KR20220032514A - long film - Google Patents

Abstract

An object of the present invention is a long film having a functional layer comprising a base film and a transferable liquid crystal cured material layer, wherein the functional layer at the end of the short film does not easily detach when the base film is peeled, and the optical properties are poor. An object of the present invention is to provide a long film capable of producing an excellent optical film with good productivity. The present invention is transferable comprising 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 functional layer, wherein the functional layer is laminated on a surface having an uneven portion of the base film, and the overall width in the short direction of the base film is A, and the width in the short direction of the uneven portion of the base film is When the sum total is B and the short direction width of the functional layer is C, a long film satisfying B+C>A is provided.

Description

long film

The present invention relates to a long film, in particular, to a long film comprising a functional layer comprising a liquid crystal cured material layer on a base film.

The elliptically polarizing plate is an optical film in which a polarizing film and a retardation plate are laminated, and for example, in a device that displays an image in a planar state such as an organic EL image display device, to prevent light reflection from the electrodes constituting the device is being used for In recent years, there exists a continuous request|requirement for weight reduction and thickness reduction with respect to organic electroluminescent image display apparatus, and further thickness reduction is calculated|required also about the retardation plate and elliptically polarizing plate used as one of the components. Among them, an optical film of a type in which a functional layer such as a retardation layer made of a liquid crystal cured material layer is formed on a base film, the base film is peeled, and the functional layer is transferred to other constituent members, such as a polarizing film, is known. (Patent Document 1).

Japanese Patent Laid-Open No. 2016-027431

The optical film having a transfer type functional layer as described above is advantageous to widen and/or elongate from the viewpoint of productivity improvement. A roll-to-roll method is used. However, when a functional layer made of a liquid crystal cured material layer formed by molecularly orienting a polymerizable liquid crystal compound in a specific direction and curing it, when the base film is peeled off during transfer, the liquid crystal cured material layer at the end of the short direction is peeled off the base film. It does not easily peel linearly with respect to a direction (flow direction), and the problem that the edge part of the liquid-crystal hardened|cured material layer is torn in a jagged shape and detaches is easy to generate|occur|produce.

Therefore, the present invention is a long film having a functional layer including a base film and a transferable liquid crystal cured material layer, and the functional layer at the end of the short direction does not easily detach when the base film is peeled, and the optical properties are An object of the present invention is to provide a long film capable of producing an excellent optical film with good productivity.

MEANS TO SOLVE THE PROBLEM The present inventors came to complete this invention, as a result of earnestly examining in order to solve the said subject. That is, this invention includes the following aspects.

[1] A transferable function comprising 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 As a long film comprising a layer,

The functional layer is laminated on the surface of the base film having an uneven portion,

A long film satisfying B + C > A when A is the total width in the short direction of the base film, B is the sum of the short direction widths of the uneven portions of the base film, and C is the short direction width of the functional layer.

[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 olefinic resin film.

[4] The long film according to any one of [1] to [3], wherein the relationship between the average in-plane thickness X of the functional layer and the maximum height Y of the convex portions of the uneven portions satisfies 1.0 < Y/X ≤ 15.0.

[5] The molecular orientation direction of the polymerizable liquid crystal compound in the cured material layer constituting the functional layer is horizontal with respect to the in-plane in the long direction of the base film, and is not parallel to the long direction of the base film; The long film according to any one of [1] to [4].

[6] The long film according to any one of [1] to [5], wherein the cured material layer constituting the functional layer satisfies the following formulas (1) and (2).

Re (450)/Re (550) ≤ 1.00 (One)

100 nm ≤ Re (550) ≤ 150 nm (2)

[In Formulas (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 material 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 formulas (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], wherein the functional layer includes a photo-alignment film.

[9] In any one of [1] to [5] above, wherein the molecular orientation direction of the polymerizable liquid crystal compound in the cured material layer constituting the functional layer is substantially perpendicular to the inside of the long direction plane of the base film. Long film described.

[10] The long film according to any one of [1] to [5] and [9], wherein the cured material layer constituting the functional layer satisfies the following formula (5).

-150 nm ≤ Rth (550) ≤ -20 nm (5)

[In formula (5), Rth (550) represents the retardation value in the thickness direction at a wavelength of 550 nm of the cured product layer.]

According to the present invention, as a long film having a functional layer comprising a base film and a transferable liquid crystal cured material layer, detachment of the functional layer at the end of the short film does not occur easily when the base film is peeled, and the optical properties are excellent It is possible to provide a long film capable of producing an optical film with good productivity.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows an example of the layer structure which looked at the long film of this invention from the short direction.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. In addition, the scope of the present invention is not limited to the embodiments described herein, and various changes can be made in a range that does not impair the spirit of the present invention.

The long film of the present invention is a transfer comprising a 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 possible functional layers. In the long film of the present invention, the transferable functional layer is laminated on the side having the concavo-convex portion of the base film, and the total width in the short direction of the base film is A, and the sum of the width in the short direction of the concavo-convex portions in the base film is B , B + C > A is satisfied when the short direction width of the functional layer is C.

Although not limited to this, FIG. 1 : is sectional drawing which shows an example of the layer structure which looked at the long film of this invention from the short direction. In FIG. 1, the elongate film 11 of this invention laminates|stacks the base film 1 and the functional layer 2, and consists of it. The uneven part 3 is formed in the both ends of the surface on which the functional layer 2 of the base film 1 is laminated|stacked, and the functional layer 2 is laminated|stacked so that a part on each uneven part 3 may overlap. The total width in the short direction of the base film 1 is A, and the sum of the widths in the short direction of the concavo-convex portions 3 formed at both ends of the base film 1 is B (B1 + B2 in Fig. 1), the functional layer 2 ), when the entire width in the short direction is C, B + C becomes larger than A.

As used herein, the term "transferable functional layer" means a layer capable of being transferred to another member such as another substrate or an optical film by peeling the base film, and is a polymerizable liquid crystal compound containing a polymerizable liquid crystal compound. and a cargo layer (hereinafter also referred to as “liquid crystal cured material layer”). The functional layer may contain layers other than a liquid-crystal hardened|cured material layer, as long as it can function as an optical film after transcription|transfer, without affecting the effect of this invention. Examples of such other layers include an alignment film, a cured resin layer such as a protective layer and a hard coat layer, and an adhesive layer for bonding a functional layer such as a liquid crystal cured material layer to other members such as a polarizing film. When the elongate film of the present invention includes a layer other than the base film and the liquid crystal cured material layer, in the present specification, all layers that are peeled off from the base film and transferred to another member are referred to as a functional layer.

As described above, in the long film of the present invention, when the total width in the short direction of the base film is A, the sum of the short direction widths of the concavo-convex portions present in the base film is B, and the short direction width of the functional layer is C. , has a configuration that satisfies B + C > A. That is, in the long film of this invention, a part of a functional layer is laminated|stacked on the at least one part uneven|corrugated part which exists in a base film. By forming an uneven|corrugated part in the edge part of a base film, when forming a functional layer on a base film, an anchor effect can be produced between the uneven|corrugated part and the functional layer laminated|stacked on this uneven|corrugated part, and adhesiveness becomes easy to improve. Moreover, when peeling a functional layer from a base film because the adhesiveness in the area|region which is not in contact with an uneven|corrugated part is relatively low, a functional layer becomes easy to peel along the uneven|corrugated part on a base film.

For example, the functional layer can be peeled linearly with respect to the peeling direction (flow direction) at the edge part of a long film by forming an uneven part with a fixed width linearly in a long direction at the edge part of a base film. Thereby, detachment of the functional layer at the end of the long film is suppressed during transfer, the functional layer having a straight and clear end cross-section can be transferred to another member, and the acquisition efficiency and yield at the time of use can be improved. In addition, in the uneven portion covered with the functional layer, pressing pressure during transportation or storage in roll form, and settling (reducing the projections on the uneven portion) with the passage of time are less likely to occur, so long-term storage Even after that, a functional layer can be peeled easily and cleanly from a base film.

It is preferable that the functional layer which comprises the elongate film of this invention is laminated|stacked on the base film over the whole width direction of the functional layer. Therefore, it is preferable that the short direction full width A of a base film, and the short direction width C of a functional layer exist in the relationship of A≥C, and it is more preferable that it is the relationship of A>C.

In this invention, it is preferable that an uneven|corrugated part exists linearly with respect to a long direction in at least one edge part of a base film, and it is more preferable that an uneven|corrugated part exists linearly with respect to a long direction in both ends of a base film. Moreover, it is more preferable that the both ends of a functional layer are respectively overlapped with the uneven|corrugated part which exists in the both ends of a base film by a fixed width, and are laminated|stacked. When a long film has such a structure, when peeling a functional layer from a base film and transcribe|transferring to another member, the said effect of this invention can be heightened more. In addition, in order to enhance the anchor effect generated between the base film and the functional layer, the layer on the side adjacent to the base film of the functional layer is preferably a layer formed by being directly applied on the base film and then cured, for example, , it is preferable that it is a liquid crystal hardened|cured material layer or a photo-alignment film.

In this invention, the peeling force at the time of peeling a functional layer from a base film becomes like this. Preferably they are 0.02 N/25 mm or more and less than 1 N/25 mm. Since moderate adhesiveness generate|occur|produces between a functional layer and a base film as peeling force is in the said range, a functional layer can be peeled along the uneven|corrugated part of a base film. Moreover, since it has moderate peelability while suppressing the detachment|desorption etc. by the functional layer adhering to a conveyance roll etc. at the time of transcription|transfer, a functional layer can be peeled easily and cleanly from a base film. From a viewpoint of the peelability from the base film of a functional layer and moderate adhesiveness, the said peeling force becomes like this. More preferably, it is 0.03 N/25 mm or more, More preferably, it is 0.05 N/25 mm or more, More preferably, it is 0.5 It is N/25 mm or less, More preferably, it is 0.3 N/25 mm or less. The peeling force can be controlled according to the width of the uneven portion formed on the base film, the height and shape of the unevenness, the material constituting the base film or the surface of the functional layer in contact with the base film, the conditions for coating and curing the functional layer, etc. .

In addition, in the present invention, the peeling force is at the interface between the functional layer and the base film, or at the interface between the layer transferred in the functional layer and the layer to be peeled off together with the base film, peeling the base film at a rate of 300 mm/min. It means the base material peeling force (N/25 mm) at the time of doing, specifically, it can measure according to the method as described in the Example mentioned 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 concavo-convex portion satisfies 1.0 < Y/X ≤ 15.0. By satisfying the above relationship between the functional layer and the concavo-convex portions on the base film, the handling properties of the long film are easily improved, and the long-term film is wound in a roll shape, and deformation (blocking) during long-term storage is suppressed. is likely to rise When the value of Y/X becomes large too much, sticking will become easy to generate|occur|produce remarkably at the edge part of a film, and distortion of a film roll (wound long film) will increase easily also in plane. In this invention, the value of Y/X becomes like this. More preferably, it is 1.5 or more, More preferably, it is 2.0 or more, More preferably, it is 12.0 or less, More preferably, it is 10.0 or less.

In the present invention, the "in-plane average thickness of the functional layer" means the total thickness of all the layers constituting the functional layer, measured in the short direction within a range not including the portion overlapping the uneven portions of the base film. do. In addition, "the maximum height of the convex part of an uneven|corrugated part" means the height from the base film surface without an uneven|corrugated part to the vertex of the convex part used as the largest height among uneven|corrugated parts. The in-plane average thickness X of the functional layer and the maximum height Y of the convex portions of the concave and convex portions can each be measured using, for example, a contact thickness gauge, and specifically, can be measured according to the method described in Examples to be described later. there is.

As a base film which comprises the elongate film of this invention, although thin glass, a resin film, etc. are mentioned, for example, From a viewpoint of workability, a resin film is preferable. As resin which comprises a resin film, For example, Polyethylene, a polypropylene, and olefin-type resin like a norbornene-type polymer (preferably cyclic olefin-type resin); polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid ester; polyacrylic acid ester; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; and plastics such as polyphenylene sulfide and polyphenylene oxide. Such a resin can be formed into a film by known means such as a solvent casting method and a melt extrusion method to be used as a substrate. As long as the effect of this invention is not affected, the surface of a base film may be surface-treated, such as a mold release process like a silicone treatment, a corona treatment, and a plasma treatment.

You may use a commercially available product as a base film. As a commercially available cellulose-ester base material, the cellulose-ester base material of Fuji Photo Film Co., Ltd. product like Fujitac film, etc. are mentioned, for example. As commercially available cyclic olefin resin, For example, cyclic olefin resin by Ticona (Germany) like "Topas (trademark)"; Cyclic olefin resin by JSR Corporation like "Aton (trademark)"; Cyclic olefin resins manufactured by Nippon Zeon Corporation such as “ZEONOR (registered trademark)” and “ZEONEX (registered trademark)”; Cyclic olefin resin by Mitsui Chemicals, Inc. like "Apel" (trademark) is mentioned. A commercially available cyclic olefin-based resin substrate can also be used. As a commercially available cyclic olefin resin base material, Sekisui Chemical Industry Co., Ltd. product cyclic olefin resin base material like "Sucina (registered trademark)" and "SCA40 (registered trademark)"; Cyclic olefin resin base material by Optes Corporation like "Zeonoa Film (trademark)"; The cyclic olefin resin base material by JSR Corporation like "Aton Film (trademark)" is mentioned.

From the viewpoint of thickness reduction, easy peeling of the functional layer from the base film, easy orientation of the polymerizable liquid crystal compound, solvent resistance, low birefringence, etc., as the base film, a cellulose-based resin film or an olefin-based resin film is preferable, and cellulose A system resin film is more preferable. In general, in a cellulosic resin film produced by a solvent casting method, it is difficult to impart a slip property to the film surface, and the adhesion with a layer laminated on the film is increased, and when wound into a long roll, sticking occurs. easy. Moreover, when feeding out this elongate film roll, there exists a possibility that peeling arises at random because a functional layer is closely_contact|adhered to the base film of a back surface, and there exists a possibility that it may fall off partially. Even in such a case, an uneven part is formed at the edge part of a base material, and the adhesiveness with the functional layer in the uneven part is further improved, and by forming a space|gap between the functional layer and the base film of the back in the area|region where there is no unevenness|corrugation, By suppressing sticking/falling off in an uneven area|region and generating a suitable difference in the adhesiveness of a base film and a functional layer between an uneven|corrugated part and an uneven|corrugated area|region, it is easy to peel a functional layer linearly from a base film in the peeling direction. can do. For this reason, the present invention may be particularly advantageous when a cellulosic resin film is used.

In this invention, the uneven|corrugated part on a base film is called so-called knurling, and normally functions as a structure for suppressing the contact and sticking of base material surfaces at the time of winding-up of a base film. What is necessary is just to select the shape, material, and formation method of such an uneven|corrugated part suitably from the conventionally well-known thing according to the base film which comprises a long film, a functional layer, desired peeling force, etc.

It is preferable to form an uneven|corrugated part in the desired area|region of the edge part of a base film, when winding up a base film, for example. An uneven part may be provided only in one surface of a base film, and may be formed in both surfaces. Moreover, although you may provide an uneven|corrugated part only in at least one edge part of a base film, in order to acquire favorable peelability from the base film of a functional layer, it is preferable to provide in the both ends of a base film.

It is preferable that an uneven|corrugated part is formed in strip|belt shape parallel to a long direction in the edge part of the short direction of a base film. The short direction width of the concave-convex portion formed in the band shape may be appropriately determined according to the short direction width of the long film, the base film or functional layer constituting the long film, desired peeling force, the thickness of the long film, etc., but usually at each end Each is a width of about 0.2 to 5% of the short direction width of the base film. When the short direction width of each uneven|corrugated part is in the said range, it will be easy to generate|occur|produce a moderate anchor effect between an uneven|corrugated part and a functional layer, and it will be easy to obtain favorable peelability of a base film and a functional layer. For example, in the case of a base film having a short direction width of 1000 to 2000 mm, the short direction width 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 it is 50 mm or less, More preferably, it is 30 mm or less, More preferably, it is 20 mm or less.

The height of the concave-convex portion may be appropriately determined according to the short direction width of the long film, the short direction width of the concavo-convex portion, the thickness of the functional layer, the base film or functional layer constituting the long film, desired peeling force, the thickness of the long film, and the like. Preferably it is 0.5 micrometer or more, More preferably, it is 1 micrometer or more, More preferably, it is 500 micrometers or less, More preferably, it is 200 micrometers or less, More preferably, it is 20 micrometers or less. When the height of each uneven|corrugated part is in the said range, it will be easy to generate|occur|produce a moderate anchor effect between an uneven|corrugated part and a functional layer, and it will be easy to obtain favorable peelability of a base film and a functional layer.

In addition, the height of the uneven|corrugated part here means the average height of each unevenness|corrugation at the time of being based on the base film surface without an uneven|corrugated part in the base film on which the functional layer is not laminated|stacked. Specifically, for example, the average total thickness is calculated by measuring the range in which the uneven portions of the base film do not exist in the width direction at a 1 mm pitch using a contact film thickness meter, and similarly, The average height of the uneven portions can be measured and calculated from the difference by calculating the average total thickness of the uneven portions by measuring the range in which the uneven portions exist.

The number (density) of the irregularities per cm 2 of the irregularities is preferably 20 or more, more preferably 50 or more, and preferably 1000 or less, more preferably 500 or less, still more preferably 200 or more. less than dogs It is preferable that each unevenness|corrugation exists uniformly in an uneven|corrugated part. When the density of each uneven|corrugated part is in the said range, it is easy to generate|occur|produce an appropriate anchor effect between an uneven|corrugated part and a functional layer, and it is easy to obtain favorable peelability of a base film and a functional layer.

As a shape of each unevenness|corrugation which comprises an uneven|corrugated part, a pyramid shape, a truncated cone shape, a spherical shape, a waveform, a grid|lattice shape, an indefinite shape, etc. are mentioned, for example. The size of each unevenness may be appropriately determined according to the short direction width of the long film, the short direction width of the uneven portions, the density of the uneven portions, the base film or functional layer constituting the long film, the desired peeling force, the thickness of the long film, and the like. For example, when the cross-sectional shape when the unevenness is cut parallel to the film surface from the base film surface is circular or substantially circular, the diameter of the cross-sectional shape is preferably about 50 to 1000 µm, more preferably It is 100-3000 micrometers.

As a method of forming an uneven|corrugated part on a base film, the method of clamping with a pair of rolls is common, for example. The one-sided pressurization using the roll embossed only on the one side of a pair of rolls may be sufficient, and the both-side pressurization using the roll embossed for both may be sufficient. Moreover, you may process with a laser etc. other than that. As a specific example of such an uneven|corrugated part, the thing of international publication 2010/143524, Unexamined-Japanese-Patent No. 2007-91784, etc. are mentioned, for example.

Moreover, you may use a commercial item as a base film which has an uneven|corrugated part. As a commercial item, the cellulose-ester base material of the Konica Minolta Opto Co., Ltd. product like "KC8UX2M", "KC8UY", and "KC4UY", etc. are mentioned.

Although the thickness of a base film may be suitably determined according to the material of a base film, etc., it is 5-300 micrometers normally, Preferably it is 10-150 micrometers. It is more preferable that it is 20-80 micrometers from a viewpoint of the quality after lengthening of a film and winding-up.

As for the short direction width of a base film, 0.5-3 m is preferable, More preferably, it is 0.6-2.5 m, More preferably, it is 0.8-2.2 m. It is preferable that a long film is wound up in roll shape, The length is 100-10000 m per 1 winding roll, More preferably, it is 500-7000 m, More preferably, it is 1000-6000 m.

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 material layer is a liquid crystal cured material layer cured in a state in which the polymerizable liquid crystal compound is oriented in a specific direction such as a horizontal direction or a vertical direction with respect to the plane of the cured material layer.

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 liquid crystal cured material layer having desired optical properties, and, for example, a conventionally known polymerizable liquid crystal compound in the field of retardation film can be used.

The polymerizable group refers to a group capable of participating in a polymerization reaction. The photopolymerizable group refers to a group capable of participating in a polymerization reaction by a reactive active species generated from a photopolymerization initiator, for example, an active radical or an acid as a polymerizable group. 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 oxiranyl group, and an oxetanyl group. can be heard Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and an acryloyloxy group is more preferable. Although a thermotropic liquid crystal may be sufficient as the liquid crystal which a polymeric liquid crystal compound shows, or a lyotropic liquid crystal may be sufficient, a thermotropic liquid crystal is preferable at the point which precise|minute film thickness control is possible. Moreover, as a good-order structure in a thermotropic liquid crystal, a nematic liquid crystal may be sufficient, a smectic liquid crystal may be sufficient, and a discotic liquid crystal may be sufficient. A polymerizable liquid crystal compound can be used individually or in combination of 2 or more types.

Examples of the polymerizable liquid crystal compound include a polymerizable liquid crystal compound generally exhibiting forward wavelength dispersibility and a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion, and only either type of polymerizable liquid crystal compound may be used, or both. It is also possible to use a mixture of types of polymerizable liquid crystal compounds. In an image display device having a functional layer transferred from the long film of the present invention, it is easy to improve the front reflection color and easy to obtain a long film with excellent optical properties. It is preferable that the polymer obtained by superposing|polymerizing in a state contains the polymeric liquid crystal compound which shows reverse wavelength dispersibility.

A polymerizable liquid crystal compound having a so-called T-shaped or H-shaped molecular structure is preferable from the viewpoint of easy expression of reverse wavelength dispersion, and a polymerizable liquid crystal compound having a T-shaped molecular structure from the viewpoint of obtaining stronger reverse wavelength dispersion. A liquid crystal compound is more preferable.

As a polymerizable liquid crystal compound, it is preferable that it is a compound which has the characteristics of following (A)-(D).

(A) It is a compound which can form 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 on the direction [intersecting direction (b)] intersecting with respect to the major axis direction (a).

(D) The long axis of the polymerizable liquid crystal compound defined in the following formula (i) by setting the sum of π electrons in the major axis direction (a) to N(πa) and the molecular weight in the major axis direction to N(Aa) π electron density in direction (a):

D(πa) = N(πa)/N(Aa) (i)

A polymerizable liquid crystal compound defined by the following formula (ii) with N(πb) as the sum of π electrons present in the crossing direction (b) and N(Ab) as the sum of molecular weights present in the crossing direction (b) π electron density in the cross direction of (b):

D(πb) = N(πb)/N(Ab) (ii)

A, formula (iii)

0 ≤ [D(πa)/D(πb)] < 1 (iii)

[that is, the pi electron density in the cross direction (b) is greater than the pi electron density in the major axis direction (a)]. As described above, the polymerizable liquid crystal compound having pi electrons on the major axis and in the direction intersecting it is generally liable to have a T-shaped structure.

In the above characteristics (A) to (D), the major axis direction (a) and the number of π electrons N are defined as follows.

- The major axis direction (a) is, for example, a rod-shaped major axis direction if it is a compound having a rod-like structure.

- The number of π electrons N(πa) present on the major axis direction (a) does not include π electrons lost by polymerization reaction.

· The number of π electrons in the long axis direction (a) N(πa) is the total number of π electrons on the long axis and π electrons conjugated thereto, for example, as a ring present in the long axis direction (a), The number of π electrons in the ring that satisfies Hickel's law is included.

- The number of π electrons N(πb) present in the crossing direction (b) does not include π electrons lost by polymerization reaction.

The polymerizable liquid crystal compound satisfying the above has a mesogenic structure in the major axis direction. A liquid crystal phase (nematic phase, smectic phase) is expressed by this mesogenic structure. In one aspect of the present invention, the polymerizable liquid crystal compound is preferably a compound capable of forming a nematic phase.

It is possible to form a nematic phase or a smectic phase by apply|coating the polymeric liquid crystal compound which satisfy|fills said (A)-(D) on the film|membrane (layer) which forms a liquid crystal cured film, and heating it more than a phase transition temperature. In the nematic phase or smectic phase formed by aligning the polymerizable liquid crystal compound, the long axis directions of the polymerizable liquid crystal compound are usually oriented so that they are parallel to each other, and this long axis direction becomes the alignment direction of the nematic phase or the smectic phase. When such a polymerizable liquid crystal compound is made into a film and polymerized in a nematic or smectic state, a polymer film composed of a polymer polymerized in a state oriented in the major axis direction (a) can be formed. This polymer film absorbs ultraviolet rays by pi electrons on the major axis direction (a) and π electrons on the cross direction (b). Here, the absorption maximum wavelength of the ultraviolet ray absorbed by the π electrons on the crossing direction (b) is λbmax. ?bmax is usually 300 nm to 400 nm. The density of π electrons satisfies the above formula (iii), and since the π electron density in the intersecting direction (b) is larger than the π electron density in the major axis direction (a), linearly polarized light having a vibrational plane in the intersecting direction (b) A polymer film in which absorption of ultraviolet rays (wavelength is λbmax) is larger than absorption of linearly polarized ultraviolet rays (wavelength is λbmax) having a vibrational plane in the major axis direction (a). The ratio (ratio of absorbance in the intersecting direction (b) of linearly polarized ultraviolet light / 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 .

The polymerizable liquid crystal compound having the above characteristics is generally one in which the birefringence of the polymer exhibits reverse wavelength dispersion when it is polymerized in a unidirectionally oriented state in many cases. Specifically, for example, the compound represented by a following formula (X) is mentioned.

In formula (X), Ar represents the divalent group which has an aromatic group which may have a substituent. As an aromatic group here, the group illustrated by (Ar-1) - (Ar-23) mentioned later is mentioned, for example. Moreover, Ar may have two or more aromatic groups. At least 1 or more of a nitrogen atom, an oxygen atom, and a sulfur atom may be contained in the aromatic group. When two or more aromatic groups contained in Ar are two or more, 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 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. 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, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or It may be substituted by the nitro group, and the carbon atom which comprises the bivalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted by the oxygen atom, a sulfur atom, or a nitrogen atom.

L ¹ , L ² , B ¹ and B ² are each independently a single bond or a divalent linking group.

k and l each independently represent an integer of 0 to 3, and satisfy the relationship of 1 ≤ k + l. Here, when 2 ≤ k+1, B ¹ and B ² , G ¹ and G ² may be the same as or different from each other, respectively.

E ¹ and E ² each independently represent a C1-C17 alkanediyl group, and a C4-C12 alkanediyl group is more preferable. In addition, a hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and -CH ₂ - contained in the alkanediyl group is substituted with -O-, -S-, -C(=O)-, there may be

P ¹ and P ² each independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.

G ¹ and G ² are each independently, preferably a 1,4-phenylenediyl 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, a halogen atom, and 1,4-cyclohexanediyl group optionally substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, more preferably 1,4-phenylenediyl group substituted with a methyl group, unsubstituted 1,4-phenylenediyl group or an unsubstituted 1,4-trans-cyclohexanediyl group, particularly preferably an unsubstituted 1,4-phenylenediyl group, or unsubstituted 1,4-trans-cyclo It is a hexanediyl group.

In addition, at least one of the plurality of G ¹ and G ² 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 a divalent alicyclic hydrocarbon. It is more preferable that it is a group.

L ¹ and L ² are each independently, 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 having 1 to 4 carbon atoms or a hydrogen atom. 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 - am. Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 each independently represent a single bond, -CH ₂ -, or -CH ₂ CH ₂ -. L ¹ and L ² are each independently, more preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, or -OCO-.

B ¹ and B ² are each independently, preferably a single bond, an 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 each independently, more preferably a single bond, -OR ^a10-1 -, -CH ₂ -, -CH ₂ CH ₂ -, -COOR ^a12-1 -, or -OCOR ^a14-1 - am. Here, R ^a10-1 , R ^a12-1 , and R ^a14-1 each independently represent a 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 - am.

From the viewpoint of expression of reverse wavelength dispersion, 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. If k = 2 and l = 2, it is preferable because it becomes a symmetric structure.

Examples of the polymerizable group represented by P ¹ or P ² include 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, an oxiranyl group. , and an oxetanyl group. Especially, an acryloyloxy group, a methacryloyloxy group, a vinyl group, and a vinyloxy group are preferable, and an acryloyloxy group and a methacryloyloxy group are more preferable.

It is preferable that Ar has at least one selected from the aromatic hydrocarbon ring which may have a substituent, the aromatic heterocyclic ring which may have a substituent, and the electron withdrawing group. As said aromatic hydrocarbon ring, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned, for example, A benzene ring and a naphthalene ring are preferable. Examples of the aromatic heterocyclic ring 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 pyrroline ring , an imidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, an oxazole ring, a benzoxazole ring, and a phenanthroline ring. Especially, 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. Moreover, when a nitrogen atom is contained in Ar, it is preferable that the said nitrogen atom has (pi) electron.

In formula (X), the total number N _π of π electrons 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, particularly preferably is greater than or equal to 16. Moreover, Preferably it is 32 or less, More preferably, it is 26 or less, More preferably, it is 24 or less.

As an aromatic group contained in Ar, the following groups are mentioned, for example.

In formulas (Ar-1) to (Ar-23), * represents a linking part, and Z ⁰ , Z ¹ and Z ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and cya. No group, nitro group, C1-C12 alkylsulfinyl group, C1-C12 alkylsulfonyl group, carboxyl group, C1-C12 fluoroalkyl group, C1-C12 alkoxy group, C1-C12 alkylthio group , N-alkylamino group having 1 to 12 carbon atoms, N,N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 12 carbon atoms, or N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms indicates Moreover, Z ⁰ , Z ¹ , and Z ² may contain a polymerizable group.

Q ¹ and Q ² each independently represent -CR ^2' R ^3' -, -S-, -NH-, -NR ^2' -, -CO- or -O-, R ^2' and R ^{3 '} represents a hydrogen atom or a C1-C4 alkyl group each independently.

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

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

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

Examples of the aromatic hydrocarbon group for Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups 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 and a naphthyl group preferred, and more preferably a phenyl group. Examples of the aromatic heterocyclic group include a nitrogen atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group, and at least one hetero atom such as an oxygen atom and a sulfur atom having 4 to carbon atoms The aromatic heterocyclic group of 20 is mentioned, A furyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group are preferable.

Y ¹ , Y ² , and Y ³ may each independently represent an optionally substituted polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring set. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring set.

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

Q ¹ and Q ² are preferably -NH-, -S-, -NR ^2' -, -O-, and R ^2' is preferably a hydrogen atom. Among these, -S-, -O-, and -NH- are especially preferable.

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

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

As the polymerizable liquid crystal compound for forming the liquid crystal cured layer in the present invention, 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. . The polymerizable liquid crystal compound (Y) generally tends to exhibit positive wavelength dispersion. These polymerizable liquid crystal compounds can be used individually or in combination of 2 or more types.

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-, - CS- or single bond. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

B12 and B13 are each 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)-O-, - OC(=O)-CH=CH-, -H, -C≡N or a single bond.

E11 represents an alkanediyl group having 1 to 12 carbon atoms, a hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms, and a hydrogen atom contained in the alkoxy group is substituted with a halogen atom, there may be In addition, -CH ₂ - constituting the alkanediyl group may be substituted with -O- or -CO-.]

It is preferable that carbon number of the aromatic hydrocarbon group and alicyclic hydrocarbon group of A11 is the range of 3-18, It is more preferable that it is the range of 5-12, It is especially preferable that it is 5 or 6. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group represented by A11 may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group, and the carbon number thereof The hydrogen atom contained in the 1-6 alkyl group and the C1-C6 alkoxy group may be substituted by the fluorine atom. A11 is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group.

As E11, a linear C1-C12 alkanediyl group is preferable. -CH ₂ - constituting the alkanediyl group may be substituted 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, hepta-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-diyl group C1-C12 linear alkanediyl groups, such as a diary; -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 especially.

B12 and B13 are each independently -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O) -O- is preferable, and -O- or -OC(=O)-O- is more preferable especially.

The polymerizable group represented by P11 is preferably a radical polymerizable group or a cation polymerizable group from the viewpoint of high polymerization reactivity, particularly photopolymerization reactivity, easy handling, and easy production of the liquid crystal compound itself. It is preferable that a sexual group is group represented by a following formula (P-11) - a formula (P-15).

[In formulas (P-11) to (P-15),

R ¹⁷ to R ²¹ each independently represent an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.]

As a specific example of the group represented by a formula (P-11) - a formula (P-15), group represented by a following formula (P-16) - a formula (P-20) is mentioned.

It is preferable that it is group represented by a formula (P-14) - a formula (P-20), and, as for P11, a vinyl group, p-stilbene group, an epoxy group, or oxetanyl group is more preferable.

It is more preferable that the group represented by P11-B11- is an acryloyloxy group or a methacryloyloxy group.

As a polymerizable liquid crystal compound (Y), the compound represented by a formula (I), a formula (II), a formula (III), a formula (IV), a formula (V), or a formula (VI) is mentioned.

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 have the same meaning as above,

A12 to A14 each independently have the same meaning as A11, B14 to B16 each independently have the same meaning as B12, B17 has the same meaning as B11, E12 has the same meaning as E11, and P12 has the same meaning as P11 am.

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, a sulfo group (-SO ₃ H), a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or a halogen atom, and -CH ₂ - constituting the alkyl group and the alkoxy group may be substituted with -O-.]

Specific examples of the polymerizable liquid crystal compound (Y) include "3.8.6 network (completely crosslinked type)" and "6.5 .1 liquid crystal material b. A compound having a polymerizable group among the compounds described in "polymerizable nematic liquid crystal material", JP-A-2010-31223, JP-A-2010-270108 , JP-A 2011-6360 , and JP-A 2011- The polymerizable liquid crystal of No. 207765 is mentioned.

As a specific example of a polymeric liquid crystal compound (Y), following formula (I-1) - a formula (I-4), a formula (II-1) - a formula (II-4), a formula (III-1) - a formula (III-26), a compound represented by a formula (IV-1) to a formula (IV-26), a formula (V-1) to a formula (V-2), and a formula (VI-1) to a formula (VI-6) can be heard In addition, in the following formula, k1 and k2 respectively independently represent the integer of 2-12. These polymerizable liquid crystal compounds (Y) are preferable from the point of the easiness of the synthesis|combination or the easiness of acquisition.

Both of the polymerizable liquid crystal compounds (X) and (Y) may be used horizontally or vertically aligned.

It is preferable that it is a polymeric liquid crystal compound which has a maximum absorption wavelength between wavelength 300-400 nm among a polymeric liquid crystal compound. When the polymerizable liquid crystal composition contains a photopolymerization initiator, there is a fear that 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 when exposed to ultraviolet light during storage, generation of reactive active species from the photopolymerization initiator and polymerization reaction and gelation of the polymerizable liquid crystal compound by the reactive species can effectively inhibit the progression of Therefore, it becomes advantageous in the point of long-term stability of a polymeric liquid crystal composition, and the orientation of the liquid crystal cured film obtained and the uniformity of a film thickness can be improved. In addition, the maximum absorption wavelength of a polymeric liquid crystal compound can be measured using the ultraviolet-visible spectrophotometer in a solvent. The solvent is a solvent capable of dissolving the 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, more preferably 85 parts by mass based on 100 parts by mass of the solid content of the polymerizable liquid crystal composition. -98 mass parts, More preferably, it is 90-95 mass parts. When content of a polymeric liquid crystal compound is in the said range, it is advantageous from a viewpoint of the orientation of the liquid crystal hardened|cured material layer obtained. Moreover, when a polymerizable liquid crystal composition contains 2 or more types of polymerizable liquid crystal compounds, it is preferable that the total amount of all the liquid crystal compounds contained in a polymeric liquid crystal composition is in the range of the said content. In addition, in this specification, the solid content of a polymeric liquid crystal composition means all the components except volatile components, such as an organic solvent, from a polymeric liquid crystal composition.

In addition to the polymerizable liquid crystal compound, the polymerizable liquid crystal composition may further contain additives such as a solvent, a photoinitiator, a leveling agent, an antioxidant, a photosensitizer, a vertical alignment accelerator, and a polymerizable non-liquid crystal compound. These components may each use only 1 type, and may use them in combination of 2 or more type.

Since a polymeric liquid crystal composition is apply|coated to a base film etc. in the state melt|dissolved in a solvent normally, 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 inactive 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 propylene. alcohol solvents, such as glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents, such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; and amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents can be used individually or in combination of 2 or more types. Among them, it is preferable to use at least one selected from the group consisting of alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents from the viewpoint of film coating, and from the viewpoint of solubility of the polymerizable liquid crystal compound In this, 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.

To [ content of the solvent in a polymeric liquid crystal composition / 100 mass parts of polymeric liquid crystal composition ], Preferably it is 50-98 mass parts, More preferably, it is 70-95 mass parts. Therefore, as for solid content which occupies for 100 mass parts of polymeric liquid crystal compositions, 2-50 mass parts is preferable. When the solid content is 50 parts by mass or less, since the viscosity of the polymerizable liquid crystal composition is low, the thickness of the film becomes substantially uniform, and there is a tendency that unevenness is less likely to occur. The solid content may be appropriately determined in consideration of the thickness of the polymerizable liquid crystal cured material layer to be manufactured.

A polymerization initiator is a compound which produces|generates reactive active species by the contribution of heat|fever or light, and can initiate polymerization reaction, such as a polymerizable liquid crystal compound. Examples of the reactive active species include radicals or active species such as cations or anions. Among these, the photoinitiator which generate|occur|produces a radical by light irradiation from a viewpoint that reaction control is easy is preferable.

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. there is. 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, manufactured by BASF Japan Co., Ltd.), Sakeol BZ, Sakeol Z, Sakeol BEE (above, manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 ( Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Corporation), Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, Adeka Optomer N-1919 Deca Accruz NCI-831, Adeca Accruz NCI-930 (above, manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (above, manufactured by Nippon Siber Hegner) and TAZ-104 (manufactured by Sanwa Chemical) can be heard

Although the photoinitiator contained in a polymeric liquid crystal composition is at least 1 type and may be used in combination of multiple types, it is preferable that it is 1 type or 2 types.

A photoinitiator can fully utilize the energy emitted from a light source, and since it is excellent in productivity, it is preferable in it being 300 nm - 400 nm of maximum absorption wavelength, It is more preferable in it being 300 nm - 380 nm, Especially, α- An acetophenone-type polymerization initiator and an oxime-type photoinitiator are preferable.

Examples of the α-acetophenone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)- 2-benzylbutan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one, and more preferably 2- methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one can As a commercial item of (alpha)-acetophenone compound, Irgacure 369, 379EG, 907 (above, BASF Japan Co., Ltd. make), Sikol BEE (made by Seiko Chemical Co., Ltd.), etc. are mentioned.

An oxime ester type photoinitiator produces|generates radicals, such as a phenyl radical and a methyl radical, when light is irradiated. Although polymerization of a polymerizable liquid crystal compound advances preferably by this radical, the oxime ester type photoinitiator which generate|occur|produces a methyl radical among them is preferable at the point with high initiation efficiency of a polymerization reaction. Moreover, it is preferable to use the photoinitiator which can utilize the ultraviolet-ray with a wavelength of 350 nm or more efficiently from a viewpoint of advancing a polymerization reaction more efficiently. As a photoinitiator which can efficiently utilize the ultraviolet-ray with a wavelength of 350 nm or more, a triazine compound and a carbazole compound containing an oxime ester structure are preferable, and the carbazole compound containing an oxime ester structure is more preferable from a viewpoint of a sensitivity. . As a commercial item of an oxime ester type photoinitiator, Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, BASF Japan Co., Ltd. make), Adeca Optomer N-1919, Adeka Accruz NCI-831 (above, manufactured by ADEKA Corporation) etc. are mentioned.

Content of a photoinitiator is 0.1-30 mass parts normally with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably it is 1-20 mass parts, More preferably, it is 1-15 mass parts. If it is in the said range, reaction of a polymeric group fully advances, and the orientation of a polymeric liquid crystal compound is hard to be 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 phenolic antioxidants, amine antioxidants, quinone antioxidants, and nitroso antioxidants, or may be secondary antioxidants selected from phosphorus antioxidants and sulfur antioxidants. When the polymerizable group of the polymerizable liquid crystal compound is a radical polymerizable group, the phosphorus-based antioxidant and the sulfur-based antioxidant, which are secondary antioxidants, are preferable at the point that the reaction is not easily inhibited.

To [ content of antioxidant / 100 mass parts of polymeric liquid crystal compounds ], Preferably it is 0.01-3.0 mass parts, More preferably, it is 0.01-1.0 mass parts.

By using a sensitizer, a photoinitiator can be made highly sensitive. As a photosensitizer, For example, xanthone, such as a xanthone and a thioxanthone; anthracenes having a substituent such as anthracene and alkyl ether; phenothiazine; Rubrene may be mentioned. As a photosensitizer, For example, xanthone, such as a xanthone and a thioxanthone; anthracenes having a substituent such as anthracene and alkyl ether; phenothiazine; Rubrene may be mentioned.

Content of a photosensitizer is 0.01-10 mass parts normally with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably it is 0.05-5 mass parts, More preferably, it is 0.1-3 mass parts.

A leveling agent is an additive which adjusts the fluidity|liquidity of a polymeric liquid crystal composition, and has the function of flattering the coating film obtained by apply|coating a composition, For example, a silicone type, a polyacrylate type, and a perfluoroalkyl type|system|group leveling agent. can be heard A commercially available product may be used as the leveling agent, specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (above, all manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, (all above, all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (or above) , all manufactured by Momentive Performance Materials Japan joint venture), fluorinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (all above, Sumitomo 3M Co., Ltd.) Manufacture), Megapac (registered trademark) R-08, Dong R-30, Dong R-90, Dong F-410, Dong F-411, Dong F-443, Dong F-445, Dong F-470, Dong F -477, East F-479, East F-482, East F-483 (above, all manufactured by DIC Co., Ltd.), Ftop (brand name) EF301, East EF303, East EF351, East EF352 (above, all Mitsubishi Material Electronics) Hwasung Co., Ltd.), Suflon (registered trademark) S-381, Dong S-382, Dong S-383, Dong S-393, Dong SC-101, Dong SC-105, KH-40, SA-100 ( All of the above, manufactured by AGC Semi-Chemical Co., Ltd.), trade names E1830, E5844 (manufactured by Daikin Fine Chemical Laboratories, Ltd.), BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N ( All are brand names: the BM Chemie company make) etc. are mentioned. A leveling agent can be used individually or in combination of 2 or more types.

0.01-10 mass parts is preferable with respect to 100 mass parts of polymeric liquid crystal compounds, and, as for content of a leveling agent, 0.05-3 mass parts is more preferable. Since content of a leveling agent exists in the said range, since there exists a tendency for the liquid-crystal hardened|cured material layer obtained to become smoother, it 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.

One aspect of this invention WHEREIN: The hardened|cured material layer (liquid crystal hardened|cured material layer) included in a functional layer has the optical characteristic shown by following formula (1) and (2). The liquid crystal cured product layer is usually a cured product (hereinafter also referred to as a “horizontal aligned liquid crystal cured product layer”) obtained by curing the polymerizable liquid crystal compound in a state oriented in the horizontal direction with respect to the cured product layer plane.

Re (450)/Re (550) ≤ 1.00 (One)

100 nm ≤ Re (550) ≤ 150 nm (2)

[In Formulas (1) and (2), Re (λ) represents an in-plane retardation value at a wavelength of λ nm.]

When Formula (1) is satisfied, the liquid crystal cured material layer exhibits so-called reverse wavelength dispersion, in which the in-plane retardation value in a short wavelength becomes smaller than the in-plane retardation value in a long wavelength. The reverse wavelength dispersion is improved, and the front color when the elliptically polarizing plate obtained by transferring the functional layer containing the liquid crystal cured material layer from the long film of the present invention to a polarizing film is applied to a display device is improved, so that 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 or less.

The said in-plane retardation value can be adjusted according to thickness dA of a liquid-crystal hardened|cured material layer. The in-plane phase difference value is given by the following formula:

Re (λ) = (nxA (λ) - nyA (λ)) × dA

[Wherein, nxA (λ) represents the principal refractive index at the wavelength λ in the layer plane of the liquid crystal cured material layer, and nyA (λ) is the wavelength λ in a direction orthogonal to the direction of nxA in the same plane as nxA. represents the refractive index of , and dA represents the layer thickness of the liquid crystal cured layer]

In order to obtain a desired in-plane retardation value (Re (λ): the in-plane retardation value of the liquid crystal cured material layer at the wavelength λ (nm)), the three-dimensional refractive index and the layer thickness dA may be adjusted. In addition, the three-dimensional refractive index depends on the molecular structure and orientation state of the polymerizable liquid crystal compound.

In addition, when the in-plane retardation Re (550) of the liquid crystal cured material layer is within the range of formula (2), the liquid crystal cured material layer functions as a so-called λ/4 plate, and when a functional layer including this is applied to a display device The effect of improving the color of the front reflection is excellent. A more preferable range of the in-plane retardation value is 130 nm ≤ Re (550) ≤ 150 nm.

Moreover, the hardened|cured material layer contained in a functional layer may have the optical characteristic represented by following formula (3) instead of said Formula (2), In this case, it is preferable to have the optical characteristic which satisfy|fills Formula (4). . Such a liquid-crystal hardened|cured material layer also becomes a horizontally aligned liquid crystal hardened|cured material layer which is normally hardened|cured in the state which oriented in the horizontal direction with respect to the hardened|cured material layer plane of a polymerizable liquid crystal compound.

200 nm ≤ Re (550) ≤ 300 nm (3)

1.00 ≤ Re (450)/Re (550) (4)

[In Formulas (3) and (4), Re (λ) represents the in-plane retardation value at the wavelength λ nm of the liquid crystal cured material layer.]

When the liquid crystal cured material layer satisfies the formulas (3) and (4), the liquid crystal cured material layer functions as a so-called λ/2 plate, and the front reflection color is improved when a functional layer including this is applied to a display device. The effect is excellent. A more preferable range of the in-plane retardation value Re (550) in this case is 220 nm ≤ Re (550) ≤ 280 nm.

Another one aspect of this invention WHEREIN: The hardened|cured material layer (liquid-crystal hardened|cured material layer) included in a functional layer has the optical characteristic represented by following formula (5). The liquid crystal cured product layer is usually a cured product (hereinafter also referred to as a “vertically aligned liquid crystal cured product layer”) obtained by curing a polymerizable liquid crystal compound in a state in which the polymerizable liquid crystal compound is oriented in a direction perpendicular to the plane of the liquid crystal cured product layer.

-150 nm ≤ Rth (550) ≤ -20 nm (5)

[In formula (5), Rth (550) represents the retardation value in the thickness direction at a wavelength of 550 nm of the cured product layer.]

When the retardation value Rth (550) of the thickness direction of a liquid crystal hardened|cured material layer is in the range of Formula (5), it is excellent in the improvement effect of the oblique reflection hue when the functional layer containing this is applied to a display device. A more preferable range of the phase difference value is -30 nm ≤ Rth (550) ≤ -100 nm.

In the present invention, when the cured material layer included in the functional layer is a vertically aligned liquid crystal cured material layer, the liquid crystal cured material layer preferably satisfies the following formulas (6), and formulas (5) and (6) It is more preferable to satisfy at the same time.

Rth(450)/Rth(550) ≤ 1.00 (6)

[In formula (6), Rth (λ) represents the retardation value in the thickness direction at the wavelength λ nm of the cured product layer.]

By satisfying said Formula (5), in the functional layer containing the vertically-aligned liquid crystal hardened|cured material layer, the fall of the ellipticity in the short wavelength side can be suppressed, and an oblique reflection hue can be improved. The value of Rth (450)/Rth (550) is more preferably 0.95 or less, still more preferably 0.92 or less, particularly preferably 0.9 or less, and preferably 0.7 or more, and more preferably 0.75 or less. or more, more preferably 0.8 or more. In addition, Rth (λ) is controllable by the three-dimensional refractive index and the film thickness dC.

The retardation value in the thickness direction is expressed by the following formula: Rth (λ) = ((nxC (λ) + nyC (λ))/2 - nzC (λ)) × dC

[wherein nxC (λ) is the in-plane principal refractive index of the liquid crystal cured material layer at a wavelength of λ nm, nyC (λ) is the refractive index in a direction orthogonal to nxC (λ) in-plane at a wavelength of λ nm, nzC (λ) represents the refractive index in the thickness direction of the liquid crystal cured material layer at a wavelength of λ nm, and when nxC (λ) = nyC (λ), nxC (λ) is the refractive index in any direction within the film plane. and dC represents the film thickness of the liquid crystal cured material layer]

Since it is determined by , in order to obtain a desired retardation value Rth (550) in the film thickness direction, the three-dimensional refractive index and the film thickness dC may be adjusted. In addition, the three-dimensional refractive index depends on the molecular structure and orientation state of the polymerizable liquid crystal compound.

The thickness of the liquid crystal cured material layer is preferably 0.1 to 5.0 µm, more preferably 0.2 to 4.0 µm, still 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 not to break easily. easier to do In the present invention, since a part of the functional layer is laminated on the uneven portion formed at the end portion of the base film, the occurrence of tearing can be effectively suppressed by an appropriate anchor effect generated at the end portion, and having a thickness within the above range In this case, it is easy to obtain the effect of the present invention more remarkably.

The long film of the present invention, for example,

A coating film of a polymerizable liquid crystal composition containing at least one kind of polymerizable liquid crystal compound is formed on a long base film or an alignment film to be described later, and the coating film is dried, and further, a polymerizable liquid crystal in the polymerizable liquid crystal composition orienting the compound, and

A step of forming a liquid crystal cured material layer by polymerizing a polymerizable liquid crystal compound by light irradiation while maintaining the alignment state

It can be prepared by a method comprising

In the present invention, the coating film of the polymerizable liquid crystal composition is formed by coating the polymerizable liquid crystal composition on the base film constituting the long film of the present invention, or on the alignment film formed on the long base film as described below. can do. As a method of applying the polymerizable liquid crystal composition to a base film, etc., a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, a coating method such as an applicator method, and a printing method such as a flexographic method are known. method can be cited.

Then, a dry coating film is formed by removing a solvent by drying etc. As a drying method, the natural drying method, the ventilation drying method, heat drying, the reduced pressure drying method, etc. are mentioned. At this time, by heating the coating film obtained from the polymerizable liquid crystal composition, the solvent is removed from the coating film by drying, and the polymerizable liquid crystal compound can be oriented in a desired direction (eg, horizontal or vertical direction) with respect to the plane of the coating film. . The heating temperature of the coating film can be appropriately determined in consideration of the materials such as the polymerizable liquid crystal compound to be used and the base material for forming the coating film. It needs to be at a higher temperature. In order to bring the polymerizable liquid crystal compound into a desired alignment state while removing the solvent contained in the polymerizable liquid crystal composition, for example, the liquid crystal phase transition temperature (smectic phase transition temperature) of the polymerizable liquid crystal compound included in the polymerizable liquid crystal composition. or nematic phase transition temperature) or higher. The heating temperature is preferably 3°C or more higher than the liquid crystal phase (nematic phase) transition temperature of the polymerizable liquid crystal compound, and more preferably 5°C or more higher than the liquid crystal phase (nematic phase) transition temperature. Although the upper limit of heating temperature is not specifically limited, In order to avoid damage to a coating film, a base material, etc. by heating, Preferably it is 180 degrees C or less, More preferably, it is 150 degrees C or less.

In addition, the liquid crystal phase transition temperature can be measured using, for example, a polarization microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analysis apparatus (TG-DTA), etc. In addition, when using two or more types in combination as a polymerizable liquid crystal compound, the said phase transition temperature is polymerization obtained by mixing all the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition in the same proportion as the composition in the polymerizable liquid crystal composition. It means the temperature measured by carrying out similarly to the case of using 1 type of polymerizable liquid crystal compound using the mixture of a liquid crystal compound. Moreover, it is generally known that the liquid crystal phase transition temperature of a polymerizable liquid crystal compound in a polymeric liquid crystal composition may become lower than the liquid crystal phase transition temperature of a polymeric liquid crystal compound single-piece|unit.

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

Although removal of the solvent from a coating film may be performed simultaneously with the heating to the liquid crystal phase transition temperature or more of a polymeric liquid crystal compound, and may be performed separately, it is preferable to perform simultaneously from a viewpoint of productivity improvement. Prior to heating the polymerizable liquid crystal compound above the liquid crystal phase transition temperature, a preliminary drying step for appropriately removing the solvent in the coating film under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize You can prepare Examples of the drying method in this preliminary drying step include a natural drying method, a ventilation drying method, heat drying, and a reduced pressure drying method, and the drying temperature (heating temperature) in the drying step is determined by the polymerizable liquid crystal compound to be used. It can determine suitably according to the kind, the kind of solvent, its boiling point, its quantity, etc.

Next, in the obtained dry coating film, the polymerizable liquid crystal compound is polymerized by light irradiation while maintaining the alignment state of the polymerizable liquid crystal compound, whereby the liquid crystal cured material layer, which is a polymer of the polymerizable liquid crystal compound present in a desired alignment state, is is formed As the polymerization method, a photopolymerization method is usually used. In the photopolymerization, as light irradiated to the dry coating film, the type of the photoinitiator contained in the dry coating film, the type of the polymerizable liquid crystal compound (in particular, the type of the polymerizable group included in the polymerizable liquid crystal compound) and the amount thereof is appropriately selected according to 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. Among them, ultraviolet light is preferable from the viewpoint of being easy to control the progress of the polymerization reaction and that one widely used in the art can be used as a photopolymerization device. It is preferable to select the kind of a polymeric liquid crystal compound and photoinitiator contained in a liquid crystal composition. Moreover, at the time of superposition|polymerization, superposition|polymerization temperature can also be controlled by irradiating light, cooling a dry coating film with suitable cooling means. When the polymerizable liquid crystal compound is polymerized at a lower temperature by employing such a cooling means, even if a substrate having relatively low heat resistance is used, a liquid crystal cured material layer can be appropriately formed. Moreover, the polymerization reaction can also be accelerated|stimulated by making the polymerization temperature high in the range which does not generate|occur|produce the problem by the heat at the time of light irradiation (transformation by heat of a base material, etc.). At the time of photopolymerization, a patterned hardened|cured material layer can also be obtained by performing masking or image development.

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 excimer laser, a wavelength range of 380 An LED light source which emits light of -440 nm, a chemical lamp, a black light lamp, a microwave excited mercury lamp, a metal halide lamp, etc. are mentioned.

Ultraviolet irradiation intensity|strength is 10-3,000 mW/cm<2> normally. Ultraviolet irradiation intensity|strength, Preferably it is intensity|strength in the wavelength range effective for activation of a photoinitiator. The time period for irradiating light is usually from 0.1 second to 10 minutes, preferably from 0.1 second to 5 minutes, more preferably from 0.1 second to 3 minutes, still more preferably from 0.1 second to 1 minute. When irradiated once or multiple times with such ultraviolet irradiation intensity, the accumulated light quantity is 10-3,000 mJ/cm<2>, Preferably it is 50-2,000 mJ/cm<2>, More preferably, it is 100-1,000 mJ/cm<2>. When the amount of accumulated light is within this range, the polymerizable liquid crystal composition can sufficiently harden and good transferability can be obtained. Moreover, coloring of the whole long film containing a liquid-crystal hardened|cured material layer can be suppressed.

In one aspect of the present invention, the liquid crystal cured material layer may be formed on the alignment layer. An alignment film has an orientation regulating force which liquid-crystal-aligns a polymeric liquid crystal compound in a desired direction. Among these, an alignment film having an orientation regulating force for aligning the polymerizable liquid crystal compound in the horizontal direction is sometimes called a horizontal alignment film, and an alignment film having an orientation regulating force for aligning the polymerizable liquid crystal compound in a vertical direction is sometimes called a vertical alignment film. By forming the liquid crystal cured material layer on the alignment film, a liquid crystal cured material layer in which the polymerizable liquid crystal compound is oriented with high accuracy can be obtained, and a functional layer exhibiting excellent optical properties when introduced into a display device or the like can be obtained. The orientation regulating force can be arbitrarily adjusted according to the type of orientation film, surface state, rubbing conditions, etc., and when the orientation film is formed of a photo-alignable polymer, it can be arbitrarily adjusted according to polarized light irradiation conditions and the like.

As an alignment film, it is preferable to have solvent resistance which does not melt|dissolve by application|coating of a polymeric liquid crystal composition, etc., and to have heat resistance in the heat processing for removal of a solvent or orientation of a polymeric liquid crystal compound. Examples of the alignment film include an alignment film containing an alignment polymer, a photo alignment film, a groove alignment film having an uneven pattern or a plurality of grooves on the surface, a stretched film stretched in the alignment direction, and the like, from the viewpoint of precision and quality of alignment angle A photo-alignment film is preferable.

Examples of the orientation polymer include polyamide and gelatin having an amide bond in the molecule, polyimide having an imide bond in the molecule, and polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacryl which is a hydrolyzate thereof. amide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters. Especially, polyvinyl alcohol is preferable. An orientation polymer can be used individually or in combination of 2 or more types.

The orientation film containing the orientation polymer is usually prepared by applying a composition in which the orientation polymer is dissolved in a solvent (hereinafter, also referred to as "orientation polymer composition") to the surface on which the orientation film is to be formed, such as a base film, to remove the solvent, or It is obtained by apply|coating an orientation polymer composition to a base material, removing a solvent, and rubbing (rubbing method). As a solvent, the thing similar to the solvent illustrated above as a solvent which can be used for a polymeric liquid crystal composition is mentioned.

The concentration of the orientation polymer in the orientation polymer composition may be in a range in which the orientation polymer material can be completely dissolved in the solvent, but is preferably 0.1 to 20%, more preferably about 0.1 to 10%, in terms of solid content with respect to the solution.

As the orientation polymer composition, a commercially available orientation 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).

As a method of apply|coating an orientation polymer composition to the surface which should form orientation films, such as a base film, the thing similar to what was illustrated as a method of apply|coating a polymeric liquid crystal composition to a base film is mentioned.

As a method of removing the solvent contained in an orientation polymer composition, the natural drying method, the ventilation drying method, heat drying, the reduced pressure drying method, etc. are mentioned.

In order to provide an orientation regulating force to an orientation film, a rubbing process can be performed as needed (rubbing method). As a method of imparting an orientation regulating force by the rubbing method, a rubbing cloth wound and rotating a rubbing roll is coated with an oriented polymer composition to a substrate and annealed to make contact with a film of an oriented polymer formed on the surface of the substrate. . When performing a rubbing process, if masking is performed, a some area|region (pattern) from which an orientation direction differs can also be formed in an orientation film.

The photo-alignment film is usually prepared by applying a composition containing a polymer and/or a monomer having a photoreactive group and a solvent (hereinafter, also referred to as "composition for photo-alignment film formation") to the surface of the substrate on which the alignment film is to be formed, and the solvent is removed. It is obtained by later irradiating polarized light (preferably, polarized light UV). The photo-alignment film is advantageous also in that the direction of an orientation regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to irradiate.

A photoreactive group means group which produces liquid-crystal orientation ability by light irradiation. Specific examples include groups that participate in photoreactions that are the origin of liquid crystal alignment ability, such as induction of molecular alignment or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photolysis reaction caused by light irradiation. Especially, group which participates in dimerization reaction or photocrosslinking reaction is preferable at the point excellent in orientation. As the photoreactive group, a group having an unsaturated bond, especially a double bond, is preferable, and a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N A group having at least one selected from the group consisting of a bond) and a carbon-oxygen double bond (C=O bond) is particularly preferred.

Examples of the photoreactive group having a C=C bond include a vinyl group, a polyene group, a stilbene group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group. Examples of the photoreactive group having a C=N bond include groups 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, and a maleimide group. These groups may have a substituent 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, or a halogenated alkyl group.

Among them, a photoreactive group involved in the photodimerization reaction is preferable, the amount of polarized light required for photoalignment is relatively small, and it is easy to obtain a photoalignment film excellent in thermal stability and stability over time. Namoyl and chalcone groups are preferred. In particular, when the liquid crystal cured material layer is formed of a polymerizable liquid crystal compound having a (meth)acryloyloxy group as a polymerizable group, since adhesiveness with the liquid crystal cured material layer can be further improved, photoreactivity to form an alignment film As a polymer which has a group, it is especially preferable that the terminal part of the said polymer side chain has a cinnamoyl group used as a cinnamic acid structure.

Examples of the solvent contained in the composition for forming a photoalignment film include the same solvents as those exemplified above as solvents usable in the polymerizable liquid crystal composition, and may be appropriately selected according to the solubility of the polymer or monomer having a photoreactive group.

Although content of the polymer or monomer which has a photoreactive group in the composition for photo-alignment film formation can be suitably adjusted according to the kind of polymer or monomer, or the thickness of the target photo-alignment film, with respect to the mass of the composition for photo-alignment film formation, at least 0.2 mass % is preferable, and the range of 0.3-10 mass % is more preferable. In addition, the polymer forming the photo alignment film is easy to manufacture, and when the aligned liquid crystal cured material layer is formed of a polymerizable liquid crystal compound having a (meth)acryloyloxy group as a polymerizable group, the liquid crystal cured material layer and It is preferable that it is a (meth)acrylic polymer at the point which can improve the adhesiveness of. In the range in which the characteristic of a photo-alignment film is not impaired remarkably, the composition for photo-alignment film formation may contain polymeric materials, such as polyvinyl alcohol and a polyimide, and a photosensitizer.

As a method of apply|coating the composition for photo-alignment film formation to the surface on which an orientation film should be formed, the method similar to the method of apply|coating an orientation polymer composition is mentioned. As a method of removing a solvent from the apply|coated composition for photo-alignment film formation, a natural drying method, ventilation drying method, heat drying, the reduced pressure drying method etc. are mentioned, for example.

In order to irradiate polarization|polarized-light, the form which irradiates polarized light UV directly to what removed the solvent from the composition for photo-alignment film formation apply|coated on the surface on which an alignment film should be formed may be sufficient. Moreover, the said polarization|polarized-light is especially preferable if it is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in a wavelength range where the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength of 250 to 400 nm is particularly preferable. Examples of the light source used for polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, and ultraviolet light lasers such as KrF and ArF, high-pressure mercury lamps, ultra-high pressure mercury lamps, and metal halide lamps. is more preferable. Among these, a high-pressure mercury-vapor lamp, an ultra-high pressure mercury lamp, and a metal halide lamp are preferable because the light emission intensity of the ultraviolet-ray of wavelength 313nm is large. Polarized UV can be irradiated by irradiating the light from the said light source through a suitable polarizer. As such a polarizer, a polarizing filter, a polarizing prism such as Glan Thompson or Glan Taylor, or a wire grid type polarizer can be used.

Moreover, when performing rubbing or polarization|polarized-light irradiation and masking, the some area|region (pattern) from which the direction of liquid-crystal orientation differs can also be formed.

A groove alignment film is a film|membrane which has an uneven|corrugated pattern or a plurality of grooves (grooves) in the film|membrane surface. When a polymerizable liquid crystal compound is applied to a film having a plurality of straight grooves arranged at equal intervals, the liquid crystal molecules are aligned in a direction along the grooves.

As a method of obtaining a groove alignment film, a method of forming an uneven pattern by performing development and rinsing after exposure through an exposure mask having a pattern-shaped slit on the surface of the photosensitive polyimide film, a method of forming a concave-convex pattern on the surface A method of forming a layer of UV-curing resin before curing, transferring the formed resin layer to a surface on which an alignment film such as a base film is to be formed, and then curing it, and UV curing resin before curing formed on the surface on which an alignment film is to be formed A method of pressing a roll-shaped disk having a plurality of grooves to the film to form irregularities, and then curing the film, etc. are mentioned.

The thickness of the alignment film (orientation film or photo alignment film containing an alignment polymer) is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 2500 nm, more preferably in the range of 10 to 1000 nm or less, still more 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 material layer constituting the functional layer is a vertically aligned liquid crystal cured material layer, the liquid crystal cured material layer contains at least one vertical alignment accelerator, so that the substrate can be formed without interposing the alignment film. The liquid crystal cured material layer can be formed directly on the surface on which the liquid crystal cured material layer is to be formed, such as on a film. In the present specification, the vertical alignment accelerator means a material that promotes the liquid crystal alignment of the polymerizable liquid crystal compound in a direction perpendicular to the plane of the cured product layer. When the liquid crystal cured material layer contains the vertical alignment accelerator, the vertically aligned liquid crystal cured material layer can be directly formed without forming a vertical alignment film on the base film or the like, so the manufacturing process of the long film is simplified and long film with good productivity Films can be made.

As a vertical alignment promoter, when a polymeric liquid crystal composition is apply|coated on a base film, the component which generates electrostatic repulsive force with respect to a polymeric liquid crystal compound in the base film side interface of a coating film is preferable. As such a component, an ionic compound is mentioned, for example, From a viewpoint of suppressing generation|occurrence|production of the orientation defect of a liquid-crystal hardened|cured material layer, it is preferable to contain the ionic compound which consists of a non-metal atom as a vertical alignment promoter. When the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound contains an ionic compound composed of non-metal atoms, in the dry coating film formed from the composition, the vertical alignment regulating force with respect to the polymerizable liquid crystal compound is expressed by electrostatic interaction, In the dry coating film, the polymerizable liquid crystal compound can be oriented in a direction perpendicular to the plane of the film. Thereby, the polymerizable liquid crystal compound can maintain a vertically aligned state to form a liquid crystal cured material layer.

Examples of the ionic compound composed of non-metal atoms (hereinafter also simply referred to as "ionic compound") include onium salts (more specifically, quaternary ammonium salts in which the nitrogen atom has a positive charge, tertiary sulfonium salts, and quaternary phosphonium salts in which the phosphorus atom has a positive charge, etc.). Among these onium salts, a quaternary onium salt is preferable from the viewpoint of further improving the vertical alignment property of the polymerizable liquid crystal compound, and from the viewpoint of improving availability and mass productivity, a quaternary phosphonium salt or a quaternary An ammonium salt is more preferable. The onium salt may have two or more quaternary onium salt sites in the molecule, and may be an oligomer or a polymer.

It is preferable that the molecular weights of an ionic compound are 100 or more and 10,000 or less. It is easy to improve the vertical alignment property of a polymeric liquid crystal compound as molecular weight is in the said range, ensuring the applicability|paintability of a polymeric liquid crystal composition. The molecular weight of the ionic compound is more preferably 5000 or less, still more preferably 3000 or less.

As a cation component of an ionic compound, an inorganic cation and organic cation are mentioned, for example. Especially, since the orientation defect of a polymeric liquid crystal compound is hard to raise|generate, an organic cation is preferable. Examples of the organic cation include imidazolium cation, pyridinium cation, ammonium cation, sulfonium cation, and phosphonium cation.

Ionic compounds generally have a counter anion. As an anion component used as the counter ion of the said cation component, an inorganic anion and organic anion are mentioned, for example. Especially, since the orientation defect of a polymeric liquid crystal compound does not raise|generate easily, an organic anion is preferable. In addition, a cation and an anion do not necessarily need to be a one-to-one correspondence.

As an anion component, the following are mentioned specifically, for example.

chloride anion [Cl ^- ],

bromide anion [Br ^- ],

iodide anion [I ^- ],

tetrachloroaluminate anion [AlCl ₄ ^- ],

heptachlorodialuminate anion [Al ₂ Cl ₇ ^- ],

tetrafluoroborate anion [BF ₄ ^- ],

hexafluorophosphate anion [PF ₆ ^- ],

perchlorate anion [ClO ₄ ^- ],

nitrate anion [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)methanide anion [(CF ₃ SO ₂ ) ₃ C ^- ],

hexafluoroacetate anion [AsF ₆ ^- ],

hexafluoroantimonate anion [SbF ₆ ^- ],

hexafluoroniobate anion [NbF ₆ ^- ],

hexafluorotantalate anion [TaF ₆ ^- ],

dimethylphosphinate anion [(CH ₃ ) ₂ POO ^- ],

(poly)hydrofluorofluoride anion [F(HF) _n ^- ] (for example, n represents an integer of 1 to 3);

dicyanamide anion [(CN) ₂ N ^- ],

thiocyanate [SCN ^- ],

perfluorobutanesulfonate anion [C ₄ F ₉ SO ₃ ^- ],

bis(pentafluoroethanesulfonyl)imide anion [(C ₂ F ₅ SO ₂ ) ₂ N ^- ],

perfluorobutanoate anion [C ₃ F ₇ COO ^- ], and

(trifluoromethanesulfonyl)(trifluoromethanecarbonyl)imide anion [(CF ₃ SO ₂ )(CF ₃ CO)N ⁻ ].

The specific example of an ionic compound can be suitably selected from the combination of the said cationic component and an anionic component. As a compound which is a combination of a specific cationic component and an anionic component, the following are mentioned, for example.

(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.

(imidazolium 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 and the like.

(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;

tetrahexylammonium bis(fluorosulfonyl)imide;

trioctylmethylammonium bis(fluorosulfonyl)imide;

(2-hydroxyethyl) trimethylammonium bis (fluorosulfonyl) imide;

tetrabutylammonium bis(trifluoromethanesulfonyl)imide;

tetrahexylammonium bis(trifluoromethanesulfonyl)imide;

trioctylmethylammonium bis(trifluoromethanesulfonyl)imide;

(2-hydroxyethyl) trimethylammonium bis (trifluoromethanesulfonyl) imide;

tetrabutylammonium p-toluenesulfonate,

tetrahexylammonium p-toluenesulfonate,

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.

(phosphonium salt)

tributyl (2-methoxyethyl) phosphonium bis (trifluoromethanesulfonyl) imide;

tributylmethylphosphoniumbis(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.

These ionic compounds may be used individually, respectively, and may be used in combination of 2 or more type. Especially, the ionic compound which consists of a phosphonium salt, a pyridinium salt, and an ammonium salt is preferable.

From the viewpoint of further improving the vertical alignment property of the polymerizable liquid crystal compound, the ionic compound preferably has an Si element and/or an F element in the molecular structure of the cation moiety. When the ionic compound has Si element and/or F element in the molecular structure of the cation moiety, the ionic compound tends 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) and the like are preferable as the ionic compound in which all constituent elements are non-metal elements.

(ionic compound (i))

(ionic compound (ii))

(ionic compound (iii))

For example, a method of improving the alignment property of liquid crystal by treating the surface of the substrate using a surfactant having an alkyl group having a long chain length to a certain extent (e.g., “Liquid crystal orientation and physical properties” in Chapter 2 of “Liquid Crystal Handbook”) The vertical alignment property of a polymeric liquid crystal compound can be improved more by applying Maruzen Co., Ltd. issue) etc.). That is, by treating the surface of the substrate using an ionic compound having an alkyl group having a long chain length to a certain extent, the vertical alignment property of the polymerizable liquid crystal compound can be effectively improved.

Specifically, it is preferable that the ionic compound satisfies the following formula (7).

5 < M < 16 (7)

In formula (7), M is represented by following formula (8).

M = (the number of covalent bonds from the positively charged atom to the molecular chain end of the substituent with the largest number of covalent bonds to the molecular chain end among the substituents directly bonded to the positively charged atom) ÷ (plus number of atoms with a charge) (8)

When the ionic compound satisfies the above (7), the vertical alignment property of the polymerizable liquid crystal compound can be effectively improved.

In addition, when two or more atoms having a positive charge exist in the molecule of the ionic compound, for a substituent having two or more atoms having a positive charge, counting from the atom having a positive charge considered as the starting point, the nearest Let the number of covalent bonds to other positively charged atoms be "the number of covalent bonds from the positively charged atom to the molecular chain end" described in the definition of M above. Moreover, when an ionic compound is an oligomer or polymer which has two or more repeating units, a structural unit is considered as one molecule, and said M is computed. When an atom having a positive charge is introduced into the ring structure, among the number of covalent bonds through the ring structure to the atom having a positive charge, or the number of covalent bonds to the end of the substituent bonded to the ring structure , where the number of covalent bonds is greater 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 a non-metal atom in the polymerizable liquid crystal composition is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the polymerizable liquid crystal compound contained in the composition. , More preferably, it is 0.1 mass part or more, More preferably, it is 5 mass parts or less, More preferably, it is 4 mass parts or less, More preferably, it is 3 mass parts or less. When content of the ionic compound which consists of a non-metal atom is in the said range, the vertical alignment property of a polymeric liquid crystal compound can be promoted effectively, maintaining favorable applicability|paintability of a polymeric liquid crystal composition.

As a vertical alignment accelerator, when a polymerizable liquid crystal composition is applied on a base film, the surface energy in the interface on the opposite side to the base film of the obtained cured product layer is lowered, whereby the polymerizable liquid crystal compound is directed perpendicular to the film plane. You may also contain a component which can exhibit the vertical orientation regulating force to orientate. As such a component, a nonionic silane compound, a leveling agent, etc. are mentioned, for example, 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 a dry coating film formed from the composition, the nonionic silane compound tends to be localized at the interface between the dry coating film and the air In this case, the vertical alignment regulating force with respect to the polymerizable liquid crystal compound can be increased, and the polymerizable liquid crystal compound can be aligned in a direction perpendicular to the film plane in the dry coating film. Thereby, the polymerizable liquid crystal compound can maintain a vertically aligned state to form a liquid crystal cured material layer.

A nonionic silane compound is a compound which is nonionic and contains 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, silsessiloxanes and alkoxysilanes (more specifically, silane coupling agent etc.) etc. are mentioned. These nonionic silane compounds may be used individually by 1 type, or may be used in combination of 2 or more type. Especially, a silane coupling agent is preferable from a viewpoint of improving more adhesiveness with the adjacent layer.

The nonionic silane compound may be of a silicone monomer type or of a silicone oligomer (polymer) type. When the silicone oligomer is expressed in the form of a (monomer)-(monomer) copolymer, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer , copolymers containing a mercaptopropyl group such as 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer and mercaptomethyltrie mercaptomethyl group-containing copolymers such as oxysilane-tetraethoxysilane copolymers; 3-Methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropyltrie oxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-methacryloyloxypropylmethyldie a copolymer containing a methacryloyloxypropyl group such as a toxysilane-tetraethoxysilane copolymer; 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane- Tetramethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloyl Oxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer a copolymer containing an acryloyloxypropyl group such as a polymer; Vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer Polymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer and vinylmethyldiethoxysilane-tetraethoxy a copolymer containing a vinyl group such as a silane copolymer; 3-Aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3- Aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyl and copolymers containing an amino group such as a methyldiethoxysilane-tetramethoxysilane copolymer and a 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer.

The silane coupling agent is a group consisting of a vinyl group, an epoxy group, a styryl group, a methacryl group, an acryl group, an amino group, an isocyanurate group, a urea group, a mercapto group, an isocyanate group, a carboxyl group, and a hydroxyl group at the terminal It is a compound containing the same functional group as at least 1 type selected from, and the Si element which has at least 1 alkoxysilyl group or a silanol group. By selecting these functional groups appropriately, it becomes possible to provide specific effects, such as improvement of the mechanical strength of the vertically-aligned liquid crystal cured material layer, surface modification, and adhesive improvement of the liquid crystal cured material layer and the adjacent layer. From an adhesive viewpoint, it is preferable that a silane coupling agent is a silane coupling agent which has an alkoxysilyl group and another different reactive group (for example, the said functional group). Moreover, it is preferable that a silane coupling agent is a silane coupling agent which has 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 alignment property of the polymerizable liquid crystal compound tends to be improved more easily, and the vertical alignment promoting effect tends to be remarkably obtained. As a polar group, an epoxy group, an amino group, an isocyanurate group, a mercapto group, a carboxyl group, and a hydroxyl group are mentioned, for example. In addition, the polar group may have a substituent or a protecting group suitably in order to control the reactivity of a silane coupling agent.

Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene ) Propylamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxy Silane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy propyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethylsilane.

In addition, commercially available silane coupling agents include, for example, KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, 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, Silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. such as KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007 can be heard

The content of the nonionic silane compound in the polymerizable liquid crystal composition is usually, with respect to 100 parts by mass of the polymerizable liquid crystal compound contained in the composition, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, further Preferably it is 0.1 mass part or more, Preferably it is 5 mass parts or less, More preferably, it is 4 mass parts or less, More preferably, it is 3 mass parts or less. When content of a nonionic silane compound is in the said range, the vertical alignment property of a polymeric liquid crystal compound can be promoted effectively, maintaining favorable applicability|paintability of a polymeric liquid crystal composition.

In the present invention, the polymerizable liquid crystal composition for forming the vertically aligned liquid crystal cured product layer preferably contains, as a vertical alignment promoter, at least one of an ionic compound composed of a non-metal atom and a non-ionic silane compound, and a non-metal atom It is more preferable to include the ionic compound consisting Since the polymerizable liquid crystal composition contains both an ionic compound composed of a non-metal atom and a non-ionic silane compound, in a dry coating film formed from the polymerizable liquid crystal composition, the static electricity derived from the ionic compound composed of a non-metal atom at the interface on the substrate side Due to the interaction and the surface energy lowering effect derived from the nonionic silane compound at the non-substrate side interface, a vertical alignment regulating force with respect to the polymerizable liquid crystal compound is generated at both interfaces of the liquid crystal cured material layer, so that the polymerizable The vertical alignment of the liquid crystal compound is more easily promoted. Thereby, the polymeric liquid crystal compound can maintain the state which vertically aligned more accurately, and can form a liquid crystal hardened|cured material layer.

In addition, a polymerizable non-liquid crystal compound 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 molecule in the polymerizable liquid crystal composition for forming the vertically aligned liquid crystal cured product layer (hereinafter, By adding a "pre-reacting compound"), the adhesion with the substrate having a hydroxyl group or a carboxyl group on the surface can be increased by corona treatment or plasma treatment, etc., and the surface treatment state of the substrate or the vertically aligned liquid crystal cured film By adjusting the kind, content, etc. of the pre-reacting compound contained, the base material peeling force P of a laminated body can be controlled. Thereby, the vertically aligned liquid crystal cured material layer formed without the vertical alignment film and the base film are laminated with optimum adhesion, and a long film exhibiting optimum substrate peeling force can be obtained.

In the present invention, when the molecular orientation direction of the polymerizable liquid crystal compound in the liquid crystal cured product constituting the functional layer is horizontal with respect to the in-plane in the long direction of the base film, and is not parallel to the long direction of the base film, The effect tends to be remarkable. When the molecular alignment direction of the polymerizable liquid crystal compound is not parallel to the long direction of the base film, it means that the polymerizable liquid crystal compound is horizontally aligned and the alignment direction is not parallel to the long direction. When the long direction of the base film and the orientation direction of the polymerizable liquid crystal compound have the above relationship, the roll to roll method is used in an optical film including a polarizing film having an absorption axis or a transmission axis in a long direction as described later. It becomes possible to transcribe|transfer a functional layer from the elongate film of this invention, and to carry out elongate bonding. On the other hand, since the orientation direction of the molecules of the polymerizable liquid crystal compound during transfer does not coincide with the peeling direction, that is, the long direction, the edge portion of the liquid crystal cured material layer tends to be jagged. Even in such a case, by forming a concave-convex portion at the end of the base material, further enhancing the adhesion with the functional layer in the concave-convex portion, and forming a fine void between the functional layer and the base film on the back surface in a region free of concavities and convexities, By suppressing sticking/falling off in an uneven|corrugated area|region and generating an appropriate difference in the adhesiveness of a base film and a functional layer between an uneven|corrugated part and an uneven|corrugated area|region, a functional layer is easy to peel linearly from a base film in the peeling direction It is possible to suppress the occurrence of tearing of the edges during transfer, thereby ensuring high productivity and quality.

Moreover, the effect tends to become remarkable also when the molecular orientation direction of the polymeric liquid crystal compound in the liquid crystal hardened|cured material which comprises a functional layer is a substantially perpendicular direction with respect to the long direction surface inside of a base film. The fact that the molecular orientation direction of the polymerizable liquid crystal compound is perpendicular to the surface in the long direction of the base film means that the polymerizable liquid crystal compound is vertically aligned. In such a case, similarly to the case where the polymerizable liquid crystal compound is horizontally aligned in the liquid crystal cured material layer, the molecular orientation direction of the polymerizable liquid crystal compound during transfer does not coincide with the peeling direction, that is, the long direction, so that the liquid crystal mirror Although the end of the cargo layer tends to be torn in a jagged shape, by forming an uneven portion at the end of the substrate and creating a suitable difference in the adhesion between the substrate film and the functional layer between the uneven portion and the region without the unevenness, the functional layer is separated from the substrate film. It becomes easy to peel off linearly in a peeling direction, and generation|occurrence|production of the tear of an edge part at the time of transcription|transfer can be suppressed, and high productivity and quality can be ensured.

The functional layer constituting the long film of the present invention may contain layers other than the liquid crystal cured material layer and the alignment film. Examples of such other layers include an adhesive layer for bonding a cured resin layer such as a protective layer or a hard coat layer, and a functional layer such as a liquid crystal cured material layer to other members such as a polarizing film. Moreover, the some liquid crystal hardened|cured material layer from which an orientation direction differs, or the some orientation film from which an orientation regulating force differs may be included.

When a cured resin layer is included, the thickness is 0.1-10 micrometers from a viewpoint of thickness reduction of the whole functional layer, Preferably it is 0.5-5 micrometers.

The cured resin layer is, for example, a film such as cycloolefin polymer (COP), polyethylene terephthalate (PET), triacetyl cellulose (TAC), or a cured resin layer forming composition containing a polymerizable monomer. A resin layer may be sufficient. From a viewpoint of thin film formation, the cured resin layer of the composition for cured resin layer formation is preferable. Although the cured resin layer may become a multilayer, it is preferable from a viewpoint of productivity that it is two or less layers, More preferably, it is a single layer. Moreover, it is preferable that the cured resin layer is optically isotropic. When the cured resin layer is optically isotropic, when combined with the liquid crystal cured material layer, the optical properties of the liquid crystal cured material layer are not easily affected, and a functional layer having high optical properties can be obtained.

In addition, in this specification, resin may be generically named on behalf of the functional group with the largest number among the polymeric groups contained in the composition for cured resin layer formation used in order to form a cured resin layer. That is, for example, among the polymerizable groups contained in the composition for forming a cured resin layer, when the number of acryloyloxy groups is the largest, it may be called an acrylic resin, and when the number of epoxy groups is the largest, it may be called an epoxy resin.

It is preferable that the cured resin layer contains at least 1 sort(s) chosen from the group which consists of an acrylic resin, an epoxy resin, an oxetane resin, a urethane resin, and a melamine resin. By including the at least 1 sort(s) of resin chosen from the above, sclerosis|hardenability is high and it becomes easy to improve reliability at the time of combining with the hardened|cured material layer of a polymerizable liquid crystal compound.

The composition for forming a cured resin layer constituting the cured resin layer is a composition containing a curable polymerizable monomer such as a radically polymerizable monomer, a cationically polymerizable monomer and a thermally polymerizable monomer as a curable compound. It is more preferable to include a radically polymerizable monomer or a cationically polymerizable monomer from the viewpoint of a high reaction rate, improving productivity, and improving reliability when combined with a cured product layer of a polymerizable liquid crystal compound.

As a radically polymerizable monomer suitable for formation of the said cured resin layer, For example, (meth)acrylate compounds, such as a polyfunctional (meth)acrylate compound; Urethane (meth)acrylate compounds, such as a polyfunctional urethane (meth)acrylate compound; Epoxy (meth)acrylate compounds, such as a polyfunctional epoxy (meth)acrylate compound; A carboxyl group-modified epoxy (meth)acrylate compound, a polyester (meth)acrylate compound, etc. are mentioned. These may use only 1 type, and may use them in combination of 2 or more type. Among them, as the polymerizable monomer, (meth)acryl from a viewpoint of improving reliability when combined with a cured product layer of a polymerizable liquid crystal compound, a viewpoint of improving adhesion with an adjacent layer, and a viewpoint of improving productivity It is preferable that the polymerizable monomer which has a royloxy group is included, It is more preferable that a polyfunctional (meth)acrylate compound is included, It is especially preferable that a polyfunctional acrylate compound is included.

The polyfunctional (meth)acrylate compound means a compound having two or more (meth)acryloyl groups, preferably (meth)acryloyloxy groups in the molecule, and examples thereof include (meth)acryloyloxy groups in the molecule. The bifunctional (meth)acrylate monomer which has two yloxy groups, the trifunctional or more than trifunctional (meth)acrylate monomer which has 3 or more (meth)acryloyloxy groups in a molecule|numerator, etc. are mentioned. In addition, in this specification, the term "(meth)acrylate" means "acrylate" or "methacrylate", and the term "(meth)acryloyl" is similarly used as "acryloyl" or It means "methacryloyl".

The polyfunctional (meth)acrylate compound may contain the polyfunctional (meth)acrylate compound of 1 type or 2 or more types. Moreover, when two or more types of polyfunctional (meth)acrylate compounds are included, between each polyfunctional (meth)acrylate compound, the number of (meth)acryloyl groups may be same or different.

Examples of the bifunctional (meth)acrylate monomer include ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6 alkylene glycol di(meth)acrylates such as hexanediol di(meth)acrylate, 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, poly polyoxyalkylene glycol di(meth)acrylates such as propylene glycol di(meth)acrylate and polytetramethylene glycol di(meth)acrylate; di(meth)acrylates of halogen-substituted alkylene glycols such as tetrafluoroethylene glycol di(meth)acrylate; di(meth)acrylates of aliphatic polyols such as trimethylolpropane di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, and pentaerythritol di(meth)acrylate; hydrogenated dicyclopentadiene or di(meth)acrylate of tricyclodecanedialkanol, such as hydrogenated dicyclopentadienyldi(meth)acrylate and tricyclodecanedimethanoldi(meth)acrylate; di(meth)acrylate of dioxane glycol or dioxane dialkanol such as 1,3-dioxane-2,5-diyldi(meth)acrylate [alias: dioxane glycol di(meth)acrylate]; di(meth)acrylate of the alkylene oxide adduct of bisphenol A or bisphenol F, such as a bisphenol A ethylene oxide adduct diacrylate product and a bisphenol F ethylene oxide adduct diacrylate product; Epoxy di(meth)acrylate of bisphenol A or bisphenol F, such as an acrylic acid adduct of bisphenol A diglycidyl ether, and an acrylic acid adduct of bisphenol F diglycidyl ether; silicone di(meth)acrylate; di(meth)acrylate of hydroxypivalic acid neopentyl glycol ester; 2,2-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]propane; 2,2-bis[4-(meth)acryloyloxyethoxyethoxycyclohexyl]propane; di(meth)acrylate of 2-(2-hydroxy-1,1-dimethylethyl)-5-ethyl-5-hydroxymethyl-1,3-dioxane]; Tris(hydroxyethyl) isocyanurate di(meth)acrylate etc. are mentioned.

The trifunctional (meth)acrylate monomer is a monomer having three (meth)acryloyl groups, preferably (meth)acryloyloxy groups in the molecule, examples of which include glycerin tri(meth)acrylate, trimethylol Propane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, reaction product of pentaerythritol tri(meth)acrylate and acid anhydride, caprolactone-modified trimethylolpropane Tri(meth)acrylate, caprolactone modified pentaerythritol tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, propylene oxide modified trimethyl Reaction product of allpropane tri(meth)acrylate, propylene oxide modified pentaerythritol tri(meth)acrylate, isocyanurate tri(meth)acrylate, caprolactone modified pentaerythritol tri(meth)acrylate and acid anhydride and a reaction product of ethylene oxide-modified pentaerythritol tri(meth)acrylate and an acid anhydride, and a reaction product of propylene oxide-modified pentaerythritol tri(meth)acrylate and an acid anhydride.

The tetrafunctional (meth)acrylate monomer is a monomer having four (meth)acryloyl groups, preferably (meth)acryloyloxy groups in the molecule, and examples thereof include ditrimethylolpropanetetra(meth)acrylate , pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified tri pentaerythritol tetra (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified tripentaerythritol tetra (meth) acrylate, propylene oxide modified pentaerythritol tetra (meth) acrylate, Propylene oxide modified tripentaerythritol tetra(meth)acrylate etc. are mentioned.

Examples of the 5-functional (meth)acrylate monomer include dipentaerythritol penta (meth) acrylate, tripentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate and an acid anhydride. Reactant, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified tripentaeryth Ritol penta (meth) acrylate, propylene oxide modified dipentaerythritol penta (meth) acrylate, propylene oxide modified tripentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate and and a reaction product of an acid anhydride, a reaction product of ethylene oxide-modified dipentaerythritol penta(meth)acrylate and an acid anhydride, a reaction product of propylene oxide-modified dipentaerythritol penta(meth)acrylate and an acid anhydride, and the like.

Examples of the 6-functional (meth)acrylate monomer include dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, 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|denatured tripentaerythritol hexa (meth)acrylate, etc. are mentioned.

Examples of the 7-functional (meth)acrylate monomer include tripentaerythritol hepta (meth) acrylate, a reaction product of tripentaerythritol hepta (meth) acrylate and an acid anhydride, caprolactone-modified tripentaerythritol hepta ( Meth) acrylate, reaction product of caprolactone-modified tripentaerythritol hepta (meth) acrylate and acid anhydride, ethylene oxide-modified tripentaerythritol hepta (meth) acrylate, ethylene oxide-modified tripentaerythritol hepta (meth) acrylic and a reaction product of a rate and an acid anhydride, propylene oxide-modified tripentaerythritol hepta (meth) acrylate, and a reaction product of propylene oxide-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride.

The 8-functional (meth)acrylate monomer is a monomer having 8 (meth)acryloyl groups, preferably (meth)acryloyloxy groups in the molecule, and examples thereof include tripentaerythritolocta (meth)acrylate , caprolactone-modified tripentaerythritol octa (meth) acrylate, ethylene oxide-modified tripentaerythritol octa (meth) acrylate, and propylene oxide-modified tripentaerythritol octa (meth) acrylate.

As a cationically polymerizable monomer suitable for formation of a cured resin layer, the epoxy compound which has an epoxy group, the oxetane compound which has an oxetanyl group, etc. are mentioned, for example.

An epoxy compound is a polymerizable monomer which has at least 1 or more epoxy group in a molecule|numerator, For example, an alicyclic epoxy compound, an aromatic epoxy compound, an aliphatic epoxy compound, etc. are mentioned.

An alicyclic epoxy compound is a compound which has in a molecule|numerator at least 1 the epoxy group couple|bonded directly with the alicyclic ring. For example, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate, Ethylenebis(3,4-epoxycyclohexanecarboxylate), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, diethylene glycol Bis(3,4-epoxycyclohexylmethyl ether), ethylene glycol bis(3,4-epoxycyclohexylmethyl) ether, etc. are mentioned. These alicyclic epoxy compounds can be used individually or in combination of 2 or more type.

An aromatic epoxy compound is a compound which has an aromatic ring and an epoxy group in a molecule|numerator. As the specific example, Bisphenol-type epoxy compounds, such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S, or its oligomer; Novolak-type epoxy resins, such as a phenol novolak epoxy resin, a cresol novolak epoxy resin, and a hydroxybenzaldehyde phenol novolak epoxy resin; polyfunctional epoxy compounds such as glycidyl ether of 2,2',4,4'-tetrahydroxydiphenylmethane and glycidyl ether of 2,2',4,4'-tetrahydroxybenzophenone; Polyfunctional epoxy resins, such as epoxidized polyvinyl phenol, etc. are mentioned. These aromatic epoxy compounds can be used individually or in combination of 2 or more types.

As for the hydrogenation epoxy compound, the nuclear hydrogenation product of said aromatic epoxy compound turns into a hydrogenation epoxy compound. These are polyhydric alcohols, typically hydrogenated bisphenols, obtained by selectively hydrogenating an aromatic polyhydroxy compound, typically bisphenol, which is a raw material of the corresponding aromatic epoxy compound, in the presence of a catalyst and under pressure as a raw material. It can be prepared by a method of reacting epichlorohydrin with this to give chlorohydrin ether, and also intramolecular ring closure with alkali. These hydrogenated epoxy compounds can be used individually or in combination of 2 or more types.

The aliphatic epoxy compound includes polyglycidyl ether of an aliphatic polyhydric alcohol or its alkylene oxide adduct. 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, and trimethylolpropane of triglycidyl ether, diglycidyl ether of polyethylene glycol, diglycidyl ether of propylene glycol, one or more alkylene oxides (ethylene oxide or and polyglycidyl ether of polyether polyol obtained by adding propylene oxide). These aliphatic epoxy compounds can be used individually or in combination of 2 or more type.

The oxetane compound is a compound containing at least one or more oxetanyl groups in the molecule, and specific examples thereof include 3-ethyl-3-hydroxymethyloxetane (also called oxetane alcohol), 2-ethylhexyloxetane, 1,4-bis[{(3-ethyloxetan-3-yl)methoxy}methyl]benzene (also called xylylenebisoxetane), 3-ethyl-3[{(3-ethyloxetane-3- yl)methoxy}methyl]oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-(cyclohexyloxy)methyl-3-ethyloxetane, etc. are mentioned.

As a thermally polymerizable monomer suitable for formation of a cured resin layer, a melamine compound is mentioned, for example. As a melamine compound, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine etc. are mentioned, for example. A melamine compound can be used individually or in combination of 2 or more types.

Moreover, as another polymerizable monomer, the combination of an isocyanate compound and the alcohol compound which has a hydroxyl group in a molecule|numerator is mentioned, A urethane resin is manufactured. The isocyanate compound used for the production of the urethane resin and the urea resin usually has two or more isocyanato groups (-NCO) in the molecule, and various diisocyanates of aromatic, aliphatic or alicyclic can be used. Specific examples include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 3,3' -Dimethyl-4,4'-diphenyl diisocyanate, xylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and nuclear hydrogenated products of diisocyanate having an aromatic ring among them. can Moreover, the alcohol compound used for a urethane resin usually has two or more hydroxyl groups in a molecule|numerator, For example, ethylene glycol, propylene glycol, 1, 3- propanediol, diethylene glycol, dipropylene glycol, neopentyl glycol. , 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 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, trimethylol Propane, glycerin, 3-methylpentane-1,3,5-triol, pentaerythritol, dipentaerythritol, tripentaerythritol, glucose, etc. are mentioned.

The polymerizable monomer is, from a viewpoint of suppressing curl generated by heating during curing or after curing, a viewpoint of improving processing characteristics, a viewpoint of adjusting adhesion with a base film or liquid crystal cured product layer, a viewpoint of improving productivity, content It can select suitably from a viewpoint of improving a medium property, and a viewpoint of improving reliability when combined with a liquid-crystal hardened|cured material layer. In this invention, it is preferable that the cured resin layer contains at least 1 sort(s) chosen from the group which consists of an acrylic resin, an epoxy resin, an oxetane resin, a urethane resin, and a melamine resin. Moreover, for example, 2 or more types of radically polymerizable monomer may be used and you may combine a radically polymerizable monomer and a cationically polymerizable monomer. 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 composition for forming a cured resin layer includes a photopolymerization initiator, a thermal polymerization initiator, a solvent, an antioxidant, a photosensitizer, a leveling agent, an antioxidant, a chain transfer agent, a light stabilizer, a tackifier, a filler, Additives such as flow modifiers, plasticizers, defoamers, pigments, antistatic agents, and ultraviolet absorbers may be further included. These additives are normally about 0.1-15 mass % with respect to the mass of solid content of the composition for cured resin layer formation. In addition, in this specification, when a solvent is contained in the composition for cured resin layer formation, solid content means the total amount of the component except the solvent from the composition.

The composition for forming a cured resin layer WHEREIN: With respect to 100 mass parts of solid content of a composition, content of a polymerizable monomer becomes like this. Preferably it is 50 mass parts or more, More preferably, it is 60 mass parts or more. If it is said range, it will be easy to improve reliability at the time of combining with a liquid-crystal hardened|cured material layer.

It is preferable that the said composition for cured resin layer formation contains the polymerization initiator. Although a photoinitiator, a thermal polymerization initiator, etc. are mentioned as a polymerization initiator, It is preferable to use a photoinitiator from a viewpoint of productivity improving. 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 light, X-ray, or electron beam, and starts radical photopolymerization according to the type of the polymerizable monomer. A Zena photocationic polymerization initiator can be used suitably. As a radical photopolymerization initiator and a photocationic polymerization initiator, the thing similar to the polymerization initiator previously illustrated as what can be specifically, mix|blended with the polymeric liquid crystal composition which forms a liquid-crystal hardened|cured material layer is mentioned.

When the composition for cured resin layer formation contains a polymerization initiator, the content is with respect to 100 mass parts of total amounts of a sclerosing|hardenable compound, Preferably it is 0.1-10 mass parts, More preferably, it is 0.5-7 mass parts. If content of a polymerization initiator is more than the said lower limit, polymerization initiation ability is fully expressed, and if content of a polymerization initiator is below the said upper limit, a polymerization initiator will become hard to remain|survive.

When the composition for forming a cured resin layer contains a solvent, it can be appropriately selected depending on the viewpoint of sufficiently dissolving the polymerizable monomer, polymerization initiator, etc. added to the composition for forming the cured resin layer, and the viewpoint of not dissolving the base film. For example, a solvent that can be used in the polymerizable liquid crystal composition described above may be used. Content of a solvent is 1-10000 mass parts with respect to 100 mass parts of total amounts of components contained in the composition for cured resin layer formation, Preferably it is 10-1000 mass parts, More preferably, about 20-500 mass parts may be sufficient. .

In this invention, the structure of a functional layer is not specifically limited, unless the effect of this invention is affected including a liquid-crystal hardened|cured material layer. In the case of including other layers such as an alignment film or a cured resin layer in addition to the liquid crystal cured material layer, the lamination order of each layer can be appropriately selected, but when the functional layer includes a liquid crystal cured material layer, an alignment film and a cured resin layer, Preferably, the liquid crystal cured material layer, the alignment film, and the cured resin layer are present adjacent to each other in this order. When each layer is laminated in this order, the uncured polymerizable liquid crystal compound is located in the deep part (alignment film side) of the liquid crystal cured material layer, in particular, in the liquid crystal cured material layer, in which a sufficient amount of light does not easily reach when the layer is cured. Even if this exists, diffusion of the uncured polymerizable liquid crystal compound can be prevented by a cured resin layer. After peeling a functional layer from a base film and transcribe|transferring to another member, the diffusion to the other member of the uncured polymerizable liquid crystal compound can be prevented with a cured resin layer. Accordingly, in the retardation plate or the elliptically polarizing plate including the functional layer transferred from the long film of the present invention, the uncured polymerizable liquid crystal compound or the like contained in the liquid crystal cured material layer is adjacent to or adjacent to the liquid crystal cured material layer. (Especially, it can suppress spreading|diffusion to an adhesive agent layer) effectively. Therefore, in one preferred aspect of the present invention, the functional layer further includes an adhesive layer, and is laminated with another optical film (eg, a polarizing film, etc.) through the adhesive layer. As such a functional layer, it is preferable that the liquid crystal cured material layer, the alignment film, and the cured resin layer exist adjacent to each other in this order, and the adhesive layer may be formed on the liquid crystal cured material layer side or may be formed on the cured resin layer side. .

When the functional layer constituting the long film of the present invention includes a cured resin layer, the cured resin layer includes, for example, a solvent after coating the composition for forming a cured resin layer as described above on the base film. In this case, it is obtained by drying off a solvent and hardening a polymerizable monomer.

As a method of apply|coating the composition for cured resin layer formation on a base film, the method similar to the method illustrated above as a method of apply|coating a polymeric liquid crystal composition on a base film is mentioned.

Moreover, as a method of drying and removing a solvent when the composition for cured resin layer formation contains a solvent, the natural drying method, the ventilation drying method, heat drying, the reduced pressure drying method etc. are mentioned, for example.

When a functional layer contains an adhesive agent layer in this invention, as an adhesive agent which comprises this, a pressure-sensitive adhesive, a dry solidification type adhesive, and a chemical reaction type adhesive are mentioned, for example. As a chemical reaction type adhesive agent, an active energy ray hardening type adhesive agent is mentioned, for example. Moreover, an adhesive agent layer may be formed as one structural layer of the functional layer of the long film of this invention, and after peeling a base film from the long film of this invention, you may form the peeling surface etc.

The pressure-sensitive adhesive usually contains a polymer and may contain a solvent. Examples of the polymer include an acrylic polymer, a silicone polymer, polyester, polyurethane, or polyether. Among them, the acrylic pressure-sensitive adhesive containing the acrylic polymer is excellent in optical transparency, has moderate wettability and cohesive force, is excellent in adhesiveness, and furthermore, has high weather resistance and heat resistance, etc., and floats under conditions of heating or humidification. Since peeling etc. do not generate|occur|produce easily, it is preferable.

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

A pressure-sensitive adhesive containing such a copolymer is preferable because it has excellent adhesiveness and can be removed relatively easily without generating glue residue or the like on the transfer object even when removed after bonding to the transfer object. 25 degrees C or less is preferable and, as for the glass transition temperature of an acrylic polymer, 0 degrees C or less is more preferable. It is preferable that the mass average molecular weight of such an acrylic polymer is 100,000 or more.

As a solvent, the solvent etc. which were illustrated as a solvent which can be used for a polymeric liquid crystal composition etc. are mentioned. The pressure-sensitive adhesive may contain a light diffusing agent. A light diffusing agent is an additive which provides light diffusivity to an adhesive, and may just be microparticles|fine-particles which have a refractive index different from the refractive index of the polymer which an adhesive contains. As a light diffusing agent, the microparticles|fine-particles which consist of an inorganic compound, and the microparticles|fine-particles which consist of an organic compound (polymer) are mentioned. Since many of the polymers which contain an acrylic polymer and which an adhesive contains as an active ingredient have a refractive index of about 1.4-1.6, it is preferable to select suitably from the light-diffusion agent whose refractive index is 1.2-1.8. The difference in refractive index between the polymer and the light diffusing agent which an adhesive contains as an active ingredient is 0.01 or more normally, and from a viewpoint of the brightness of a display apparatus, and display property, 0.01-0.2 are preferable. As for the microparticles|fine-particles used as a light diffusing agent, spherical microparticles|fine-particles, also microparticles|fine-particles close to monodisperse are preferable, and microparticles|fine-particles whose average particle diameter is 2-6 micrometers are more preferable. The refractive index is measured by a general minimum declination method or an Abbe refractometer.

As microparticles|fine-particles which consist of an inorganic compound, aluminum oxide (refractive index 1.76), silicon oxide (refractive index 1.45), etc. are mentioned. As fine particles made of an organic compound (polymer), melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), methyl methacrylate/styrene copolymer resin beads (refractive index 1.50 to 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 resin beads (refractive index 1.46). Content of a light-diffusion agent is 3-30 mass parts with respect to 100 mass parts of polymers normally.

Although the thickness in particular of a pressure-sensitive adhesive is not restrict|limited since it determines with the adhesive force etc., Usually, they are 1 micrometer - 40 micrometers. From points, such as workability and durability, 3 micrometers - 25 micrometers are preferable and, as for the said thickness, 5 micrometers - 20 micrometers are more preferable. When the thickness of the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive is 5 µm to 20 µm, the brightness when viewed from the front or obliquely viewed from the display device provided with the optical film including the functional layer transferred from the long film of the present invention By maintaining , it is possible to prevent blurring or blurring of the display image from occurring easily.

The dry solidifying adhesive may contain the solvent. The dry-solidifying adhesive contains, as a main component, 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, or a urethane resin, and further contains a polyhydric aldehyde, an epoxy compound, an epoxy resin, a melamine compound, and a zirconia and a composition containing a crosslinking agent or a curable compound such as a compound and a zinc compound. Examples of the 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 include an ethylene-maleic acid copolymer, an itaconic acid copolymer, an acrylic acid copolymer, an acrylamide copolymer, a saponified product 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 etc. are mentioned. Content of the polyvinyl alcohol-type resin in an aqueous adhesive agent is 1-10 mass parts normally with respect to 100 mass parts of water, Preferably it is 1-5 mass parts.

As a urethane resin, a polyester-type ionomer type|mold urethane resin etc. are mentioned. The polyester-based ionomer-type urethane resin as used herein is a urethane resin having a polyester skeleton, and is a resin in which a small amount of an ionic component (hydrophilic component) is introduced. Since such an ionomer type urethane resin is emulsified in water without using an emulsifier and becomes an emulsion, it can be set as an aqueous adhesive agent. When using a polyester ionomer type urethane resin, it is effective to mix|blend a water-soluble epoxy compound as a crosslinking agent.

As the epoxy resin, a polyamide epoxy obtained by reacting epichlorohydrin with a polyamide polyamine obtained by reaction of a polyalkylene polyamine such as diethylenetriamine or triethylenetetramine with a dicarboxylic acid such as adipic acid resin etc. are mentioned. As commercially available products of such polyamide epoxy resin, "Sumirez Resin (registered trademark) 650" and "Sumirez Resin 675" (above, manufactured by Sumika Chemtex Co., Ltd.), "WS-525" (manufactured by Nippon PMC Co., Ltd.), etc. can be heard When mix|blending an epoxy resin, the addition amount is 1-100 mass parts normally with respect to 100 mass parts of polyvinyl alcohol-type resin, Preferably it is 1-50 mass parts.

The thickness of the pressure-sensitive adhesive layer formed of the dry-solidifying adhesive is usually 0.001 to 5 µm, preferably 0.01 to 2 µm, more preferably 0.01 to 0.5 µm. When the pressure-sensitive adhesive layer formed of the dry-solidifying adhesive is too thick, the appearance tends to be poor.

The active energy ray-curable adhesive may contain the solvent. An active energy ray hardening-type adhesive agent is an adhesive agent which receives irradiation of an active energy ray and hardens. 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, a cationically polymerizable curing component such as an epoxy compound, and Adhesives that contain both radical polymerizable curing components such as acrylic compounds, and further contain a cationic polymerization initiator and a radical polymerization initiator, and adhesives that do not contain these polymerization initiators and are cured by irradiation with an electron beam.

Especially, the radically polymerizable active energy ray hardening-type adhesive agent containing an acryl-type hardening component and a photoradical polymerization initiator, and the cationic polymeric active energy ray hardening-type adhesive agent containing an epoxy compound and a photocationic polymerization initiator are preferable. As an acryl-type hardening component, (meth)acrylates, such as methyl (meth)acrylate and hydroxyethyl (meth)acrylate, (meth)acrylic acid, etc. are mentioned. The active energy ray hardening-type adhesive agent containing an epoxy compound may contain compounds other than an epoxy compound further. As a compound other than an epoxy compound, an oxetane compound, an acryl compound, etc. are mentioned.

As a radical photopolymerization initiator and a photocationic polymerization initiator, the polymerization initiator similar to what was illustrated as what can be used for a polymerizable liquid crystal composition is mentioned. Content of a radical polymerization initiator and a cationic polymerization initiator is 0.5-20 mass parts normally with respect to 100 mass parts of active energy ray hardening-type adhesive agents, Preferably it is 1-15 mass parts.

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

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 formation of the liquid crystal cured material layer.

The long film of the present invention uses the Roll to Roll method to peel the functional layer from the base film and transfer it to another optical film, etc. It is excellent in the suppression effect of the tear in the edge part of the functional layer after transcription|transfer and detachment|desorption. As a result, the functional layer can be transferred with good productivity while maintaining the optical properties of the functional layer possessed by the long film. can be used

For example, from the long film of the present invention having a functional layer including a liquid crystal cured material layer satisfying the formulas (1) and (2) or (3) and (4), the base film is peeled off and the functional layer An elliptically polarizing plate can be manufactured by transferring to a polarizing film. At this time, you may bond a functional layer and a polarizing film together by interposing an adhesive agent layer as needed.

A polarizing film is a film which has a polarizing function, and the film etc. which contain as a polarizer the stretched film which made the dye which has absorption anisotropy adsorb|suck, and the film which apply|coated the dye which has absorption anisotropy are mentioned. As a dye which has absorption anisotropy, a dichroic dye is mentioned, for example.

A film comprising, as a polarizer, a stretched film to which a dye having absorption anisotropy is adsorbed is usually used in a step of uniaxially stretching a polyvinyl alcohol-based resin film, by dyeing the polyvinyl alcohol-based resin film with a dichroic dye, the dichroic dye At least one surface of the polarizer manufactured through a process of adsorbing the polyvinyl alcohol-based resin film to which the dichroic dye is adsorbed, a process of treating the polyvinyl alcohol-based resin film with an aqueous solution of boric acid, and a process of washing with water after treatment with an aqueous boric acid solution, through an adhesive It is manufactured by sandwiching it with a transparent protective film.

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

The saponification degree of polyvinyl alcohol-type resin is about 85-100 mol% normally, Preferably it is 98 mol% or more. The polyvinyl alcohol-type resin may be modified|denatured, for example, polyvinyl formal and polyvinyl acetal modified|denatured with aldehydes can also be used. The polymerization degree of polyvinyl alcohol-type resin is about 1,000-10,000 normally, Preferably it is the range of 1,500-5,000.

What formed such a polyvinyl alcohol-type resin into a film is used as a raw film of a polarizing film. The method for forming a polyvinyl alcohol-type resin into a film is not specifically limited, A film can be formed by a well-known method. The film thickness of a polyvinyl alcohol-type raw film can be about 10-150 micrometers, for example.

Uniaxial stretching of a polyvinyl alcohol-type resin film can be performed before dyeing with a dichroic dye, simultaneously with dyeing, or after dyeing|staining. When performing uniaxial stretching after dyeing|staining, this uniaxial stretching may be implemented before a boric-acid process, and may be implemented during a boric-acid process. Moreover, it is also possible to perform uniaxial stretching in these several steps. In uniaxial stretching, you may uniaxially stretch between the rolls from which circumferential speed differs, and you may stretch uniaxially using a hot roll. Moreover, uniaxial stretching may be dry extending|stretching extending|stretching in air|atmosphere, and wet extending|stretching which extends|stretches in the state which made the polyvinyl alcohol-type resin film swell using a solvent may be sufficient as it. The draw ratio is usually about 3 to 8 times.

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

As a dichroic dye, iodine and a dichroic organic dye are specifically used. Examples of the dichroic organic dye include a dichroic direct dye composed of a disazo compound such as C.I. DIRECT RED 39, and a dichroic direct dye composed of a compound such as trisazo and tetrakisazo. It is preferable that the polyvinyl alcohol-type resin film performs the immersion process with respect to water before a dyeing process.

When using an iodine as a dichroic dye, the method of dyeing by immersing a polyvinyl alcohol-type resin film in the aqueous solution containing an iodine and potassium iodide is usually employ|adopted. Content of the iodine in this aqueous solution is about 0.01-1 mass part normally per 100 mass parts of water. Moreover, content of potassium iodide is about 0.5-20 mass parts normally per 100 mass parts of water. The temperature of the aqueous solution used for dyeing|dyeing is about 20-40 degreeC normally. Moreover, the immersion time (dyeing time) with respect to this aqueous solution is about 20 to 1,800 second normally.

On the other hand, when using a dichroic organic dye as a dichroic dye, the method of dyeing by immersing a polyvinyl alcohol-type resin film in the aqueous solution containing a water-soluble dichroic dye is usually employ|adopted. Content of the dichroic organic dye in this aqueous solution is about 1x10 ^-4 - 10 mass parts normally per 100 mass parts of water, Preferably it is 1x10 ^-3 - 1 mass part, More preferably 1 x 10 ^-3 to 1 x 10 ^-2 parts by mass. This aqueous solution may contain inorganic salts, such as sodium sulfate, as a dyeing aid. The temperature of the dichroic dye aqueous solution used for dyeing is about 20-80 degreeC normally. Moreover, the immersion time (dyeing time) with respect to this aqueous solution is about 10 to 1,800 second normally.

The boric acid treatment after dyeing|dyeing with a dichroic dye can be performed by the method of immersing the dyed polyvinyl alcohol-type resin film in boric-acid aqueous solution normally. Content of the boric acid in this boric-acid aqueous solution is about 2-15 mass parts normally per 100 mass parts of water, Preferably it is 5-12 mass parts. When iodine is used as a dichroic dye, it is preferable that this aqueous boric acid solution contains potassium iodide, and content of potassium iodide in that case is about 0.1-15 mass parts normally per 100 mass parts of water, Preferably it is 5 -12 parts by mass. The immersion time with respect to boric-acid aqueous solution is about 60 to 1,200 second normally, Preferably it is 150 to 600 second, More preferably, it is 200 to 400 second. The temperature of a boric acid process is 50 degreeC or more normally, Preferably it is 50-85 degreeC, More preferably, it is 60-80 degreeC.

The polyvinyl alcohol-type resin film after a boric acid process is water washing process normally. The water washing process can be performed by the method of immersing the polyvinyl alcohol-type resin film by which the boric acid process was carried out, for example in water. The temperature of the water in a water washing process is about 5-40 degreeC normally. Moreover, immersion time is about 1-120 second normally.

A drying process is performed after water washing, and a polarizer is obtained. A drying process can be implemented using a hot-air dryer or a far-infrared heater, for example. The temperature of a drying process is about 30-100 degreeC normally, Preferably it is 50-80 degreeC. The time of a drying process is about 60 to 600 second normally, Preferably it is 120 to 600 second. By a drying process, the moisture content of a polarizer is reduced to a practical use grade. The moisture content is normally about 5-20 mass %, Preferably it is 8-15 mass %. If the moisture content is within the above range, a polarizer having moderate flexibility and good thermal stability is obtained.

In this way, the thickness of the polarizer obtained by performing uniaxial stretching, dyeing|staining by a dichroic dye, boric acid treatment, water washing, and drying to a polyvinyl alcohol-type resin film becomes like this. Preferably it is 5-40 micrometers.

As a film to which the dye which has absorption anisotropy was apply|coated, the film obtained by apply|coating the composition containing the dichroic dye which has liquid crystallinity, or the composition containing a dichroic dye and a polymeric liquid crystal, etc. are mentioned. The said film, Preferably, it has a protective film on the single side|surface or both surfaces. As said protective film, the thing similar to the base film illustrated above is mentioned.

A film coated with a dye having absorption anisotropy is preferably thin, but when it is too thin, the strength decreases and workability tends to be poor. The thickness of the said film is 20 micrometers or less normally, Preferably it is 5 micrometers or less, More preferably, it is 0.5-3 micrometers.

As a film which apply|coated the pigment|dye which has the said absorption anisotropy, the film of Unexamined-Japanese-Patent No. 2012-33249 etc. is mentioned specifically,.

A polarizing film is obtained by laminating|stacking a transparent protective film on the at least one surface of the polarizer obtained in this way through an adhesive agent. As a transparent protective film, the same transparent film as the base film illustrated above can be used preferably.

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

Optical laminates, such as an elliptically polarizing plate containing the functional layer transcribe|transferred from the elongate film of this invention, can be used for various display devices.

A display device is a device which has a display element, and contains a light emitting element or a light emitting device as a light emitting source. Examples of the display device include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (eg, an electric field emission display device (FED) ), surface field emission display device (SED)), electronic paper (display device using electronic ink or electrophoresis element, plasma display device, projection display device (eg, grating light valve (GLV) display device, digital micromirror device) (DMD)) and a piezoelectric ceramic display, etc. Liquid crystal display devices include a transmissive liquid crystal display, a transflective liquid crystal display, a reflective liquid crystal display, a direct view liquid crystal display, and a projection liquid crystal display. Including any of etc. These display devices may be a display device that displays a two-dimensional image, or a stereoscopic display device that displays a three-dimensional image. In particular, comprising the functional layer transferred from the long film of the present invention The elliptically polarizing plate can be preferably used for an organic electroluminescence (EL) display device and an inorganic electroluminescence (EL) display device, and can also be preferably used for a liquid crystal display device or a touch panel display device. The apparatus can express favorable image display characteristics by providing the elliptically polarizing plate which has high reliability.

Example

Hereinafter, the present invention will be described in more detail by way of Examples. In addition, unless otherwise indicated, "%" and "part" in an example mean mass % and mass part, respectively.

1. Example 1

(1) Preparation of the composition (A1) for forming a horizontal alignment film

5 parts (weight average molecular weight: 30000) of the photo-alignment material of the following structure and 95 parts of cyclopentanone (solvent) were mixed as a component, and the obtained mixture was stirred at 80 degreeC for 1 hour, The composition (A1) for horizontal alignment film formation was obtained .

(2) Preparation of polymerizable liquid crystal compound

In order to use it for formation of a horizontal alignment liquid crystal cured film, the polymeric liquid crystal compound (X1) and polymerizable liquid crystal compound (Y1) which have the following molecular structure were prepared, respectively. Polymerizable liquid crystal compound (X1) was manufactured according to the method of Unexamined-Japanese-Patent No. 2010-31223. Moreover, the polymerizable liquid crystal compound (Y1) was manufactured according to the method of Unexamined-Japanese-Patent No. 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 leveling agent "BYK-361N" (manufactured by BYK-Chemie), 0.25 parts by mass of leveling agent "F-556" (manufactured by DIC Corporation), and 2-dimethyl as a photoinitiator Amino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (“Irgacure (registered trademark) 369 (Irg369)” manufactured by BASF Japan Co., Ltd.) 3 parts by mass and “Irgacure” manufactured by BASF Japan Co., Ltd. 7.5 parts by mass of Gacure OXE-03” was added. Moreover, cyclopentanone was added so that solid content concentration might be set to 13 %. The polymerizable liquid crystal composition (B1) was obtained by stirring this mixture at 80 degreeC for 1 hour.

A 1 mg/50 ml tetrahydrofuran solution of the polymerizable liquid crystal compound (X1) was prepared, and a measurement sample was obtained. A measurement sample is placed in a measurement cell with an optical path length of 1 cm, and an absorption spectrum is measured by setting it in an ultraviolet and visible spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation), and from the obtained absorption spectrum, the wavelength at which the maximum absorption is obtained As a result of reading, the maximum absorption wavelength _λmax in the wavelength range of 300 to 400 nm was 350 nm.

(4) Preparation of liquid crystal cured material layer

Composition (A1) for forming a horizontal alignment film on a triacetyl cellulose film (KC4UY, manufactured by Konica Minolta Co., Ltd.) in which uneven portions each having a short direction width of 15 mm (a total of 30 mm in the short direction width) are formed at both ends of the substrate (A1) was applied by the die coating method so as to have a width indicated as "functional layer coating width C" in Table 1. At this time, the edge part of the coating film of the composition (A1) for horizontal alignment film formation was each located inside by 7.5 mm from both ends of a base film, and it applied so that it may coat|cover each 7.5 mm at the uneven|corrugated part of both ends of the coating film. Then, after heating and drying at 100 ° C. for 2 minutes, 100 mJ (based on 313 nm) is irradiated with polarized UV light so that the direction of the orientation regulating force forms an angle of 45 ° with respect to the long direction of the film, and the horizontal alignment film on the film formed. As a result of measuring the film thickness of the obtained horizontal alignment film with an ellipsometer, it was 0.2 micrometer. Subsequently, the polymerizable liquid crystal composition (B1) is applied on the horizontal alignment film by a die coating method with the same width as the film so that the average film thickness of the coating film is 17 µm, and heat-dried at 120°C for 2 minutes, and also ultraviolet rays By irradiating an ultraviolet-ray from the side to which the polymeric liquid crystal composition (B1) was apply|coated using the irradiation apparatus (in nitrogen atmosphere, the accumulated light quantity in wavelength 365nm: 500 mJ/cm<2>), liquid crystal cured material layer/horizontal alignment film/ A long film (length: 2000 m) made of a 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-type film thickness meter for a long film of the base film/horizontal alignment film/liquid crystal cured material layer, within the range not caught on the concave-convex part of the end, the functional layer (horizontal alignment film and liquid crystal mirror) at the same point It was 2 micrometers as a result of checking the average in-plane average thickness X of the functional layer by subtracting the average base material thickness content measured in the width direction from the base film powder after peeling (which consists of a cargo layer). Moreover, the maximum height Y of the convex part was 7 micrometers similarly measured by the 1 mm pitch of the elongate film edge part at the same position in the width direction with a contact-type film thickness meter. After storing this wound up long film in an environment of 23°C and 55%RH for one week, it was fed out. As a result, there was no significant sticking in the plane and no drop-off of the functional layer.

(5) Characteristic evaluation of long films

<Evaluation of peelability of functional layer>

A 25-micrometer pressure-sensitive adhesive manufactured by Lintec Co., Ltd. was pasted together so that it might become inside every 5 mm from the coating edge part of a functional layer, and the Konica Minolta Co., Ltd. triacetyl cellulose film (KC6UA) was pasted together on it. This triacetyl cellulose film was peeled parallel to the direction of a long picture, the functional layer was transcribed, and the functional layer peeling state on the side of the base film after transcription|transfer was visually observed by reflection under a fluorescent lamp.

The case where peeling satisfactorily parallel to a long direction was made into (circle), for example, the case where the peeling defect used as a sawtooth shape occurred was judged as x. A result is shown in Table 2.

<Measurement of base material peeling force>

After sampling the central part in the width direction of the long film consisting of a functional layer and a base film, and corona-treating the liquid crystal cured material layer side, 12 cm long x 10 cm x 0.7 mm thick through a 25 μm pressure-sensitive adhesive manufactured by Lintec Co., Ltd. It was bonded to glass (composition: base film/functional layer/adhesive layer/glass). About the obtained sample, the 25-mm width cut-out was made with the cutter from the base material side. The produced sample was set in the autograph "EZ-L" by Shimadzu Corporation, and the peeling force at the time of peeling a 25 mm width base material at the speed|rate of 300 mm/min in the parallel direction with respect to a glass surface was confirmed. A result is shown in Table 2.

<Measurement of retardation value of liquid crystal cured material layer>

Corona treatment is performed on the liquid crystal cured material layer side of the long film consisting of the above-described base film, horizontal alignment film, and liquid crystal cured material layer, and the length of 4 cm × width 4 cm × thickness of 0.7 mm through a 25 μm pressure-sensitive adhesive manufactured by Lintec Co., Ltd. After bonding to glass, the base film was peeled. Re (450) and Re (550) of the liquid crystal cured material layer were measured using KOBRA-WPR manufactured by Oji Instruments Co., Ltd., and α=Re (450)/Re (550) was calculated. A result is shown in Table 2.

2. Example 2

(1) Preparation of the composition (C1) for forming a cured resin layer

Dipentaerythritol hexaacrylate (Aronix M-403 polyfunctional acrylate manufactured by Toa Synthesis Co., Ltd.) 50 parts, acrylate resin (Evecryl 4858 manufactured by Daicel Yusibi Co., Ltd.) 50 parts, 2-methyl-1[4- (Methylthio)phenyl]-2-morpholinopropan-1-one (Irgacure 907; manufactured by Chiba Specialty Chemicals) 3 parts by dissolving 250 parts of isopropanol is prepared, and curing comprising an acrylate compound A composition (C1) for forming a resin layer was obtained.

(2) Preparation of cured resin layer

On the triacetyl cellulose film in which the uneven|corrugated part similar to Example 1 was formed, the composition (C1) for cured resin layer formation was apply|coated by the die-coating method so that it might become the width shown as "functional layer coating width C" in Table 1. At this time, it applied so that the edge part of the coating film of the composition for cured resin layer formation (C1) may each be located inside by 7.5 mm from both ends of a base film, and coat|cover each 7.5 mm at the uneven|corrugated part of both ends of the coating film. Then, after drying at 60 degreeC for 1 minute, using an ultraviolet irradiation apparatus, ultraviolet-ray is irradiated from the surface side which apply|coated the composition (C1) for cured resin layer formation further (in nitrogen atmosphere, accumulated light quantity in wavelength 365nm) : 400 mJ/cm 2 ) to form a cured resin layer. At this time, as a result of measuring Re (550) separately for the laminate of the triacetyl cellulose film and the cured resin layer with "KOBRA-WPR" by Oji Instruments Co., Ltd., the retardation value was 5 nm or less, and it was confirmed that it was optically isotropic.

Then, on the obtained cured resin layer, a horizontal alignment film and a liquid crystal cured material layer were formed in the same manner as in Example 1 to obtain a 1000 m long film composed of a liquid crystal cured material layer/horizontal alignment film/cured resin layer/base film. The obtained long film was wound around an FRP core having an inner diameter of 6 inches. It was 4 micrometers when the in-plane average thickness X of the functional layer which consists of this cured resin layer/horizontal alignment film/liquid crystal hardened|cured material layer was confirmed. Moreover, the maximum height Y of a convex part was 9 micrometers. After storing the wound up long film in an environment of 23°C and 55%RH for one week, it was fed out. As a result, there was no significant sticking in the plane and no drop-off of the functional layer. It carried out similarly to Example 1, and evaluated peelability etc. A result is shown in Table 2.

3. Example 3

As the base film, a base COP film (ZF-14-50) manufactured by Nippon Zeon Co., Ltd. was used, and a heated embossing roll was pressed to form knurled portions each having a width of 12.5 mm on both ends of the base film, followed by corona treatment. On this base film, the composition (C1) for cured resin layer formation was apply|coated by the die-coating method so that it might become the width shown as "functional layer coating width C" of Table 1. At this time, it applied so that the edge part of the coating film of the composition for cured resin layer formation (C1) might each be located inside by 7.5 mm from both ends of a base film, respectively, and coat|cover 5 mm at a time on the uneven|corrugated part of both ends of the coating film. Other than that, it was 4 micrometers as a result of carrying out similarly to Example 2, manufacturing a long film, and confirming the in-plane average thickness X of a functional layer. Moreover, the maximum height Y of the convex part was 8 micrometers. After storing the wound up long film in an environment of 23°C and 55%RH for one week, it was fed out. As a result, there was no remarkable sticking in the plane and no drop-off of the functional layer. It carried out similarly to Example 1, and evaluated peelability etc. A result is shown in Table 2.

4. Example 4

(1) Preparation of polymerizable liquid crystal composition (B2)

With respect to 100 parts by mass of the polymerizable liquid crystal compound (X2) prepared with reference to Japanese Patent Laid-Open No. 2016-81035, 0.10 parts by mass of a leveling agent "BYK-361N" (manufactured by BYK-Chemie), a leveling agent "F-556" ” (manufactured by DIC) 0.25 parts by mass and 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one as a photopolymerization initiator (manufactured by BASF Japan Co., Ltd. “Irgacure (registered)” Trademark) 369 (Irg369)") 3 parts by mass and 7.5 parts by mass of "Irgacure OXE-03" manufactured by BASF Japan Co., Ltd. were added. Moreover, cyclopentanone was added so that solid content concentration might be set to 13 %. The polymerizable liquid crystal composition (B2) was obtained by stirring this mixture at 80 degreeC for 1 hour.

A 1 mg/50 ml tetrahydrofuran solution of the polymerizable liquid crystal compound (X2) was prepared, and a measurement sample was obtained. A measurement sample is placed in a measurement cell with an optical path length of 1 cm, and an absorption spectrum is measured by setting it in an ultraviolet and visible spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation), and from the obtained absorption spectrum, the wavelength at which the maximum absorption is obtained As a result of reading, the maximum absorption wavelength _λmax 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). As a result of confirming the in-plane average thickness X of the functional layer, it was 2 micrometers. Moreover, the maximum height Y of the convex part was 7 micrometers. After storing the wound up long film in an environment of 23°C and 55%RH for one week, it was fed out. As a result, there was no remarkable sticking in the plane and no drop-off of the functional layer. It carried out similarly to Example 1, and evaluated peelability etc. A result is shown in Table 2.

5. Example 5

(1) Preparation of polymerizable liquid crystal composition (B3)

With respect to 100 parts by mass of the polymerizable liquid crystal compound (X3) prepared with reference to International Patent Publication No. 2015/025793, 0.10 parts by mass of a leveling agent "BYK-361N" (manufactured by BYK-Chemie), a leveling agent "F-556" (manufactured by DIC Corporation) 0.25 parts by mass and 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one as a photopolymerization initiator (“Irgacure (registered trademark)” manufactured by BASF Japan Co., Ltd.) ) 369 (Irg369)") 3 parts by mass and 7.5 parts by mass of "Irgacure OXE-03" manufactured by BASF Japan Co., Ltd. were added. Moreover, cyclopentanone was added so that solid content concentration might be set to 13 %. The polymerizable liquid crystal composition (B3) was obtained by stirring this mixture at 80 degreeC for 1 hour.

A 1 mg/50 ml tetrahydrofuran solution of the polymerizable liquid crystal compound (X3) was prepared, and a measurement sample was obtained. A measurement sample is placed in a measurement cell with an optical path length of 1 cm, and an absorption spectrum is measured by setting it in an ultraviolet and visible spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation), and from the obtained absorption spectrum, the wavelength at which the maximum absorption is obtained As a result of reading, the maximum absorption wavelength _λmax in the wavelength range of 300 to 400 nm was 352 nm.

Polymerizable Liquid Crystal Compound (X3)

A long film was prepared in the same manner as in Example 1 except that (B3) was used instead of the polymerizable liquid crystal composition (B1). As a result of confirming the in-plane average thickness X of the functional layer, it was 2 micrometers. Moreover, the maximum height Y of the convex part was 7 micrometers. After storing the wound up long film in an environment of 23°C and 55%RH for one week, it was fed out. As a result, there was no remarkable sticking in the plane and no drop-off of the functional layer. It carried out similarly to Example 1, and evaluated peelability etc. A result is shown in Table 2.

6. Example 6

(1) Preparation of polymerizable liquid crystal composition (B4)

Liquid crystal compound LC242 represented by the following formula (LC242): With respect to 100 parts by mass of PaliocolorLC242 (registered trademark of BASF Corporation), 0.10 parts by mass of a leveling agent "BYK-361N" (manufactured by BYK-Chemie), a leveling agent "F-556" ( DIC Corporation) 0.25 mass parts and 3 mass parts of polymerization initiator Irg369 were added, and cyclopentanone was added so that solid content concentration might be 13 mass parts. The polymerizable liquid crystal composition (B4) was obtained by stirring this mixture at 80 degreeC for 1 hour.

Polymerizable Liquid Crystal Compound (LC242)

Liquid crystal compound LC242: PaliocolorLC242 (registered trademark of BASF)

As the base film, a triacetyl cellulose film having the same uneven portions as in Example 1 was used, and on this triacetyl cellulose film, the composition (A1) for forming a horizontal alignment film was used as “functional layer coating width C” in Table 1 It apply|coated by the die-coating method so that it might become the width shown. At this time, the edge part of the coating film of the composition (A1) for horizontal alignment film formation was each located inside by 7.5 mm from both ends of a base film, and it applied so that it may coat|cover each 7.5 mm at the uneven|corrugated part of both ends of the coating film. Then, after heating and drying at 100 ° C. for 2 minutes, 100 mJ (based on 313 nm) is irradiated with polarized UV light so that the direction of the orientation regulating force forms an angle of 15 ° with respect to the long direction of the film, and the horizontal alignment film on the film formed. As a result of measuring the film thickness of the obtained horizontal alignment film with an ellipsometer, it was 0.2 micrometer. Subsequently, the polymerizable liquid crystal composition (B4) is applied on the horizontal alignment film by a die coating method with the same width as the film so that the average film thickness of the coating film is 17 µm, and heat-dried at 80°C for 1 minute, and further ultraviolet rays Using an irradiation device, by irradiating ultraviolet rays from the side to which the polymerizable liquid crystal composition was applied (in a nitrogen atmosphere, the accumulated light quantity at a wavelength of 365 nm: 500 mJ/cm 2 ), the liquid crystal cured material layer/horizontal alignment film/base film A 500 m long film formed was obtained. The obtained long film was wound around an FRP core having an inner diameter of 6 inches. As a result of confirming the in-plane average thickness X of the functional layer, it was 2 micrometers. Moreover, the maximum height Y of the convex part was 8 micrometers. After storing the wound up long film in an environment of 23°C and 55%RH for one week, it was fed out. As a result, there was no remarkable sticking in the plane and no drop-off of the functional layer. It carried out similarly to Example 1, and evaluated peelability etc. A result is shown in Table 2.

7. Example 7

(1) Preparation of vertically aligned polymerizable liquid crystal composition (B5)

A mixed solution of 13 parts by mass of "KBE-903" manufactured by Shin-Etsu Chemical Industry Co., Ltd. and 87 parts by mass of cyclopentanone, and a mixed solution of 13 parts by mass of "Karenz MOI-EG" manufactured by Showa Denko Co., Ltd. and 87 parts by mass of cyclopentanone, KBE -903: Karenz MOI-EG = 1.00: 1.35 (mass ratio) is mixed, and then kept at 30° C. for 16 hours, and a functional group that can react with a hydroxyl group or a carboxyl group (hydroxysilyl group) and (meth) A liquid mixture (hereinafter, sometimes referred to as liquid mixture (1)) containing a compound (pre-reacted compound) having an acryloyl group (acryloyl group) in the molecule was obtained.

Then, the polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (Y1) were mixed by mass ratio 90:10, and the mixture was obtained. With respect to 100 parts by mass of the obtained mixture, 0.25 parts by mass of leveling agent "F-556" (manufactured by DIC), 2.0 parts by mass of ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802, light 6 parts by mass of Irgacure369E (manufactured by BASF Japan Co., Ltd.) as a polymerization initiator, 1.0 parts by mass of Shin-Nakamura Chemical Industry Co., Ltd. "APG-700" (bifunctional) added as a polymerizable non-liquid crystalline compound having two or more (meth)acryloyl groups and cyclopentanone was added so that the solid content concentration was 13%. In addition, a compound (pre-reacting 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 a mixture of the polymerizable liquid crystal compound (X1) and (Y1) The liquid mixture (1) was added so that it might become 2.35 mass parts with respect to it, and the mixture was obtained. The vertical alignment polymerizable liquid crystal composition (B5) was obtained by stirring the obtained mixture at 80 degreeC for 1 hour.

Ionic compound A:

On a triacetyl cellulose film ((KC4UY, Konica Minolta Co., Ltd.)) on which the same uneven portions as in Example 1 were formed, a vertically aligned polymerizable liquid crystal composition (B5) was applied in Table 1 so that the average film thickness of the coating film was 9.5 µm It was applied by the die coating method with a width indicated as "functional layer coating width C" of . At this time, it applied so that the edge part of the coating film of the vertically-aligned polymeric liquid crystal composition (B5) might be located in each 7.5 mm from the both ends of a base film, respectively, and coat|cover each 7.5 mm on the uneven|corrugated part of both ends of the coating film. Next, after heat-drying at 120 degreeC for 90 second, using the ultraviolet irradiation apparatus, ultraviolet-ray is irradiated from the side to which the polymeric liquid crystal composition (B5) was apply|coated (in nitrogen atmosphere, the accumulated light quantity in wavelength 365nm: 500 mJ /cm2), a long film composed of a liquid crystal cured material layer/base film of 1000 m was obtained. The obtained long film was wound around an FRP core having an inner diameter of 6 inches. As a result of confirming this in-plane average thickness X, it was 1 micrometer. Moreover, the maximum height Y of a convex part was 6 micrometers. After storing the wound up long film in an environment of 23°C and 55%RH for one week, it was fed out. As a result, there was no remarkable sticking in the plane and no drop-off of the functional layer. It carried out similarly to Example 1, and evaluated peelability etc. A result is shown in Table 2.

<Rth measurement of vertically aligned liquid crystal cured material layer>

The base film prepared in the above procedure and the (vertical alignment) liquid crystal cured material layer were corona treated on the liquid crystal cured material layer side of the long film, and the length 4 cm × width 4 cm × through the 25 μm pressure-sensitive adhesive manufactured by Lintec. After bonding to 0.7 mm-thick glass, the base film was peeled. With respect to the obtained laminate comprising the glass, pressure-sensitive adhesive, and liquid crystal cured material layer, using KOBRA-WPR manufactured by Oji Measuring Instruments Co., Ltd., the incident angle of light to the sample for measuring optical properties was changed to obtain a front retardation value, and 40° with respect to the fast axis. The phase difference value at the time of inclination was measured. The average refractive index in each wavelength was measured using the ellipsometer M-220 by the Nippon Spectroscopy Co., Ltd. product. In addition, the above-mentioned in-plane average thickness was used for the film thickness. From the above-mentioned front phase difference value, phase difference value when tilted by 40° to the center of the leading axis, average refractive index, and film thickness, Oji measurement equipment technical data (http: //www.oji-keisoku.co.jp/products/ kobra/reference.html) to calculate the three-dimensional refractive index. From the obtained three-dimensional refractive index, the optical properties of each vertically aligned liquid crystal cured material layer were calculated according to the following formula. A result is shown in Table 2.

RthC (λ) = ((nxC (λ) + nyC (λ))/2 - nzC (λ)) × dC

In addition, RthC((lambda)) shows the phase difference value of the thickness direction of the vertically-aligned liquid crystal hardened|cured material layer in wavelength (lambda) nm. In addition, nxC (λ) is the in-plane principal refractive index of the vertically aligned liquid crystal cured material layer at a wavelength of λ nm, nyC (λ) is the refractive index in a direction orthogonal to nxC (λ) in the plane at a wavelength of λ nm, nzC (λ) represents the refractive index in the thickness direction of the vertically aligned liquid crystal cured material layer at a wavelength of λ nm, and when nxC (λ) = nyC (λ), nxC (λ) is an arbitrary direction within the film plane. It can be set as refractive index, and dC shows the film thickness of the vertically-aligned liquid crystal hardened|cured material layer.

8. Example 8

A cured resin layer was prepared on the triacetylcellulose film in the same manner as in Example 2, and a long film was prepared in the same manner as in Example 7. As a result of confirming the in-plane average thickness X of the functional layer, it was 3 micrometers. Moreover, the maximum height Y of the convex part was 8 micrometers. After storing the wound up long film in an environment of 23°C and 55%RH for one week, it was fed out. As a result, there was no significant sticking in the plane and no drop-off of the functional layer. It carried out similarly to Example 1, and evaluated peelability etc. A result is shown in Table 2.

9. Example 9

Using a base COP film (ZF-14-50) manufactured by Nippon Zeon Co., Ltd. as a base film, the heated embossing roll was pressed to form knurled portions each having a width of 12.5 mm on both ends of the base film, and corona treatment was performed. On this base film, the composition (C1) for cured resin layer formation was apply|coated by the die-coating method so that it might become the width shown as "functional layer coating width C" of Table 1. At this time, it applied so that the edge part of the coating film of the composition for cured resin layer formation (C1) might each be located inside by 7.5 mm from both ends of a base film, respectively, and coat|cover 5 mm at a time on the uneven|corrugated part of both ends of the coating film. Other than that, it carried out similarly to Example 8, and obtained the long film. As a result of confirming the in-plane average thickness X of the functional layer, it was 3 micrometers. Moreover, the maximum height Y of a convex part was 11 micrometers. After storing the wound up long film in an environment of 23°C and 55%RH for one week, it was fed out. As a result, there was no remarkable sticking in the plane and no drop-off of the functional layer. It carried out similarly to Example 1, and evaluated peelability etc. A result is shown in Table 2.

10. Example 10

(1) Preparation of composition (A2) for forming a vertical alignment film

0.5% polyimide ("Sunever SE-610" manufactured by Nissan Chemical Industry Co., Ltd.), 72.3% N-methyl-2-pyrrolidone, 18.1% 2-butoxyethanol, 9.1% ethylcyclohexane, and 0.01% of DPHA (manufactured by Shin-Nakamura Chemical) was mixed to prepare a composition for forming a vertical alignment film (A2).

As a base film, the COP film in which the knurling part was formed similarly to Example 9 was used. On this COP film, the composition (A2) for vertical alignment film formation was apply|coated by the die-coating method so that it might become the width shown as "functional layer coating width C" of Table 1. At this time, the edge part of the coating film of the composition for vertical alignment film formation (A2) was respectively located inside by 7.5 mm from both ends of a base film, and it apply|coated so that it may coat|cover each 5 mm in the uneven|corrugated part of both ends of the coating film. It was heat-dried at 80 degreeC for 1 minute, and the vertical alignment film was formed on the said film. Subsequently, the polymerizable liquid crystal composition (B4) is applied on the vertical alignment film by a die coating method with the same width as that of the film so that the average film thickness of the coating film is 5 µm, dried by heating at 80°C for 1 minute, and further ultraviolet rays By irradiating an ultraviolet-ray from the surface side to which the polymeric liquid crystal composition (B4) was apply|coated using the irradiation apparatus (in nitrogen atmosphere, the accumulated light amount in wavelength 365nm: 500mJ/cm<2>), liquid crystal cured material layer/vertical alignment film/ A long film made of a base film was obtained. As a result of confirming the in-plane average thickness X of the functional layer, it was 1 micrometer. Moreover, the maximum height Y of a convex part was 9 micrometers. After storing the wound long film in an environment of 23°C and 55%RH for 1 week, it was fed out. As a result, there was no remarkable sticking in the plane and no drop-off of the functional layer. It carried out similarly to Example 1, and evaluated peelability etc. A result is shown in Table 2.

11. Comparative Example 1

On the triacetyl cellulose film in which the uneven|corrugated part is formed similar to Example 1, the composition for horizontal alignment film formation (A1) and a polymeric liquid crystal composition (B1) are apply|coated so that it may become the width shown as "functional layer coating width C" in Table 1 A long film was obtained in the same manner as in Example 1 except for the above. In addition, as for the application of the composition (A1) for forming a horizontal alignment film, the ends of the coating film of the composition (A1) for forming a horizontal alignment film are located on the inside by 25 mm from both ends of the base film, respectively, in the uneven portions formed at both ends of the base film It was applied so that both ends of the coating film were not caught.

As a result of confirming the in-plane average thickness X of the functional layer, it was 2 micrometers. Moreover, the maximum height Y of a convex part was 2 micrometers. After storing the wound long film in an environment of 23°C and 55%RH for one week, when it was fed out, sticking occurred within the plane, and deformation of the film roll was observed. Moreover, as a result of the peelability evaluation of a functional layer, the edge part was torn in a jagged shape, and it fell off. It carried out similarly to Example 1, and evaluated peelability etc. A result is shown in Table 2.

1 base film
2 functional layer
3 Concavo-convex
11 long film
A short direction width of the base film
Short direction width of B1 and B2 irregularities
Short direction width of C functional layer

Claims (10)

A transferable functional layer comprising 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; As a long film made by
The functional layer is laminated on the surface of the base film having an uneven portion,
A long film satisfying B + C > A when A is the total width in the short direction of the base film, B is the sum of the short direction widths of the uneven portions of the base film, and C is the short direction width of the functional layer. The method of claim 1,
The long film whose peeling force from the base film of a functional layer is 0.02 N/25 mm or more and less than 1 N/25 mm. 3. The method of claim 1 or 2,
A long film, wherein the base film is a cellulose-based resin film or an olefin-based resin film. 4. The method according to any one of claims 1 to 3,
A long film in which the relationship between the in-plane average thickness X of the functional layer and the maximum height Y of the convex portions of the uneven portions satisfies 1.0 < Y/X ≤ 15.0. 5. The method according to any one of claims 1 to 4,
An elongate film, wherein the molecular orientation direction of the polymerizable liquid crystal compound in the cured material layer constituting the functional layer is horizontal with respect to the in-plane in the long direction of the base film, and is not parallel to the elongate direction of the base film. 6. The method according to any one of claims 1 to 5,
The long film in which the said hardened|cured material layer which comprises a functional layer satisfy|fills following formula (1) and (2).
Re (450)/Re (550) ≤ 1.00 (1)
100 nm ≤ Re (550) ≤ 150 nm (2)
[In Formulas (1) and (2), Re (λ) represents an in-plane retardation value at a wavelength of λ nm.] 6. The method according to any one of claims 1 to 5,
The long film in which the said cured|curing material layer which comprises a functional layer satisfy|fills following formula (3) and (4).
200 nm ≤ Re (550) ≤ 300 nm (3)
1.00 ≤ Re (450)/Re (550) (4)
[In formulas (3) and (4), Re (λ) represents an in-plane retardation value at a wavelength of λ nm.] 8. The method according to any one of claims 1 to 7,
A long film in which the functional layer contains a photo-alignment film. 6. The method according to any one of claims 1 to 5,
A long film, wherein the molecular orientation direction of the polymerizable liquid crystal compound in the cured product layer constituting the functional layer is substantially perpendicular to the surface in the long direction of the base film. 10. The method according to any one of claims 1 to 5 and 9,
The long film in which the said hardened|cured material layer which comprises a functional layer satisfy|fills following formula (5).
-150 nm ≤ Rth (550) ≤ -20 nm (5)
[In formula (5), Rth (550) represents the retardation value in the thickness direction at a wavelength of 550 nm of the cured product layer.]

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