin-based resins such as polyethylene, polypropylene；The cyclic polyolefins hydrocarbon system tree such as norbornene-based polymer Rouge；The polyester based resins such as polyethylene terephthalate, polyethylene naphthalate；(methyl) acrylic acid, poly- (methyl) Methyl acrylate etc. (methyl) acrylic resin；Tri acetyl cellulose, diacetyl cellulose, cellulose-acetate propionate etc. Cellulose esters system resin；The vinyl alcohol resins such as polyvinyl alcohol, polyvinyl acetate；Polycarbonate-based resin；Polystyrene Resin；Polyarylate system resin；Polysulfones system resin；Polyether sulfone system resin；Polyamide resin；Polyimides system resins；Polyether-ketone It is resin；Polyphenylene sulfide system resin；Polyphony Ether resin；And their mixture, copolymer etc..In these resins, excellent Choosing uses any in cyclic polyolefin hydrocarbon system resin, polyester based resin, cellulose esters system resin and (methyl) acrylic resin Person or their mixture.

Substrate layer can be the single layer of a kind of resin or the single layer for mixing two or more resin, it is possible to have 2 layers or more Multilayered structure.In situation with multi-layer structure, the resin for constituting each layer can be mutually the same, can also be different, can also be with For coating/solidified material layer as hard conating.

Arbitrary additive can be added in the resin material for constituting the film formed by resin material.As additive, It can be mentioned, for example ultraviolet absorbing agent, antioxidant, lubricant, plasticizer, release agent, anti-coloring agent, fire retardant, nucleating agent, Antistatic agent, pigment and colorant etc..

The thickness of first base material layer and the second substrate layer is not particularly limited, usually from the operability such as intensity, treatability Aspect is set out, preferably 1~300 μm, more preferably 10~200 μm, further preferably 30~120 μm.

There is the second liquid of the case where aftermentioned first alignment layer or subsidiary substrate layer in the first liquid crystal layer of subsidiary substrate layer In the case that crystal layer has aftermentioned second orientation layer, in order to improve adaptation, the Yi Ji of first base material layer and first alignment layer The adaptation of two substrate layers and second orientation layer, can be to the table of the side that form first alignment layer of at least first base material layer The surface of the side that form second orientation layer of face and at least the second substrate layer carries out sided corona treatment, corona treatment, fire Flame processing etc., can also form prime coat etc..

Substrate layer can be removed from liquid crystal layer or aftermentioned oriented layer (first alignment layer or second orientation layer), substrate layer and liquid The size of peeling force between crystal layer or oriented layer needs to consider the sequence of peeling base layer to determine.In addition to using in substrate layer Other than the upper measurement test film with liquid crystal layer or the measurement test film with oriented layer and liquid crystal layer on substrate layer, Peeling force can measure in the same manner as the method for the peeling force between adhesive layer with measurement peeling layer.Substrate layer and liquid crystal layer take It is preferably 0.01~0.50N/25mm to the peeling force between layer, more preferably 0.03~0.20N/25mm, further preferably 0.05~0.18N/25mm.If peeling force is lower than above-mentioned lower limit value, deposit during transport in substrate layer and liquid crystal layer or The risk floated is generated between oriented layer.In addition, there are following risks: because closely sealed if peeling force is more than above-mentioned upper limit value Property be too high to for liquid crystal layer or liquid crystal layer and oriented layer to be transferred to another liquid crystal layer or optical film etc., manufacture optics During transporting each component in the process of the optical laminate of laminated body or subsidiary adhesive layer, removing interface changes.

Peeling force (hereinafter sometimes referred to as " between first base material layer and the first liquid crystal layer or aftermentioned first alignment layer One peeling force ") and the second substrate layer and the second liquid crystal layer or aftermentioned second orientation layer between peeling force (hereinafter sometimes referred to as " the second peeling force ") difference be preferably 0.01N/25mm or more, more preferably 0.03N/25mm or more.From subsidiary substrate layer In the case that liquid crystal layer laminates first remove first base material layer, the second peeling force is preferably made to be greater than the first peeling force, from incidentally In the case that the liquid crystal layer laminates of substrate layer first remove the second substrate layer, the first peeling force is preferably made to be greater than the second peeling force. In addition, the viewpoint processed from strip goes out in the case where first removing first base material layer from the liquid crystal layer laminates of subsidiary substrate layer Hair, the relationship of peeling force < the first peeling force the second peeling force of < between preferably the second peeling layer and the second adhesive layer.

(oriented layer)

First liquid crystal layer of subsidiary substrate layer can include first alignment layer between first base material layer and the first liquid crystal layer. In addition, the second liquid crystal layer of subsidiary substrate layer can include second orientation layer between the second substrate layer and the second liquid crystal layer.

First alignment layer and second orientation layer have the first liquid crystal layer and the second liquid crystal for making to be formed in these oriented layer Liquid-crystal compounds contained in layer carries out the orientation control force of liquid crystal aligning towards desired orientation.As first alignment layer and second Oriented layer can enumerate the orientation polymeric layer formed by orientation polymer, the light orientation formed by light orientation polymer Polymeric layer, the groove orientation layer in layer surface with relief pattern or multiple grooves (groove), first alignment layer and second Oriented layer can be the layer of identical type, or different types of layer.The thickness of first alignment layer and second orientation layer is logical It is often 10~4000nm, preferably 50~3000nm.

Orientation polymeric layer can be by being coated on substrate layer (first base material layer or the second substrate layer) by orientation Polymer is dissolved in the composition after solvent, removes solvent, is formed further according to needing to carry out brushing processing.In this case, For the orientation polymeric layer formed by orientation polymer, orientation control force can be according to the table of orientation polymer Surface state or brushing condition are arbitrarily adjusted.

Light orientation polymeric layer can be by will include polymer with photoreactive group or monomer and include molten The composition of agent is coated on substrate layer (first base material layer or the second substrate layer), and irradiates the light such as ultraviolet light to be formed.Especially exist Horizontal direction embodied under the case where orientation control force etc., can be formed by irradiation polarised light.In this case, light is taken For tropism polymeric layer, orientation control force can appoint according to the polarizing light irradiation condition etc. for light orientation polymer The adjustment of meaning ground.

Groove orientation layer can use such as following methods to be formed, that is, across the exposure of the slit with pattern form With the method that mask is exposed, develops to photosensitive polyimide film surface etc. and forms relief pattern；There is ditch on surface The uncured layer that active energy ray-curable resin is formed in the plate master of slot, is needed on substrate layer (first for the layer Substrate layer or the second substrate layer) and carry out cured method；It is formed and is lived on substrate layer (first base material layer or the second substrate layer) Property energy ray-curable resin uncured layer, will have indent and convex roll stamper is pressed into the layer etc., formed it is concave-convex simultaneously It is allowed to cured method etc..

It, can when removing first base material layer in the case where the first liquid crystal layer of subsidiary substrate layer includes first alignment layer To be peeled off together first alignment layer and first base material layer, first alignment layer can also be remained on the first liquid crystal layer.Subsidiary It, can be by second orientation layer when removing the second substrate layer in the case that second liquid crystal layer of substrate layer includes second orientation layer It is peeled off together with the second substrate layer, second orientation layer can also be remained on the second liquid crystal layer.It is explained, by first alignment layer Being peeled off together with first base material layer or remaining on the first liquid crystal layer can set by adjusting the relationship of the closing force of each interlayer It is fixed, such as can use above-mentioned sided corona treatment, corona treatment, flame treatment, the prime coat etc. carried out to first base material layer Surface treatment or the ingredient of liquid crystal layer formation composition used to form the first liquid crystal layer adjust.Similarly, It can use the surface treatment for carrying out the second substrate layer to be peeled off together second orientation layer and the second substrate layer, the can also be made Two oriented layer remain on the second liquid crystal layer.

In the case where remaining first alignment layer on the first liquid crystal layer, the first adhesive layer be can be set in first alignment layer On.In addition, the second adhesive layer can be set in second orientation layer in the case where remaining second orientation layer on the second liquid crystal layer On.

(circularly polarizing plate)

The optical laminate of present embodiment can be used as circularly polarizing plate come using.The optics shown in (b) using Fig. 4 In the case that laminated body 70 is used as circularly polarizing plate, optical film 60 can be set as to the inclined of polarizing film, polarization plates or subsidiary protective film Vibration plate, is set as 1/2 wavelength phase difference layer for the first liquid crystal layer 12, and the second liquid crystal layer 22 is set as 1/4 wavelength phase difference layer.Or Person, on the basis of optical film 60 is set as the polarization plates of polarizing film, polarization plates or subsidiary protective film as described above, by the One liquid crystal layer 12 is set as 1/4 wavelength phase difference layer of inverse wave length dispersibility, and the second liquid crystal layer 22 is set as positive c plate, thus may be used To obtain circularly polarizing plate.

Embodiment

The present invention is further illustrated hereinafter, showing Examples and Comparative Examples, still, the present invention is not by these The restriction of example.Unless otherwise specified, then embodiment, " % " and " part " in comparative example are quality % and mass parts.

(measurement (1) of curling)

The length on one side will be become from the optical laminate of subsidiary adhesive layer obtained in each embodiment, each comparative example For the diamond shape and its diagonal line and the direction MD and the direction the TD cutting sheet that parallel mode is cut into respectively of 100mm, in temperature After placing 24 hours in the environment of 23 DEG C of degree, relative humidity 55%, the first spacer, test piece are removed.To the test film It after sufficiently removing electricity, upward by the concave surface of test film, is placed on datum level (horizontal platform), distinguishes for 4 angles of test film Measure its height apart from datum level.About measured value, if test film is placed in base in such a way that protective film side becomes upside The curling is set as just crimp then in the case where the angle of test film floats by quasi- face, and indicates angular distance base with positive The height in quasi- face.On the other hand, if test film is placed in datum level in such a way that protective film side becomes downside, in test film Angle float in the case where, which is set as inverse curling, and the height of angular distance datum level is indicated with negative value.

About the measured value that the test film for the optical laminate from subsidiary adhesive layer obtains, will be in and the direction MD The average value of the measured value of the height of 2 angular distance datum levels on parallel diagonal line will be in as actual measurement MD crimp values The average value of the measured value of the height of 2 angular distance datum levels on the diagonal line parallel with the direction TD is as actual measurement TD curling Value.

In addition, the polarization plates of the subsidiary protective film used in each embodiment, each comparative example, also using as described above The step of for 4 angles of the test film cut measure its height apart from datum level respectively, and using as described above The step of measured value is averaged, for the polarization plates of subsidiary protective film, calculate actual measurement MD crimp values and actual measurement TD crimp values.

The optical laminate of subsidiary adhesive layer will be subtracted from the actual measurement MD crimp values of the polarization plates of resulting subsidiary protective film Actual measurement MD crimp values it is resulting value as have protective film when subsidiary adhesive layer optical laminate MD crimp values.Equally Ground will subtract the actual measurement of the optical laminate of subsidiary adhesive layer from the actual measurement TD crimp values of the polarization plates of resulting subsidiary protective film The TD crimp values of the optical laminate of subsidiary adhesive layer when the resulting value of TD crimp values is as with protective film.

(measurement (2) of curling)

From the cutting sheet that the optical laminate of the subsidiary adhesive layer obtained in each embodiment, each comparative example is cut into, After being peeled off together protective film together with the first spacer, test piece is in addition to this, same using the measurement (1) with above-mentioned curling The step of sample, the actual measurement MD crimp values and actual measurement TD crimp values of the optical laminate after calculating removing protective film.It is explained, closes In measured value, if test film is placed in datum level in such a way that polarization plates side becomes upside, float at the angle of test film In the case of, which is set as just crimp, and the height of angular distance datum level is indicated with positive.It on the other hand, if will Test film is placed in datum level in such a way that polarization plates side becomes downside, then in the case where the angle of test film floats, by the volume Song is set as inverse curling, and the height of angular distance datum level is indicated with negative value.

In addition, about the cutting being cut into from the polarization plates of the subsidiary protective film used in each embodiment, each comparative example In piece remove protective film after polarization plates, also using as described above the step of for the test film cut 4 angles distinguish Measure its height apart from datum level, and using as described above the step of measured value is averaged, to calculate removing The actual measurement MD crimp values and actual measurement TD crimp values of polarization plates after protective film.

By the optical laminate after subtracting removing protective film from the actual measurement MD crimp values of the polarization plates after removing protective film The MD crimp values of the optical laminate of subsidiary adhesive layer when the actual measurement resulting value of MD crimp values is set as unprotect film.Similarly, By TD volumes of actual measurement of the optical laminate after subtracting removing protective film from the actual measurement TD crimp values of the polarization plates after removing protective film The TD crimp values of the optical laminate of subsidiary adhesive layer when the bent resulting value of value is set as unprotect film.

MD crimp values and TD crimp values obtained in measurement (1) and (2) about above-mentioned curling, if the value is positive or 0, It then indicates to inhibit inverse curling, in addition, absolute value is bigger in the case where the value is negative, then it represents that inverse curling more aggravates.

(preparation that two sides is attached to the adhesive layer of spacer)

Adhesive has been manufactured using the following method.Have blender, thermometer, reflux condenser, Dropping feeder and 97.0 parts of n-butyl acrylate, 1.0 parts of acrylic acid, acrylic acid 2- hydroxy methacrylate 0.5 are put into the reaction vessel of nitrogen ingress pipe Part, 200 parts of ethyl acetate and 2,2 ' -0.08 part of azodiisobutyronitriles set the air in above-mentioned reaction vessel with nitrogen It changes.Reaction solution is warming up to 60 DEG C while stirring in a nitrogen atmosphere, after reacting it 6 hours, is cooled to room temperature.To gained The weight average molecular weight of a part of solution is determined, and as a result confirmation obtains (methyl) propylene that weight average molecular weight is 1,800,000 Acid ester polymer.

By above-mentioned resulting 100 parts of (solid component scaled values of (methyl) acrylate polymer；It is same as below), as different Trimethylolpropane modified toluene diisocyanate (the TOSOH Co., Ltd's system, trade name " Coronate of cyanate system crosslinking agent L ") 0.30 part and as silane coupling agent 3- glycidoxypropyltrime,hoxysilane (Shin-Etsu Chemial Co., Ltd System, trade name " KBM403 ") 0.30 part of mixing, it fully stirs, is diluted with ethyl acetate, thus obtain adhesive combination The coating solution of object.

The de- of the first spacer (LINTEC Co. Ltd. system: SP-PLR382190) of peeling layer is being constituted using spreading machine The coating solution of above-mentioned adhesive composition is applied in mould process face (release surface) in such a way that the thickness after drying reaches 25 μm, Later, 1 minute dry at 100 DEG C, adhesive layer is formed, the opposing face fitting in the face for being fitted with spacer of adhesive layer is another The second spacer of piece (LINTEC corporation: SP-PLR381031) obtains the adhesive layer that two sides is attached to spacer.

(preparation of adhesive composite)

After cation-curable ingredient a1~a3 shown in will be following and cationic polymerization initiators mix, remix following Shown in cationic polymerization initiators and sensitizer, carry out deaeration later, be prepared into the adhesive composite of light-cured type.Give Illustrate, following use levels is based on solid content.

Cation-curable ingredient a1 (70 parts):

3 ', 4 ' -3 ', 4 ' -7-oxa-bicyclo[4.1.0 of epoxycyclohexyl-methyl formic acid esters (trade name: CEL2021P, Daicel company System)

Cation-curable ingredient a2 (20 parts):

Neopentyl glycol diglycidyl ether (trade name: EX-211, Nagase ChemteX corporation)

Cation-curable ingredient a3 (10 parts):

2- ethylhexyl glycidyl ether (trade name: EX-121, Nagase ChemteX corporation)

Cationic polymerization initiators (2.25 parts (solid content)):

Trade name: the 50% polypropylene carbonate ester solution of CPI-100 (San-Apro corporation)

Sensitizer (2 parts):

Isosorbide-5-Nitrae-diethoxy naphthalene

(preparations of the polarization plates (1) of subsidiary protective film)

30 μm of thickness of polyvinyl alcohol films (99.9 moles of average degree of polymerization about 2,400, saponification degree % or more) are impregnated in After 30 DEG C of pure water, it is impregnated at 30 DEG C in the aqueous solution that iodine/potassium iodide/water mass ratio is 0.02/2/100.Later, exist It is impregnated at 56.5 DEG C in the aqueous solution that potassium iodide/boric acid/water mass ratio is 12/5/100.Then, using 8 DEG C of pure water pair It is dry at 90 DEG C after film is cleaned, it obtains making iodine gas absorption quantity polarizing film made of polyvinyl alcohol film.It stretches with wet type It stretches to carry out, is mainly carried out in iodine staining and boric acid processing, total stretching ratio is 5.7 times.Resulting polarizing film is to make iodine Gas absorption quantity film made of polyvinyl alcohol film, with a thickness of 12 μm.

Next, the unilateral coating in the polarizing film dissolves 3 parts of carboxy-modified polyvinyl alcohols (from can relative to 100 parts of water The trade name " KL-318 " that Le Li company obtains) and polyamide of the addition as water-soluble epoxy resin in the aqueous solution Epoxy additive (trade name " Sumirez Resin 650 (30) " that is obtained from Taoka Chemical Industries Co. Ltd., solid at The aqueous solution that point concentration is 30%) epoxy bonding agent obtained from 1.5 parts, the absorption with the angle of slow axis relative to polarizing film Axis mode at 45 ° is bonded the transparent norbornene resin film after the drawn as 30 μm of thickness of protective layer.To the film A surface implement surface treatment, and become by another face and be bonded in a manner of the binding face of polarizing film.? The other side of polarizing film uses above-mentioned epoxy bonding agent to be bonded as 20 μm of thickness of tri acetyl cellulose of protective layer Resin film.The polarization plates in the two-sided stacking matcoveredn of polarizing film are obtained in this way.Again in the table of norbornene resin film Surface treatment surface side be fitted in be formed on 38 μm of thickness polyethylene terephthalate (PET) film 15 μm acrylic acid series it is viscous The protective film for closing layer, obtains the polarization plates (1) of 115 μm of thickness of subsidiary protective film.The actual measurement of the polarization plates of the subsidiary protective film MD crimp values are 0mm, and actual measurement TD crimp values are 18mm.In addition, the actual measurement MD crimp values of the polarization plates after removing protective film are 20mm, actual measurement TD crimp values are -2mm.

(preparations of the polarization plates (2) of subsidiary protective film)

Using dry type stretching by 20 μm of thickness of polyvinyl alcohol film (99.9 moles of average degree of polymerization about 2,400, saponification degree % More than) about 5 times are uniaxially stretched to, then impregnated 1 minute in 60 DEG C of pure water in the state of keeping tensioning, later, at 28 DEG C Under iodine/potassium iodide/water mass ratio be 0.05/5/100 aqueous solution in impregnate 60 seconds.Later, in iodate at 72 DEG C It is impregnated 300 seconds in the aqueous solution that potassium/boric acid/water mass ratio is 8.5/8.5/100.Then, 20 are cleaned with 26 DEG C of pure water It is dry at 65 DEG C after second, obtain making iodine gas absorption quantity 7 μm of thickness of polarizing film made of polyvinyl alcohol film.

Next, the unilateral coating in the polarizing film dissolves 3 parts of carboxy-modified polyvinyl alcohols (from can relative to 100 parts of water The trade name " KL-318 " that Le Li company obtains) and polyamide of the addition as water-soluble epoxy resin in the aqueous solution Epoxy additive (trade name " Sumirez Resin 650 (30) " that is obtained from Taoka Chemical Industries Co. Ltd., solid at The aqueous solution that point concentration is 30%) epoxy bonding agent obtained from 1.5 parts, it is bonded transparent as 13 μm of thickness of protective layer Norbornene resin film.The polarization plates in the single side stacking matcoveredn of polarizing film are obtained in this way.Again in orbornene-based tree Being fitted on 38 μm of thickness polyethylene terephthalate (PET) film with the surface of polarizing film opposite side for adipose membrane is formed There is the protective film of 15 μm of acrylic acid series adhesive layers, obtains the polarization plates (2) of 73 μm of thickness of subsidiary protective film.The subsidiary protective film Polarization plates actual measurement MD crimp values be -20mm, actual measurement TD crimp values be 1mm.In addition, the reality of the polarization plates after removing protective film Survey MD crimp values are 4mm, and actual measurement TD crimp values are -1mm.

(preparation of the second liquid crystal layer of the first liquid crystal layer of subsidiary substrate layer and subsidiary substrate layer)

(light redirecting layer forms the preparation for using composition (1))

Following ingredients is mixed, gained mixture is stirred 1 hour at 80 DEG C of temperature, thus obtains light redirecting layer shape At with composition (1).

Light orientation material (5 parts):

[changing 2]

Solvent (95 parts): cyclopentanone

(oriented layer forms the preparation for using composition (2))

Add in the Sunever SE-610 (Nissan Chemical Ind Ltd's system) as commercially available orientation polymer Enter butoxy ethanol, obtains oriented layer formation composition (2).Resulting oriented layer is formed in composition (2), solid at Split-phase is 1% for the content ratio of the composition total amount, and solvent is 99% relative to the content ratio of the composition total amount. The solid content of Sunever SE-610 is converted by the concentration recorded in product specification book.

(liquid crystal layer forms the preparation for using composition (A-1))

Following ingredients is mixed, gained mixture is stirred 1 hour at 80 DEG C, thus obtains liquid crystal layer formation group It closes object (A-1).Polymerizable liquid crystal compound A1 and polymerizable liquid crystal compound A2 utilizes Japanese Unexamined Patent Publication 2010-31223 bulletin The method of middle record synthesizes.

Polymerizable liquid crystal compound A1 (80 parts):

[changing 3]

Polymerizable liquid crystal compound A2 (20 parts):

[changing 4]

Polymerization initiator (6 parts):

2- dimethylamino -2- benzyl -1- (4- morphlinophenyl) butane -1- ketone (Irgacure 369；Ciba Specialty Chemicals corporation)

Solvent (400 parts): cyclopentanone

(liquid crystal layer forms the preparation for using composition (B-1))

Following ingredients is mixed, after gained mixture is stirred 1 hour at 80 DEG C, is cooled to room temperature, obtains liquid crystal Layer, which is formed, uses composition (B-1).

Polymerizable liquid crystal compound LC242 (BASF AG's system) (19.2%):

[changing 5]

Polymerization initiator (0.5%):

Irgacure (registered trademark) 907 (BASF JAPAN corporation)

Reaction additives (1.1%):

Laromer (registered trademark) LR-9000 (BASF JAPAN corporation)

Solvent (79.1%): propylene glycol 1- monomethyl ether 2- acetic acid esters

(manufacture of the first liquid crystal layer of subsidiary substrate layer)

Using corona treatment plant (AGF-B10, Kasuga Electric K. K.'s system), in output power 0.3kW, processing speed Under conditions of 3m/ minutes, 1 processing is carried out to 100 μm of thickness of polyethylene terephthalate (PET) films.Use bar coater It is coated with light redirecting layer formation composition (1) on the surface for implementing sided corona treatment, it is 1 minute dry at 80 DEG C, use polarization Light UV irradiation unit (SPOT CURE SP-7；USHIO Electric Co., Ltd system), with 100mJ/cm²Accumulated light implement it is inclined The light UV that shakes exposes, and obtains light redirecting layer.With laser microscope (LEXT, Olympus Co., Ltd's system) to gained light redirecting layer Thickness is determined, result 100nm.

Then, using bar coater, coating liquid crystal layer formation is with composition (A-1) in light redirecting layer, the drying 1 at 120 DEG C After minute, using high-pressure sodium lamp (Unicure VB-15201BY-A, USHIO Electric Co., Ltd system), ultraviolet light (nitrogen is irradiated Under atmosphere, wavelength: 365nm, the accumulated light at wavelength 365nm: 1000mJ/cm²), it is consequently formed as phase separation layer First liquid crystal layer obtains the first liquid crystal layer of subsidiary substrate layer.First liquid crystal layer with a thickness of 2 μm.

(manufacture of the second liquid crystal layer of subsidiary substrate layer)

Using corona treatment plant (AGF-B10, Kasuga Electric K. K.'s system), in output power 0.3kW, processing speed Under conditions of 3m/ minutes, 1 processing is carried out to 38 μm of thickness of polyethylene terephthalate (PET) films.Existed with bar coater The surface coating oriented layer for implementing sided corona treatment, which is formed, uses composition (2), 1 minute dry at 90 DEG C, obtains oriented layer.Benefit The thickness of gained oriented layer is determined, result 34nm with laser microscope (LEXT, Olympus Co., Ltd's system).

Then, using bar coater, coating liquid crystal layer formation is with composition (B-1) in oriented layer, 1 point of the drying at 90 DEG C Zhong Hou irradiates ultraviolet light (nitrogen gas using high-pressure sodium lamp (Unicure VB-15201BY-A, USHIO Electric Co., Ltd system) Under atmosphere, wavelength: 365nm, the accumulated light at wavelength 365nm: 1000mJ/cm²), as phase separation layer is consequently formed Two liquid crystal layers obtain the second liquid crystal layer of subsidiary substrate layer.Second liquid crystal layer with a thickness of 1 μm.

(embodiment 1)

It is subsidiary using the first liquid crystal layer of the subsidiary substrate layer of above-mentioned preparation, the second liquid crystal layer of subsidiary substrate layer and two sides The adhesive layer of spacer, the process shown in FIG. 1 to FIG. 5 obtain the optical laminate of subsidiary adhesive layer.Specifically according to lower section Formula carries out.

To the second liquid crystal layer (direction MD length 300mm × TD direction length 200mm) of the subsidiary substrate layer of above-mentioned preparation The second liquid crystal layer side surface implement sided corona treatment (800W, 10m/min, stick width 700mm, 1Pass).Use coating machine The bar coater of Co. Ltd. system (first physical and chemical) reaches on the sided corona treatment face with the thickness of bonding agent cured layer 1 μm of side Formula applies the adhesive composite of above-mentioned preparation, is formed adhesive composite layer ((c) referring to Fig.1).Then, with it is above-mentioned same To the first liquid crystal layer of the subsidiary substrate layer of the above-mentioned preparation (direction the MD direction length 300mm × TD length under conditions of sample The first liquid crystal layer side 200mm) implements sided corona treatment, using adhering device (" LPA3301 " of Fujipla corporation), by this Sided corona treatment face and the adhesive composite layer being formed on the second liquid crystal layer of subsidiary substrate layer be bonded after (referring to Fig.1 (d)), from the second liquid crystal layer side of subsidiary substrate layer, using the ultraviolet lamp with conveyer belt, (lamp uses Fusion " the H Valve " of UV Systems corporation), it with exposure intensity is 390mW/cm in the region UVA², accumulated light 420mJ/ cm²Mode irradiate ultraviolet light, with exposure intensity be 400mW/cm in the region UVB², accumulated light 400mJ/cm²Mode shine It penetrates ultraviolet light, solidifies adhesive composite, obtain the liquid crystal layer laminates of subsidiary substrate layer (referring to (a) of Fig. 2).It is said It is bright, if calculating bonding agent cured layer obtained by above-mentioned adhesive composite layer solidifies using above-mentioned calculation method at room temperature Storage modulus is then about 3000MPa.

To the polarization plates (1) (direction MD length 300mm × TD direction length 200mm) of the subsidiary protective film of above-mentioned preparation Implement sided corona treatment (800W, 10m/min, stick with the face of protective film side opposite side (tri acetyl cellulose resin film side) Width 700mm, 1Pass).In addition, being attached to adhesive layer (300mm × 200mm) removing the of spacer from the two sides of above-mentioned preparation Two spacers.Using automatic laminating machine utilizing HALTEC, carry out the sided corona treatment faces of the polarization plates (1) of subsidiary protective film with by from two The adhesive layer that face is attached to spacer removes the second spacer and the fitting of the monolithic of the adhesive layer that exposes, obtains the inclined of subsidiary adhesive layer Vibration plate (referring to (b) of Fig. 3).

Using automatic laminating machine utilizing HALTEC, the subsidiary substrate layer for the liquid crystal layer laminates for removing subsidiary substrate layer will be passed through PET film (100 μm of thickness) in first liquid crystal layer and the face (face of the first liquid crystal layer side) exposed with by from subsidiary adhesive layer Polarization plates remove the first spacer and the adhesive layer that exposes carries out monolithic fitting, obtain the optical laminate of subsidiary substrate layer (referring to (a) of Fig. 4).It, will be by removing the resulting optical laminate for being attached to substrate layer using automatic laminating machine utilizing HALTEC PET film (38 μm of thickness) in second liquid crystal layer of subsidiary substrate layer and the face (face of the second liquid crystal layer side) exposed with by from The adhesive layer (300mm × 200mm) that the two sides of above-mentioned preparation is attached to spacer remove the second spacer and the adhesive layer that exposes into The fitting of row monolithic obtains the optical laminate (1) of subsidiary adhesive layer (referring to (b) of Fig. 5).To the light of resulting subsidiary adhesive layer The measurement (1) and (2) that laminated body (1) is crimped are learned, the MD crimp values and TD of the optical laminate (1) of subsidiary adhesive layer are calculated Crimp values.The results are shown in Table 1 for it.

(embodiment 2)

Instead of the polarization plates (1) of subsidiary protective film using above-mentioned preparation subsidiary protective film polarization plates (2), except this with Outside, obtain the optical laminate (2) of subsidiary adhesive layer similarly to Example 1 (referring to (b) of Fig. 5).To resulting subsidiary viscous The measurement (1) and (2) that the optical laminate (2) of layer is crimped are closed, MD volumes of the optical laminate (2) of subsidiary adhesive layer is calculated Song value and TD crimp values.The results are shown in Table 1 for it.

(embodiment 3)

Using similarly to Example 1 the step of obtain the liquid crystal layer laminates of subsidiary substrate layer (referring to (a) of Fig. 2).Make With automatic laminating machine utilizing HALTEC, the first liquid crystal layer of the subsidiary substrate layer for the liquid crystal layer laminates for removing subsidiary substrate layer will be passed through In PET film (100 μm of thickness) and expose face (face of the first liquid crystal layer side) with by from the two sides of above-mentioned preparation incidentally between The adhesive layer that the adhesive layer (300mm × 200mm) of spacing body is removed the second spacer and exposed carries out monolithic fitting, is incidentally glued Close the liquid crystal layer laminates of layer.It, will be by being removed from the liquid crystal layer laminates of subsidiary adhesive layer using automatic laminating machine utilizing HALTEC The protection of the polarization plates (1) (300mm × 200mm) of first spacer and the adhesive layer that exposes and the subsidiary protective film of above-mentioned preparation The opposite side (tri acetyl cellulose resin film side) of film side carries out monolithic fitting, obtains the optics stacking of subsidiary substrate layer Body.

It, will be by removing the of the subsidiary substrate layer of the optical laminate of subsidiary substrate layer using automatic laminating machine utilizing HALTEC PET film (38 μm of thickness) in two liquid crystal layers and the face (face of the second liquid crystal layer side) exposed with by from the two sides of above-mentioned preparation The adhesive layer that the adhesive layer (300mm × 200mm) of subsidiary spacer is removed the second spacer and exposed carries out monolithic fitting, obtains The optical laminate (3) of subsidiary adhesive layer.The measurement (1) that the optical laminate (3) of resulting subsidiary adhesive layer is crimped And (2), calculate the MD crimp values and TD crimp values of the optical laminate (3) of subsidiary adhesive layer.The results are shown in Table 1 for it.

(comparative example 1)

It is subsidiary using the first liquid crystal layer of the subsidiary substrate layer of above-mentioned preparation, the second liquid crystal layer of subsidiary substrate layer and two sides The adhesive layer of spacer obtains optical laminate using Fig. 7 and process shown in Fig. 8, using the optical laminate, is attached to The optical laminate of adhesive layer.Specifically, the polarization plates (1) and two sides using the subsidiary protective film of above-mentioned preparation are incidentally spaced The adhesive layer of part, using similarly to Example 1 the step of obtain the polarization plates of subsidiary adhesive layer.Use automatic laminating machine utilizing HALTEC, by the attached of the adhesive layer exposed by the polarization plates of being attached to adhesive layer from this first spacer of removing and above-mentioned preparation First liquid crystal layer of the first liquid crystal layer (direction MD length 300mm × TD direction length 200mm) with substrate layer carries out monolithic patch It closes (referring to (c) of Fig. 7).

Then, it using automatic laminating machine utilizing HALTEC, will be attached to by removing with what the polarization plates (1) of subsidiary protective film were bonded PET film (100 μm of thickness) in first liquid crystal layer of substrate layer and the face (face of the first liquid crystal layer side) exposed with by from upper The two sides for stating preparation is attached to the adhesive layer (300mm × 200mm) of spacer and removes the second spacer and the adhesive layer that exposes carries out Monolithic fitting, and then the first spacer of removing (referring to (a) of Fig. 8).Using automatic laminating machine utilizing HALTEC, removing will be passed through First spacer and the adhesive layer that exposes and the subsidiary substrate layer of above-mentioned preparation the second liquid crystal layer (direction MD length 300mm × The direction TD length 200mm) the second liquid crystal layer carry out monolithic fitting, obtain subsidiary substrate layer optical laminate (Fig. 8's (c))。

It, will be by removing subsidiary substrate from the optical laminate of resulting subsidiary substrate layer using automatic laminating machine utilizing HALTEC PET film (38 μm of thickness) in second liquid crystal layer of layer and the face (face of the second liquid crystal layer side) exposed with by from above-mentioned preparation Two sides be attached to the adhesive layer (300mm × 200mm) of spacer and remove the second spacer and the adhesive layer that exposes carries out monolithic patch It closes, obtains the optical laminate (4) of subsidiary adhesive layer.The optical laminate (4) of resulting subsidiary adhesive layer is crimped It measures (1) and (2), calculates the MD crimp values and TD crimp values of the optical laminate (4) of subsidiary adhesive layer.Its result such as 1 institute of table Show.

(comparative example 2)

Instead of the polarization plates (1) of subsidiary protective film using above-mentioned preparation subsidiary protective film polarization plates (2), except this with Outside, the optical laminate (5) of subsidiary adhesive layer is got similarly with comparative example 1.Optics stacking to resulting subsidiary adhesive layer The measurement (1) and (2) that body (5) is crimped calculate the MD crimp values and TD curling of the optical laminate (5) of subsidiary adhesive layer Value.The results are shown in Table 1 for it.

[table 1]

As shown in table 1, it is known that: compared with being attached to the optical laminate of adhesive layer obtained in comparative example 1 and 2, embodiment 1 The optical laminate of subsidiary adhesive layer obtained in~3 inhibits inverse curling, according to the optical layer illustrated in above embodiment The manufacturing method of the optical laminate of the manufacturing method of stack and subsidiary adhesive layer, is able to suppress inverse curling.

Claims

1. a kind of manufacturing method of optical laminate is to be sequentially laminated with optical film, the first adhesive layer, the first liquid crystal layer, glue The manufacturing method of the optical laminate of agent cured layer and the second liquid crystal layer is connect,

The manufacturing method includes:

Prepare the process of the first liquid crystal layer of subsidiary substrate layer, the first liquid crystal layer of the subsidiary substrate layer has first base material layer With first liquid crystal layer for polymerizeing polymerizable liquid crystal compound on the first base material layer and being formed；

Prepare the process of the second liquid crystal layer of subsidiary substrate layer, the second liquid crystal layer of the subsidiary substrate layer has the second substrate layer With second liquid crystal layer for polymerizeing polymerizable liquid crystal compound on second substrate layer and being formed；

By the second liquid crystal layer of the first liquid crystal layer of the subsidiary substrate layer and the subsidiary substrate layer with first liquid crystal layer It is laminated with second liquid crystal layer across the opposite mode of the bonding agent cured layer, to obtain the liquid of subsidiary substrate layer The process of crystal layer laminated body；

The first base material layer is at least removed from the liquid crystal layer laminates of the subsidiary substrate layer, to obtain liquid crystal layer laminates Process；And

Expose surface side across described the in first by removing the liquid crystal layer laminates that the first base material layer exposes The process of optical film described in one bonding layer stackup.

2. the manufacturing method of optical laminate according to claim 1, wherein the process that the optical film is laminated includes:

First adhesive layer is formed on the optical film, thus the process for obtaining the optical film of subsidiary adhesive layer；And

By first dew of first adhesive layer and the liquid crystal layer laminates in the optical film of the subsidiary adhesive layer The process being bonded.

3. the manufacturing method of optical laminate according to claim 2, wherein the optical film for obtaining subsidiary adhesive layer Process include:

Prepare the process for being laminated with the first adhesive layer of the subsidiary peeling layer of first adhesive layer and the first peeling layer；And

After first adhesive layer in first adhesive layer of the subsidiary peeling layer is bonded with the optical film, removing The process of first peeling layer.

4. the manufacturing method of optical laminate according to claim 1, wherein the process that the optical film is laminated includes:

First adhesive layer is formed in first exposed surface of the liquid crystal layer laminates, so that it is viscous to obtain subsidiary first The process for closing the liquid crystal layer laminates of layer；And

First adhesive layer in the liquid crystal layer laminates of subsidiary first adhesive layer is bonded with the optical film Process.

5. the manufacturing method of optical laminate according to claim 4, wherein the liquid for obtaining subsidiary first adhesive layer The process of crystal layer laminated body includes:

By described the of first adhesive layer and the liquid crystal layer laminates in the first adhesive layer of the subsidiary peeling layer After one exposed surface is bonded, the process of removing first peeling layer.

6. the manufacturing method of optical laminate according to any one of claims 1 to 5, wherein described to obtain subsidiary base The process of the liquid crystal layer laminates of material layer includes:

Second liquid crystal of first liquid crystal layer and the subsidiary substrate layer in the first liquid crystal layer of the subsidiary substrate layer Second liquid crystal layer in layer at least one of on form the process of adhesive composite layer, the adhesive composite Adhesive composite of the layer comprising being used to form the bonding agent cured layer；And

By the second liquid crystal layer of the first liquid crystal layer of the subsidiary substrate layer and the subsidiary substrate layer with first liquid crystal layer After being laminated with second liquid crystal layer across the opposite mode of the adhesive composite layer, by the adhesive composite The process that layer is solidified to form the bonding agent cured layer.

7. the manufacturing method of optical laminate described according to claim 1~any one of 6, wherein the optical film includes Polarization plates.

8. the manufacturing method of optical laminate according to any one of claims 1 to 7, wherein the optical film includes The polarization plates of the subsidiary protective film of protective film are laminated in at least single side of polarization plates.

9. the manufacturing method of optical laminate described according to claim 1~any one of 8, wherein described to obtain liquid crystal layer The process of laminated body is to remove the first base material layer from the liquid crystal layer laminates of the subsidiary substrate layer and do not remove described the The process of two substrate layers,

It further include the process for removing second substrate layer after the process that the optical film is laminated.

10. the manufacturing method of optical laminate described according to claim 1~any one of 8, wherein obtain the liquid crystal layer The process of laminated body is to remove the first base material layer and second substrate from the liquid crystal layer laminates of the subsidiary substrate layer Layer, thus the process for obtaining liquid crystal layer laminates.

11. a kind of manufacturing method of the optical laminate of subsidiary adhesive layer, be sequentially laminated with optical film, the first adhesive layer, First liquid crystal layer, bonding agent cured layer, the second liquid crystal layer and the second adhesive layer subsidiary adhesive layer optical laminate manufacture Method,

The manufacturing method includes:

Prepare the process of the optical laminate manufactured using the manufacturing method of optical laminate described in claim 9 or 10； And

Expose surface side stacking described second in second by removing the optical laminate that second substrate layer exposes The process of adhesive layer.

12. the manufacturing method of the optical laminate of subsidiary adhesive layer according to claim 11, wherein stacking described second The process of adhesive layer includes:

Prepare the process for being laminated with the second adhesive layer of the subsidiary peeling layer of second adhesive layer and the second peeling layer；And

By described second of second adhesive layer and the optical laminate in the second adhesive layer of the subsidiary peeling layer The process that exposed surface is bonded.

13. a kind of manufacturing method of the optical laminate of subsidiary adhesive layer, be sequentially laminated with optical film, the first adhesive layer, First liquid crystal layer, bonding agent cured layer, the second liquid crystal layer and the second adhesive layer subsidiary adhesive layer optical laminate manufacture Method,

The manufacturing method includes:

Second substrate layer is at least removed from the liquid crystal layer laminates of the subsidiary substrate layer, to obtain liquid crystal layer laminates Process；

Expose surface side in second by removing the liquid crystal layer laminates that second substrate layer exposes and is laminated described the Two adhesive layers, thus the process for obtaining the liquid crystal layer laminates of subsidiary second adhesive layer；

Described in the liquid crystal layer laminates of liquid crystal layer laminates or subsidiary second adhesive layer from the subsidiary substrate layer are removed The process of first base material layer；And

In the first dew of the liquid crystal layer laminates by removing subsidiary second adhesive layer that the first base material layer exposes Process of the surface side across optical film described in the first bonding layer stackup out.

14. the manufacturing method of the optical laminate of subsidiary adhesive layer according to claim 13, wherein described to be attached to The process of the liquid crystal layer laminates of second adhesive layer includes:

By described the of second adhesive layer and the liquid crystal layer laminates in the second adhesive layer of the subsidiary peeling layer After two exposed surface are bonded, the process of removing second peeling layer.