WO2021006068A1

WO2021006068A1 - Long film

Info

Publication number: WO2021006068A1
Application number: PCT/JP2020/025189
Authority: WO
Inventors: 敬之名田; 伸行幡中
Original assignee: 住友化学株式会社
Priority date: 2019-07-11
Filing date: 2020-06-26
Publication date: 2021-01-14
Also published as: JP2021015188A; KR20220032514A; JP7339039B2; CN114051586A; TW202110614A

Abstract

The present invention addresses the problem of providing a long film which has a base material film and a functional layer comprising a transferable cured liquid crystal layer, and which is not susceptible to separation of the functional layer at an end part in the short-side direction when the base material film is removed, while being capable of producing an optical film having excellent optical characteristics with high productivity.　The present invention provides a long film which comprises: a long base material film that has a recessed and projected part on at least one end in the short-side direction of at least one surface; and a transferable functional layer that comprises a layer of a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound. With respect to this long film, the functional layer is superposed on the surface having the recessed and projected part of the base material film; and if A is the full width of the base material film in the short-side direction, B is the total width of the recessed and projected part of the base material film in the short-side direction, and C is the width of the functional layer in the short-side direction, (B + C) > A is satisfied.

Description

Long film

The present invention relates to a long film, particularly a long film having a functional layer including a liquid crystal cured product layer on a base film.

The elliptical polarizing plate is an optical film in which a polarizing film and a retardation plate are laminated. For example, in a device such as an organic EL image display device that displays an image in a flat state, light reflection by electrodes constituting the device is used. It is used to prevent. In recent years, there have been continuous demands for weight reduction and thinning of organic EL image display devices, and further thinning is also required for retardation plates and elliptical polarizing plates, which are one of the constituent elements. ing. Under such circumstances, after forming a functional layer such as a retardation layer composed of a cured liquid crystal layer on the base film, the base film is peeled off and the functional layer is transferred to another constituent member such as a polarizing film. The type of optical film to be used is known (Patent Document 1).

Japanese Unexamined Patent Publication No. 2016-027431

It is advantageous to widen and / or lengthen the optical film having the transfer type functional layer as described above from the viewpoint of improving productivity, and the functional layer is made into another optical film from the long optical film. When transferring to a film, the so-called Roll to Roll method is usually used. However, the functional layer composed of the liquid crystal cured product layer obtained by molecularly orienting the polymerizable liquid crystal compound in a specific direction and curing the liquid crystal cured product layer is based on the liquid crystal cured product layer at the end in the short direction when the base film is peeled off during transfer. It is difficult to peel the material film linearly with respect to the peeling direction (flow direction), and there is a tendency that the edge portion of the liquid crystal cured product layer is torn off in a jagged manner.

Therefore, the present invention is a long film having a base film and a functional layer including a transferable liquid crystal cured product layer, and the functional layer at the end in the short direction is detached when the base film is peeled off. It is an object of the present invention to provide a long film capable of producing an optical film which is difficult and has excellent optical characteristics with high productivity.

As a result of diligent studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention includes the following aspects.
[1] A cured product layer of a polymerizable liquid crystal composition containing a long base film having uneven portions at at least one end in the short direction of at least one surface and at least one polymerizable liquid crystal compound. A long film comprising a transferable functional layer containing
The functional layer is laminated on the surface having the uneven portion of the base film.
A long film satisfying B + C> A when the total width of the base film in the short direction is A, the total width of the uneven portions of the base film in the short direction is B, and the width of the functional layer in the short direction is C.
[2] The long film according to the above [1], wherein the peeling force of the functional layer from the base film is 0.02 N / 25 mm or more and less than 1 N / 25 mm.
[3] The long film according to the above [1] or [2], wherein the base film is a cellulosic resin film or an olefin resin film.
[4] Any of the above [1] to [3], wherein the relationship between the in-plane average thickness X of the functional layer and the maximum height Y of the convex portion of the uneven portion satisfies 1.0 <Y / X ≦ 15.0. The long film described in Crab.
[5] The molecular orientation direction of the polymerizable liquid crystal compound in the cured product layer constituting the functional layer is horizontal with respect to the long direction plane of the base film, and the long direction of the base film. The long film according to any one of [1] to [4] above, which is not parallel to the film.
[6] The long film according to any one of [1] to [5], wherein the cured product layer constituting the functional layer satisfies the following formulas (1) and (2).
Re (450) / Re (550) ≤ 1.00 (1)
100 nm ≤ Re (550) ≤ 150 nm (2)
[In equations (1) and (2), Re (λ) represents an in-plane retardation value at a wavelength of λ nm. ]
[7] The long film according to any one of [1] to [5], wherein the cured product layer constituting the functional layer satisfies the following formulas (3) and (4).
200 nm ≤ Re (550) ≤ 300 nm (3)
1.00 ≤ Re (450) / Re (550) (4)
[In equations (3) and (4), Re (λ) represents an in-plane retardation value at a wavelength of λ nm. ]
[8] The long film according to any one of [1] to [7] above, wherein the functional layer contains a photoalignment film.
[9] The above-mentioned [1] to [1], wherein the molecular orientation direction of the polymerizable liquid crystal compound in the cured product layer constituting the functional layer is substantially vertical with respect to the longitudinal plane of the base film. The long film according to any one of [5].
[10] The long film according to any one of [1] to [5] and [9], wherein the cured product layer constituting the functional layer satisfies the following formula (5).
-150 nm ≤ Rth (550) ≤ -20 nm (5)
[In the formula (5), Rth (550) indicates the phase difference value in the thickness direction of the cured product layer at a wavelength of 550 nm. ]

According to the present invention, it is a long film having a base film and a functional layer including a transferable liquid crystal cured product layer, and the functional layer at the end in the short direction is detached when the base film is peeled off. It is possible to provide a long film that is difficult to produce and can produce an optical film having excellent optical characteristics with high productivity.

It is schematic cross-sectional view which shows an example of the layer structure seen from the short direction of the long film of this invention.

Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described here, and various modifications can be made without impairing the gist of the present invention.

The long film of the present invention is a cured product of a polymerizable liquid crystal composition containing a base film having an uneven portion at at least one end in the short direction of at least one surface and at least one polymerizable liquid crystal compound. It has a transferable functional layer including a layer. In the long film of the present invention, the transferable functional layer is laminated on the surface side of the base film having the uneven portion, and the entire width of the base film in the short direction is A, and the uneven portion existing in the base film. When the total width in the short direction is B and the width in the short direction of the functional layer is C, B + C> A is satisfied.

FIG. 1 is a cross-sectional view showing an example of a layer structure of the long film of the present invention viewed from the short direction, although not limited to this. In FIG. 1, the long film 11 of the present invention is formed by laminating a base film 1 and a functional layer 2. Concavo-convex portions 3 are provided at both ends of the surface on which the functional layer 2 of the base film 1 is laminated, and the functional layer 2 is laminated so as to overlap a part of each uneven portion 3. The total width of the base film 1 in the short direction is A, the total width of the uneven portions 3 provided at both ends of the base film 1 in the short direction is B (B1 + B2 in FIG. 1), and the total width of the functional layer 2 in the short direction When C is, B + C becomes larger than A.

As used herein, the term "transferable functional layer" means a layer capable of peeling off a base film and transferring it to another member such as another base material or an optical film, and is a polymerizable liquid crystal compound. Includes a cured product layer of a polymerizable liquid crystal compound containing the above (hereinafter, also referred to as “liquid crystal cured product layer”). The functional layer may include a layer other than the liquid crystal cured product layer as long as it does not affect the effect of the present invention and can function as an optical film after transfer. As such other layers, an adhesive for adhering an alignment film, a cured resin layer such as a protective layer or a hard coat layer, and a functional layer such as a liquid crystal cured product layer to other members such as a polarizing film. Layers and the like can be mentioned. When the long film of the present invention includes a layer other than the base film and the liquid crystal cured product layer, in the present specification, the functional layer includes all the layers that are peeled off from the base film and transferred to other members. ..

In the long film of the present invention, as described above, the total width of the base film in the short direction is A, the total width of the uneven portions existing in the base film in the short direction is B, and the width of the functional layer in the short direction is C. In some cases, it has a configuration that satisfies B + C> A. That is, in the long film of the present invention, a part of the functional layer is laminated on at least a part of the uneven portion existing in the base film. By providing the uneven portion at the end of the base film, an anchor effect can be generated between the uneven portion and the functional layer laminated on the uneven portion when the functional layer is formed on the base film. , The adhesion is easily improved. Further, since the adhesion in the region not in contact with the uneven portion is relatively lowered, when the functional layer is peeled from the base film, the functional layer is easily peeled off along the uneven portion on the base film.

For example, by providing an uneven portion with a constant width linearly in the long direction at the end of the base film, the functional layer is peeled linearly with respect to the peeling direction (flow direction) at the end of the long film. can do. This suppresses the detachment of the functional layer at the end of the long film during transfer, and the functional layer with a straight and clean end cross section can be transferred to another member, resulting in improved take-up efficiency and yield during use. Can be improved. In addition, since the uneven portion covered with the functional layer is less likely to be pressed during transportation or when stored in a roll shape, and settled with the passage of time (the protrusion of the uneven portion becomes smaller), even after long-term storage. The functional layer can be easily and neatly peeled off from the base film.

It is preferable that the functional layer constituting the long film of the present invention is laminated on the base film over the entire width direction of the functional layer. Therefore, it is preferable that the overall width A in the short direction of the base film and the width C in the short direction of the functional layer have a relationship of A ≧ C, and more preferably A> C.

In the present invention, it is preferable that at least one end of the base film has irregularities linearly in the elongated direction, and both ends of the substrate film are linearly uneven in the elongated direction. It is more preferable that the portion is present. Further, it is more preferable that both ends of the functional layer are laminated so as to overlap with the uneven portions existing at both ends of the base film with a certain width. When the long film has such a structure, the above-mentioned effect of the present invention can be further enhanced when the functional layer is peeled from the base film and transferred to another member. Further, in order to enhance the anchoring effect generated between the base film and the functional layer, a layer on the side adjacent to the base film of the functional layer is formed by being directly applied onto the base film and then cured. Is preferable, for example, a liquid crystal cured product layer or a photoalignment film is preferable.

In the present invention, the peeling force when peeling the functional layer from the base film is preferably 0.02 N / 25 mm or more and less than 1 N / 25 mm. When the peeling force is within the above range, an appropriate adhesion is generated between the functional layer and the base film, so that the functional layer can be peeled along the uneven portion of the base film. At the same time, the functional layer can be easily and neatly peeled from the base film because it has an appropriate peelability while suppressing detachment due to the functional layer adhering to the transport roll or the like during transfer. From the viewpoint of the peelability of the functional layer from the base film and the appropriate adhesion, the peeling force is more preferably 0.03 N / 25 mm or more, further preferably 0.05 N / 25 mm or more, and more preferably. Is 0.5 N / 25 mm or less, more preferably 0.3 N / 25 mm or less. The peeling force depends on the width of the uneven portion provided on the base film, the height and shape of the unevenness, the material constituting the surface of the base film and the functional layer in contact with the base film, the conditions for applying and curing the functional layer, etc. Can be controlled.
In the present invention, the peeling force is based at a speed of 300 mm / min at the interface between the functional layer and the base film, or at the interface between the transferred layer in the functional layer and the layer to be peeled together with the base film. It means the base material peeling force (N / 25 mm) when peeling the material film, and can be specifically measured according to the method described in Examples described later.

In the present invention, it is preferable that the relationship between the in-plane average thickness X of the functional layer and the maximum height Y of the convex portion of the uneven portion satisfies 1.0 <Y / X ≦ 15.0. By satisfying the above relationship between the functional layer and the uneven portion on the base film, the handleability of the long film is easily improved, and the long film is miswound when wound in a roll shape and during long-term storage. The effect of suppressing the deformation (blocking) of the film tends to increase. If the Y / X value becomes too large, sticking is likely to occur remarkably at the edge of the film, and the film roll (wound long film) is likely to be deformed even in the plane. In the present invention, the value of Y / X is more preferably 1.5 or more, further preferably 2.0 or more, still more preferably 12.0 or less, still more preferably 10.0 or less.
In the present invention, the "in-plane average thickness of the functional layer" is an in-plane measurement of the total thickness of all the layers constituting the functional layer in the short direction within a range not including a portion overlapping the uneven portion of the base film. Means the average value. Further, the "maximum height of the convex portion of the uneven portion" means the height from the base film surface without the uneven portion to the apex of the convex portion which is the maximum height in the uneven portion. The in-plane average thickness X of the functional layer and the maximum height Y of the convex portion of the uneven portion can be measured using, for example, a contact film thickness meter, and specifically, the method described in Examples described later. Can be measured according to.

Examples of the base film constituting the long film of the present invention include thin film glass and resin film, but a resin film is preferable from the viewpoint of processability. Examples of the resin constituting the resin film include olefin resins (preferably cyclic olefin resins) such as polyethylene, polypropylene, and norbornene polymers; polyvinyl alcohol; polyethylene terephthalates; polymethacrylic acid esters; polyacrylic acid esters; Cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyether ketone; plastics such as polyphenylene sulfide and polyphenylene oxide. Such a resin can be formed into a film by a known means such as a solvent casting method and a melt extrusion method to form a base material. As long as it does not affect the effect of the present invention, the surface of the base film may be subjected to surface treatment such as mold release treatment such as silicone treatment, corona treatment, and plasma treatment.

A commercially available product may be used as the base film. Examples of the commercially available cellulose ester base material include a cellulose ester base material manufactured by Fuji Photo Film Co., Ltd. such as Fujitac Film. Commercially available cyclic olefin resins include, for example, cyclic olefin resins manufactured by Ticona (Germany) such as "Topas (registered trademark)"; cyclic olefins manufactured by JSR Corporation such as "Arton (registered trademark)". Resins; Cyclic olefin resins manufactured by Nippon Zeon Co., Ltd. such as "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)"; Mitsui such as "Apel" (registered trademark) Cyclic olefin resin manufactured by Chemical Corporation can be mentioned. A commercially available cyclic olefin resin base material can also be used. As commercially available cyclic olefin resin base materials, cyclic olefin resin base materials manufactured by Sekisui Chemical Industry Co., Ltd. such as "Scina (registered trademark)" and "SCA40 (registered trademark)"; "Zeonoa film (registered trademark)" A cyclic olefin resin base material manufactured by Optes Co., Ltd .; a cyclic olefin resin base material manufactured by JSR Corporation such as "Arton Film (registered trademark)" can be mentioned.

The base film is a cellulosic resin film or an olefin-based film from the viewpoints of thinning, easy peeling of the functional layer from the base film, easy orientation of the polymerizable liquid crystal compound, solvent resistance, and low compound refractive property. A resin film is preferable, and a cellulosic resin film is more preferable. In general, a cellulosic resin film produced by a solvent casting method has difficulty in imparting slipperiness to the film surface, has high adhesion to a layer laminated on the film, and is wound into a long roll shape. At that time, sticking is likely to occur. Further, when this long film roll is unwound, the functional layer is in close contact with the base film on the back surface, so that it may be randomly peeled off and partially fall off. Even in such a case, an uneven portion is provided at the end of the base material to further enhance the adhesion with the functional layer in the uneven portion, and in a region without unevenness, between the functional layer and the base film on the back surface. By providing a gap, sticking / dropping in a non-concavo-convex region is suppressed, and an appropriate difference is generated in the adhesion between the base film and the functional layer between the concavo-convex portion and the non-concavo-convex region. , The functional layer can be easily peeled off linearly from the base film in the peeling direction. Therefore, the present invention may be particularly advantageous when a cellulosic resin film is used.

In the present invention, the uneven portion on the base film is so-called knurling, and usually functions as a structure for suppressing contact or sticking between the base film surfaces when the base film is wound up. .. The shape, material, and forming method of such uneven portions may be appropriately selected from conventionally known ones according to the base film and functional layer constituting the long film, the desired peeling force, and the like.

The uneven portion is preferably formed in a desired region at the end of the base film, for example, when the base film is wound up. The uneven portion may be formed on only one surface of the base film or on both sides. Further, the uneven portion may be provided only on at least one end of the base film, but in order to obtain good peelability of the functional layer from the base film, it is provided at both ends of the base film. Is preferable.

It is preferable that the uneven portion is provided in a strip shape parallel to the long direction at the end of the base film in the short direction. The width of the uneven portion provided in the strip shape in the short direction is appropriately determined according to the width in the short direction of the long film, the base film and functional layer constituting the long film, the desired peeling force, the thickness of the long film, and the like. However, usually, the width at each end is about 0.2 to 5% of the width in the short direction of the base film. When the width of each uneven portion in the short direction is within the above range, an appropriate anchor effect is likely to occur between the uneven portion and the functional layer, and good peelability between the base film and the functional layer is likely to be obtained. For example, in the case of a base film having a width in the short direction of 1000 to 2000 mm, the width in the short direction of the uneven portion is preferably 1 mm or more, more preferably 3 mm or more, still more preferably 5 mm or more, and preferably 50 mm or less. It is more preferably 30 mm or less, still more preferably 20 mm or less.

The height of the uneven portion is the width in the short direction of the long film, the width in the short direction of the uneven portion, the thickness of the functional layer, the base film or functional layer constituting the long film, the desired peeling force, and the thickness of the long film. It may be decided as appropriate according to the above. It is preferably 0.5 μm or more, more preferably 1 μm or more, and preferably 500 μm or less, more preferably 200 μm or less, still more preferably 20 μm or less. When the height of each uneven portion is within the above range, an appropriate anchor effect is likely to occur between the uneven portion and the functional layer, and good peelability between the base film and the functional layer is likely to be obtained.
The height of the uneven portion referred to here means the average height of each uneven portion when the surface of the base film having no uneven portion is used as a reference in the base film on which the functional layers are not laminated. Specifically, for example, the average total thickness is calculated by measuring the area where the uneven portion of the base film does not exist with a 1 mm pitch in the width direction using a contact type film thickness meter, and similarly at the same position in the width direction. By calculating the average total thickness of the uneven portion by measuring the range in which the uneven portion exists at the end portion, the average height of the uneven portion can be measured and calculated from the difference.

The number (density) of the unevenness per 1 cm ^{2 of the} uneven portion is preferably 20 or more, more preferably 50 or more, preferably 1000 or less, more preferably 500 or less, still more preferably 200 or less. .. It is preferable that each unevenness is uniformly present in the uneven portion. When the density of each uneven portion is within the above range, an appropriate anchor effect is likely to occur between the uneven portion and the functional layer, and good peelability between the base film and the functional layer is likely to be obtained.

Examples of the shape of each unevenness constituting the uneven portion include a pyramidal trapezoid, a conical trapezoid, a circular hill, a corrugated shape, a lattice shape, and an indeterminate shape. The size of each unevenness includes the width in the short direction of the long film, the width in the short direction of the uneven portion, the density of the uneven portion, the base film and the functional layer constituting the long film, the desired peeling force, the thickness of the long film, etc. It may be decided as appropriate according to the above. For example, when the unevenness is cut in parallel with the film surface on the base film surface, the cross-sectional shape is circular or substantially circular, and the diameter of the cross-sectional shape is preferably about 50 to 1000 μm, more preferably 100 to 100. It is 3000 μm.

As a method of forming the uneven portion on the base film, for example, a method of sandwiching the uneven portion with a pair of rolls is common. It may be a one-sided push using an embossed roll on only one side of a pair of rolls, or a two-sided push using an embossed roll on both sides. In addition, it may be processed with another laser or the like. Specific examples of such uneven portions include those described in International Publication No. 2010/143524, JP-A-2007-91784, and the like.
Further, a commercially available product may be used as the base film having the uneven portion. Examples of commercially available products include cellulose ester substrates manufactured by Konica Minolta Opto Co., Ltd. such as "KC8UX2M", "KC8UY", and "KC4UY".

The thickness of the base film may be appropriately determined according to the material of the base film and the like, but is usually 5 to 300 μm, preferably 10 to 150 μm. From the viewpoint of lengthening the film and quality after winding, it is more preferably 20 to 80 μm.

The width of the base film in the short direction is preferably 0.5 to 3 m, more preferably 0.6 to 2.5 m, and even more preferably 0.8 to 2.2 m. The long film is preferably wound in a roll shape, and the length thereof is preferably 100 to 10000 m, more preferably 500 to 7000 m, and further preferably 1000 to 6000 m per winding roll.

The functional layer constituting the long film of the present invention includes a cured product layer of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound. The cured product layer is a liquid crystal cured product layer in which the polymerizable liquid crystal compound is cured in a state of being oriented in a specific direction such as a horizontal direction or a vertical direction with respect to the cured product layer plane.

In the present invention, the polymerizable liquid crystal compound is a liquid crystal compound having a polymerizable group, particularly a photopolymerizable group. The polymerizable liquid crystal compound is not particularly limited as long as it can form a cured liquid crystal layer having desired optical properties, and for example, a polymerizable liquid crystal compound conventionally known in the field of retardation film can be used.

A polymerizable group is a group that can participate in a polymerization reaction. The photopolymerizable group is a polymerizable group and refers to a group that can participate in the polymerization reaction by a reactive active species generated from the photopolymerization initiator, for example, an active radical or an acid. Examples of the photopolymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxylanyl group, an oxetanyl group and the like. Of these, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxylanyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable. The liquid crystal property exhibited by the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a liotropic liquid crystal, but a thermotropic liquid crystal is preferable in that precise film thickness control is possible. The phase-ordered structure of the thermotropic liquid crystal may be a nematic liquid crystal, a smectic liquid crystal, or a discotic liquid crystal. The polymerizable liquid crystal compound can be used alone or in combination of two or more.

Examples of the polymerizable liquid crystal compound include a polymerizable liquid crystal compound exhibiting positive wavelength dispersibility and a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility, and it is also possible to use only one of the polymerizable liquid crystal compounds. It can be used, or both types of polymerizable liquid crystal compounds can be mixed and used. In an image display device that is transferred from the long film of the present invention and incorporates a functional layer, it is easy to improve the specular hue and it is easy to obtain a long film having excellent optical characteristics. It is preferable that the polymer obtained by polymerizing in the state of being oriented to contains a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility.

From the viewpoint of easily exhibiting reverse wavelength dispersibility, a polymerizable liquid crystal compound having a so-called T-shaped or H-shaped molecular structure is preferable, and from the viewpoint of obtaining stronger reverse wavelength dispersion, polymerizable liquid crystal compound having a T-shaped molecular structure is preferable. Liquid crystal compounds are more preferred.

The polymerizable liquid crystal compound is preferably a compound having the following characteristics (A) to (D).
(A) A compound capable of forming a nematic phase or a smectic phase.
(B) The polymerizable liquid crystal compound has π electrons in the long axis direction (a).
(C) It has π electrons in the direction [intersection direction (b)] that intersects the major axis direction (a).
(D) A polymerizable liquid crystal compound defined by the following formula (i), where the total number of π electrons existing in the major axis direction (a) is N (πa) and the total molecular weight existing in the major axis direction is N (Aa). Π electron density in the major axis direction (a) of
D (πa) = N (πa) / N (Aa) (i)
The polymerizable liquid crystal compound defined by the following formula (ii), where the total number of π electrons existing in the crossing direction (b) is N (πb) and the total molecular weight existing in the crossing direction (b) is N (Ab). Π electron density in the crossing direction (b) of
D (πb) = N (πb) / N (Ab) (ii)
And, the formula (iii)
0 ≦ [D (πa) / D (πb)] <1 (iii)
[That is, the π electron density in the crossing direction (b) is larger than the π electron density in the major axis direction (a)]. As described above, a polymerizable liquid crystal compound having a major axis and π electrons in the crossing direction with respect to the major axis tends to have a T-shaped structure in general.

In the features (A) to (D) above, the major axis direction (a) and the number of π electrons N are defined as follows.
The major axis direction (a) is, for example, the rod-shaped major axis direction of a compound having a rod-like structure.
-The number of π electrons N (πa) existing in the long axis direction (a) does not include π electrons that disappear due to the polymerization reaction.
The number of π electrons N (πa) existing in the major axis direction (a) is the total number of π electrons on the major axis and π electrons conjugated thereto, for example, existing in the major axis direction (a). It contains the number of π electrons present in the ring that satisfies Hückel's law.
-The number of π electrons N (πb) existing in the crossing direction (b) does not include π electrons that disappear due to the polymerization reaction.
The polymerizable liquid crystal compound satisfying the above has a mesogen structure in the major axis direction. The liquid crystal phase (nematic phase, smectic phase) is expressed by this mesogen structure. In one aspect of the present invention, the polymerizable liquid crystal compound is preferably a compound capable of forming a nematic phase.

A nematic phase or a smectic phase is formed by applying a polymerizable liquid crystal compound satisfying the above (A) to (D) on a film (layer) forming a liquid crystal cured film and heating it above the phase transition temperature. Is possible. In the nematic phase or smectic phase formed by orienting the polymerizable liquid crystal compound, the polymerizable liquid crystal compounds are usually oriented so that the major axis directions are parallel to each other, and the major axis direction is the nematic phase or smectic phase. Is the orientation direction of. When such a polymerizable liquid crystal compound is formed into a film and polymerized in a nematic phase or a smectic phase, a polymer film composed of a polymer oriented in the long axis direction (a) can be formed. .. This polymer film absorbs ultraviolet rays by π electrons in the long axis direction (a) and π electrons in the crossing direction (b). Here, the absorption maximum wavelength of ultraviolet rays absorbed by π electrons in the crossing direction (b) is defined as λbmax. λbmax is usually 300 nm to 400 nm. The density of π electrons satisfies the above equation (iii), and since the π electron density in the crossing direction (b) is larger than the π electron density in the major axis direction (a), the oscillating surface in the crossing direction (b). The absorption of linearly polarized ultraviolet rays (wavelength is λbmax) having a vibration plane in the long axis direction (a) is larger than the absorption of linearly polarized ultraviolet rays (wavelength is λbmax) having a vibration plane. The ratio (the ratio of the absorbance in the crossing direction (b) of the linearly polarized ultraviolet rays / the absorbance in the major axis direction (a)) is, for example, more than 1.0, preferably 1.2 or more, usually 30 or less, for example, 10 or less. Is.

In general, a polymerizable liquid crystal compound having the above characteristics often exhibits a reverse wavelength dispersibility in the birefringence of the polymer when polymerized in a state of being oriented in one direction. Specifically, for example, a compound represented by the following formula (X) can be mentioned.

In formula (X), Ar represents a divalent group having an aromatic group which may have a substituent. Examples of the aromatic group referred to here include groups exemplified by (Ar-1) to (Ar-23) described later. Further, Ar may have two or more aromatic groups. The aromatic group may contain at least one or more of a nitrogen atom, an oxygen atom and a sulfur atom. When two or more aromatic groups are contained in Ar, the two or more aromatic groups may be bonded to each other by a single bond or a divalent bonding group such as -CO-O- or -O-. ..
G ¹ and G ² independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, respectively. Here, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and carbon. The carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted with an alkoxy group, a cyano group or a nitro group of the number 1 to 4, and the carbon atom constitutes an oxygen atom or a sulfur atom. Alternatively, it may be substituted with a nitrogen atom.
L ¹ , L ² , B ¹ and B ² are independently single-bonded or divalent linking groups, respectively.
k and l each independently represent an integer of 0 to 3, and satisfy the relationship of 1 ≦ k + l. Here, when 2 ≦ k + l, B ¹ and B ² , G ¹ and G ² may be the same as or different from each other.
E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms, and an alkanediyl group having 4 to 12 carbon atoms is more preferable. Further, the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and -CH _2- contained in the alkanediyl group is -O-, -S-, -C (= O)-. It may be replaced with.
P ¹ and P ² independently represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.

G ¹ and G ² are each independently substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, preferably a 1,4-phenylenediyl group. , A 1,4-cyclohexanediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1 substituted with a methyl group. , 4-phenylenediyl group, unsubstituted 1,4-phenylenediyl group, or unsubstituted 1,4-trans-cyclohexanediyl group, particularly preferably unsubstituted 1,4-phenylenediyl group, or no substituent. It is a substituted 1,4-trans-cyclohexanediyl group.
Further, at least one of a plurality of G ¹ and G ² present is preferably a divalent alicyclic hydrocarbon group, and at least one of G ¹ and G ² bonded to L ¹ or L ² is present. More preferably, it is a divalent alicyclic hydrocarbon group.

L ¹ and L ² are independent of each other, preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a1 OR ^a2- , -R ^a3 COOR ^a4- , -R ^a5. ^{^{^{OCOR a6 -, - R a7 OC}}} = OOR a8 -, - N = N -, - CR c = CR d -, or -C≡C-. Here, R ^a1 to R ^a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^c and R ^d represent an alkyl group or a hydrogen atom having 1 to 4 carbon atoms. L ¹ and ^{L 2} are each independently more preferably a single ^{_{_{bond, -OR a2-1 -, - CH 2}}} -, - CH 2 CH 2 -, - COOR a4-1 -, or ^{-OCOR a6-1} - in is there. Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 independently represent either single bond, -CH _2- , or -CH ₂ CH _2- . L ¹ and L ² are independent, more preferably single bond, -O-, -CH ₂ CH _2- , -COO-, -COOCH ₂ CH _2- , or -OCO-, respectively.

B ¹ and B ² are independent, preferably single bond, alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a9 OR ^a10- , -R ^a11 COOR ^a12- , -R ^a13. OCOR ^a14- or-R ^a15 OC = OOR ^a16- . Here, R ^a9 to R ^a16 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms. B ¹ and B ² are independent, more preferably single-bonded, -OR ^a10-1- , -CH _2- , -CH ₂ CH _2- , ^{-COOR a12-1-} , or -OCOR ^a14-1- . is there. Here, R ^a10-1 , R ^a12-1 , and R ^a14-1 independently represent either single bond, -CH _2- , or -CH ₂ CH _2- . B ¹ and ^{B 2} are each independently more preferably a single _{_{bond, -O -, - CH 2 CH}} 2 -, - COO -, - COOCH 2 CH 2 -, - OCO-, or -OCOCH ₂ CH ₂ - in is there.

From the viewpoint of expressing inverse wavelength dispersibility, k and l are preferably in the range of 2 ≦ k + l ≦ 6, preferably k + l = 4, and more preferably k = 2 and l = 2. When k = 2 and l = 2, a symmetrical structure is obtained, which is preferable.

The polymerizable group represented by P ¹ or P ² includes an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, and an oxylanyl group. , And an oxetanyl group and the like. Of these, acryloyloxy group, methylenedioxy group, vinyl group and vinyloxy group are preferable, and acryloyloxy group and methylenedioxy group are more preferable.

Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle which may have a substituent, and an electron-withdrawing group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring and the like, and a benzene ring and a naphthalene ring are preferable. Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrrolin ring, an imidazole ring, and a pyrazole ring. , Thiazole ring, benzothiazole ring, thienotiazole ring, oxazole ring, benzoxazole ring, phenanthroline ring and the like. Among them, it is preferable to have a thiazole ring, a benzothiazole ring, or a benzofuran ring, and it is more preferable to have a benzothiazole ring. When Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

In the formula (X), the total number of π electrons N _π contained in the group represented by Ar is usually 6 or more, preferably 8 or more, more preferably 10 or more, still more preferably 14 or more. Especially preferably, it is 16 or more. Further, it is preferably 32 or less, more preferably 26 or less, and further preferably 24 or less.

Examples of the aromatic group contained in Ar include the following groups.

In formulas (Ar-1) to (Ar-23), * marks represent connecting parts, and Z ⁰ , Z ¹ and Z ² are independently hydrogen atoms, halogen atoms, and alkyl having 1 to 12 carbon atoms. Group, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, alkylsulfonyl group having 1 to 12 carbon atoms, carboxyl group, fluoroalkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, Alkylthio group with 1 to 12 carbon atoms, N-alkylamino group with 1 to 12 carbon atoms, N, N-dialkylamino group with 2 to 12 carbon atoms, N-alkylsulfamoyl group with 1 to 12 carbon atoms or carbon Represents an N, N-dialkylsulfamoyl group of numbers 2-12. Further, Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

Q ¹ and ^{Q 2} each ^{^{independently, -CR 2 'R 3' -}} , - S -, - NH -, - NR 2 '-, - CO- or -O- and represents, R ^2' and ^{R 3 '} Independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

J ¹ and J ² independently represent a carbon atom or a nitrogen atom, respectively.

Y ¹ , Y ² and Y ³ each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.

W ¹ and W ² independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.

Examples of the aromatic hydrocarbon group in Y ¹ , Y ² and Y ³ include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a biphenyl group, and a phenyl group. , A naphthyl group is preferable, and a phenyl group is more preferable. The aromatic heterocyclic group has 4 to 20 carbon atoms containing at least one heteroatom such as a nitrogen atom such as a frill group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group or a benzothiazolyl group, an oxygen atom and a sulfur atom. Examples thereof include an aromatic heterocyclic group, and a fryl group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group are preferable.

Y ¹ , Y ² and Y ³ may be independently substituted polycyclic aromatic hydrocarbon groups or polycyclic aromatic heterocyclic groups, respectively. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.

Z ⁰ , Z ¹ and Z ² are preferably hydrogen atoms, halogen atoms, alkyl groups having 1 to 12 carbon atoms, cyano groups, nitro groups, and alkoxy groups having 1 to 12 carbon atoms, respectively. ⁰ is more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group, and Z ¹ and Z ² are further preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, and a cyano group. Further, Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

Q ¹ and ^{Q 2,} -NH -, - S -, - NR 2 '-, - O- are preferable, R ^2' is preferably a hydrogen atom. Of these, -S-, -O-, and -NH- are particularly preferable.

Among the formulas (Ar-1) to (Ar-23), the formulas (Ar-6) and (Ar-7) are preferable from the viewpoint of molecular stability.

In formulas (Ar-16) to (Ar-23), Y ¹ may form an aromatic heterocyclic group together with the nitrogen atom to which it is attached and Z ⁰ . Examples of the aromatic heterocyclic group include those described above as the aromatic heterocycle that Ar may have. For example, a pyrrole ring, an imidazole ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and an indol. Examples thereof include a ring, a quinoline ring, an isoquinoline ring, a purine ring, and a pyrrolidine ring. This aromatic heterocyclic group may have a substituent. Further, Y ¹ may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted as described above, together with the nitrogen atom to which the Y ¹ is bonded and Z ⁰ . For example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring and the like can be mentioned.

In the present invention, as the polymerizable liquid crystal compound forming the liquid crystal cured product layer, for example, a compound containing a group represented by the following formula (Y) (hereinafter, also referred to as “polymerizable liquid crystal compound (Y)”) may be used. Good. The polymerizable liquid crystal compound (Y) generally tends to exhibit positive wavelength dispersibility. These polymerizable liquid crystal compounds can be used alone or in combination of two or more.

P11-B11-E11-B12-A11-B13- (Y)
[In formula (Y), P11 represents a polymerizable group.
A11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group.
B11 is -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ^16- , -NR ^16- CO-, -CO-,- Represents CS- or single bond. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
B12 and B13 are independently -C≡C-, -CH = CH-, -CH _2- CH _2-, -O-, -S-, -C (= O)-, -C (= O). ) -O-, -OC (= O)-, -OC (= O) -O-, -CH = N-, -N = CH-, -N = N-, -C (= O) ) -NR ^16- , -NR ^16- C (= O)-, -OCH _2- , -OCF _2- , -CH ₂ O-, -CF ₂ O-, -CH = CH-C (= O)- Represents O-, -OC (= O) -CH = CH-, -H, -C≡N or a single bond.
E11 represents an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms, and the hydrogen atom contained in the alkoxy group may be substituted. May be substituted with a halogen atom. Further, -CH _2- constituting the alkanediyl group may be replaced with -O- or -CO-. ]

The carbon number of the aromatic hydrocarbon group and the alicyclic hydrocarbon group of A11 is preferably in the range of 3 to 18, more preferably in the range of 5 to 12, and particularly preferably in the range of 5 or 6. preferable. The hydrogen atom contained in the divalent alicyclic hydrocarbon group represented by A11 and the divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and the like. It may be substituted with a cyano group or a nitro group, and the hydrogen atom contained in the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be substituted with a fluorine atom. As A11, a cyclohexane-1,4-diyl group and a 1,4-phenylene group are preferable.

As E11, a linear alkanediyl group having 1 to 12 carbon atoms is preferable. -CH _2- constituting the alkanediyl group may be replaced with -O-.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane. -1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group and dodecane-1,12- linear alkanediyl group having 1 to 12 carbon atoms such as diyl _{_{_{_{group; -CH 2 -CH 2 -O-CH}}}} 2 -CH 2 -, - CH 2 -CH 2 -O-CH 2 -CH 2 -O- CH ₂ -CH ₂ - and _{_{_{_{-CH 2 -CH 2 -O-CH 2}}}} -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 - and the like.
As B11, -O-, -S-, -CO-O-, and -O-CO- are preferable, and -CO-O- is more preferable.
As B12 and B13, -O-, -S-, -C (= O)-, -C (= O) -O-, -OC (= O)-, -OC, respectively. (= O) -O- is preferable, and -O- or -OC (= O) -O- is more preferable.

As the polymerizable group represented by P11, a radically polymerizable group or a cationically polymerizable group is preferable in that it has high polymerization reactivity, particularly photopolymerization reactivity, and it is easy to handle and the liquid crystal compound itself is easy to produce. Therefore, the polymerizable group is preferably a group represented by the following formulas (P-11) to (P-15).

[In formulas (P-11) to (P-15),
R ¹⁷ to R ²¹ each independently represent an alkyl group or a hydrogen atom having 1 to 6 carbon atoms. ]

Specific examples of the groups represented by the formulas (P-11) to (P-15) include the groups represented by the following formulas (P-16) to (P-20).

P11 is preferably a group represented by the formulas (P-14) to (P-20), and more preferably a vinyl group, a p-stilbene group, an epoxy group or an oxetanyl group.
It is more preferable that the group represented by P11-B11- is an acryloyloxy group or a methacryloyloxy group.

Examples of the polymerizable liquid crystal compound (Y) include compounds represented by formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI).
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-B16-E12-B17-P12 (I)
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-F11 (II)
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-E12-B17-P12 (III)
P11-B11-E11-B12-A11-B13-A12-B14-A13-F11 (IV)
P11-B11-E11-B12-A11-B13-A12-B14-E12-B17-P12 (V)
P11-B11-E11-B12-A11-B13-A12-F11 (VI)
[During the ceremony,
A11, B11 to B13 and P11 are synonymous with the above.
A12 to A14 are independently synonymous with A11, B14 to B16 are independently synonymous with B12, B17 is synonymous with B11, E12 is synonymous with E11, and P12 is synonymous with P11. is there.
F11 is a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxyl group, a methylol group, a formyl group, and a sulfo group. _(-SO 3 H), carboxyl, alkoxycarbonyl group or a halogen atom having 1 to 10 carbon atoms, -CH ₂ constituting the alkyl group and alkoxy group - is also have I replace the -O- Good. ]

As a specific example of the polymerizable liquid crystal compound (Y), "3.8.6 network (completely crosslinked type)" of the liquid crystal handbook (edited by the liquid crystal handbook editorial committee, published by Maruzen Co., Ltd. on October 30, 2000). , A compound having a polymerizable group among the compounds described in "6.5.1 Liquid crystal material b. Polymerizable nematic liquid crystal material", JP-A-2010-31223, JP-A-2010-270108, JP-A. Examples thereof include the polymerizable liquid crystals described in JP-A-2011-6360 and JP-A-2011-207765.

Specific examples of the polymerizable liquid crystal compound (Y) include the following formulas (I-1) to (I-4), formulas (II-1) to (II-4), and formulas (III-1) to formulas (III-1) to. (III-26), formulas (IV-1) to formulas (IV-26), formulas (V-1) to formulas (V-2), and formulas (VI-1) to formulas (VI-6). Examples include compounds. In the following formula, k1 and k2 independently represent integers of 2 to 12. These polymerizable liquid crystal compounds (Y) are preferable in terms of ease of synthesis or availability.

Both the polymerizable liquid crystal compounds (X) and (Y) can be used in a horizontal orientation or in a vertical orientation.

Among the polymerizable liquid crystal compounds, it is preferable that the polymerizable liquid crystal compound has a maximum absorption wavelength between 300 and 400 nm. When the polymerizable liquid crystal composition contains a photopolymerization initiator, the polymerization reaction and gelation of the polymerizable liquid crystal compound may proceed during long-term storage. However, if the maximum absorption wavelength of the polymerizable liquid crystal compound is 300 to 400 nm, even if ultraviolet light is exposed during storage, the reaction active species are generated from the photopolymerization initiator and the polymerizable liquid crystal compound by the reactive liquid compound is generated. The progress of polymerization reaction and gelation can be effectively suppressed. Therefore, it is advantageous in terms of long-term stability of the polymerizable liquid crystal composition, and the orientation and film thickness uniformity of the obtained liquid crystal cured film can be improved. The maximum absorption wavelength of the polymerizable liquid crystal compound can be measured in a solvent using an ultraviolet-visible spectrophotometer. The solvent is a solvent capable of dissolving a polymerizable liquid crystal compound, and examples thereof include chloroform.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, based on 100 parts by mass of the solid content of the polymerizable liquid crystal composition. Yes, more preferably 85 to 98 parts by mass, still more preferably 90 to 95 parts by mass. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured product layer. When the polymerizable liquid crystal composition contains two or more kinds of polymerizable liquid crystal compounds, it is preferable that the total amount of all the liquid crystal compounds contained in the polymerizable liquid crystal composition is within the above content range. Further, in the present specification, the solid content of the polymerizable liquid crystal composition means all the components excluding volatile components such as organic solvents from the polymerizable liquid crystal composition.

In addition to the polymerizable liquid crystal compound, the polymerizable liquid crystal composition further contains additives such as a solvent, a photopolymerization initiator, a leveling agent, an antioxidant, a photosensitizer, a vertical orientation accelerator, and a polymerizable non-liquid crystal compound. It may be included. As for each of these components, only one kind may be used, or two or more kinds may be used in combination.

Since the polymerizable liquid crystal composition is usually applied to a base film or the like in a state of being dissolved in a solvent, it is preferable to contain a solvent. As the solvent, a solvent capable of dissolving the polymerizable liquid crystal compound is preferable, and a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound is preferable. Examples of the solvent include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol and alcohols such as propylene glycol monomethyl ether. Solvents: Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone. Ketone solvent; aliphatic hydrocarbon solvent such as pentane, hexane and heptane; alicyclic hydrocarbon solvent such as ethylcyclohexane; aromatic hydrocarbon solvent such as toluene and xylene; nitrile solvent such as acetonitrile; tetrahydrofuran and dimethoxyethane and the like Ether solvent; chlorine-containing solvent such as chloroform and chlorobenzene; amide-based solvent such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone, etc. Be done. These solvents can be used alone or in combination of two or more. Above all, from the viewpoint of film coating, it is preferable to use at least one selected from an alcohol solvent, an ester solvent, a ketone solvent, a chlorine-containing solvent, an amide solvent and an aromatic hydrocarbon solvent, and the solubility of the polymerizable liquid crystal compound is preferable. From the above viewpoint, it is more preferable to use at least one selected from an ester solvent, a ketone solvent, an amide solvent, and an aromatic hydrocarbon solvent.

The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, and more preferably 70 to 95 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content in 100 parts by mass of the polymerizable liquid crystal composition is preferably 2 to 50 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition is low, so that the thickness of the film becomes substantially uniform, and unevenness tends to be less likely to occur. The solid content can be appropriately determined in consideration of the thickness of the polymerizable liquid crystal cured product layer to be produced.

The polymerization initiator is a compound that can generate a reactive species by the contribution of heat or light and initiate a polymerization reaction such as a polymerizable liquid crystal compound. Examples of the reactive active species include active species such as radicals or cations or anions. Of these, a photopolymerization initiator that generates radicals by light irradiation is preferable from the viewpoint of easy reaction control.

Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, triazine compounds, iodonium salts and sulfonium salts. Specifically, Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (above, BASF Japan Co., Ltd.) (Made), Sakeol BZ, Sakeall Z, Sakeol BEE (manufactured by Seiko Kagaku Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), ADEKA PUTMER SP- 152, ADEKA OPTMER SP-170, ADEKA OPTMER N-1717, ADEKA OPTMER N-1919, ADEKA ARCULDS NCI-831, ADEKA ARCULDS NCI-930 (all manufactured by ADEKA Corporation), TAZ-A, TAZ -PP (above, manufactured by Nippon Sibel Hegner) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.) can be mentioned.
The photopolymerization initiator contained in the polymerizable liquid crystal composition is at least one kind, and a plurality of kinds may be used in combination, but one kind or two kinds are preferable.

Since the photopolymerization initiator can fully utilize the energy emitted from the light source and is excellent in productivity, the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, and above all, the α-acetophenone type. A polymerization initiator and an oxime-based photopolymerization initiator are preferable.

Examples of the α-acetophenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1. -On and 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butane-1-one and the like, more preferably 2-methyl-2-morpholino-1- ( Included are 4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-one. Examples of commercially available α-acetophenone compounds include Irgacure 369, 379EG, 907 (all manufactured by BASF Japan Ltd.) and Sequol BEE (manufactured by Seiko Kagaku Co., Ltd.).

The oxime ester-based photopolymerization initiator generates radicals such as phenyl radicals and methyl radicals when irradiated with light. The polymerization of the polymerizable liquid crystal compound proceeds preferably by this radical, and among them, the oxime ester-based photopolymerization initiator that generates a methyl radical is preferable in that the polymerization reaction initiation efficiency is high. Further, from the viewpoint of allowing the polymerization reaction to proceed more efficiently, it is preferable to use a photopolymerization initiator that can efficiently utilize ultraviolet rays having a wavelength of 350 nm or more. As the photopolymerization initiator capable of efficiently utilizing ultraviolet rays having a wavelength of 350 nm or more, a triazine compound or a carbazole compound having an oxime ester structure is preferable, and a carbazole compound having an oxime ester structure is more preferable from the viewpoint of sensitivity. Commercially available oxime ester-based photopolymerization initiators include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, manufactured by BASF Japan Ltd.), ADEKA PUTMER N-1919, and ADEKA ARCULDS NCI-831. (The above is manufactured by ADEKA CORPORATION) and the like.

The content of the photopolymerization initiator is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. Is. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and the orientation of the polymerizable liquid crystal compound is not easily disturbed.

In the present invention, an antioxidant may be added to the composition for the purpose of controlling the stability of the composition. The antioxidant may be a primary antioxidant selected from phenol-based antioxidants, amine-based antioxidants, quinone-based antioxidants, and nitroso-based antioxidants, as well as phosphorus-based antioxidants and sulfur. It may be a secondary antioxidant selected from the system antioxidants. When the polymerizable group of the polymerizable liquid crystal compound is a radically polymerizable group, phosphorus-based antioxidants and sulfur-based antioxidants, which are secondary antioxidants, are preferable from the viewpoint that the reaction is not easily inhibited.

The content of the antioxidant is preferably 0.01 to 3.0 parts by mass, and more preferably 0.01 to 1.0 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound.

By using a sensitizer, the photopolymerization initiator can be made highly sensitive. Examples of the photosensitizer include xanthones such as xanthones and thioxanthones; anthracenes having substituents such as anthracene and alkyl ethers; phenothiazines; rubrenes. Examples of the photosensitizer include xanthones such as xanthones and thioxanthones; anthracenes having substituents such as anthracene and alkyl ethers; phenothiazines; rubrenes.

The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 0.1 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. 3 parts by mass.

The leveling agent is an additive having a function of adjusting the fluidity of the polymerizable liquid crystal composition and flattening the coating film obtained by applying the composition, for example, silicone-based, polyacrylate-based and par. Fluoroalkyl-based leveling agents can be mentioned. Commercially available products may be used as the leveling agent. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Toray Dow Corning Co., Ltd.). , KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all of which are made by Momentive Performance Materials Japan LLC), Florinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (all of which are Sumitomo 3M Co., Ltd.) (Manufactured by), Megafuck (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-470, F -477, F-479, F-482, F-483 (all manufactured by DIC Co., Ltd.), Ftop (trade name) EF301, EF303, EF351, EF352 (all Mitsubishi) Material Denshi Kasei Co., Ltd.), Surflon (registered trademark) S-381, S-382, S-383, S-393, SC-101, SC-105, KH-40, SA-100 (All of the above are manufactured by AGC Seimi Chemical Co., Ltd.), trade name E1830, E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N ( In each case, the product name: BM Chemie) and the like can be mentioned. The leveling agent can be used alone or in combination of two or more.

The content of the leveling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, the obtained liquid crystal cured product layer tends to be smoother, which is preferable.

The polymerizable liquid crystal composition can be obtained by stirring the polymerizable liquid crystal compound and components other than the polymerizable liquid crystal compound such as a solvent and a photopolymerization initiator at a predetermined temperature.

In one aspect of the present invention, the cured product layer (liquid crystal cured product layer) included in the functional layer has optical properties represented by the following formulas (1) and (2). The liquid crystal cured product layer is usually a cured product obtained by curing the polymerizable liquid crystal compound in a state of being horizontally oriented with respect to the surface of the cured product layer (hereinafter, also referred to as "horizontally oriented liquid crystal cured product layer"). is there.
Re (450) / Re (550) ≤ 1.00 (1)
100 nm ≤ Re (550) ≤ 150 nm (2)
[In equations (1) and (2), Re (λ) represents an in-plane retardation value at a wavelength of λ nm. ]
When the formula (1) is satisfied, the liquid crystal cured product layer exhibits so-called inverse wavelength dispersibility in which the in-plane retardation value at a short wavelength is smaller than the in-plane retardation value at a long wavelength. This is because the reverse wavelength dispersibility is improved and the front hue is improved when an elliptical polarizing plate obtained by transferring the functional layer including the liquid crystal cured product layer from the long film of the present invention to a polarizing film is applied to a display device. , Re (450) / Re (550) is preferably 0.70 or more, more preferably 0.78 or more, and preferably less than 1, more preferably 0.95 or less, still more preferably 0.92. It is as follows.

The in-plane retardation value can be adjusted by adjusting the thickness dA of the liquid crystal cured product layer. The in-plane phase difference value is calculated by the following formula:
Re (λ) = (nxA (λ) -nyA (λ)) × dA
[In the formula, nxA (λ) represents the main refractive index at the wavelength λ in the layer plane of the cured liquid crystal layer, and nyA (λ) is the wavelength λ in the same plane as nxA and orthogonal to the direction of nxA. Represents the refractive index at, dA represents the layer thickness of the liquid crystal cured product layer]
In order to obtain a desired in-plane retardation value (Re (λ): in-plane retardation value of the liquid crystal cured product layer at wavelength λ (nm)), the three-dimensional refractive index and layer thickness dA are determined. And can be adjusted. The three-dimensional refractive index depends on the molecular structure and orientation of the polymerizable liquid crystal compound.

Further, when the in-plane phase difference Re (550) of the liquid crystal cured product layer is within the range of the formula (2), the liquid crystal cured product layer functions as a so-called λ / 4 plate, and the functional layer including this functions as a display device. It is excellent in the effect of improving the specular hue when applied to. A more preferable range of the in-plane retardation value is 130 nm ≦ Re (550) ≦ 150 nm.

Further, the cured product layer included in the functional layer may have optical characteristics represented by the following formula (3) instead of the above formula (2). In this case, the optical characteristics satisfying the formula (4) are obtained. It is preferable to have. Such a liquid crystal cured product layer is also usually a horizontally oriented liquid crystal cured product layer formed by curing the polymerizable liquid crystal compound in a state of being horizontally oriented with respect to the cured product layer plane.
200 nm ≤ Re (550) ≤ 300 nm (3)
1.00 ≤ Re (450) / Re (550) (4)
[In equations (3) and (4), Re (λ) represents an in-plane retardation value of the liquid crystal cured product layer at a wavelength of λ nm. ]
When the liquid crystal cured product layer satisfies the formulas (3) and (4), the liquid crystal cured product layer functions as a so-called λ / 2 plate, and the specular hue is improved when the functional layer including the liquid crystal cured product layer is applied to the display device. Excellent effect. A more preferable range of the in-plane retardation value Re (550) in this case is 220 nm ≦ Re (550) ≦ 280 nm.

In another aspect of the present invention, the cured product layer (liquid crystal cured product layer) included in the functional layer has optical characteristics represented by the following formula (5). The liquid crystal cured product layer is usually a cured product obtained by curing the polymerizable liquid crystal compound in a state of being oriented perpendicular to the plane of the liquid crystal cured product layer (hereinafter, also referred to as "vertically oriented liquid crystal cured product layer"). Is.
-150 nm ≤ Rth (550) ≤ -20 nm (5)
[In the formula (5), Rth (550) represents the phase difference value in the thickness direction of the cured product layer at a wavelength of 550 nm. ]
When the phase difference value Rth (550) in the thickness direction of the liquid crystal cured product layer is within the range of the equation (5), the effect of improving the orthorhombic reflection hue when the functional layer including this is applied to the display device is excellent. A more preferable range of the retardation value is −30 nm ≦ Rth (550) ≦ -100 nm.

In the present invention, when the cured product layer included in the functional layer is a vertically oriented liquid crystal cured product layer, the liquid crystal cured product layer preferably satisfies the following formula (6), and formulas (5) and (6) are simultaneously applied. It is more preferable to meet.
Rth (450) / Rth (550) ≤ 1.00 (6)
[In the formula (6), Rth (λ) represents the phase difference value in the thickness direction of the cured product layer at the wavelength λ nm. ]
By satisfying the above formula (5), it is possible to suppress a decrease in ellipticity on the short wavelength side in the functional layer including the vertically oriented liquid crystal cured product layer, and it is possible to improve the orthorhombic reflection hue. The value of Rth (450) / Rth (550) is more preferably 0.95 or less, further preferably 0.92 or less, particularly preferably 0.9 or less, and preferably 0.7 or more. , More preferably 0.75 or more, still more preferably 0.8 or more. Rth (λ) can be controlled by the three-dimensional refractive index and the film thickness dC.

The phase difference value in the thickness direction is the following formula: Rth (λ) = ((nxC (λ) + nyC (λ)) / 2-nzC (λ)) × dC
[In the formula, nxC (λ) is the in-plane main refractive index of the liquid crystal cured product layer at a wavelength of λ nm, and nyC (λ) is the refractive index at wavelength λ nm in the direction orthogonal to nxC (λ), nzC ( λ) indicates the refractive index in the thickness direction of the liquid crystal cured product layer at a wavelength of λ nm, and when nxC (λ) = nyC (λ), nxC (λ) is the refractive index in any direction in the film plane. DC indicates the thickness of the cured liquid crystal layer]
Therefore, in order to obtain the phase difference value Rth (550) in the desired film thickness direction, the three-dimensional refractive index and the film thickness dC may be adjusted. The three-dimensional refractive index depends on the molecular structure and orientation of the polymerizable liquid crystal compound.

The thickness of the liquid crystal cured product layer is preferably 0.1 to 5.0 μm, more preferably 0.2 to 4.0 μm, and even more preferably 0.4 to 3.0 μm. As the thickness of the liquid crystal cured layer increases, the mechanical strength also increases and the functional layer tends to be difficult to cut. If the thickness of the liquid crystal cured product layer is within the above range, the functional layer is transferred to another optical film or the like. It is easy for the optics to occur. In the present invention, since a part of the functional layer is laminated on the uneven portion provided at the end portion of the base film, the occurrence of scratching is effectively suppressed by the appropriate anchor effect generated at the end portion. It is possible to obtain the effect of the present invention more remarkably when the thickness is in the above range.

The long film of the present invention is, for example,
A coating film of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound is formed on a long base film or an alignment film described later, and the coating film is dried and the polymerizable liquid crystal composition is formed. The step of orienting the polymerizable liquid crystal compound in the liquid crystal composition, and
It can be produced by a method including a step of polymerizing a polymerizable liquid crystal compound by light irradiation while maintaining an oriented state to form a cured liquid crystal layer.

In the present invention, the coating film of the polymerizable liquid crystal composition is on a base film constituting the long film of the present invention, or on an alignment film formed on a long base film as described later. It can be formed by applying a polymerizable liquid crystal composition to the film. Examples of the method for applying the polymerizable liquid crystal composition to a base film or the like include a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an applicator method and other coating methods, and a flexographic method and the like. Known methods such as a method can be mentioned.

Then, the solvent is removed by drying or the like to form a dry coating film. Examples of the drying method include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method. At this time, the coating film obtained from the polymerizable liquid crystal composition is heated to dry-remove the solvent from the coating film, and the polymerizable liquid crystal compound is placed in a desired direction (for example, horizontal or vertical) with respect to the coating film plane. Can be oriented in the direction). The heating temperature of the coating film can be appropriately determined in consideration of the polymerizable liquid crystal compound to be used and the material of the base material or the like forming the coating film, but in order to make the polymerizable liquid crystal compound phase transition to the liquid crystal phase state, Usually, it is necessary that the temperature is equal to or higher than the liquid crystal phase transition temperature. In order to bring the polymerizable liquid crystal compound into a desired orientation state while removing the solvent contained in the polymerizable liquid crystal composition, for example, the liquid crystal phase transition temperature (smetic phase) of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. It can be heated to a temperature higher than the transition temperature or the nematic phase transition temperature). The heating temperature is preferably 3 ° C. or higher, more preferably 5 ° C. or higher, higher than the liquid crystal phase (nematic phase) transition temperature of the polymerizable liquid crystal compound. The upper limit of the heating temperature is not particularly limited, but is preferably 180 ° C. or lower, more preferably 150 ° C. or lower in order to avoid damage to the coating film, the base material, etc. due to heating.
The liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like. When two or more kinds of polymerizable liquid crystal compounds are used in combination, the phase transition temperature is a polymerization in which all the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition are mixed at the same ratio as the composition in the polymerizable liquid crystal composition. It means a temperature measured by using a mixture of sex liquid crystal compounds in the same manner as when one kind of polymerizable liquid crystal compound is used. Further, it is generally known that the liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition may be lower than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound alone.

The heating time can be appropriately determined depending on the heating temperature, the type of the polymerizable liquid crystal compound used, the type of the solvent, its boiling point and its amount, etc., but is usually 0.5 to 10 minutes, preferably 0.5. ~ 5 minutes.

The solvent may be removed from the coating film at the same time as heating the polymerizable liquid crystal compound to the liquid crystal phase transition temperature or higher, or separately, but it is preferable to remove the solvent at the same time from the viewpoint of improving productivity. Before heating the polymerizable liquid crystal compound to a temperature equal to or higher than the liquid crystal phase transition temperature, the solvent in the coating film is appropriately added under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize. A pre-drying step may be provided for removal. Examples of the drying method in the pre-drying step include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method, and the drying temperature (heating temperature) in the drying step is the type of polymerizable liquid crystal compound used and the solvent. It can be appropriately determined according to the type of the above, its boiling point, its amount and the like.

Next, in the obtained dry coating film, the polymerizable liquid crystal compound is polymerized by light irradiation while maintaining the orientation state of the polymerizable liquid crystal compound, whereby the polymer of the polymerizable liquid crystal compound existing in the desired orientation state is used. A certain liquid crystal cured product layer is formed. As the polymerization method, a photopolymerization method is usually used. In photopolymerization, the light irradiating the dry coating film includes the type of photopolymerization initiator contained in the dry coating film and the type of polymerizable liquid crystal compound (particularly, the type of polymerizable group contained in the polymerizable liquid crystal compound). And appropriately selected according to the amount. Specific examples thereof include one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays and γ-rays, and active energy rays such as active electron beams. Be done. Among them, ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction and it is possible to use a photopolymerization apparatus widely used in the art, so that photopolymerization can be performed by ultraviolet light. It is preferable to select the type of the polymerizable liquid crystal compound or the photopolymerization initiator contained in the polymerizable liquid crystal composition. Further, at the time of polymerization, the polymerization temperature can be controlled by irradiating light while cooling the dry coating film by an appropriate cooling means. By adopting such a cooling means, if the polymerizable liquid crystal compound is polymerized at a lower temperature, the liquid crystal cured product layer can be appropriately formed even if the base material has a relatively low heat resistance. It is also possible to promote the polymerization reaction by raising the polymerization temperature within a range in which defects due to heat during light irradiation (deformation due to heat of the base material, etc.) do not occur. At the time of photopolymerization, a patterned cured product layer can also be obtained by masking or developing.

Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excima laser, and a wavelength range. Examples thereof include an LED light source that emits 380 to 440 nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.

The ultraviolet irradiation intensity is usually 10 to 3,000 mW / cm ² . The ultraviolet irradiation intensity is preferably the intensity in the wavelength region effective for activating the photopolymerization initiator. The time for irradiating light is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, still more preferably 0.1 seconds to 1 minute. is there. When irradiated once or multiple times with such an ultraviolet irradiation intensity, the integrated light intensity is 10 to 3,000 mJ / cm ² , preferably 50 to 2,000 mJ / cm ² , and more preferably 100 to 1,000 mJ / cm. It is ² . When the integrated light amount is within this range, the polymerizable liquid crystal composition is sufficiently cured and good transferability can be obtained. In addition, it is possible to suppress the coloring of the entire long film including the liquid crystal cured product layer.

In one aspect of the present invention, the liquid crystal cured product layer can be formed on the alignment film. The alignment film has an orientation regulating force that orients the polymerizable liquid crystal compound in a desired direction. Among these, an alignment film having an orientation regulating force for orienting a polymerizable liquid crystal compound in the horizontal direction may be referred to as a horizontal alignment film, and an alignment film having an orientation restricting force for orienting a polymerizable liquid crystal compound in the vertical direction may be referred to as a vertical alignment film. By forming the liquid crystal cured product layer on the alignment film, it is possible to obtain a liquid crystal cured product layer in which the polymerizable liquid crystal compound is accurately oriented, and a functional layer exhibiting excellent optical characteristics when incorporated into a display device or the like can be obtained. Obtainable. The orientation regulating force can be arbitrarily adjusted according to the type of alignment film, surface condition, rubbing conditions, etc., and when the alignment film is formed of a photoalignable polymer, it is arbitrarily adjusted according to polarization irradiation conditions, etc. It is possible to do.

The alignment film preferably has solvent resistance that does not dissolve when the polymerizable liquid crystal composition is applied, and also has heat resistance in heat treatment for removing the solvent and aligning the polymerizable liquid crystal compound. Examples of the alignment film include an alignment film containing an orientation polymer, a photoalignment film, a grub alignment film having an uneven pattern or a plurality of grooves on the surface, a stretched film stretched in the orientation direction, and the like, and the accuracy of the orientation angle A photoalignment film is preferable from the viewpoint of quality.

Examples of the oriented polymer include polyamides and gelatins having an amide bond in the molecule, polyimide having an imide bond in the molecule and polyamic acid, which is a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, and poly. Examples thereof include oxazol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid esters. Of these, polyvinyl alcohol is preferable. The oriented polymer can be used alone or in combination of two or more.

The alignment film containing the alignment polymer is usually formed by applying a composition in which the alignment polymer is dissolved in a solvent (hereinafter, also referred to as “alignment polymer composition”) to a surface such as a base film on which the alignment film should be formed. , The solvent is removed, or the oriented polymer composition is applied to the substrate, the solvent is removed, and rubbing is performed (rubbing method). Examples of the solvent include the same solvents as those exemplified above as the solvents that can be used in the polymerizable liquid crystal composition.

The concentration of the oriented polymer in the oriented polymer composition may be in the range where the oriented polymer material can be completely dissolved in the solvent, but is preferably 0.1 to 20% in terms of solid content with respect to the solution, and is 0. .1 to 10% is more preferable.

As the orientation polymer composition, a commercially available alignment film material may be used as it is. Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark, manufactured by JSR Corporation).

Examples of the method of applying the oriented polymer composition to the surface of the base film or the like on which the oriented film should be formed include the same methods as those exemplified as the method of applying the polymerizable liquid crystal composition to the base film.

Examples of the method for removing the solvent contained in the oriented polymer composition include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.

A rubbing process can be performed as needed to impart orientation regulating force to the alignment film (rubbing method). As a method of imparting orientation-regulating force by the rubbing method, a rubbing cloth is wrapped around a rotating rubbing roll, and an orientation polymer composition is applied to the substrate and annealed to form the surface of the substrate. A method of contacting a film of an oriented polymer can be mentioned. If masking is performed during the rubbing treatment, a plurality of regions (patterns) having different orientation directions can be formed on the alignment film.

The photoalignment film is usually a base material on which a composition containing a polymer and / or a monomer having a photoreactive group and a solvent (hereinafter, also referred to as “composition for forming a photoalignment film”) is to be formed. It is obtained by coating on a surface, removing the solvent, and then irradiating with polarized light (preferably polarized UV). The photoalignment film is also advantageous in that the direction of the orientation regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.

A photoreactive group is a group that produces a liquid crystal alignment ability when irradiated with light. Specific examples thereof include groups involved in photoreactions that are the origin of liquid crystal orientation ability such as molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction generated by light irradiation. Of these, groups involved in the dimerization reaction or photocrosslinking reaction are preferable because they are excellent in orientation. As the photoreactive group, an unsaturated bond, particularly a group having a double bond is preferable, and a carbon-carbon double bond (C = C bond), a carbon-nitrogen double bond (C = N bond), and a nitrogen-nitrogen bond are used. A group having at least one selected from the group consisting of a double bond (N = N bond) and a carbon-oxygen double bond (C = O bond) is particularly preferable.

Examples of the photoreactive group having a C = C bond include a vinyl group, a polyene group, a stilbene group, a stillbazole group, a stillvazolium group, a chalcone group, a cinnamoyl group and the like. Examples of the photoreactive group having a C = N bond include a group having a structure such as an aromatic Schiff base and an aromatic hydrazone. Examples of the photoreactive group having an N = N bond include an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, a formazan group, and a group having an azoxybenzene structure. Examples of the photoreactive group having a C = O bond include a benzophenone group, a coumarin group, an anthraquinone group, a maleimide group and the like. These groups may have substituents such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group and an alkyl halide group.

Among them, a photoreactive group involved in a photodimerization reaction is preferable, and a photoalignment film having a relatively small amount of polarized light required for photoalignment and excellent thermal stability and stability over time can be easily obtained. The photoreactive group is preferably a cinnamoyl group or a chalcone group. In particular, when the cured liquid crystal layer is formed of a polymerizable liquid crystal compound having a (meth) acryloyloxy group as a polymerizable group, the adhesion to the cured liquid crystal layer can be further improved, so that the alignment film can be formed. As the polymer having a photoreactive group to be formed, a polymer having a cinnamoyl group such that the terminal portion of the side chain of the polymer has a cinnamoic acid structure is particularly preferable.

Examples of the solvent contained in the composition for forming a photoalignment film include the same solvents as those exemplified above as the solvents that can be used in the polymerizable liquid crystal composition, and the solubility of the polymer or monomer having a photoreactive group can be mentioned. It can be appropriately selected accordingly.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted depending on the type of the polymer or monomer and the thickness of the target photo-alignment film, but the composition for forming a photo-alignment film. It is preferably at least 0.2% by mass, more preferably in the range of 0.3 to 10% by mass, based on the mass of the above. Further, the polymer forming the photoalignment film is easy to produce, and when the oriented liquid crystal cured product layer is formed from a polymerizable liquid crystal compound having a (meth) acryloyloxy group as a polymerizable group, the liquid crystal curing is performed. A (meth) acrylic polymer is preferable because it can improve the adhesion to the material layer. The composition for forming a photoalignment film may contain a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer as long as the characteristics of the photoalignment film are not significantly impaired.

Examples of the method of applying the composition for forming a photoalignment film to the surface on which the alignment film should be formed include the same method as the method of applying the alignment polymer composition. Examples of the method for removing the solvent from the applied composition for forming a photoalignment film include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.

In order to irradiate the polarized light, the polarized UV may be directly irradiated to the composition for forming the photoalignment film coated on the surface on which the alignment film should be formed from which the solvent is removed. Further, it is particularly preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in the wavelength range in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength in the range of 250 to 400 nm is particularly preferable. Examples of the light source used for the polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet light lasers such as KrF and ArF, and high-pressure mercury lamps, ultra-high pressure mercury lamps and metal halide lamps. preferable. Among these, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp are preferable because they have a high emission intensity of ultraviolet rays having a wavelength of 313 nm. Polarized UV can be irradiated by irradiating the light from the light source through an appropriate polarizer. As such a polarizer, a polarizing filter, a polarizing prism such as Gran Thomson or Gran Tailor, or a wire grid type polarizer can be used.

If masking is performed during rubbing or polarized light irradiation, it is possible to form a plurality of regions (patterns) in which the directions of liquid crystal orientation are different.

The groove alignment film is a film having an uneven pattern or a plurality of grooves on the surface of the film. When the polymerizable liquid crystal compound is applied to a film having a plurality of linear grubs arranged at equal intervals, the liquid crystal molecules are oriented in the direction along the groove.

As a method of obtaining a grub alignment film, a method of forming an uneven pattern by performing exposure and rinsing treatment after exposure through an exposure mask having a pattern-shaped slit on the surface of the photosensitive polyimide film, and a plate having grooves on the surface. A method of forming a layer of UV-curable resin before curing on a shaped master, transferring the formed resin layer to a surface such as a base film on which an alignment film should be formed, and then curing, and forming an alignment film. Examples thereof include a method in which a roll-shaped master having a plurality of grooves is pressed against a film of a UV-curable resin before curing formed on a power surface to form irregularities, and then the film is cured.

The thickness of the alignment film (alignment film containing an alignment polymer or photoalignment film) is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 2500 nm, more preferably 10 to 1000 nm or less, and further preferably. Is in the range of 10 to 500 nm, particularly preferably 50 to 250 nm.

In the present invention, when the liquid crystal cured product layer constituting the functional layer is a vertically oriented liquid crystal cured product layer, the liquid crystal cured product layer contains at least one kind of vertical alignment accelerator, so that the liquid crystal cured product layer does not go through the alignment film. , The liquid crystal cured product layer can be formed directly on the surface on which the liquid crystal cured product layer should be formed, such as on the base film. In the present specification, the vertical orientation accelerator means a material that promotes the liquid crystal orientation of the polymerizable liquid crystal compound in the direction perpendicular to the plane of the cured product layer. Since the liquid crystal cured product layer contains the vertical alignment accelerator, the vertically oriented liquid crystal cured product layer can be directly formed without forming the vertical alignment film on the base film or the like, so that the manufacturing process of the long film can be performed. It is possible to produce a long film with simplification and high productivity.

As the vertical orientation accelerator, a component that causes an electrostatic repulsive force against the polymerizable liquid crystal compound at the interface on the base film side of the coating film when the polymerizable liquid crystal composition is applied onto the base film is preferable. .. Examples of such a component include an ionic compound, and from the viewpoint of suppressing the occurrence of orientation defects in the liquid crystal cured product layer, the vertical alignment accelerator preferably contains an ionic compound composed of non-metal atoms. When the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound contains an ionic compound composed of non-metal atoms, the dry coating film formed from the composition is vertically oriented with respect to the polymerizable liquid crystal compound by electrostatic interaction. The restrictive force is exhibited, and the polymerizable liquid crystal compound can be oriented in the dry coating film in the direction perpendicular to the film plane. As a result, the liquid crystal cured product layer can be formed while maintaining the vertically oriented state of the polymerizable liquid crystal compound.

Examples of the ionic compound composed of non-metal atoms (hereinafter, also simply referred to as “ionic compound”) include, for example, an onium salt (more specifically, a quaternary ammonium salt in which a nitrogen atom has a positive charge, a third. Class sulfonium salts, quaternary phosphonium salts in which the phosphorus atom has a positive charge, etc.) can be mentioned. Of these onium salts, a quaternary onium salt is preferable from the viewpoint of further improving the vertical orientation of the polymerizable liquid crystal compound, and a quaternary phosphonium salt or a quaternary from the viewpoint of improving availability and mass productivity. Ammonium salts are more preferred. The onium salt may have two or more quaternary onium salt moieties in the molecule, and may be an oligomer or a polymer.

The molecular weight of the ionic compound is preferably 100 or more and 10,000 or less. When the molecular weight is within the above range, it is easy to improve the vertical orientation of the polymerizable liquid crystal compound while ensuring the coatability of the polymerizable liquid crystal composition. The molecular weight of the ionic compound is more preferably 5000 or less, still more preferably 3000 or less.

Examples of the cation component of the ionic compound include an inorganic cation and an organic cation. Of these, organic cations are preferable because orientation defects of the polymerizable liquid crystal compound are unlikely to occur. Examples of the organic cation include imidazolium cation, pyridinium cation, ammonium cation, sulfonium cation, phosphonium cation and the like.

Ionic compounds generally have a counter anion. Examples of the anion component that becomes the counter ion of the cation component include an inorganic anion and an organic anion. Of these, organic anions are preferable because orientation defects of the polymerizable liquid crystal compound are unlikely to occur. It should be noted that the cation and the anion do not necessarily have to have a one-to-one correspondence.

Specific examples of the anion component include the following.
Chloride anion [Cl ^-],
Bromide anion [Br ^-],
Iodide anion [I ^-],
Tetrachloroaluminate anion [AlCl ₄ ^-],
Hepta-chloro-di-aluminate anion _[Al 2 Cl ₇ ^-],
Tetrafluoroborate anion [BF ₄ ^-],
Hexafluorophosphate anion [PF ₆ ^-],
Perchlorate anions [ClO ₄ ^-],
Nitrate anions [NO ₃ ^-],
Acetate anion _[CH 3 COO ^-],
Trifluoroacetate anion _[CF 3 COO ^-],
Fluorosulfonate anion [FSO ₃ ^-],
Methanesulfonate anion _[CH 3 SO ₃ ^-],
Trifluoromethanesulfonate anion _[CF 3 SO ₃ ^-],
p- toluenesulfonate anion _{_{_{[p-CH 3 C 6 H 4}}} SO 3 - ],
Bis (fluorosulfonyl) imide anion _[(FSO ₂₎ 2 N ^-],
Bis (trifluoromethanesulfonyl) imide anion _{_{_{[(CF 3 SO 2) 2 N}}} - ],
Tris (trifluoromethanesulfonyl) meth acetonide anion _{_{_{[(CF 3 SO 2) 3 C}}} - ],
Hexafluoro Ah cell anion [AsF ₆ ^-],
Hexafluoroantimonate anion [SbF ₆ ^-],
Hexafluoro niobate anions [NbF ₆ ^-],
Hexafluoro tantalate anion [TaF ₆ ^-],
Dimethyl phosphinate anion _[(CH ₃₎ 2 POO ^-],
(Poly) hydrofluoroether fluoride anion [F _{(HF) n} ^-] (e.g., n represents an integer of 1-3),
Dicyanamide anion _[(CN) 2 N ^-],
Thiocyanate anion [SCN ^-],
Perfluorobutane sulfonate anion _[C 4 _F 9 SO ₃ ^-],
Bis (pentafluoroethane sulfonyl) imide anion _{_{_{_{[(C 2 F 5 SO 2)}}}} 2 N - ],
Perfluoro butanoate anion _[C 3 _F 7 COO ^-], and (trifluoromethanesulfonyl) (trifluoromethane carbonyl) imide anion _{_{_{[(CF 3 SO 2) (CF}}} 3 CO) N - ].

Specific examples of the ionic compound can be appropriately selected from the combination of the above-mentioned cation component and anion component. Examples of the compound which is a specific combination of the cation component and the anion component include the following.

(Pyridinium salt)
N-hexylpyridinium hexafluorophosphate,
N-octylpyridinium hexafluorophosphate,
N-Methyl-4-hexylpyridinium hexafluorophosphate,
N-Butyl-4-methylpyridinium hexafluorophosphate,
N-octyl-4-methylpyridinium hexafluorophosphate,
N-hexylpyridinium bis (fluorosulfonyl) imide,
N-octylpyridinium bis (fluorosulfonyl) imide,
N-Methyl-4-hexylpyridinium bis (fluorosulfonyl) imide,
N-Butyl-4-methylpyridinium bis (fluorosulfonyl) imide,
N-octyl-4-methylpyridinium bis (fluorosulfonyl) imide,
N-hexylpyridinium bis (trifluoromethanesulfonyl) imide,
N-octylpyridinium bis (trifluoromethanesulfonyl) imide,
N-Methyl-4-hexylpyridinium bis (trifluoromethanesulfonyl) imide,
N-Butyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide,
N-octyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide,
N-hexylpyridinium p-toluenesulfonate,
N-octylpyridinium p-toluenesulfonate,
N-Methyl-4-hexylpyridinium p-toluenesulfonate,
N-Butyl-4-methylpyridinium p-toluenesulfonate, and N-octyl-4-methylpyridinium p-toluenesulfonate.

(Imidazole salt)
1-Ethyl-3-methylimidazolium hexafluorophosphate,
1-Ethyl-3-methylimidazolium bis (fluorosulfonyl) imide,
1-Ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide,
1-Ethyl-3-methylimidazolium p-toluenesulfonate,
1-Butyl-3-methylimidazolium methanesulfonate, etc.

(Pyrrolidinium salt)
N-Butyl-N-Methylpyrrolidinium Hexafluorophosphate,
N-Butyl-N-Methylpyrrolidinium bis (fluorosulfonyl) imide,
N-Butyl-N-Methylpyrrolidinium bis (trifluoromethanesulfonyl) imide,
N-Butyl-N-methylpyrrolidinium p-toluenesulfonate and the like.

(Ammonium salt)
Tetrabutylammonium hexafluorophosphate,
Tetrabutylammonium bis (fluorosulfonyl) imide,
Tetrahexyl ammonium bis (fluorosulfonyl) imide,
Trioctylmethylammonium bis (fluorosulfonyl) imide,
(2-Hydroxyethyl) trimethylammonium bis (fluorosulfonyl) imide,
Tetrabutylammonium bis (trifluoromethanesulfonyl) imide,
Tetrahexyl ammonium bis (trifluoromethanesulfonyl) imide,
Trioctylmethylammonium bis (trifluoromethanesulfonyl) imide,
(2-Hydroxyethyl) trimethylammonium bis (trifluoromethanesulfonyl) imide,
Tetrabutylammonium p-toluenesulfonate,
Tetrahexyl ammonium p-toluene sulfonate,
Trioctylmethylammonium p-toluenesulfonate,
(2-Hydroxyethyl) trimethylammonium p-toluenesulfonate,
(2-Hydroxyethyl) trimethylammonium dimethylphosphinate 1- (3-trimethoxysilylpropyl) -1,1,1-tributylammonium bis (trifluoromethanesulfonyl) imide,
1- (3-Trimethoxysilylpropyl) -1,1,1-trimethylammonium bis (trifluoromethanesulfonyl) imide,
1- (3-Trimethoxysilylbutyl) -1,1,1-tributylammonium bis (trifluoromethanesulfonyl) imide,
1- (3-Trimethoxysilylbutyl) -1,1,1-trimethylammonium bis (trifluoromethanesulfonyl) imide,
N-{(3-Triethoxysilylpropyl) Carbamoyloxyethyl)} -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide, and N- [2- {3- (3-trimethoxysilylpropylamino) ) -1-Oxopropoxy} ethyl] -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide.

(Phoenium salt)
Tributyl (2-methoxyethyl) phosphonium bis (trifluoromethanesulfonyl) imide,
Tributylmethylphosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-trimethyl-1-[(trimethoxysilyl) methyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-trimethyl-1- [2- (trimethoxysilyl) ethyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-trimethyl-1- [3- (trimethoxysilyl) propyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-trimethyl-1- [4- (trimethoxysilyl) butyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-Tributyl-1-[(trimethoxysilyl) methyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-Tributyl-1- [2- (trimethoxysilyl) ethyl] phosphonium bis (trifluoromethanesulfonyl) imide, and 1,1,1-tributyl-1- [3- (trimethoxysilyl) propyl] Phosphonium bis (trifluoromethanesulfonyl) imide.
Each of these ionic compounds may be used alone, or two or more thereof may be used in combination. Of these, an ionic compound composed of a phosphonium salt, a pyridinium salt, and an ammonium salt is preferable.

From the viewpoint of further improving the vertical orientation of the polymerizable liquid crystal compound, it is preferable that the ionic compound has a Si element and / or an F element in the molecular structure of the cation site. When the ionic compound has a Si element and / or an F element in the molecular structure of the cation moiety, the ionic compound is likely to segregate on the surface of the cured product layer formed of the polymerizable liquid crystal compound. Among them, the following ionic compounds (i) to (iii) are preferable as the ionic compounds in which all the constituent elements are non-metal elements.

(Ionic compound (i))

(Ionic compound (ii))

(Ionic compound (iii))

For example, a method of treating the surface of a substrate with a surfactant having an alkyl group having a long chain length to some extent to improve the orientation of the liquid crystal (for example, Chapter 2 of "Liquid Crystal Handbook", Orientation and Physical Properties of Liquid Crystal (Maruzen) The vertical orientation of the polymerizable liquid crystal compound can be further improved by applying)). That is, the vertical orientation of the polymerizable liquid crystal compound can be effectively improved by treating the surface of the substrate with an ionic compound having an alkyl group having a long chain length to some extent.

Specifically, it is preferable that the ionic compound satisfies the following formula (7).
5 <M <16 (7)
In the formula (7), M is represented by the following formula (8).
M = (Among the substituents directly bonded to the positively charged atom, the number of covalent bonds from the positively charged atom to the end of the molecular chain of the substituent having the largest number of covalent bonds to the end of the molecular chain ) ÷ (Number of atoms with a positive charge) (8)
When the ionic compound satisfies the above (7), the vertical orientation of the polymerizable liquid crystal compound can be effectively improved.

When there are two or more positively charged atoms in the molecule of the ionic compound, the substituents having two or more positively charged atoms are counted from the positively charged atoms considered as the base point. The number of covalent bonds to the closest atom having a positive charge is defined as "the number of covalent bonds from the atom having a positive charge to the end of the molecular chain" described in the definition of M above. When the ionic compound is an oligomer or polymer having two or more repeating units, the constituent unit is considered as one molecule and the above M is calculated. When a positively charged atom is incorporated into the ring structure, the number of covalent bonds to the positively charged atom via the ring structure, or to the end of the substituent bonded to the ring structure. Of the number of covalent bonds in the above, the one having the larger number of covalent bonds is defined as "the number of covalent bonds from an atom having a positive charge to the end of the molecular chain" described in the definition of M above.

The content of the ionic compound composed of non-metal atoms in the polymerizable liquid crystal composition is usually 0.01 part by mass or more, more preferably 0.01 part by mass or more, based on 100 parts by mass of the polymerizable liquid crystal compound contained in the composition. It is 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 5 parts by mass or less, more preferably 4 parts by mass or less, still more preferably 3 parts by mass or less. When the content of the ionic compound composed of non-metal atoms is within the above range, the vertical orientation of the polymerizable liquid crystal compound can be effectively promoted while maintaining good coatability of the polymerizable liquid crystal composition. it can.

When the polymerizable liquid crystal composition is applied onto the base film as a vertical orientation accelerator, the polymerizable liquid crystal compound can be obtained by lowering the surface energy at the interface of the cured product layer opposite to the base film. It may contain a component capable of exerting a vertical orientation restricting force for orienting in the direction perpendicular to the film plane. Examples of such a component include a nonionic silane compound and a leveling agent, and a nonionic silane compound is preferable. When the polymerizable liquid crystal composition contains a nonionic silane compound, the nonionic silane compound lowers the surface tension of the composition, and in the dry coating film formed from the composition, the dry coating film and the air interface Nonionic silane compounds tend to be unevenly distributed in the film, and the force for restricting vertical orientation with respect to the polymerizable liquid crystal compound can be increased, and the polymerizable liquid crystal compound can be oriented in the direction perpendicular to the film plane in the dry coating film. As a result, the liquid crystal cured product layer can be formed while maintaining the vertically oriented state of the polymerizable liquid crystal compound.

The nonionic silane compound is a compound that is nonionic and contains a Si element. Nonionic silane compounds include, for example, silicon polymers such as polysilanes, silicone resins such as silicone oils and silicone resins, and organic-inorganic silane compounds such as silicone oligomers, silces siloxane and alkoxysilanes (more specifically). Is a silane coupling agent, etc.). One of these nonionic silane compounds may be used alone, or two or more thereof may be used in combination. Of these, a silane coupling agent is preferable from the viewpoint of further improving the adhesion with the adjacent layer.

The nonionic silane compound may be a silicone monomer type or a silicone oligomer (polymer) type. When the silicone oligomer is shown in the form of a (monomer)-(monomer) copolymer, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercapto Propyl group-containing copolymers such as propyltriethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetra Mercaptomethyl group-containing copolymers such as ethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer and mercaptomethyltriethoxysilane-tetraethoxysilane copolymer; 3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3 -Methacloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane- Tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-methacryloxyylopropylmethyldiethoxysilane-tetraethoxysilane copolymer Copolymers containing methacryloyloxypropyl groups such as 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetramethoxy Silane copolymer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxy Acryloyloxypropyl group-containing copolymers such as propylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer; vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane -Tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxy Vinyl group-containing copolymers such as silane-tetramethoxysilane copolymer and vinylmethyldiethoxysilane-tetraethoxysilane copolymer; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane Copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetra Examples thereof include amino group-containing copolymers such as ethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer.

The silane coupling agent is selected from the group consisting of a vinyl group, an epoxy group, a styryl group, a methacryl group, an acrylic group, an amino group, an isocyanurate group, a ureido group, a mercapto group, an isocyanate group, a carboxyl group, and a hydroxyl group at the end. It is a compound containing a Si element having a functional group such as at least one thereof and at least one alkoxysilyl group or silanol group. By appropriately selecting these functional groups, unique effects such as improvement of mechanical strength of the vertically oriented liquid crystal cured product layer, surface modification, and improvement of adhesion between the liquid crystal cured product layer and the adjacent layer are imparted. It becomes possible. From the viewpoint of adhesion, it is preferable that the silane coupling agent is a silane coupling agent having an alkoxysilyl group and another different reactive group (for example, the above-mentioned functional group). Further, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and a polar group. When the silane coupling agent has at least one alkoxysilyl group and at least one polar group in its molecule, the vertical orientation of the polymerizable liquid crystal compound is more likely to be improved, and the vertical orientation promoting effect can be remarkably obtained. There is a tendency. Examples of the polar group include an epoxy group, an amino group, an isocyanurate group, a mercapto group, a carboxyl group and a hydroxyl group. The polar group may appropriately have a substituent or a protecting group in order to control the reactivity of the silane coupling agent.

Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-. (2-Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltri Methoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane and 3-glycidoxypropylethoxydimethylsilane Can be mentioned.

Examples of commercially available silane coupling agents include KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, and KBM-403. , KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE Silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. such as -9103, KBM-573, KBM-575, KBM-9569, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007. Can be mentioned.

The content of the nonionic silane compound in the polymerizable liquid crystal composition is usually 0.01 part by mass or more, more preferably 0.05 part by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound contained in the composition. It is more than parts by mass, more preferably 0.1 part by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass or less, still more preferably 3 parts by mass or less. When the content of the nonionic silane compound is within the above range, the vertical orientation of the polymerizable liquid crystal compound can be effectively promoted while maintaining good coatability of the polymerizable liquid crystal composition.

In the present invention, the polymerizable liquid crystal composition for forming the vertically oriented liquid crystal cured product layer contains at least one of an ionic compound composed of non-metal atoms and a non-ionic silane compound as a vertical orientation accelerator. It is more preferable to contain an ionic compound composed of a non-metal atom, and it is more preferable to contain both an ionic compound composed of a non-metal atom and a non-ionic silane compound. In a dry coating film formed from a polymerizable liquid crystal composition by the polymerizable liquid crystal composition containing both an ionic compound composed of non-metal atoms and a non-ionic silane compound, the non-metal at the substrate side interface is formed. Vertical orientation with respect to the polymerizable liquid crystal compound at both interfaces of the cured liquid crystal layer due to the electrostatic interaction derived from the ionic compound consisting of atoms and the surface energy lowering effect derived from the non-ionic silane compound at the non-base material side interface. Since the regulatory force is generated, the vertical orientation of the polymerizable liquid crystal compound is more likely to be promoted. As a result, the liquid crystal cured product layer can be formed while maintaining the state in which the polymerizable liquid crystal compound is more accurately vertically oriented.

Further, a polymerizable non-liquid crystal such as a compound having a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth) acryloyl group in the polymerizable liquid crystal composition for forming a vertically oriented liquid crystal cured product layer in the molecule. By adding a compound (hereinafter, also referred to as "pre-reaction compound"), the adhesion to a base material having a hydroxyl group or a carboxyl group on the surface can be improved by corona treatment, plasma treatment, etc., and the surface of the base material can be improved. The substrate peeling force P of the laminate can be controlled by adjusting the treatment state, the type and content of the pre-reaction compound contained in the vertically oriented liquid crystal cured film, and the like. As a result, it is possible to obtain a long film in which the vertically oriented liquid crystal cured product layer formed without the vertically oriented film and the base film are laminated with the optimum adhesive force and exhibit the optimum base material peeling force.

In the present invention, the molecular orientation direction of the polymerizable liquid crystal compound in the cured liquid crystal product constituting the functional layer is horizontal with respect to the long direction plane of the base film and in the long direction of the base film. On the other hand, the effect tends to be remarkable when the directions are not parallel. The molecular orientation direction of the polymerizable liquid crystal compound is not parallel to the elongated direction of the base film, which means that the polymerizable liquid crystal compound is horizontally oriented and the orientation direction is not parallel to the elongated direction. When the long direction of the base film and the orientation direction of the polymerizable liquid crystal compound have the above relationship, Roll to an optical film or the like including a polarizing film having an absorption axis or a transmission axis in the long direction as described later. Using the Roll method, it is possible to transfer the functional layer from the long film of the present invention and bond it in a long length. On the other hand, since the molecular orientation direction of the polymerizable liquid crystal compound does not coincide with the peeling direction, that is, the elongated direction during transfer, the end portion of the liquid crystal cured product layer is easily torn off. Even in such a case, an uneven portion is provided at the end of the base material to further enhance the adhesion with the functional layer in the uneven portion, and between the functional layer and the base film on the back surface in a region without unevenness. By providing fine voids, sticking / dropping in the non-concavo-convex region is suppressed, and an appropriate difference is generated in the adhesion between the base film and the functional layer between the concavo-convex portion and the non-concavo-convex region. This makes it easier for the functional layer to peel off linearly from the base film in the peeling direction, suppresses the occurrence of tearing at the edges during transfer, and ensures high productivity and quality.

Further, the effect tends to be remarkable even when the molecular orientation direction of the polymerizable liquid crystal compound in the cured liquid crystal product constituting the functional layer is substantially vertical with respect to the long direction plane of the base film. .. When the molecular orientation direction of the polymerizable liquid crystal compound is vertical with respect to the long direction plane of the base film, it means that the polymerizable liquid crystal compound is vertically oriented. In such a case, the molecular orientation direction of the polymerizable liquid crystal compound does not coincide with the peeling direction, that is, the elongated direction during transfer, as in the case where the polymerizable liquid crystal compound is horizontally oriented in the liquid crystal cured product layer. The edge of the liquid crystal cured product layer is easily torn off, but the edge of the base material is provided with an uneven portion so that the adhesion between the base film and the functional layer is appropriate between the uneven portion and the region without unevenness. By making a difference, the functional layer can be easily peeled linearly from the base film in the peeling direction, the occurrence of tearing at the end can be suppressed during transfer, and high productivity and quality can be ensured.

The functional layer constituting the long film of the present invention may include a layer other than the liquid crystal cured product layer and the alignment film. Examples of such other layers include a curable resin layer such as a protective layer and a hard coat layer, and an adhesive layer for adhering a functional layer such as a liquid crystal cured product layer to another member such as a polarizing film. Can be mentioned. Further, a plurality of cured liquid crystal layers having different orientation directions and a plurality of alignment films having different orientation regulating forces may be included.

When the cured resin layer is included, the thickness thereof is 0.1 to 10 μm, preferably 0.5 to 5 μm from the viewpoint of thinning the entire functional layer.

The cured resin layer is, for example, a cured resin layer obtained by curing a film such as cycloolefin polymer (COP), polyethylene terephthalate (PET), or triacetyl cellulose (TAC), or a composition for forming a cured resin layer containing a polymerizable monomer. It may be. From the viewpoint of thinning, the cured resin layer of the composition for forming the cured resin layer is preferable. The cured resin layer may be composed of multiple layers, but from the viewpoint of productivity, it is preferably two or less layers, and more preferably a single layer. Further, the cured resin layer is preferably optically isotropic. If the cured resin layer is optically isotropic, it is possible to obtain a functional layer having high optical characteristics, which does not easily affect the optical characteristics of the liquid crystal cured product layer when combined with the liquid crystal cured product layer.
In the present specification, among the polymerizable groups contained in the composition for forming a cured resin layer used for forming the cured resin layer, the resin is collectively referred to as a representative of the most numerous functional groups. is there. That is, for example, among the polymerizable groups contained in the composition for forming a cured resin layer, an acrylic resin is used when the number of acryloyloxy groups is the largest, and an epoxy resin is used when the number of epoxy groups is the largest. May be called.

The cured resin layer preferably contains at least one selected from the group consisting of acrylic resin, epoxy resin, oxetane resin, urethane resin and melamine resin. By containing at least one resin selected from the above, the curability is high, and it becomes easy to improve the reliability when combined with the cured product layer of the polymerizable liquid crystal compound.

The composition for forming a curable resin layer constituting the curable resin layer is a composition containing a curable polymerizable monomer such as a radical polymerizable monomer, a cationically polymerizable monomer, and a thermopolymerizable monomer as a curable compound. It is more preferable to contain a radically polymerizable monomer or a cationically polymerizable monomer because the reaction rate is high, the productivity is improved, and the reliability when combined with the cured product layer of the polymerizable liquid crystal compound is easily improved. ..

Examples of the radically polymerizable monomer suitable for forming the cured resin layer include (meth) acrylate compounds such as polyfunctional (meth) acrylate compounds; and urethane (meth) acrylate compounds such as polyfunctional urethane (meth) acrylate compounds; Epoxy (meth) acrylate compounds such as functional epoxy (meth) acrylate compounds; carboxyl group-modified epoxy (meth) acrylate compounds, polyester (meth) acrylate compounds and the like can be mentioned. These may be used alone or in combination of two or more. Among them, as the polymerizable monomer, from the viewpoint of improving the reliability when combined with the cured product layer of the polymerizable liquid crystal compound, the viewpoint of improving the adhesion with the adjacent layer, and the viewpoint of improving the productivity (meta). ) It is preferable to contain a polymerizable monomer having an acryloyloxy group, more preferably to contain a polyfunctional (meth) acrylate compound, and particularly preferably to contain a polyfunctional acrylate compound.

A polyfunctional (meth) acrylate compound means a compound having two or more (meth) acryloyl groups in the molecule, preferably a (meth) acryloyloxy group, and an example thereof is (meth) acryloyloxy in the molecule. Examples thereof include a bifunctional (meth) acrylate monomer having two groups, a trifunctional or higher (meth) acrylate monomer having three or more (meth) acryloyloxy groups in the molecule, and the like. In the present specification, the term "(meth) acrylate" means "acrylate" or "methacrylate", and the term "(meth) acryloyl" also means "acryloyl" or "methacryloyl".

The polyfunctional (meth) acrylate compound may contain one kind or two or more kinds of polyfunctional (meth) acrylate compounds. When two or more kinds of polyfunctional (meth) acrylate compounds are contained, the number of (meth) acryloyl groups may be the same or different between the respective polyfunctional (meth) acrylate compounds.

Examples of the bifunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di. (Meta) acrylate, alkylene glycol di (meth) acrylate such as 1,9-nonanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polyoxyalkylene glycol such as polytetramethylene glycol di (meth) acrylate. Di (meth) acrylate; Di (meth) acrylate of halogen-substituted alkylene glycol such as tetrafluoroethylene glycol di (meth) acrylate; trimethylolpropandi (meth) acrylate, ditrimethylolpropandi (meth) acrylate, pentaerythritol di ( Di (meth) acrylate of an aliphatic polyol such as meta) acrylate; hydrogenated dicyclopentadiene or tricyclodecandi such as hydrogenated dicyclopentadienyldi (meth) acrylate and tricyclodecanedimethanol di (meth) acrylate. Di (meth) acrylate of alkanol; di (meth) acrylate of dioxane glycol or dioxan dialkanol such as 1,3-dioxane-2,5-diyldi (meth) acrylate [also known as dioxane glycol di (meth) acrylate]; bisphenol Di (meth) acrylate of alkylene oxide adduct of bisphenol A or bisphenol F such as A ethylene oxide adduct diacrylate, bisphenol F ethylene oxide adduct diacrylate; acrylic acid adduct of bisphenol A diglycidyl ether, bisphenol F Epoxy di (meth) acrylate of bisphenol A or bisphenol F such as acrylic acid adduct of diglycidyl ether; silicone di (meth) acrylate; di (meth) acrylate of hydroxypivalate neopentyl glycol ester; 2,2-bis [4 -(Meta) Acryloyloxyethoxy Ethoxyphenyl] propane; 2,2-bis [4- (meth) acryloyloxyethoxyethoxycyclohexyl] propane; 2- (2-hydroxy-1,1-dimethylethyl) -5-ethyl-5-hydroxymethyl-1, 3-Dioxane] di (meth) acrylate; tris (hydroxyethyl) isocyanurate di (meth) acrylate and the like can be mentioned.

The trifunctional (meth) acrylate monomer is a monomer having three (meth) acryloyl groups in the molecule, preferably a (meth) acryloyloxy group, and examples thereof include glycerin tri (meth) acrylate and trimethyl propane. Tri (meth) acrylate, ditrimethylol propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate and acid anhydride reaction product, caprolactone-modified trimethylol propantri (meth) acrylate, caprolactone Modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified trimethylol propanthry (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylol propanthry (meth) acrylate, propylene oxide-modified pentaerythritol tri (Meta) acrylate, isocyanurate tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride reaction product, ethylene oxide-modified pentaerythritol tri (meth) acrylate and acid anhydride reaction product, Examples thereof include a reaction product of a propylene oxide-modified pentaerythritol tri (meth) acrylate and an acid anhydride.

The tetrafunctional (meth) acrylate monomer is a monomer having four (meth) acryloyl groups in the molecule, preferably a (meth) acryloyloxy group, and examples thereof include ditrimethylolpropanetetra (meth) acrylate and penta. Erislitol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, ethylene oxide-modified penta Examples thereof include erythritol tetra (meth) acrylate, ethylene oxide-modified tripenta erythritol tetra (meth) acrylate, propylene oxide-modified pentaerythritol tetra (meth) acrylate, and propylene oxide-modified tripenta erythritol tetra (meth) acrylate.

Examples of the pentafunctional (meth) acrylate monomer include dipentaerythritol penta (meth) acrylate, tripentaerythritol penta (meth) acrylate, a reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, and caprolactone-modified dipenta. Erislitol penta (meth) acrylate, caprolactone-modified tripenta erythritol penta (meth) acrylate, ethylene oxide-modified dipenta erythritol penta (meth) acrylate, ethylene oxide-modified tripenta erythritol penta (meth) acrylate, propylene oxide-modified dipenta erythritol penta Meta) acrylate, propylene oxide-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride reaction product, ethylene oxide-modified dipentaerythritol penta (meth) acrylate and acid anhydride Examples thereof include a reaction product of propylene oxide-modified dipentaerythritol penta (meth) acrylate and an acid anhydride.

Examples of the hexafunctional (meth) acrylate monomer include dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and caprolactone-modified tripentaerythritol hexa (meth) acrylate. , Ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified tripentaerythritol hexa (meth) acrylate, propylene oxide-modified dipentaerythritol hexa (meth) acrylate, propylene oxide-modified tripentaerythritol hexa (meth) acrylate, etc. Can be mentioned.

Examples of the seven-functional (meth) acrylate monomer include tripentaerythritol hepta (meth) acrylate, a reaction product of trypentaerythritol hepta (meth) acrylate and an acid anhydride, caprolactone-modified tripentaerythritol hepta (meth) acrylate, and caprolactone-modified. Reaction product of trypenta erythritol hepta (meth) acrylate and acid anhydride, ethylene oxide-modified tripenta erythritol hepta (meth) acrylate, reaction product of ethylene oxide-modified tripenta erythritol hepta (meth) acrylate and acid anhydride, propylene Examples thereof include an oxide-modified tripentaerythritol hepta (meth) acrylate and a reaction product of a propylene oxide-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride.

The octafunctional (meth) acrylate monomer is a monomer having eight (meth) acryloyl groups, preferably (meth) acryloyloxy groups in the molecule, and examples thereof include tripentaerythritol octa (meth) acrylate and caprolactone. Examples thereof include modified tripentaerythritol octa (meth) acrylate, ethylene oxide-modified tripentaerythritol octa (meth) acrylate, and propylene oxide-modified tripentaerythritol octa (meth) acrylate.

Examples of the cationically polymerizable monomer suitable for forming the cured resin layer include an epoxy compound having an epoxy group and an oxetane compound having an oxetaneyl group.

The epoxy compound is a polymerizable monomer having at least one epoxy group in the molecule, and examples thereof include an alicyclic epoxy compound, an aromatic epoxy compound, and an aliphatic epoxy compound.
The alicyclic epoxy compound is a compound having at least one epoxy group directly bonded to the alicyclic ring in the molecule. For example, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate, ethylenebis (3,4-epoxy) Cyclohexanecarboxylate), bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, diethyleneglycolbis (3,4-epoxycyclohexylmethyl ether), ethyleneglycolbis (3,4-epoxycyclohexylmethyl ether) 3,4-Epoxycyclohexylmethyl) ether and the like can be mentioned. These alicyclic epoxy compounds can be used alone or in combination of two or more.

Aromatic epoxy compounds are compounds that have an aromatic ring and an epoxy group in the molecule. Specific examples thereof include bisphenol type epoxy compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and bisphenol S diglycidyl ether or oligomers thereof; phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac epoxy. Novolac type epoxy resin such as resin; polyfunctional epoxy compound such as 2,2', 4,4'-tetrahydroxydiphenylmethane glycidyl ether, 2,2', 4,4'-tetrahydroxybenzophenone glycidyl ether ; Examples include polyfunctional epoxy resins such as epoxidized polyvinylphenol. These aromatic epoxy compounds can be used alone or in combination of two or more.

As for the hydrogenated epoxy compound, the nuclear hydrogenation of the above aromatic epoxy compound becomes the hydrogenated epoxy compound. These are polyvalents obtained by selectively hydrogenating aromatic polyhydroxy compounds, typically bisphenols, which are the raw materials of the corresponding aromatic epoxy compounds, in the presence of a catalyst and under pressure. It can be produced by a method in which an alcohol, typically hydrogenated bisphenols, is used as a raw material, and epichlorohydrin is reacted with the raw material to form a chlorohydrin ether, which is further closed in the molecule with an alkali. These hydrogenated epoxy compounds can be used alone or in combination of two or more.

Aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Specific examples thereof include diglycidyl ether of neopentyl glycol, diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, and polyethylene. By adding one or more alkylene oxides (ethylene oxide or propylene oxide) to aliphatic polyhydric alcohols such as glycol diglycidyl ether, propylene glycol diglycidyl ether, ethylene glycol, propylene glycol, and glycerin. Examples thereof include polyglycidyl ether, which is a polyether polyol obtained. These aliphatic epoxy compounds can be used alone or in combination of two or more.

An oxetane compound is a compound containing at least one oxetane group in the molecule, and specific examples thereof include 3-ethyl-3-hydroxymethyloxetane (also called oxetane alcohol), 2-ethylhexyl oxetane, and 1,4-. Bis [{(3-ethyloxetane-3-yl) methoxy} methyl] benzene (also called xylylene bisoxetane), 3-ethyl-3 [{(3-ethyloxetane-3-yl) methoxy} methyl] oxetane, Examples thereof include 3-ethyl-3- (phenoxymethyl) oxetane and 3- (cyclohexyloxy) methyl-3-ethyloxetane.

Examples of the thermopolymerizable monomer suitable for forming the cured resin layer include melamine compounds. Examples of the melamine compound include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine and the like. The melamine compound can be used alone or in combination of two or more.

Further, as another polymerizable monomer, a combination of an isocyanate compound and an alcohol compound having a hydroxyl group in the molecule can be mentioned, and a urethane resin is produced. The isocyanate compounds used in the production of urethane resins and urea resins usually have two or more isocyanato groups (-NCO) in the molecule, and various aromatic, aliphatic or alicyclic diisocyanates can be used. it can. Specific examples include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenedi isocyanate, 3,3'-dimethyl-4,4' Examples thereof include -diphenyl diisocyanate, xylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and a nuclear hydrogenated diisocyanate having an aromatic ring. In addition, alcohol compounds used in urethane resins usually have two or more hydroxyl groups in the molecule, and for example, ethylene glycol, propylene glycol, 1,3-propanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1 , 3-Butandiol, 1,4-Butanediol, 1,6-Hexanediol, 1,9-Nonandiol, 1,10-Decandiol, 2,2,4-trimethyl-1,3-Pentanediol, 3 -Methyl-1,5-pentanediol, neopentyl glycol ester of hydroxypivalic acid, 1,4-cyclohexanediol, spiroglycol, tricyclodecanedimethylol, bisphenol A, hydrogenated bisphenol A, trimethylolethane, trimethylolpropane , Glycerin, 3-methylpentane-1,3,5-triol, pentaerythritol, dipentaerythritol, tripentaerythritol, glucose and the like.

The above-mentioned polymerizable monomer has a viewpoint of suppressing curl generated by heating during curing or after curing, a viewpoint of improving processing characteristics, a viewpoint of adjusting adhesion to a base film or a liquid crystal cured product layer, and improving productivity. It can be appropriately selected from the viewpoint of improving the solvent resistance, improving the reliability when combined with the liquid crystal cured product layer. In the present invention, the cured resin layer preferably contains at least one selected from the group consisting of acrylic resin, epoxy resin, oxetane resin, urethane resin and melamine resin. Further, for example, two or more kinds of radically polymerizable monomers may be used, or a radically polymerizable monomer and a cationically polymerizable monomer may be combined. In particular, it is preferable to contain a radically polymerizable monomer from the viewpoint of improving productivity.

In addition to the above-mentioned polymerizable monomer, the cured resin layer forming composition includes a photopolymerization initiator, a thermal polymerization initiator, a solvent, an antioxidant, a photosensitizer, a leveling agent, an antioxidant, a chain transfer agent, and a photostabilizer. Additives such as agents, tackifiers, fillers, flow modifiers, plasticizers, antifoaming agents, dyes, antistatic agents, and UV absorbers can be further included. These additives are usually about 0.1 to 15% by mass with respect to the mass of the solid content of the composition for forming the cured resin layer. In the present specification, the solid content means the total amount of the components excluding the solvent from the composition when the solvent is contained in the composition for forming the cured resin layer.

In the composition for forming a cured resin layer, the content of the polymerizable monomer is preferably 50 parts by mass or more, and more preferably 60 parts by mass or more with respect to 100 parts by mass of the solid content of the composition. Within the above range, it is easy to improve the reliability when combined with the liquid crystal cured product layer.

The cured resin layer forming composition preferably contains a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, but it is preferable to use a photopolymerization initiator from the viewpoint of improving productivity. The photopolymerization initiator is not particularly limited as long as it can initiate curing of the polymerizable monomer by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and is adapted to the type of the polymerizable monomer. A photoradical polymerization initiator or a photocationic polymerization initiator can be appropriately used. Specific examples of the photoradical polymerization initiator and the photocationic polymerization initiator include the same polymerization initiators exemplified above as those that can be blended in the polymerizable liquid crystal composition forming the liquid crystal cured product layer. Be done.

When the composition for forming a cured resin layer contains a polymerization initiator, the content thereof is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 with respect to 100 parts by mass of the total amount of the curable compound. It is a mass part. When the content of the polymerization initiator is at least the above lower limit value, the polymerization initiator ability is sufficiently exhibited, and when the content of the polymerization initiator is at least the above upper limit value, the polymerization initiator is less likely to remain.

When the cured resin layer forming composition contains a solvent, depending on the viewpoint of sufficiently dissolving the polymerizable monomer and the polymerization initiator added to the cured resin layer forming composition and the viewpoint of not dissolving the base film. It can be selected as appropriate. For example, a solvent that can be used in the polymerizable liquid crystal composition described above can be used. The content of the solvent is about 1 to 10000 parts by mass, preferably 10 to 1000 parts by mass, and more preferably about 20 to 500 parts by mass with respect to 100 parts by mass of the total amount of the components contained in the composition for forming the cured resin layer. It may be there.

In the present invention, the configuration of the functional layer is not particularly limited as long as it includes a liquid crystal cured product layer and does not affect the effect of the present invention. When other layers such as an alignment film and a cured resin layer are included in addition to the liquid crystal cured product layer, the stacking order of each layer can be appropriately selected, but when the functional layer includes the liquid crystal cured product layer, the alignment film and the cured resin layer. , Preferably, the liquid crystal cured product layer, the alignment film, and the cured resin layer are adjacent to each other in this order. When each layer is laminated in this order, uncured polymerizable material is formed in the cured liquid crystal layer, particularly in the deep part (alignment film side) of the cured liquid crystal layer in which a sufficient amount of light is difficult to reach when the layer is cured. Even if the liquid crystal compound is present, the cured resin layer can prevent the uncured polymerizable liquid crystal compound from diffusing. After the functional layer is peeled off from the base film and transferred to another member, the cured resin layer can prevent the uncured polymerizable liquid crystal compound from diffusing into other members. As a result, in the retardation plate or elliptical polarizing plate including the functional layer transferred from the long film of the present invention, the uncured polymerizable liquid crystal compound contained in the liquid crystal cured product layer is close to or close to the liquid crystal cured product layer. It is possible to effectively suppress the diffusion to the adjacent layer (particularly the adhesive layer). Therefore, in a preferred embodiment of the present invention, the functional layer further comprises an adhesive layer and is laminated with another optical film (eg, a polarizing film) via the adhesive layer. As such a functional layer, it is preferable that the liquid crystal cured product layer, the alignment film, and the cured resin layer are adjacent to each other in this order, and the adhesive layer may be provided on the liquid crystal cured product layer side. , May be provided on the cured resin layer side.

When the functional layer constituting the long film of the present invention contains a cured resin layer, the cured resin layer is, for example, after applying the composition for forming a cured resin layer as described above on the base film, and then a solvent. When is contained, the solvent is dried and removed, and the polymerizable monomer is cured.

Examples of the method for applying the cured resin layer forming composition on the base film include the same methods as those exemplified above as the method for applying the polymerizable liquid crystal composition on the base film and the like.

Further, examples of the method for drying and removing the solvent when the composition for forming the cured resin layer contains a solvent include a natural drying method, a ventilation drying method, a heat drying method, and a vacuum drying method.

When the functional layer contains an adhesive layer in the present invention, examples of the adhesive constituting the functional layer include a pressure-sensitive adhesive, a dry-solidified adhesive, and a chemical reaction adhesive. Examples of the chemical reaction type adhesive include an active energy ray-curable adhesive. The adhesive layer may be provided as one constituent layer of the functional layer of the long film of the present invention, or may be provided on the peeled surface or the like after peeling the base film from the long film of the present invention. May be good.

The pressure-sensitive pressure-sensitive adhesive usually contains a polymer and may contain a solvent. Examples of the polymer include acrylic polymers, silicone-based polymers, polyesters, polyurethanes, and polyethers. Among them, the acrylic adhesive containing an acrylic polymer has excellent optical transparency, moderate wettability and cohesive force, excellent adhesiveness, and high weather resistance and heat resistance, and is heated. It is preferable because it is unlikely to float or peel off under humid conditions.

As the acrylic polymer, (meth) acrylate in which the alkyl group of the ester portion is an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group or a butyl group, and (meth) acrylic acid or hydroxyethyl (meth) acrylate A copolymer with a (meth) acrylic monomer having a functional group such as the above is preferable.

The pressure-sensitive pressure-sensitive adhesive containing such a copolymer has excellent adhesiveness, and even when it is removed after being bonded to the transferred body, it is relatively easy without causing adhesive residue on the transferred body. It is preferable because it can be removed. The glass transition temperature of the acrylic polymer is preferably 25 ° C. or lower, more preferably 0 ° C. or lower. The mass average molecular weight of such an acrylic polymer is preferably 100,000 or more.

Examples of the solvent include the solvents mentioned as the solvents that can be used for the polymerizable liquid crystal composition and the like. The pressure-sensitive pressure-sensitive adhesive may contain a light diffusing agent. The light diffusing agent is an additive that imparts light diffusing property to the pressure-sensitive adhesive, and may be fine particles having a refractive index different from that of the polymer contained in the pressure-sensitive adhesive. Examples of the light diffusing agent include fine particles made of an inorganic compound and fine particles made of an organic compound (polymer). Most of the polymers contained in the pressure-sensitive adhesive as an active ingredient, including acrylic polymers, have a refractive index of about 1.4 to 1.6, and therefore, from a light diffusing agent having a refractive index of 1.2 to 1.8. It is preferable to select an appropriate one. The difference in refractive index between the polymer contained in the pressure-sensitive adhesive as an active ingredient and the light diffusing agent is usually 0.01 or more, and is preferably 0.01 to 0.2 from the viewpoint of brightness and displayability of the display device. The fine particles used as the light diffusing agent are preferably spherical fine particles, which are also close to monodisperse, and more preferably fine particles having an average particle size of 2 to 6 μm. The index of refraction is measured by a common minimum declination method or an Abbe refractometer.

Examples of the fine particles made of the inorganic compound include aluminum oxide (refractive index 1.76) and silicon oxide (refractive index 1.45). The fine particles made of an organic compound (polymer) include melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), and methyl methacrylate / styrene copolymer resin beads (refractive index 1.50). ~ 1.59), Polycarbonate beads (refractive index 1.55), polyethylene beads (refractive index 1.53), polystyrene beads (refractive index 1.6), polyvinyl chloride beads (refractive index 1.46), and silicone Examples thereof include resin beads (refractive index 1.46). The content of the light diffusing agent is usually 3 to 30 parts by mass with respect to 100 parts by mass of the polymer.

The thickness of the pressure-sensitive adhesive is determined according to its adhesive force and the like, and is not particularly limited, but is usually 1 μm to 40 μm. From the viewpoint of workability, durability and the like, the thickness is preferably 3 μm to 25 μm, more preferably 5 μm to 20 μm. When the display device including the optical film including the functional layer transferred from the long film of the present invention is viewed from the front by setting the thickness of the adhesive layer formed from the adhesive to 5 μm to 20 μm. It is possible to maintain the brightness when viewed from an angle or to prevent bleeding or blurring of the displayed image.

The dry solidified adhesive may contain a solvent. The dry-solidified adhesive contains a polymer of a monomer having a protonic functional group such as a hydroxyl group, a carboxyl group or an amino group and an ethylenically unsaturated group as a main component, or a urethane resin as a main component, and further has a multivalent value. Examples thereof include compositions containing a cross-linking agent such as an aldehyde, an epoxy compound, an epoxy resin, a melamine compound, a zirconia compound, and a zinc compound, or a curable compound. Examples of the polymer of the monomer having a protonic functional group such as a hydroxyl group, a carboxyl group or an amino group and an ethylenically unsaturated group include ethylene-maleic acid copolymer, itaconic acid copolymer, acrylic acid copolymer and acrylamide. Examples thereof include copolymers, saponified products of polyvinyl acetate, and polyvinyl alcohol-based resins.

Examples of the polyvinyl alcohol-based resin include polyvinyl alcohol, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, methylol group-modified polyvinyl alcohol, and amino group-modified polyvinyl alcohol. Can be mentioned. The content of the polyvinyl alcohol-based resin in the water-based adhesive is usually 1 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of water.

Examples of the urethane resin include polyester ionomer type urethane resin and the like. The polyester-based ionomer-type urethane resin referred to here is a urethane resin having a polyester skeleton, in which a small amount of an ionic component (hydrophilic component) is introduced. Since the ionomer type urethane resin is emulsified in water to form an emulsion without using an emulsifier, it can be used as a water-based adhesive. When a polyester ionomer type urethane resin is used, it is effective to add a water-soluble epoxy compound as a cross-linking agent.

Examples of the epoxy resin include polyamide epoxy resins obtained by reacting epichlorohydrin with polyamide polyamines obtained by reacting polyalkylene polyamines such as diethylenetriamine or triethylenetetramine with dicarboxylic acids such as adipic acid. Commercially available products of the polyamide epoxy resin include "Smiley's Resin (registered trademark) 650" and "Smiley's Resin 675" (manufactured by Sumika Chemtex Co., Ltd.) and "WS-525" (manufactured by Nippon PMC Co., Ltd.). And so on. When the epoxy resin is blended, the amount added is usually 1 to 100 parts by mass, preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polyvinyl alcohol-based resin.

The thickness of the adhesive layer formed from the dry-solidified adhesive is usually 0.001 to 5 μm, preferably 0.01 to 2 μm, and more preferably 0.01 to 0.5 μm. is there. If the adhesive layer formed from the dry-solidified adhesive is too thick, the appearance tends to be poor.

The active energy ray-curable adhesive may contain a solvent. The active energy ray-curable adhesive is an adhesive that is cured by being irradiated with active energy rays. Examples of the active energy ray-curable adhesive include a cationically polymerizable adhesive containing an epoxy compound and a cationic polymerization initiator, a radically polymerizable adhesive containing an acrylic curing component and a radical polymerization initiator, and an epoxy compound. An adhesive containing both a cationically polymerizable curing component such as, and a radically polymerizable curing component such as an acrylic compound, and further containing a cationic polymerization initiator and a radical polymerization initiator, and these polymerization initiators are included. Examples thereof include an adhesive that is cured by irradiating an electron beam without using it.

Among them, a radically polymerizable active energy ray-curable adhesive containing an acrylic curing component and a photoradical polymerization initiator, and a cationically polymerizable active energy ray-curable adhesive containing an epoxy compound and a photocationic polymerization initiator. Agents are preferred. Examples of the acrylic curing component include (meth) acrylates such as methyl (meth) acrylate and hydroxyethyl (meth) acrylate, and (meth) acrylic acid. The active energy ray-curable adhesive containing an epoxy compound may further contain a compound other than the epoxy compound. Examples of the compound other than the epoxy compound include an oxetane compound and an acrylic compound.

Examples of the photoradical polymerization initiator and the photocationic polymerization initiator include the same polymerization initiators as exemplified as those that can be used in the polymerizable liquid crystal composition. The content of the radical polymerization initiator and the cationic polymerization initiator is usually 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the active energy ray-curable adhesive.

The active energy ray-curable adhesive further contains an ion trap agent, an antioxidant, a chain transfer agent, a tackifier, a thermoplastic resin, a filler, a flow conditioner, a plasticizer, an antifoaming agent and the like. You may.

Examples of active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays and electron beams, and ultraviolet rays and electron beams are preferable. Preferred ultraviolet irradiation conditions are the same as the curing conditions of the polymerizable liquid crystal composition at the time of forming the liquid crystal cured product layer.

In the long film of the present invention, when the functional layer is peeled from the base film and transferred to another optical film or the like by using the Roll to Roll method, the functional layer is peeled in the peeling direction (long direction). It is easy to peel off linearly, and has an excellent effect of suppressing tearing and detachment at the end of the functional layer during and after transfer. As a result, the functional layer can be transferred with high productivity while maintaining the optical characteristics of the functional layer possessed by the long film, so that optics such as a retardation plate and an elliptical polarizing plate, which require high optical characteristics, can be transferred. It can be suitably used for producing a laminate.

For example, the base film is peeled off from a long film of the present invention having a functional layer containing a liquid crystal cured product layer satisfying the above formulas (1) and (2) or (3) and (4) to obtain the functional layer. An elliptical polarizing plate can be produced by transferring to a polarizing film. At this time, if necessary, the functional layer and the polarizing film may be bonded to each other via an adhesive layer.

The polarizing film is a film having a polarizing function, and examples thereof include a stretched film in which a dye having an absorption anisotropy is adsorbed and a film containing a film coated with a dye having an absorption anisotropy as a polarizer. Examples of the dye having absorption anisotropy include a dichroic dye.

A film containing a stretched film having a dye having absorption anisotropy adsorbed as a polarizer is usually obtained by uniaxially stretching a polyvinyl alcohol-based resin film and dyeing the polyvinyl alcohol-based resin film with a bicolor dye. At least of the polarizer produced through a step of adsorbing a bicolor dye, a step of treating a polyvinyl alcohol-based resin film on which the bicolor dye is adsorbed with an aqueous boric acid solution, and a step of washing with water after treatment with the aqueous boric acid solution. It is produced by sandwiching one surface with a transparent protective film via an adhesive.

The polyvinyl alcohol-based resin is obtained by saponifying the polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith is used. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

The degree of saponification of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, preferably in the range of 1,500 to 5,000.

A film formed of such a polyvinyl alcohol-based resin is used as a raw film for a polarizing film. The method for forming the film of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method. The film thickness of the polyvinyl alcohol-based raw film can be, for example, about 10 to 150 μm.

The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with a dichroic dye, at the same time as dyeing, or after dyeing. When the uniaxial stretching is performed after dyeing, the uniaxial stretching may be performed before the boric acid treatment or during the boric acid treatment. It is also possible to perform uniaxial stretching at these multiple stages. In uniaxial stretching, rolls having different peripheral speeds may be uniaxially stretched, or thermal rolls may be used to uniaxially stretch. Further, the uniaxial stretching may be a dry stretching in which stretching is performed in the atmosphere, or a wet stretching in which the polyvinyl alcohol-based resin film is swollen using a solvent. The draw ratio is usually about 3 to 8 times.

Dyeing of a polyvinyl alcohol-based resin film with a dichroic dye is performed, for example, by immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye.

Specifically, iodine or a dichroic organic dye is used as the dichroic dye. Examples of the dichroic organic dye include C.I. I. Examples thereof include a dichroic direct dye composed of a disazo compound such as DIRECT RED 39, and a dichroic direct dye composed of a compound such as trisazo and tetrakisazo. The polyvinyl alcohol-based resin film is preferably immersed in water before the dyeing treatment.

When iodine is used as the dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide and dyeing is usually adopted. The iodine content in this aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water. The content of potassium iodide is usually about 0.5 to 20 parts by mass per 100 parts by mass of water. The temperature of the aqueous solution used for dyeing is usually about 20 to 40 ° C. The immersion time (staining time) in this aqueous solution is usually about 20 to 1,800 seconds.

On the other hand, when a dichroic organic dye is used as the dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye and dyeing is usually adopted. The content of the dichroic organic dye in this aqueous solution is usually about 1 × 10 ^-4 to 10 parts by mass, preferably 1 × 10 ^-3 to 1 part by mass, more preferably 1 × 10 ^-3 to 1 part by mass, per 100 parts by mass of water. Is 1 × 10 ^-3 to 1 × 10 ^-2 parts by mass. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid. The temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80 ° C. The immersion time (staining time) in this aqueous solution is usually about 10 to 1,800 seconds.

The boric acid treatment after dyeing with a dichroic dye can usually be performed by immersing the dyed polyvinyl alcohol-based resin film in an aqueous boric acid solution. The content of boric acid in this aqueous boric acid solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. When iodine is used as the bicolor dye, this boric acid aqueous solution preferably contains potassium iodide, and the content of potassium iodide in that case is usually 0.1 to 100 parts by mass per 100 parts by mass of water. It is about 15 parts by mass, preferably 5 to 12 parts by mass. The immersion time in the boric acid aqueous solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the boric acid treatment is usually 50 ° C. or higher, preferably 50 to 85 ° C., and more preferably 60 to 80 ° C.

The polyvinyl alcohol-based resin film after boric acid treatment is usually washed with water. The water washing treatment can be performed, for example, by immersing the boric acid-treated polyvinyl alcohol-based resin film in water. The temperature of water in the washing treatment is usually about 5 to 40 ° C. The immersion time is usually about 1 to 120 seconds.

After washing with water, it is dried to obtain a polarizer. The drying process can be performed using, for example, a hot air dryer or a far-infrared heater. The temperature of the drying treatment is usually about 30 to 100 ° C, preferably 50 to 80 ° C. The drying treatment time is usually about 60 to 600 seconds, preferably 120 to 600 seconds. By the drying treatment, the moisture content of the polarizer is reduced to a practical level. The water content is usually about 5 to 20% by mass, preferably 8 to 15% by mass. When the water content is within the above range, a polarizer having appropriate flexibility and good thermal stability can be obtained.

The thickness of the polarizer obtained by uniaxially stretching, dyeing with a dichroic dye, boric acid treatment, washing with water and drying on the polyvinyl alcohol-based resin film is preferably 5 to 40 μm.

The film coated with the dye having absorption anisotropy includes a composition containing a dichroic dye having liquid crystal properties, a film obtained by applying a composition containing a dichroic dye and a polymerizable liquid crystal, and the like. Can be mentioned. The film preferably has a protective film on one or both sides thereof. Examples of the protective film include the same base film as those exemplified above.

The film coated with the dye having absorption anisotropy is preferably thin, but if it is too thin, the strength is lowered and the processability tends to be inferior. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

Specific examples of the film coated with the dye having absorption anisotropy include the films described in JP-A-2012-33249.

A polarizing film can be obtained by laminating a transparent protective film on at least one surface of the polarizing element thus obtained via an adhesive. As the transparent protective film, a transparent film similar to the base film exemplified above can be preferably used.

When the long film of the present invention contains a horizontally oriented liquid crystal cured product layer as a functional layer, when the functional layer is transferred from the long film of the present invention to a polarizing film, the horizontally oriented liquid crystal cured product layer constituting the functional layer It is preferable to transfer the film so that the angle formed by the slow axis (optical axis) and the absorption axis of the polarizing film is 45 ± 5 °.

An optical laminate such as an elliptical polarizing plate containing a functional layer transferred from a long film of the present invention can be used in various display devices.
The display device is a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source. Display devices include liquid crystal display devices, organic electroluminescence (EL) display devices, inorganic electroluminescence (EL) display devices, touch panel display devices, electron emission display devices (for example, electric field emission display devices (FED), surface electric field emission display devices). (SED)), electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection type display device (for example, grating light valve (GLV) display device, display device having a digital micromirror device (DMD)). ) And piezoelectric ceramic displays. The liquid crystal display device includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, a projection type liquid crystal display device, and the like. These display devices may be display devices that display two-dimensional images or three-dimensional display devices that display three-dimensional images. In particular, functions transferred from the long film of the present invention. The elliptical polarizing plate including a layer can be suitably used for an organic electroluminescence (EL) display device and an inorganic electroluminescence (EL) display device, and can also be suitably used for a liquid crystal display device and a touch panel display device. The display device of the above can exhibit good image display characteristics by providing an elliptical polarizing plate having high reliability.

Hereinafter, the present invention will be described in more detail with reference to Examples. In addition, "%" and "part" in an example mean mass% and mass part, respectively, unless otherwise specified.

1. 1. Example 1
(1) Preparation of Composition for Forming Horizontal Alignment Film (A1) 5 parts (weight average molecular weight: 30,000) of a photo-alignable material having the following structure and 95 parts of cyclopentanone (solvent) were mixed as components to obtain a mixture. The mixture was stirred at 80 ° C. for 1 hour to obtain a composition for forming a horizontal alignment film (A1).

(2) Preparation of Polymerizable Liquid Crystal Compound A polymerizable liquid crystal compound (X1) and a polymerizable liquid crystal compound (Y1) having the following molecular structures were prepared for use in forming a horizontally oriented liquid crystal cured film. The polymerizable liquid crystal compound (X1) was produced according to the method described in JP-A-2010-31223. The polymerizable liquid crystal compound (Y1) was produced according to the method described in JP-A-2009-173893.

Polymerizable liquid crystal compound (X1)

Polymerizable liquid crystal compound (Y1)

(3) Preparation of Polymerizable Liquid Crystal Composition (B1) The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (Y1) were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the obtained mixture, 0.10 parts by mass of the leveling agent "BYK-361N" (manufactured by BYK-Chemie) and 0.25 parts by mass of the leveling agent "F-556" (manufactured by DIC) were added. As a photopolymerization initiator, 3 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one (BASF Japan Co., Ltd. "Irgacure (registered trademark) 369 (Irg369)") and BASF 7.5 parts by mass of "Irgacure OXE-03" manufactured by Japan Co., Ltd. was added. Further, cyclopentanone was added so that the solid content concentration was 13%. The mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition (B1).

A 1 mg / 50 mL tetrahydrofuran solution of the polymerizable liquid crystal compound (X1) was prepared, and a sample for measurement was obtained. Place the measurement sample in a measurement cell with an optical path length of 1 cm, set it in an ultraviolet-visible spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation), measure the absorption spectrum, and obtain the maximum absorption degree from the obtained absorption spectrum. When the wavelength was read, the maximum absorption wavelength λ _max in the wavelength range of 300 to 400 nm was 350 nm.

(4) Preparation of Liquid Crystal Cured Material Layer A triacetyl cellulose film (KC4UY, manufactured by Konica Minolta Co., Ltd.) in which uneven portions having a width of 15 mm in the short direction (total width of 30 mm in the short direction) are provided on both ends of the base material. ), The composition for forming a horizontal alignment film (A1) was applied by a die coating method so as to have a width shown as "functional layer coating width C" in Table 1. At this time, the edges of the coating film of the horizontal alignment film forming composition (A1) are located 7.5 mm inward from both ends of the base film, and 7.5 mm each on the uneven portions at both ends of the coating film. It was applied to cover it. Next, after heating and drying at 100 ° C. for 2 minutes, polarized UV is irradiated on the film at 100 mJ (based on 313 nm) so that the direction of the orientation regulating force is an angle of 45 ° with respect to the elongated direction of the film. A horizontal alignment film was formed. The film thickness of the obtained horizontal alignment film was measured with an ellipsometer and found to be 0.2 μm. Subsequently, the polymerizable liquid crystal composition (B1) was applied onto a horizontally oriented film with the same width as the film by a die coating method so that the average film thickness of the coating film was 17 μm, and dried by heating at 120 ° C. for 2 minutes. Then, using an ultraviolet irradiation device, the cured liquid crystal is further irradiated with ultraviolet rays from the surface side on which the polymerizable liquid crystal composition (B1) is applied (integrated light amount at a wavelength of 365 nm under a nitrogen atmosphere: 500 mJ / cm ² ). A long film (length: 2000 m) composed of a layer / horizontally oriented film / base film was obtained. The obtained long film was wound around an FRP core having an inner diameter of 6 inches.
From the average total thickness measured in the width direction with a contact film thickness meter for the long film of the base film / horizontal alignment film / liquid crystal cured product layer within the range that does not cover the uneven part at the end, the functional layer at the same location ( The in-plane average thickness X of the functional layer was confirmed by subtracting the average substrate thickness measured in the width direction from the substrate film after peeling (consisting of the horizontally aligned film and the cured liquid crystal layer). there were. Similarly, the maximum height Y of the convex portion measured at a pitch of 1 mm by a contact type film thickness meter at the end of the long film at the same position in the width direction was 7 μm. When this wound long film was stored in a 23 ° C. 55% RH environment for 1 week and then fed out, there was no noticeable sticking in the plane and no dropout of the functional layer.

(5) Characteristic evaluation of long film <Evaluation of peelability of functional layer>
A 25 μm pressure-sensitive adhesive manufactured by Lintec Corporation was bonded so as to be 5 mm inside from the coated end of the functional layer, and a triacetyl cellulose film (KC6UA) manufactured by Konica Minolta Co., Ltd. was bonded thereto. The triacetyl cellulose film was peeled off in parallel with the elongated direction, the functional layer was transferred, and the peeled state of the functional layer on the base film side after the transfer was visually observed under a fluorescent lamp by reflection.
The case where the peeling was successful in parallel with the long direction was judged as ◯, and the case where the peeling defect such as jaggedness occurred was judged as ×. The results are shown in Table 2.

<Measurement of substrate peeling force>
After sampling the central part of the long film composed of the functional layer and the base film in the width direction and performing corona treatment on the liquid crystal cured product layer side, a 25 μm pressure-sensitive adhesive manufactured by Lintec Corporation is used to mediate 12 cm in length × 10 cm in width × It was affixed to glass having a thickness of 0.7 mm (composition: base film / functional layer / adhesive layer / glass). A 25 mm wide notch was made from the base material side of the obtained sample with a cutter. The prepared sample was set on an autograph "EZ-L" manufactured by Shimadzu Corporation, and the peeling force when peeling a 25 mm wide base material at a speed of 300 mm / min in the direction parallel to the glass surface was confirmed. The results are shown in Table 2.

<Measurement of phase difference value of liquid crystal cured product layer>
The liquid crystal cured product layer side of the long film composed of the above-mentioned base film, the horizontally aligned film, and the liquid crystal cured product layer is subjected to corona treatment, and is subjected to a 25 μm pressure-sensitive adhesive manufactured by Lintec Corporation to be 4 cm in length × 4 cm in width × thickness. After bonding to 0.7 mm glass, the base film was peeled off. Re (450) and Re (550) of the liquid crystal cured product layer were measured using KOBRA-WPR manufactured by Oji Measuring Instruments Co., Ltd., and α = Re (450) / Re (550) was calculated. The results are shown in Table 2.

2. 2. Example 2
(1) Preparation of composition for forming a cured resin layer (C1) 50 parts of dipentaerythritol hexaacrylate (Aronix M-403 polyfunctional acrylate manufactured by Toa Synthetic Co., Ltd.), acrylate resin (Evecryl 4858 manufactured by Dycel UCB Co., Ltd.) 50 A solution prepared by dissolving 3 parts of 2-methyl-1 [4- (methylthio) phenyl] -2-molyphorinopropan-1-one (Irgacure 907; manufactured by Ciba Specialty Chemicals) in 250 parts of isopropanol was prepared. A composition for forming a cured resin layer (C1) containing an acrylate compound was obtained.

(2) Preparation of Cured Resin Layer The composition for forming a cured resin layer (C1) is applied to the "functional layer coating width C" in Table 1 on a triacetyl cellulose film provided with the same uneven portions as in Example 1. It was applied by the die coating method so as to have the width shown as. At this time, the edges of the coating film of the cured resin layer forming composition (C1) are located 7.5 mm inward from both ends of the base film, and 7.5 mm each on the uneven portions at both ends of the coating film. It was applied to cover it. Then, after drying at 60 ° C. for 1 minute, ultraviolet rays are further irradiated from the surface side coated with the cured resin layer forming composition (C1) using an ultraviolet irradiation device (integrated light amount at a wavelength of 365 nm under a nitrogen atmosphere: 400 mJ. / Cm ² ) to form a cured resin layer. At this time, when Re (550) of the laminated body of the triacetyl cellulose film and the cured resin layer was separately measured by Oji Measuring Instruments Co., Ltd. "KOBRA-WPR", the retardation value was 5 nm or less, and it was optically anisotropic. I confirmed that he was the one.
Subsequently, by forming a horizontally aligned film and a liquid crystal cured product layer on the obtained cured resin layer in the same manner as in Example 1, the liquid crystal cured product layer / horizontally aligned film / cured resin layer / base film can be obtained. A long film of 1000 m was obtained. The obtained long film was wound around an FRP core having an inner diameter of 6 inches. When the in-plane average thickness X of the functional layer composed of the cured resin layer / horizontal alignment film / liquid crystal cured product layer was confirmed, it was 4 μm. The maximum height Y of the convex portion was 9 μm. When the wound long film was stored in a 23 ° C. 55% RH environment for 1 week and then fed out, there was no noticeable sticking in the plane and no dropout of the functional layer. The peelability and the like were evaluated in the same manner as in Example 1. The results are shown in Table 2.

3. 3. Example 3
A base material COP film (ZF-14-50) manufactured by Nippon Zeon Corporation was used as the base film, and heated embossed rolls were pressed against the base film to provide 12.5 mm wide knurling portions on both ends of the base film, and corona treatment was performed. Was carried out. The cured resin layer forming composition (C1) was applied onto this base film by a die coating method so as to have a width shown as "functional layer coating width C" in Table 1. At this time, the edges of the coating film of the cured resin layer forming composition (C1) are located 7.5 mm inward from both ends of the base film, and the uneven portions at both ends of the coating film are coated by 5 mm each. Was applied. Except for this, a long film was prepared in the same manner as in Example 2, and the in-plane average thickness X of the functional layer was confirmed to be 4 μm. The maximum height Y of the convex portion was 8 μm. When the wound long film was stored in a 23 ° C. 55% RH environment for 1 week and then fed out, there was no noticeable sticking in the plane and no dropout of the functional layer. The peelability and the like were evaluated in the same manner as in Example 1. The results are shown in Table 2.

4. Example 4
(1) Preparation of Polymerizable Liquid Liquid Composition Composition (B2) With respect to 100 parts by mass of the polymerizable liquid crystal compound (X2) prepared with reference to JP-A-2016-81035, the leveling agent "BYK-361N" (BYK-). 0.10 parts by mass of Chemie), 0.25 parts by mass of leveling agent "F-556" (manufactured by DIC), and 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) as a photopolymerization initiator. ) Butan-1-one (“Irgacure (registered trademark) 369 (Irg369)” manufactured by BASF Japan Co., Ltd.) and 7.5 parts by mass of “Irgacure OXE-03” manufactured by BASF Japan Co., Ltd. were added. Further, cyclopentanone was added so that the solid content concentration was 13%. The mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition (B2).

A 1 mg / 50 mL tetrahydrofuran solution of the polymerizable liquid crystal compound (X2) was prepared, and a sample for measurement was obtained. Place the measurement sample in a measurement cell with an optical path length of 1 cm, set it in an ultraviolet-visible spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation), measure the absorption spectrum, and obtain the maximum absorption degree from the obtained absorption spectrum. When the wavelength was read, the maximum absorption wavelength λ _max in the wavelength range of 300 to 400 nm was 352 nm.

Polymerizable liquid crystal compound (X2)

A long film was produced in the same manner as in Example 1 except that (B2) was used instead of the polymerizable liquid crystal composition (B1). When the in-plane average thickness X of the functional layer was confirmed, it was 2 μm. The maximum height Y of the convex portion was 7 μm. When the wound long film was stored in a 23 ° C. 55% RH environment for 1 week and then fed out, there was no noticeable sticking in the plane and no dropout of the functional layer. The peelability and the like were evaluated in the same manner as in Example 1. The results are shown in Table 2.

5. Example 5
(1) Preparation of Polymerizable Liquid Liquid Composition Composition (B3) The leveling agent "BYK-361N" (BYK) was prepared with reference to International Patent Publication No. 2015/025793 for 100 parts by mass of the polymerizable liquid crystal compound (X3). -Chemie) 0.10 parts by mass, leveling agent "F-556" (DIC) 0.25 parts by mass, and 2-dimethylamino-2-benzyl-1- (4-morpholino) as a photopolymerization initiator 3 parts by mass of phenyl) butane-1-one (“Irgacure (registered trademark) 369 (Irg369)” manufactured by BASF Japan Ltd.) and 7.5 parts by mass of “Irgacure OXE-03” manufactured by BASF Japan Ltd. were added. Further, cyclopentanone was added so that the solid content concentration was 13%. The mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition (B3).

A 1 mg / 50 mL tetrahydrofuran solution of the polymerizable liquid crystal compound (X3) was prepared, and a sample for measurement was obtained. Place the measurement sample in a measurement cell with an optical path length of 1 cm, set it in an ultraviolet-visible spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation), measure the absorption spectrum, and obtain the maximum absorption degree from the obtained absorption spectrum. When the wavelength was read, the maximum absorption wavelength λ _max in the wavelength range of 300 to 400 nm was 352 nm.

Polymerizable liquid crystal compound (X3)

A long film was produced in the same manner as in Example 1 except that (B3) was used instead of the polymerizable liquid crystal composition (B1). When the in-plane average thickness X of the functional layer was confirmed, it was 2 μm. The maximum height Y of the convex portion was 7 μm. When the wound long film was stored in a 23 ° C. 55% RH environment for 1 week and then fed out, there was no noticeable sticking in the plane and no dropout of the functional layer. The peelability and the like were evaluated in the same manner as in Example 1. The results are shown in Table 2.

6. Example 6
(1) Preparation of Polymerizable Liquid Crystal Composition (B4) The leveling agent "BYK-361N" (BYK-Chemie) with respect to 100 parts by mass of the liquid crystal compound LC242: Palocolor LC242 (registered trademark of BASF) represented by the following formula (LC242). ) 0.10 parts by mass, leveling agent "F-556" (manufactured by DIC) 0.25 parts by mass, and polymerization initiator Irg369 3 parts by mass were added so that the solid content concentration became 13 parts by mass. Cyclopentanone was added. The mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition (B4).

Polymerizable liquid crystal compound (LC242)
Liquid crystal compound LC242: Palocolor LC242 (registered trademark of BASF)

As the base film, a triacetyl cellulose film having the same uneven portions as in Example 1 was used, and the composition for forming a horizontal alignment film (A1) was placed on the triacetyl cellulose film in the "functional layer" of Table 1. The film was applied by a die coating method so as to have a width indicated as "coating width C". At this time, the edges of the coating film of the horizontal alignment film forming composition (A1) are located 7.5 mm inward from both ends of the base film, and 7.5 mm each on the uneven portions at both ends of the coating film. It was applied to cover it. Next, after heating and drying at 100 ° C. for 2 minutes, polarized UV is irradiated on the film at 100 mJ (based on 313 nm) so that the direction of the orientation regulating force is at an angle of 15 ° with respect to the elongated direction of the film. A horizontal alignment film was formed. The film thickness of the obtained horizontal alignment film was measured with an ellipsometer and found to be 0.2 μm. Subsequently, the polymerizable liquid crystal composition (B4) was applied onto a horizontally oriented film with the same width as the film by a die coating method so that the average film thickness of the coating film was 17 μm, and dried by heating at 80 ° C. for 1 minute. Then, using an ultraviolet irradiation device, ultraviolet rays are irradiated from the surface side on which the polymerizable liquid crystal composition is applied (integrated light amount at a wavelength of 365 nm under a nitrogen atmosphere: 500 mJ / cm ² ) to obtain a cured liquid crystal layer / horizontal. A long film composed of an alignment film / base film was obtained at 500 m. The obtained long film was wound around an FRP core having an inner diameter of 6 inches. When the in-plane average thickness X of the functional layer was confirmed, it was 2 μm. The maximum height Y of the convex portion was 8 μm. When the wound long film was stored in a 23 ° C. 55% RH environment for 1 week and then fed out, there was no noticeable sticking in the plane and no dropout of the functional layer. The peelability and the like were evaluated in the same manner as in Example 1. The results are shown in Table 2.

7. Example 7
(1) Preparation of Vertically Oriented Polymerizable Liquid Liquid Composition (B5) A mixed solution of 13 parts by mass of "KBE-903" manufactured by Shinetsu Chemical Industry Co., Ltd. and 87 parts by mass of cyclopentanone, and "Carens" manufactured by Showa Denko Co., Ltd. A mixed solution of 13 parts by mass of "MOI-EG" and 87 parts by mass of cyclopentanone was mixed so as to have KBE-903: Karenz MOI-EG = 1.00: 1.35 (mass ratio), and then 30 ° C. A mixed solution containing a compound (pre-reaction compound) having a functional group (hydroxysilyl group) capable of reacting with a hydroxyl group or a carboxyl group and a (meth) acryloyl group (acryloyl group) in the molecule (pre-reaction compound). Hereinafter, it may be referred to as a mixed solution (1)).
Subsequently, the polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (Y1) were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the obtained mixture, 0.25 parts by mass of the leveling agent "F-556" (manufactured by DIC) and ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802. ) 2.0 parts by mass, Irgacure369E (manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator 6 parts by mass, as a polymerizable non-liquidity compound having two or more (meth) acryloyl groups, "APG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. -700 "(bifunctional) 1.0 part by mass was added, and cyclopentanone was added so that the solid content concentration was 13%. Further, a compound (pre-reaction compound) having a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth) acryloyl group in the molecule is added to 100 parts by mass of the mixture of the polymerizable liquid crystal compounds (X1) and (Y1). The mixture (1) was added so as to have a volume of 2.35 parts by mass to obtain a mixture. The obtained mixture was stirred at 80 ° C. for 1 hour to obtain a vertically oriented polymerizable liquid crystal composition (B5).

Ionic compound A:

A vertically oriented polymerizable liquid crystal composition (B5) is applied onto a triacetyl cellulose film ((KC4UY, manufactured by Konica Minolta Co., Ltd.)) provided with the same uneven portions as in Example 1, and the average film thickness of the coating film is The film was coated by the die coating method with a width shown as "functional layer coating width C" in Table 1 so as to have a thickness of 9.5 μm. At this time, the edges of the coating film of the vertically oriented polymerizable liquid crystal composition (B5) are located 7.5 mm inward from both ends of the base film, and 7.5 mm each on the uneven portions at both ends of the coating film. It was applied to cover it. Next, after heating and drying at 120 ° C. for 90 seconds, ultraviolet rays are irradiated from the surface side to which the polymerizable liquid crystal composition (B5) is applied using an ultraviolet irradiation device (integrated light amount at a wavelength of 365 nm under a nitrogen atmosphere: 500 mJ / cm. ² ) A long film composed of a liquid crystal cured product layer / base film was obtained in an amount of 1000 m. The obtained long film was wound around an FRP core having an inner diameter of 6 inches. When this in-plane average thickness X was confirmed, it was 1 μm. The maximum height Y of the convex portion was 6 μm. When the wound long film was stored in a 23 ° C. 55% RH environment for 1 week and then fed out, there was no noticeable sticking in the plane and no dropout of the functional layer. The peelability and the like were evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Rth measurement of vertically oriented liquid crystal cured product layer>
Corona treatment was performed on the liquid crystal cured product layer side of the base film produced by the above procedure and the long film composed of the (vertically oriented) liquid crystal cured product layer, and the length was 4 cm × via a 25 μm pressure-sensitive adhesive manufactured by Lintec Corporation. After bonding to a glass having a width of 4 cm and a thickness of 0.7 mm, the base film was peeled off. For the obtained laminate composed of glass, adhesive, and liquid crystal cured product layer, the angle of incidence of light on the sample for measuring optical characteristics was changed using KOBRA-WPR manufactured by Oji Measuring Instruments Co., Ltd. to change the front phase difference value. , And the phase difference value when tilted by 40 ° to the center of the phase advance axis was measured. The average refractive index at each wavelength was measured using an ellipsometer M-220 manufactured by JASCO Corporation. Moreover, the above-mentioned in-plane average thickness was used as the film thickness. From the above-mentioned front phase difference value, phase difference value when tilted by 40 ° to the center of the phase advance axis, average refractive index, and film thickness value, Oji Measuring Instruments Technical Data (http://www.oji-keisoku.co. The three-dimensional refractive index was calculated with reference to (.jp / products / kobra / reference.html). From the obtained three-dimensional refractive index, the optical characteristics of each vertically oriented liquid crystal cured product layer were calculated according to the following formula. The results are shown in Table 2.
RthC (λ) = ((nxC (λ) + nyC (λ)) / 2-nzC (λ)) × dC
RthC (λ) represents a phase difference value in the thickness direction of the vertically oriented liquid crystal cured product layer at a wavelength of λ nm. Further, nxC (λ) is the in-plane main refractive index of the vertically oriented liquid crystal cured product layer at a wavelength of λ nm, and nyC (λ) is the refractive index in the in-plane direction orthogonal to nxC (λ) at a wavelength of λ nm, nzC. (Λ) indicates the refractive index in the thickness direction of the vertically oriented liquid crystal cured product layer at a wavelength of λ nm, and when nxC (λ) = nyC (λ), nxC (λ) is in an arbitrary direction in the film plane. It can be a refractive index, and dC indicates the thickness of the vertically oriented liquid crystal cured product layer.

8. Example 8
A cured resin layer was prepared on the triacetyl cellulose film in the same manner as in Example 2, and a long film was further prepared in the same manner as in Example 7. When the in-plane average thickness X of the functional layer was confirmed, it was 3 μm. The maximum height Y of the convex portion was 8 μm. When the wound long film was stored in a 23 ° C. 55% RH environment for 1 week and then fed out, there was no noticeable sticking in the plane and no dropout of the functional layer. The peelability and the like were evaluated in the same manner as in Example 1. The results are shown in Table 2.

9. Example 9
A base material COP film (ZF-14-50) manufactured by Nippon Zeon Corporation was used as the base film, and heated embossed rolls were pressed against the base film to provide 12.5 mm wide knurling portions on both ends of the base film, and corona treatment was performed. Was carried out. The cured resin layer forming composition (C1) was applied onto this base film by a die coating method so as to have a width shown as "functional layer coating width C" in Table 1. At this time, the edges of the coating film of the cured resin layer forming composition (C1) are located 7.5 mm inward from both ends of the base film, and the uneven portions at both ends of the coating film are coated by 5 mm each. Was applied. A long film was obtained in the same manner as in Example 8 except for the above. When the in-plane average thickness X of the functional layer was confirmed, it was 3 μm. The maximum height Y of the convex portion was 11 μm. When the wound long film was stored in a 23 ° C. 55% RH environment for 1 week and then fed out, there was no noticeable sticking in the plane and no dropout of the functional layer. The peelability and the like were evaluated in the same manner as in Example 1. The results are shown in Table 2.

10. Example 10
(1) Preparation of Composition for Forming Vertical Alignment Film (A2) 0.5% Polyimide (“Sunever SE-610” manufactured by Nissan Chemical Industry Co., Ltd.), 72.3% N-methyl-2-pyrrolidone, 18 A composition (A2) for forming a vertical alignment film was prepared by mixing 1% 2-butoxyethanol, 9.1% ethylcyclohexane, and 0.01% DPHA (manufactured by Shin-Nakamura Chemical Co., Ltd.).

As the base film, a COP film provided with a knurling portion was used as in Example 9. The composition for forming a vertically oriented film (A2) was applied onto this COP film by a die coating method so as to have a width shown as "functional layer coating width C" in Table 1. At this time, the edges of the coating film of the vertical alignment film forming composition (A2) are located 7.5 mm inward from both ends of the base film, and the uneven portions at both ends of the coating film are coated by 5 mm each. Was applied. The film was dried by heating at 80 ° C. for 1 minute to form a vertically oriented film on the film. Subsequently, the polymerizable liquid crystal composition (B4) was applied onto a vertically aligned film with the same width as the film by a die coating method so that the average film thickness of the coating film was 5 μm, and dried by heating at 80 ° C. for 1 minute. Then, by further irradiating ultraviolet rays from the surface side coated with the polymerizable liquid crystal composition (B4) using an ultraviolet irradiation device (integrated light amount at a wavelength of 365 nm in a nitrogen atmosphere: 500 mJ / cm ² ), the cured liquid crystal product is obtained. A long film composed of a layer / vertical alignment film / base film was obtained. When the in-plane average thickness X of the functional layer was confirmed, it was 1 μm. The maximum height Y of the convex portion was 9 μm. When the wound long film was stored in a 23 ° C. 55% RH environment for 1 week and then fed out, there was no noticeable sticking in the plane and no dropout of the functional layer. The peelability and the like were evaluated in the same manner as in Example 1. The results are shown in Table 2.

11. Comparative Example 1
The composition for forming a horizontal alignment film (A1) and the polymerizable composition (A1) so as to have a width shown as "functional layer coating width C" in Table 1 on a triacetyl cellulose film provided with the same uneven portions as in Example 1. A long film was obtained in the same manner as in Example 1 except that the liquid crystal composition (B1) was applied. In the application of the horizontal alignment film forming composition (A1), the edges of the coating film of the horizontal alignment film forming composition (A1) are located 25 mm inward from both ends of the base film, respectively, and the base material is applied. The coating was applied so that both ends of the coating film did not cover the uneven portions provided on both ends of the film.
When the in-plane average thickness X of the functional layer was confirmed, it was 2 μm. The maximum height Y of the convex portion was 2 μm. When the wound long film was stored in an environment of 23 ° C. and 55% RH for one week and then fed out, sticking occurred in the plane and deformation of the film roll was observed. In addition, as a result of the evaluation of the peelability of the functional layer, the end portion was jagged and fell off. The peelability and the like were evaluated in the same manner as in Example 1. The results are shown in Table 2.

1: Base film 2: Functional layer 3: Concavo-convex portion 11: Long film A: Short-length direction width of base film B1 and B2: Short-length direction width of uneven portion C: Short-length direction width of functional layer

Claims

A transfer containing a long base film having an uneven portion at at least one end in the short direction of at least one surface and a cured product layer of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound. A long film comprising a possible functional layer.
The functional layer is laminated on the surface having the uneven portion of the base film.
A long film satisfying B + C> A when the total width of the base film in the short direction is A, the total width of the uneven portions of the base film in the short direction is B, and the width of the functional layer in the short direction is C.
The long film according to claim 1, wherein the peeling force of the functional layer from the base film is 0.02 N / 25 mm or more and less than 1 N / 25 mm.
The long film according to claim 1 or 2, wherein the base film is a cellulosic resin film or an olefin resin film.
The long length according to any one of claims 1 to 3, wherein the relationship between the in-plane average thickness X of the functional layer and the maximum height Y of the convex portion of the uneven portion satisfies 1.0 <Y / X ≦ 15.0. the film.
The molecular orientation direction of the polymerizable liquid crystal compound in the cured product layer constituting the functional layer is horizontal with respect to the long direction plane of the base film and with respect to the long direction of the base film. The long film according to any one of claims 1 to 4, which is not in the parallel direction.
The long film according to any one of claims 1 to 5, wherein the cured product layer constituting the functional layer satisfies the following formulas (1) and (2).
Re (450) / Re (550) ≤ 1.00 (1)
100 nm ≤ Re (550) ≤ 150 nm (2)
[In equations (1) and (2), Re (λ) represents an in-plane retardation value at a wavelength of λ nm. ]
The long film according to any one of claims 1 to 5, wherein the cured product layer constituting the functional layer satisfies the following formulas (3) and (4).
200 nm ≤ Re (550) ≤ 300 nm (3)
1.00 ≤ Re (450) / Re (550) (4)
[In equations (3) and (4), Re (λ) represents an in-plane retardation value at a wavelength of λ nm. ]
The long film according to any one of claims 1 to 7, wherein the functional layer contains a photoalignment film.
Any of claims 1 to 5, wherein the molecular orientation direction of the polymerizable liquid crystal compound in the cured product layer constituting the functional layer is substantially vertical with respect to the longitudinal plane of the base film. The long film described in.
The long film according to any one of claims 1 to 5 and 9, wherein the cured product layer constituting the functional layer satisfies the following formula (5).
-150 nm ≤ Rth (550) ≤ -20 nm (5)
[In the formula (5), Rth (550) indicates the phase difference value in the thickness direction of the cured product layer at a wavelength of 550 nm. ]