JP2012123210A - Method for manufacturing laminate, laminate, optical compensation element, and liquid crystal device - Google Patents

Abstract

A method of manufacturing a laminate including an optically anisotropic resin layer having a smaller tilt is provided.
A method of manufacturing a laminate including a resin layer having a liquid crystal alignment surface and an optically anisotropic resin layer includes providing a layer of a polymerization curable first liquid composition on a substrate, A mold having a reversal pattern to be oriented is pressed against the first liquid composition layer, and the first liquid composition is polymerized and cured while the mold is pressed against the first liquid composition layer. Forming a layer of cured resin, removing the mold from the layer of cured resin, exposing the surface in contact with the mold to form a liquid crystal aligning surface, and forming a liquid crystal aligning surface composed of the cured resin A resin layer having a cholesteric liquid crystalline and polymerization-curable second liquid composition layer containing a liquid crystalline monomer and a chiral monomer on the liquid crystal aligning surface of the resin layer, on the liquid crystal aligning surface To orient the second liquid composition, and includes obtaining an optically anisotropic resin layer a second liquid composition is polymerized and cured in a state of being oriented.
[Selection figure] None

Description

  The present invention relates to a method for manufacturing a laminate, a laminate, an optical compensation element, and a liquid crystal device.

  Several techniques relating to a method of manufacturing a laminate, a laminate, an optical compensation element, or a liquid crystal device are disclosed.

  For example, in Japanese Patent Application Laid-Open No. 2007-072262 (Patent Document 1), the following steps (1) to (8): (1) a long support is sent out, and (2) a resin layer is formed on the long support (3) The surface of the resin layer is continuously rubbed to form an alignment layer, (4) one side or both sides of the support is removed, and (5) a coating liquid containing a cholesteric liquid crystalline compound is prepared. The coating layer is applied to the rubbing surface of the alignment layer and dried to form a coating film. (6) The coating film is heated and aged to cholesterically align the molecules of the liquid crystalline compound. (7) Irradiate ultraviolet light. The coating film is cured to form an optically anisotropic layer having a front retardation (Re) substantially not 0, and (8) winding up as a long optical film in the order of (1) to (8) Manufacturing method of optical film, optical film produced by the method, A polarizing plate having an optical film and a pair of protective films sandwiching the polarizing film, wherein at least one of the pair of protective films is the optical film, and a liquid crystal display having the polarizing plate An apparatus is disclosed.

  However, in a conventional technique such as the technique disclosed in Patent Document 1, an optically anisotropic layer containing a cholesteric-aligned cholesteric liquid crystalline compound is provided in a rubbing-treated alignment layer. A tilt of molecules of the cholesteric liquid crystalline compound contained in the anisotropic layer may occur. As a result, the retardation of the optically anisotropic layer contained in the optical film may be an asymmetric value with respect to the viewing angle with respect to the optically anisotropic layer.

  In addition, crystallization or alignment defects of the cholesteric liquid crystalline compound contained in the optically anisotropic layer may occur. As a result, the haze of the optically anisotropic layer contained in the optical film may occur.

  Furthermore, polyimide may be used as the resin contained in the alignment layer, but the alignment layer containing polyimide may be colored (yellowish). On the other hand, although polyvinyl alcohol may be used as resin contained in an orientation layer, the water resistance of the orientation layer containing polyvinyl alcohol may not be favorable.

  In addition, the cholesteric alignment regulating force of the cholesteric liquid crystalline compound by the alignment layer formed by continuously rubbing the resin layer surface may be insufficient.

Japanese Patent Laid-Open No. 2007-072262

  The first object of the present invention is to provide a method for producing a laminate including an optically anisotropic resin layer having a smaller tilt.

  The second object of the present invention is to provide a laminate including an optically anisotropic resin layer having a smaller tilt.

  The third object of the present invention is to provide an optical compensation element including a laminate including an optically anisotropic resin layer having a smaller tilt.

  A fourth object of the present invention is to provide a liquid crystal device including an optical compensation element including a laminate including an optically anisotropic resin layer having a smaller tilt.

  According to a first aspect of the present invention, there is provided a method for producing a laminate including a resin layer having a liquid crystal orientation surface and an optically anisotropic resin layer. Providing a mold having a reversal pattern of liquid crystal alignment pattern against the first liquid composition layer, and pressing the mold against the first liquid composition layer. The liquid composition is polymerized and cured to form a cured resin layer, and by removing the mold from the cured resin layer, the surface in contact with the mold is exposed to form the liquid crystal alignment surface. Obtaining a resin layer having the liquid crystal aligning surface composed of the cured resin, and having a cholesteric liquid crystalline and heavy polymer containing a liquid crystalline monomer and a chiral monomer on the liquid crystal aligning surface of the resin layer. Providing a layer of a curable second liquid composition, orienting the second liquid composition on the liquid crystal orientation surface, and in the oriented state, the second liquid composition. It is a method for producing a laminate, comprising polymerizing and curing to obtain an optically anisotropic resin layer.

  2nd aspect of this invention is a laminated body manufactured by the method of manufacturing the laminated body which is 1st aspect of this invention.

  According to a third aspect of the present invention, there is provided a resin layer having a liquid crystal aligning surface formed by transfer using a mold, and a cholesteric liquid crystallinity and polymerization that is aligned on the liquid crystal aligning surface and polymerized and cured in the alignment state. And an optically anisotropic resin layer composed of a polymerized cured product of a curable liquid composition.

  According to a fourth aspect of the present invention, there is provided an optical compensation element that optically compensates at least a part of the anisotropy of the refractive index of the element having an anisotropy of the refractive index. It is an optical compensation element characterized by including a body.

  According to a fifth aspect of the present invention, in the liquid crystal device including a layer containing liquid crystal, the liquid crystal device further includes the optical compensation element according to the third aspect of the present invention.

  According to the first aspect of the present invention, it is possible to provide a method for producing a laminate including an optically anisotropic resin layer having a smaller tilt.

  According to the second aspect of the present invention and the third aspect of the present invention, it is possible to provide a laminate including an optically anisotropic resin layer having a smaller tilt.

  According to the fourth aspect of the present invention, it is possible to provide an optical compensation element including a laminate including an optically anisotropic resin layer having a smaller tilt.

  According to the fifth aspect of the present invention, it is possible to provide a liquid crystal device including an optical compensation element including a laminate including an optically anisotropic resin layer having a smaller tilt.

FIG. 1 is a diagram schematically illustrating an example of a method for producing a laminate according to the first embodiment of the present invention. FIG. 2 is a diagram schematically illustrating an example of a mold in the method for manufacturing a laminated body according to the first embodiment of the present invention and an example of a laminated body according to the second embodiment of the present invention. FIG. 3 is a diagram illustrating an example of an optical compensation element according to the third embodiment of the present invention. FIG. 4 is a diagram illustrating an example of a liquid crystal device according to the fourth embodiment of the present invention.

  Next, embodiments of the present invention will be described with reference to the accompanying drawings.

  FIG. 1 is a diagram schematically illustrating an example of a method for producing a laminate according to the first embodiment of the present invention. 1A to 1G show respective steps in an example of a method for producing a laminate according to the first embodiment of the present invention.

  The method for producing a laminate according to the first embodiment of the present invention shown in FIG. 1 includes a resin layer 17 and an optically anisotropic resin layer 16 having a liquid crystal orientation surface as shown in FIG. It is a method of manufacturing the laminated body 10 containing. First, as shown in FIG. 1 (a), a layer 12 of a polymerization curable first liquid composition is provided on a substrate 11. Next, as shown in FIG. 1B, a mold 13 having a reversal pattern of the liquid crystal alignment pattern is pressed against the first liquid composition layer 12. Next, as shown in FIG. 1C, the first liquid composition is polymerized and cured in a state where the mold 13 is pressed against the first liquid composition layer 12 to form a cured resin layer 14. . Next, as shown in FIG. 1 (d), by removing the mold 13 from the layer of the cured resin, the surface that has been in contact with the mold is exposed to form the liquid crystal alignment surface, and from the cured resin, A resin layer 17 having the above-described liquid crystal alignment surface is obtained. Next, as shown in FIG. 1 (e), a layer 15 of a cholesteric liquid crystalline and polymerization curable second liquid composition containing a liquid crystalline monomer and a chiral monomer in the resin layer 17 having the liquid crystal orientation surface. Is provided. Then, the second liquid composition on the liquid crystal alignment surface is aligned. Next, as shown in FIG. 1F, the optically anisotropic resin layer 16 is obtained by polymerizing and curing the second liquid composition in the oriented state. Finally, as shown in FIG. 1G, the base material 11 is removed from the resin layer 17 having a liquid crystal orientation surface.

  The method for manufacturing the laminate according to the first embodiment of the present invention shown in FIG. 1 is at least shown in FIGS. 1 (a), (b), (c), (d), (e), and (f). Includes steps as shown. On the other hand, the method for manufacturing the laminate according to the first embodiment of the present invention shown in FIG. 1 may further include a step as shown in FIG.

  According to the method for producing a laminate according to the first embodiment of the present invention as shown in FIG. 1, it is possible to provide a method for producing a laminate comprising an optically anisotropic resin layer having a smaller tilt. It becomes possible. More specifically, it becomes possible to form the resin layer 17 having a liquid crystal alignment surface capable of providing the optically anisotropic resin layer 16 having a smaller tilt. As a result, it becomes possible to provide a method for producing a laminate including an optically anisotropic resin layer in which the asymmetry of retardation with respect to vision is reduced or prevented.

  In addition, it is possible to provide a method for manufacturing a laminate including an optically anisotropic resin layer in which crystallization of liquid crystal is reduced or prevented. Furthermore, it becomes possible to provide a method for producing a laminate including an optically anisotropic resin layer in which alignment defects of liquid crystals are reduced or prevented. As a result, it is possible to provide a method for producing a laminate including an optically anisotropic resin layer in which haze is reduced or prevented.

  In addition, it is possible to provide a method for producing a laminate including an optically anisotropic resin layer having improved orientation.

  Further, it is possible to provide a method for producing a reduced color or colorless laminate including an optically anisotropic resin layer.

  Furthermore, it becomes possible to provide a method for producing a laminate having improved solvent resistance and / or water resistance, including an optically anisotropic resin layer.

  Furthermore, it becomes possible to provide a method for producing a laminate having a smaller thickness, including an optically anisotropic resin layer.

  Here, the form of the substrate 11 is not particularly limited, and as the substrate 11, a plate-like substrate (substrate) or a film-like substrate can be used. Although the material of the base material 11 is not specifically limited, Usually, it is glass, a polymer, or a mixture of polymers. Examples of the polymer that is the material of the base material 11 include polyolefins such as polyethylene, polypropylene, polycycloolefin (norbornene polymer, etc.), polycarbonate, polyvinyl chloride, polystyrene, polyacrylonitrile, polysulfone, polyarylate, polyethylene terephthalate. (PET), polyvinyl alcohol, and cellulose ester. Further, homopolymers or copolymers obtained from at least one of acrylic monomers such as acrylic acid and acrylic acid esters and methacrylic monomers such as methacrylic acid and methacrylic acid esters may be mentioned.

  Moreover, the thickness of the base material 11 is not specifically limited. When the substrate 11 is a polymer film, the thickness of the substrate 11 is, for example, 20 μm to 500 μm, preferably 50 μm to 200 μm, and more preferably 50 μm to 100 μm. When the thickness of the base material 11 is 20 μm or more, the mechanical strength of the base material 11 which is a polymer film is higher. Moreover, when the base material 11 is a glass-made base material, it is preferable that thickness is 10-1000 micrometers, and it is especially preferable that it is 20-200 micrometers.

  In addition, when the base material 11 is a polymer film, it is also possible to manufacture the base material 11 by a solvent cast method or a melt extrusion method.

  The first liquid composition is a polymerization curable composition. The composition is preferably a photocurable composition. The photocurable composition is preferably a composition comprising a compound having an addition-polymerizable unsaturated group (for example, a polymerization-functional UV-curable compound) and a photopolymerization initiator. The photopolymerization initiator is a compound that causes a radical polymerization reaction or an ionic polymerization reaction to the photopolymerizable compound by light.

  The compound having an addition polymerizable unsaturated group (hereinafter referred to as a polymerizable monomer) is preferably a photopolymerizable monomer. Here, the photopolymerizable monomer is, for example, a monomer that is polymerized and cured by irradiation with ultraviolet rays. When the polymerizable monomer is a photopolymerizable monomer, even if at least one of the base material 11 and the mold 13 is made of a resin, the thermal change is reduced or prevented, and the polymerization property is reduced. The monomer can be polymerized and cured in a shorter time and more uniformly. As a result, a cured resin obtained by polymerizing and curing the first liquid composition can be obtained more easily. The polymerizable monomer can be selected such that the cured resin has a reduced color or is colorless and transparent. Moreover, it can select so that cured resin may have better solvent resistance and / or water resistance.

  Examples of the photopolymerizable monomer include monomers having an acryloyl group or a methacryloyl group such as acrylic acid, methacrylic acid, acrylate, methacrylate, acrylamide, and methacrylamide, monomers having a vinyl group such as vinyl ether and vinyl ester, Examples thereof include monomers having an allyl group such as allyl ether and allyl ester, monomers having a cyclic ether group, and styrene compounds. The photocurable monomer is preferably a monomer having an acryloyl group or a methacryloyl group, and more preferably an acrylate or a methacrylate.

As acrylate or methacrylate, for example,
(A) Phenoxyethyl acrylate (methacrylate), benzyl acrylate (methacrylate), stearyl acrylate (methacrylate), lauryl acrylate (methacrylate), 2-ethylhexyl acrylate (methacrylate), ethoxyethyl acrylate (methacrylate), methoxyethyl acrylate (methacrylate), Glycidyl acrylate (methacrylate), tetrahydrofurfryl acrylate (methacrylate), allyl acrylate (methacrylate), 2-hydroxyethyl acrylate (methacrylate), 2-hydroxypropyl acrylate (methacrylate), N, N-diethylaminoethyl acrylate (methacrylate), N, N-dimethylaminoethyl acrylate (meta Monoacrylates such as relate), dimethylaminoethyl acrylate (methacrylate), methyladamantyl acrylate (methacrylate), ethyladamantyl acrylate (methacrylate), hydroxyadamantyl acrylate (methacrylate), adamantyl acrylate (methacrylate), isobornyl acrylate (methacrylate) Or monomethacrylate,
(B) 1,3-butanediol diacrylate (methacrylate), 1,4-butanediol diacrylate (methacrylate), 1,6-hexanediol diacrylate (methacrylate), diethylene glycol diacrylate (methacrylate), triethylene glycol di Diacrylate or dimethacrylate such as acrylate (methacrylate), tetraethylene glycol diacrylate (methacrylate), neopentyl glycol diacrylate (methacrylate), polyoxyethylene glycol diacrylate (methacrylate), tripropylene glycol diacrylate (methacrylate),
(C) a triacrylate or trimethacrylate such as trimethylolpropane triacrylate (methacrylate), pentaerythritol triacrylate (methacrylate), and
(D) An acrylate having four or more polymerizable functional groups or a methacrylate having four or more polymerizable functional groups, such as dipentaerythritol hexaacrylate (methacrylate).

  Examples of the vinyl ether include alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether, and (hydroxyalkyl) vinyl (such as 4-hydroxybutyl vinyl ether).

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl cyclohexanecarboxylate, and vinyl benzoate.

  Examples of allyl ethers include alkyl allyl ethers such as ethyl allyl ether, propyl allyl ether, (iso) butyl allyl ether, and cyclohexyl allyl ether.

  Examples of allyl esters include alkyl allyl esters such as ethyl allyl ester, propyl allyl ester, and isobutyl allyl ester.

  Examples of the monomer having a cyclic ether group include a monomer having an oxetanyl group, a monomer having an oxiranyl group, and a monomer having a spiro ortho ether group.

  The polymerizable monomer preferably has two or more polymerizable functional groups, preferably two or three polymerizable functional groups, and has two polymerizable functional groups. More preferably.

  Here, when the polymerizable monomer has two or more polymerizable functional groups, the polymerizable monomer can be cross-linked, so that the heat resistance and solvent resistance of the cured resin can be improved. become. As a result, for example, when the resin layer 17 having a liquid crystal orientation surface is provided with the second liquid composition layer 15 containing a solvent and a liquid crystalline monomer and a chiral monomer, the solvent contained in the second liquid composition. It becomes possible to reduce or prevent the dissolution of the resin layer 17 having a liquid crystal alignment surface. Alternatively, as described later, the liquid crystal monomer contained in the second liquid composition layer 15 and the second liquid composition layer 15 are heated by providing the second liquid composition layer 15 on the layer 17 having the liquid crystal orientation surface. When the chiral monomer is cholesterically aligned, it is possible to reduce or prevent a change in the layer 17 having the liquid crystal aligning surface due to heating.

  The molecular weight of the polymerizable monomer is preferably 100 or more and 800 or less, and more preferably 200 or more and 600 or less.

  Furthermore, when the first liquid composition contains a photopolymerizable monomer as a polymerizable monomer, the first liquid composition is preferably a radical polymerization or ionic polymerization of the photopolymerizable monomer. In order to contain a photopolymerization initiator.

  Examples of the photopolymerization initiator include (A) acetophenone photopolymerization initiator, (B) benzoin photopolymerization initiator, (C) benzophenone photopolymerization initiator, (D) thioxanthone photopolymerization initiator, ( E) photoinitiators containing fluorine atoms such as perfluoro (tert-butyl peroxide) and perfluorobenzoyl peroxide, and (F) α-acyl oxime esters, benzyl- (o-ethoxycarbonyl) -α-monooxime, Others such as acylphosphine oxide, glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylthiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, and tert-butyl peroxypivalate The photoinitiator of this is mentioned.

  Here, in the first liquid composition, the ratio of the mass of the photopolymerizable monomer to the total mass of the photopolymerizable monomer and the photopolymerization initiator is preferably 90 or more and 99 or less. In this case, the unreacted photopolymerization initiator can be reduced and the photopolymerizable monomer can be polymerized more easily.

  In addition, the first liquid composition may contain a surfactant. When the first liquid composition contains a surfactant, the mold 13 can be more easily removed from the cured resin layer 14 obtained by polymerizing and curing the first liquid composition. Become.

  Examples of the surfactant include a fluoroalkyl group which may have an etheric oxygen atom, a silicone chain, or a compound having an alkyl group having 4 to 24 carbon atoms. The surfactant more preferably includes a compound having a fluoroalkyl group. Examples of the fluoroalkyl group include a perfluoroalkyl group, a polyfluoroalkyl group, and a perfluoropolyether group. Examples of the silicone chain include dimethyl silicone and methylphenyl silicone. Examples of the alkyl group having 4 to 24 carbon atoms include n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, lauryl group, and octadecyl group. Is mentioned. The alkyl group having 4 to 24 carbon atoms may be a linear group or a branched group.

  Here, the amount of the surfactant in the first liquid composition is such that the coating property of the solution of the second liquid composition applied to the layer 17 having the liquid crystal alignment surface and the mold from the layer 14 of the cured resin. It is determined by the peelability to peel 13.

  More specifically, when the amount of the surfactant contained in the first liquid composition is increased, the releasability of peeling the mold 13 from the cured resin layer 14 tends to be improved. On the other hand, when the amount of the surfactant contained in the first liquid composition is decreased, the applicability of the second liquid composition to the resin layer 17 having a liquid crystal orientation surface tends to be improved.

  In addition, the contact angle of water with respect to the surface of the resin layer 17 having a liquid crystal orientation surface is preferably 50 ° or more and 90 ° or less, and more preferably 60 ° or more and 80 ° or less. When the contact angle of water is 50 ° or more, the mold 13 can be more easily peeled from the resin layer 17 having the liquid crystal orientation surface. On the other hand, when the contact angle of water is 90 ° or less, when the second liquid composition is applied to the resin layer 17 having the liquid crystal alignment surface, the second liquid composition is repelled. It can be reduced or prevented. As a result, it becomes possible to improve the adhesion between the resin layer 17 having a liquid crystal alignment surface and the layer 15 of the second liquid composition. In addition, the contact angle of water with respect to the surface of the resin layer 17 which has a liquid crystal aligning surface is measured using a contact angle measuring apparatus according to JISK6768.

  In order to provide the base material 11 with the layer 12 of the polymerization curable first liquid composition, for example, the base material 11 is coated with the polymerization curable first liquid composition. Examples of the coating method include a potting method, a spin coating method, a roll coating method, a die coating method, a spray coating method, a casting method, a dip coating method, screen printing, and a transfer method. Here, the viscosity of the first liquid composition at a temperature of 25 ° C. is preferably 1 mPa seconds to 2000 mPa seconds, and more preferably 5 mPa seconds to 1000 mPa seconds. In this case, the first liquid composition layer 12 having a smooth surface can be more easily formed by means such as spin coating. The viscosity of the first liquid composition at a temperature of 25 ° C. is measured by using a rotary viscometer. The viscosity of the first liquid composition can be adjusted by using a solvent as a diluent.

  As for the mold 13, when the first liquid composition contains a photopolymerizable monomer, the material of the mold 13 is preferably a material that is transparent to light for polymerizing the photopolymerizable monomer. It is. In this case, the photopolymerizable monomer contained in the first liquid composition layer 12 can be polymerized and cured by irradiating the first liquid composition layer 12 with light through the mold 13. Become.

  Examples of materials that can be used for the mold 13 to transmit light to polymerize a photopolymerizable monomer such as ultraviolet rays include glass, polyethylene-terephthalate (PET), polycarbonate (PC), and polyvinyl chloride ( PVC), polymethyl methacrylate (PMMA), cycloolefin polymer (COP), and transparent fluororesin.

  In addition, what is necessary is just to irradiate light from the base material 11 side, when the material of the mold 13 is opaque with respect to the light which polymerizes a photopolymerizable monomer.

  Further, the mold 13 having a reversal pattern of the pattern for aligning the liquid crystal may be, for example, a substrate with an alignment film subjected to rubbing treatment or a resin film subjected to rubbing treatment (for example, PET film subjected to rubbing treatment). Here, the rubbing-treated surface of the mold 13 constitutes a reverse pattern of the pattern for aligning the liquid crystal. The mold 13 having such a reversal pattern for aligning the liquid crystal can be obtained with relatively high accuracy by, for example, rubbing a resin film.

  Alternatively, the mold 13 having the reverse pattern of the pattern for aligning the liquid crystal may be, for example, a mold having a periodic uneven structure (groove structure). Here, the periodic concavo-convex structure (groove structure) of the mold 13 constitutes a reverse pattern of the pattern for aligning the liquid crystal.

  FIG. 2 is a diagram schematically illustrating an example of a mold in the method for manufacturing a laminated body according to the first embodiment of the present invention and an example of a laminated body according to the second embodiment of the present invention. Here, Fig.2 (a) is a figure which illustrates schematically the example of the mold in the method of manufacturing the laminated body which concerns on 1st embodiment of this invention. Moreover, FIG.2 (b) is a figure which illustrates roughly the example of the laminated body which concerns on 2nd embodiment of this invention. That is, the example of the laminated body according to the second embodiment of the present invention as shown in FIG. 2B is obtained by the method of manufacturing the laminated body according to the first embodiment of the present invention as shown in FIG. It is an example of the laminated body manufactured.

An example of the mold shown in FIG. 2A is a mold 13 having a periodic uneven structure (groove structure) as shown in FIG. In FIG. 2A, P, L ₀ , and H are the pitch of the periodic concavo-convex structure of the mold 13, the width of the periodic convex portion (line portion) of the mold 13, and the periodicity of the mold 13, respectively. It is the height of a convex part (line part).

When the mold 13 as shown in FIG. 2A is used, in the step of FIG. 1F, the resin layer 17 and the optically anisotropic resin layer 16 having a liquid crystal orientation surface as shown in FIG. The laminated body 10 containing is obtained. In FIG. 2B, P, L, and H respectively indicate the pitch of the periodic concavo-convex structure formed on the resin layer 17 (or optically anisotropic resin layer 16) having the liquid crystal alignment surface, and the liquid crystal alignment. The width of the periodic protrusions (line portions) formed on the resin layer 17 having a crystalline surface (or the width of the periodic depressions formed on the optically anisotropic resin layer 16), and a liquid crystal alignment surface It is the height of the periodic convex part (line part) formed in the resin layer 17 (or the depth of the periodic concave part formed in the optically anisotropic resin layer 16). The values of P, L, and H for the resin layer 17 having the liquid crystal orientation surface shown in FIG. 2B are the values of P, P-L ₀ , and H for the mold 13 shown in FIG. Is equivalent to In FIG. 2B, n ₁ and n ₂ are the refractive indices (optically anisotropic resin layers) of the material filling the periodic concave portions (groove portions) of the resin layer 17 having the liquid crystal orientation surface, respectively. 16 and the refractive index of the material of the resin layer 17 having a liquid crystal orientation surface.

Here, the force (orientation regulating force / anchoring force) W for orienting the liquid crystal expressed by the resin layer 17 having the liquid crystal orientation surface provided with a pattern for orienting the liquid crystal is:
W = (1/2) × (elastic constant of liquid crystal) × H ² × (2π / P) ³
It is represented by

  That is, the resin having the liquid crystal alignment surface formed by using the mold 13 as the height H of the periodic protrusions of the mold 13 is larger and as the pitch P of the periodic uneven structure of the mold 13 is smaller. The force W for aligning the liquid crystal expressed by the layer 17 increases. Thus, the liquid crystal expressed by the resin layer 17 having the liquid crystal orientation surface is aligned by the shape of the periodic uneven structure of the mold 13 regardless of the type of the material of the resin layer 17 having the liquid crystal orientation surface. The force W can be controlled.

Here, the force W for aligning the liquid crystal expressed by the resin layer 17 having the liquid crystal aligning surface is preferably 1 × 10 ⁻⁵ J / m ² or more, and more preferably 5 × 10 ⁻⁵ J. / M ² or more. When the force W for aligning the liquid crystal expressed by the resin layer 17 having the liquid crystal orientation surface is 1 × 10 ⁻⁵ J / m ² or more, the liquid crystal contained in the second liquid composition layer It becomes possible to perform better orientation. As a result, the haze of the optically anisotropic resin layer 16 can be reduced.

  In addition, the resin layer 17 having a liquid crystal alignment surface provided with a pattern for aligning liquid crystals preferably has structural birefringence given by the pattern for aligning liquid crystals. When the mold 13 having a reversal pattern for aligning the liquid crystalline polymer is a mold having a periodic uneven structure (groove structure) as shown in FIG. 2A, the liquid crystalline polymer is aligned. It is possible to provide structural birefringence due to the periodic concavo-convex structure (groove structure) of the mold 13 to the cured resin layer 14 that gives the resin layer 17 having a liquid crystal orientation surface with a pattern to be formed. . In addition, the periodic uneven structure of the mold 13 and the periodic uneven structure of the resin layer 17 having the liquid crystal orientation surface alternately have a plurality of convex portions and a plurality of concave portions that are completely or substantially equivalent. means.

A resin layer 17 having a liquid crystal orientation surface shown in FIG. 2B provided by a mold 13 having a periodic uneven structure (groove structure) and a material filling the periodic concave portions (groove portions) of the layer 17 The structural birefringence δ of the structure consisting of
_{δ = (n y -n x)} × H
n _y = {f × (n ₂ ) ² + (1−f) × (n ₁ ) ² } ^1/2
_{n x = {f × (n} 2) -2 + (1-f) × (n 1) -2} -1/2
It is represented by

Here, n ₂ is the refractive index of the material of the layer 17 with respect to the wavelength of light passing through the structure, and n ₁ is a periodic uneven structure of the layer 17 with respect to the wavelength of light passing through the structure ( Is the refractive index of the material filling the groove structure), and H is the height of the convex part (or the depth of the concave part) of the periodic concavo-convex structure. Note that when the material of the layer 17 is a material having a refractive index anisotropy (birefringent material), n ₂ represents the wavelength of light passing through the structure and the light passing through the structure. It is the refractive index of the material of the layer 17 in the direction orthogonal to the traveling direction. Similarly, when the material filling the periodic uneven structure (groove structure) of the layer 17 is a material having a refractive index anisotropy (birefringent material), n ₁ It is the refractive index of the material which fills the periodic uneven structure (groove structure) of the layer 17 in the direction orthogonal to the wavelength of light passing through and the traveling direction of light passing through the structure. Further, f is a filling factor represented by f = L / P, L is the width of the convex portion of the periodic uneven structure of the structure, and P is the width of the periodic uneven structure of the structure. The pitch, 0 <f <1. Incidentally, n _y is periodic longitudinal direction of the convex portion of the concavo-convex structure of the structure: represents the effective refractive index of the (y-direction periodicity without direction) along the structure, n _x is the period of the structure The effective refractive index of the structure along the short direction (x direction: direction with periodicity) of the convex part of a typical uneven structure.

For example, the structural birefringence δ ₁ of the resin layer 17 having a liquid crystal alignment surface shown in FIG. 2B is n ₂ = wavelength of light passing through the layer 17 (and passing through the layer 17 in the above equation). The refractive index of the material of the layer 17 (in the direction orthogonal to the light traveling direction), n ₁ = the refractive index of air with respect to the wavelength of the light passing through the layer 17, H = the convex portion of the periodic concavo-convex structure of the layer 17 The height (or the depth of the concave portion), L = the width of the convex portion of the periodic concavo-convex structure of the layer 17, and P = the pitch of the periodic concavo-convex structure of the layer 17 are obtained.

That is, the structural birefringence δ ₁ of the resin layer 17 having the liquid crystal orientation surface provided by the mold 13 having a periodic uneven structure (groove structure) is changed to the periodic convex portion (line portion) of the mold 13. The ratio L _{0 of the} height H and the width L ₀ (where L ₀ = P−L) of the periodic protrusions (line portions) of the mold 13 to the pitch P of the periodic uneven structure of the mold 13. If / P = 1−L / P = 1−f and the refractive index of air is n ₁ , the refractive index n ₂ of the periodic convex portion (line portion) of the resin layer 17 having the liquid crystal alignment surface is adjusted. Can be controlled. For example, when the height H of the periodic convex portion (line portion) of the mold 13 is increased, the structure of the resin layer 17 having liquid crystal alignment provided by the mold 13 having the periodic uneven structure (groove structure). The birefringence δ ₁ can be increased. Also, it increased by increasing the refractive index n ₂ of the periodic protrusions of the resin layer 17 having a liquid crystal alignment surface. Although different depending on the value of n _2, the structural birefringence δ can be increased by setting f to 0.4 to 0.6.

Further, the structural birefringence of the structure composed of the resin layer 17 having the liquid crystal orientation surface shown in FIG. 2B and the optically anisotropic resin layer 16 filling the periodic concave portions (groove portions) of the layer 17. [delta] ₂ is in the above equation, the refractive index of the material of the n 2 ₌ layers 17 and the layer 17 of (a direction orthogonal to the traveling direction of the light passing through the well layer 17 and the layer 16) a wavelength of light passing through the layer 16 , N ₁ = wavelength of light passing through layers 17 and 16 and the refractive index of the material of layer 16 in the direction orthogonal to the direction of travel of light passing through layers 17 and 16; H = layer 17 (or layer 16 ), The height of the convex portion of the periodic concavo-convex structure (or the depth of the concave portion), L = the width of the convex portion of the periodic concavo-convex structure of the layer 17 (or the width of the concave portion of the periodic concavo-convex structure of the layer 16). ), P = the pitch of the periodic concavo-convex structure of the layer 17 (or layer 16). It is done.

That is, the structural birefringence δ ₂ of the structure composed of the resin layer 17 having a liquid crystal alignment surface and the optically anisotropic resin layer 16 filling the periodic concave portions (groove portions) of the layer 17 is It can be controlled by adjusting the refractive index n ₁ and the refractive index n ₂ of the periodic convex portion (line portion) of the layer 17. For example, the structural birefringence δ ₂ can be increased as the difference between n ₁ and n ₂ increases. Although different depending on the values of n ₁ and n _2, the structural birefringence δ ₂ can be increased by setting f to 0.4 to 0.6. For example, when n ₁ = 1.7 and n ₂ = 1.5, the structural birefringence δ ₂ takes a maximum value when f = 0.5.

As described above, for example, the resin layer 17 having the liquid crystal orientation surface and the recesses (the groove portion) are formed by the periodic structure of the optically anisotropic resin layer 16 filling the recess (groove portion). The optically anisotropic resin layer 16 filling the groove portion) may provide retardation to the polarized light passing through the resin layer 17 having a liquid crystal orientation surface and the optical anisotropic resin layer 16 filling the concave portion (groove portion). It becomes possible. For example, a compensator for controlling a phase difference of polarized light by using a resin layer 17 having a liquid crystal alignment surface and an optically anisotropic resin layer 16 filling a recess (groove portion) having structural birefringence due to a periodic structure. It can also be used as a (wavelength plate). In this case, the resin layer 17 having a liquid crystal alignment surface and the optically anisotropic resin layer 16 filling the concave portion (groove portion) have the polarization retardation required for the compensation plate (wave plate). As shown, H and L ₀ / P (= 1−f) of the mold 13, the refractive index n ₁ of the optically anisotropic resin layer 16, and the refractive index n ₂ of the resin layer 17 having a liquid crystal orientation surface. Adjust the value.

  The retardation value given to the polarized light by the resin layer 17 having a liquid crystal alignment surface and the optically anisotropic resin layer 16 filling the concave portion (groove portion) is preferably 5 nm or more, more preferably 10 nm or more. is there. The retardation value given to polarized light by the resin layer 17 having a liquid crystal orientation surface and the optically anisotropic resin layer 16 filling the recess (groove portion) of the resin layer 17 having the liquid crystal orientation surface is 5 nm or more. In this case, the retardation value given to the polarized light by the laminate 10 can be controlled more easily.

  When the viscosity of the first liquid composition at a temperature of 25 ° C. is 1 mPa · second or more and 2000 mPa · second or less, the mold 13 having a reversal pattern of the pattern for aligning the liquid crystal is preferably at room temperature. It is pressed against the layer 12 of the first liquid composition. In this case, when the mold 13 is pressed against the first liquid composition layer 12, unevenness in the thickness of the first liquid composition layer 12 (pattern given to the first liquid composition layer 12) It is possible to reduce unevenness in the image.

  Next, the polymerizable monomer contained in the first liquid composition layer 12 is polymerized and cured in a state where the mold 13 is pressed against the first liquid composition layer 12. Here, when the polymerizable monomer is polymerized and cured, depending on the functional number of the polymerizable monomer, a crosslinking reaction may be involved. This makes it possible to form the cured resin layer 14 on the substrate 11 more easily. Next, after forming the cured resin layer 14, the mold 13 is removed from the cured resin layer 14 to expose the surface in contact with the mold 13 to form a liquid crystal alignment surface. A resin layer 17 having a liquid crystal alignment surface is obtained.

  In the case where the polymerizable monomer contained in the layer 12 of the first liquid composition is a photopolymerizable monomer, in order to polymerize and cure the photopolymerizable monomer, for example, ultraviolet rays are used in the first liquid composition. By irradiating the layer 12, the photopolymerizable monomer can be polymerized and cured. As the ultraviolet light, for example, light of a high-pressure mercury lamp (frequency: 1.5 kHz to 2.0 kHz, main wavelength light: irradiation energy at 255 nm, 315 nm, 365 nm, and 365 nm: 1000 mJ) can be used.

  Here, the thickness of the resin layer 17 having a liquid crystal alignment surface (the direction of the height H of the convex portions of the concavo-convex structure of the resin layer 17 excluding the height H of the convex portions of the concavo-convex structure of the resin layer 17 The thickness of the resin layer 17 is preferably 3 μm or more and 30 μm or less, and more preferably 10 μm or more and 20 μm or less. When the thickness of the resin layer 17 having a liquid crystal alignment surface is preferably 3 μm or more, the strength of the resin layer 17 can be improved. The tensile strength of the resin layer 17 is preferably 30 MPa or more. When the tensile strength of the resin layer 17 is 30 MPa or more, the mechanical strength of the resin layer 17 can be improved, and the durability against bending of the laminate 10 can be improved. become. On the other hand, when the thickness of the resin layer 17 is 30 μm or less, the transmittance of the resin layer 17 can be improved and the angle dependency of the transmittance of the resin layer 17 can be reduced. Is possible. For example, the transmittance of the resin layer 17 having a thickness of 200 μm with respect to ultraviolet rays having a wavelength of 360 nm is preferably 92% or more. In this case, the photopolymerizable monomer contained in the first liquid composition layer 12 can be more efficiently polymerized and cured by ultraviolet rays, and the yellowness of the resin layer 17 is reduced. It becomes possible.

  The cured resin layer 14 obtained by polymerizing the polymerizable monomer contained in the first liquid composition layer 12 is preferably transparent to visible light. In this case, it becomes possible to reduce or prevent the color of the resin layer 17 having a liquid crystal alignment surface.

  Furthermore, the cured resin layer 14 obtained by polymerizing and curing the first liquid composition is preferably one having an isotropic refractive index (no or little refractive index anisotropy). . In this case, it becomes possible to reduce or prevent the anisotropy of the refractive index due to the material of the resin layer 17 having the liquid crystal orientation surface. As a result, the retardation given to the polarized light transmitted through the laminate 10 by the structural birefringence provided by the resin layer 17 having a liquid crystal orientation surface and the refractive index anisotropy of the optically anisotropic resin layer 16 is more easily obtained. It becomes possible to control.

  The cured resin layer 14 is preferably an amorphous resin. In this case, it becomes possible to reduce or prevent crystallization of the optically anisotropic resin layer 16 provided on the resin layer 17 having a liquid crystal alignment surface.

  Further, the haze value of the resin layer 17 having a liquid crystal orientation surface is preferably 0.5 or less, and more preferably 0.1 or less. When the haze value of the resin layer 17 is 0.5 or less, the haze value of the stacked body 10 can be reduced.

  Next, the layer 15 of the second liquid composition is provided on the surface provided with a pattern for aligning liquid crystals in the resin layer 17 having a liquid crystal alignment surface. The second liquid composition is a cholesteric liquid crystalline and polymerization curable composition containing a liquid crystalline monomer and a chiral monomer.

Here, the liquid crystalline monomer is a compound having a polymerizable functional group and a mesogenic group. The polymerizable functional group is preferably the same group as the polymerizable functional group possessed by the polymerizable monomer contained in the first liquid composition. Preferably, it is an acryloyloxy group (CH ₂ ═CHCOO—), a methacryloyloxy group (CH ₂ ═C (CH ₃ ) COO—), a vinyl group, an allyl group, or a cyclic ether group, and more preferably an acryloyloxy group. Or it is a methacryloyloxy group.

  The mesogenic group contributes to the anisotropy of the liquid crystalline monomer. The mesogenic group is preferably a group containing at least one of an alicyclic hydrocarbon ring, an aromatic hydrocarbon ring and a heterocyclic ring. Moreover, when there are a plurality of rings contained in the mesogenic group, any of a ring directly bonded to each other and a ring indirectly bonded via a linking group may be used. The number of rings contained in the mesogenic group is preferably 2 or more and 4 or less, more preferably 2 or 3. When the number of rings contained in the mesogenic group is 2 or more, the liquid crystal properties of the liquid crystal monomer can be expressed more easily. On the other hand, when the number of rings contained in the mesogenic group is 4 or less, the melting point of the liquid crystalline monomer can be lowered. For this reason, when the second liquid composition is polymerized and cured, it is possible to reduce the precipitation of crystals of the liquid crystalline monomer. As a result, it becomes possible to reduce or prevent haze of the optically anisotropic resin layer 16.

  The liquid crystalline monomer is preferably a liquid crystalline monomer having at least two polymerizable functional groups. The liquid crystalline monomer having at least two polymerizable functional groups is a crosslinkable liquid crystalline monomer. For this reason, the liquid crystalline monomer and the chiral monomer contained in the second liquid composition can be polymerized and cured, and the cholesteric liquid crystal obtained from the liquid crystalline monomer and the chiral monomer can be crosslinked. As a result, the helical structure of the cholesteric liquid crystal in the optically anisotropic resin layer 16 can be further stabilized. In addition, the heat resistance and solvent resistance of the optically anisotropic resin layer 16 can be improved. For example, a further layer can be laminated on the optically anisotropic resin layer 16 using a solvent.

The liquid crystalline monomer is more preferably a liquid crystalline monomer having two polymerizable functional groups. As a liquid crystalline monomer having two polymerizable functional groups, for example, the following formula (A):
^{_{CH 2 = CR 1 -COO- (CH}} 2) m1 - (O) n1 -X-M-Y- (O) n2 - (CH 2) m2 -OCO-CR 2 = CH 2 ... (A)
In this case, the compound represented by
R ¹ and R ² are each independently a hydrogen atom or a methyl group,
m1 and m2 are each independently an integer of 0 to 12,
n1 is 0 when m1 is 0, and is 1 when m1 is an integer of 1 to 12,
n2 is 0 when m2 is 0, and is 1 when m2 is an integer of 1 to 12,
X and Y are each independently a single bond, —COO—, —OCO—, or —CO—;
M is a mesogenic group in which two or more rings are bonded directly or via a linking group.

  M1 and 2 are preferably each independently an integer of 1 to 12, more preferably an integer of 2 to 6.

As the liquid crystalline monomer represented by the above formula (A), for example,
^{_{CH 2 = CR 1 -COO- (CH}} 2) s O-Ph-COO-Ph-O (CH 2) t -OCO-CR 2 = CH 2,
^{_{CH 2 = CR 1 -COO- (CH}} 2) s O-Ph-Z 1 -Ph-Z 2 -Ph-O (CH 2) t -OCO-CR 2 = CH 2,
^{_{CH 2 = CR 1 -COO- (CH}} 2) s O-Ph-Ph-O (CH 2) t -OCO-CR 2 = CH 2,
^{_{CH 2 = CR 1 -COO- (CH}} 2) s O-Ph-C≡C-Ph-O (CH 2) t -OCO-CR 2 = CH 2,
^{_{CH 2 = CR 1 -COO- (CH}} 2) s O-COO-Ph-Z 1 -Ph-Z 2 -Ph-OCO-O (CH 2) t -OCO-CR 2 = CH 2, and CH ₂ = ^{_{CR 1 -COO- (CH 2) s}} O-CO-Ph-Z 1 -Ph-Z 2 -Ph-CO-O (CH 2) t -OCO-CR 2 = CH 2
In this case, the compound represented by
R ¹ and R ² are each independently a hydrogen atom or a methyl group,
s and t are each independently an integer of 1 to 12,
Z ¹ and Z ² are each independently a single bond, —COO—, —OCO—, or —CO—,
Ph is a 1,4-phenylene group which may be substituted with a methyl group or a methoxy group.

On the other hand, a chiral monomer is a compound having a polymerizable functional group and an asymmetric carbon center. The polymerizable functional group is preferably an acryloyloxy group (CH ₂ ═CHCOO—), a methacryloyloxy group (CH ₂ ═C (CH ₃ ) COO—), a vinyl group, an allyl group, or a cyclic ether group, and more Preferably, it is an acryloyloxy group or a methacryloyloxy group.

  Examples of the chiral monomer include a compound disclosed in JP-A-9-506088, a chiral compound disclosed in JP-A-2003-137878, and a chiral agent disclosed in JP-A-2007-169178.

  The chiral monomer is represented by, for example, the following formula I disclosed in JP2003-13787A

化合物が挙げられる。

Compounds.

    Examples of such compounds include, for example,

また、カイラル性モノマーは、例えば、特開２００７−１６９１７８に開示される、一般式（Ａ）

Further, the chiral monomer is represented by, for example, the general formula (A) disclosed in JP2007-169178A.

又は一般式（Ｂ）

Or general formula (B)

で表される化合物が挙げられる。

The compound represented by these is mentioned.

  Examples of such compounds include, for example,

が、挙げられる。

Is mentioned.

  The chiral monomer preferably includes a chiral monomer having two or more polymerizable functional groups. A chiral monomer having two or more polymerizable functional groups is a crosslinkable chiral monomer. For this reason, the liquid crystalline monomer and the chiral monomer contained in the second liquid composition can be polymerized and cured and crosslinked. As a result, the helical structure of the cholesteric liquid crystal in the optically anisotropic resin layer 16 can be further stabilized. In addition, the heat resistance and solvent resistance of the optically anisotropic resin layer 16 can be improved. For example, a further layer can be laminated on the optically anisotropic resin layer 16 using a solvent.

The ratio of the amount of the chiral monomer to the total amount of the liquid crystalline monomer and the chiral monomer is determined by the helical pitch of the cholesteric liquid crystal (or the selective reflection wavelength of the cholesteric liquid crystal) in the optical anisotropic resin layer 16 and the HTP ( Helical Twisting Power). Here, HTP of the chiral monomer is
HTP = (PC) ⁻¹
P represents the pitch (μm) of the cholesteric liquid crystal due to the chiral monomer, and C represents the concentration (mass%) of the chiral monomer in the second liquid composition 15 containing the chiral monomer (however, In the case where the second liquid composition contains a solvent, the concentration of the chiral monomer relative to the amount excluding the solvent). Therefore, the spiral pitch of the cholesteric liquid crystal (or the selective reflection wavelength of the cholesteric liquid crystal) in the optically anisotropic resin layer 16 is controlled by adjusting the ratio of the amount of the chiral monomer to the total amount of the liquid crystalline monomer and the chiral monomer. Is possible. For example, the helical pitch of the cholesteric liquid crystal can be adjusted so that the selective reflection wavelength of the cholesteric liquid crystal is in the ultraviolet region or the visible light region.

  Further, the HTP of the chiral monomer is preferably 20 or more. When the HTP of the chiral monomer is 20 or more, when obtaining the helical pitch of the cholesteric liquid crystal in the optically anisotropic resin layer 16, the ratio of the amount of the chiral monomer to the total amount of the liquid crystalline monomer and the chiral monomer Can be reduced. That is, the characteristics (such as the anisotropy of the refractive index) of the cholesteric liquid crystal in the optically anisotropic resin layer 16 can be improved more easily.

  The second liquid composition preferably contains at least one of a polymerization initiator and a surfactant. Examples of the polymerization initiator contained in the second liquid composition include a photopolymerization initiator contained in the first liquid composition. When the second liquid composition contains a polymerization initiator, the second liquid composition can be polymerized more efficiently. Examples of the surfactant contained in the second liquid composition include the surfactant contained in the first liquid composition. When the second liquid composition contains a surfactant, the liquid crystalline monomer and the chiral monomer can be more easily cholesterically aligned in the layer 15 of the second liquid composition.

  Next, in order to cholesterically align the liquid crystalline monomer and the chiral monomer in the second liquid composition layer 15, for example, the liquid crystal monomer liquid crystal is heated by heating the second liquid composition layer 15. The temperature of the second liquid composition layer 15 is maintained within the temperature range. Thereby, the liquid crystalline monomer and the chiral monomer contained in the layer 15 of the second liquid composition can be cholesterically aligned by the pattern for aligning the liquid crystal in the resin layer 17 having the liquid crystal aligning surface. For example, when the resin layer 17 having a liquid crystal orientation surface has a periodic uneven structure, the liquid crystalline monomer and the chiral monomer contained in the layer 15 of the second liquid composition have a helical axis, The cholesteric alignment is performed so that the resin layer 17 is in a direction substantially perpendicular to the bottom surface of the periodic concave portion (groove portion) of the resin layer 17. This makes it possible to reduce or prevent crystallization and orientation defects of the optically anisotropic resin layer 16. In addition, the selective reflection wavelength band of the cholesteric liquid crystal in the optically anisotropic resin layer 16 becomes clearer.

Next, the optically anisotropic resin layer 16 is formed by polymerizing and curing the cholesteric-aligned liquid crystalline monomer and the chiral monomer contained in the second liquid composition layer 15 while maintaining the alignment state. . This optically anisotropic resin layer 16 exhibits cholesteric liquid crystallinity. Here, when the liquid crystalline monomer and the chiral monomer are polymerized and cured, a crosslinking reaction may be accompanied. In order to form the optically anisotropic resin layer 16, for example, when the liquid crystalline monomer and the chiral monomer are respectively photopolymerizable monomers, a photopolymerizable monomer such as ultraviolet rays is polymerized and cured. The second liquid composition layer 15 is irradiated with possible light.
In order to improve the reaction yield of the liquid crystalline monomer and the chiral monomer contained in the second liquid composition, the layer 15 of the second liquid composition is preferably irradiated with light in a nitrogen atmosphere. The reaction yield of the liquid crystalline monomer and the chiral monomer contained in the second liquid composition is preferably 70% or more. When the reaction yield is 70% or more, it becomes possible to improve the heat resistance and solvent resistance of the optically anisotropic resin layer 16.

  The transmittance of the second liquid composition layer 15 having a thickness of 200 μm with respect to ultraviolet rays having a wavelength of 360 nm is preferably 92% or more. In this case, the liquid crystalline monomer and the chiral monomer contained in the second liquid composition layer 15 can be polymerized and cured more efficiently, and the yellowness of the optically anisotropic resin layer 16 can be reduced. It becomes possible to reduce.

  The optically anisotropic resin layer 16 thus obtained has an anisotropy of refractive index by cholesteric liquid crystal.

  The laminate 10 including the resin layer 17 having the liquid crystal orientation surface and the optically anisotropic resin layer 16 is obtained by the procedure as described above. 1 may further include removing the base material 11 from the resin layer 17 having a liquid crystal alignment surface provided with a pattern for aligning liquid crystallinity. In this case, the base material 11 is removed from the resin layer 17 having the liquid crystal orientation surface, thereby including the resin layer 17 not including the base material 11 and having the liquid crystal orientation surface, and the optically anisotropic resin layer 16. The laminated body 10 can be obtained. In this way, the thickness of the stacked body 10 can be reduced.

  Although not shown in FIG. 1, in the same manner as the resin layer 17 having a liquid crystal alignment surface, the optically anisotropic resin layer 16 has a liquid crystal alignment surface provided with a pattern for horizontally aligning liquid crystals. A resin layer is laminated. Further, similarly to the optically anisotropic resin layer 16, a layer containing a liquid crystalline polymer in which mesogens are horizontally aligned can be further laminated on the resin layer. In this case, the retardation of the laminate 10 can be further adjusted by a layer containing a liquid crystalline polymer in which mesogens are horizontally aligned.

  FIG. 3 is a diagram illustrating an example of an optical compensation element according to the third embodiment of the present invention.

  The optical compensation element 30 shown in FIG. 3 is an optical compensation element that optically compensates for at least a part of the refractive index anisotropy of an element having a refractive index anisotropy. The optical compensation element 30 shown in FIG. 3 includes the laminate 10 including the resin layer 17 having the liquid crystal alignment surface and the optically anisotropic resin layer 16 as shown in FIGS. 1 and 2. The optical compensation element 30 shown in FIG. 3 has two glass substrates 31 with antireflection films that sandwich the laminate 10 therebetween. Further, the optical compensation element 30 shown in FIG. 3 may include a horizontal alignment liquid crystal layer 32 including a liquid crystalline polymer in which mesogens are horizontally aligned between two glass substrates 31 with antireflection films.

  Here, the optical compensation element 30 shown in FIG. 3 compensates for at least a part of the refractive index anisotropy of the element having refractive index anisotropy by the refractive index anisotropy of the optically anisotropic resin layer 16. Is possible. In addition, the optical compensation element 30 shown in FIG. 3 has a refractive index anisotropy of an element having a refractive index anisotropy when the resin layer 17 having a liquid crystal orientation surface has a structural birefringence. It is also possible to compensate at least a part by the structural birefringence of the resin layer 17. Furthermore, when the optical compensation element 30 shown in FIG. 3 includes the horizontal alignment liquid crystal layer 32, at least a part of the refractive index anisotropy of the element having the refractive index anisotropy is reduced in the horizontal alignment liquid crystal layer 32. It is also possible to compensate by the anisotropy of the refractive index.

  In particular, the optical compensation element 30 shown in FIG. 3 includes the laminate 10 including the optically anisotropic resin layer 16 having a smaller tilt as shown in FIGS. 1 and 2, so that the asymmetry of retardation with respect to vision is reduced. It is possible to provide a compensated or prevented optical compensation element.

  FIG. 4 is a diagram illustrating an example of a liquid crystal device according to the fourth embodiment of the present invention.

  The liquid crystal device 40 shown in FIG. 4 is a liquid crystal device including a layer containing liquid crystal, and further includes an optical compensation element 30 as shown in FIG. A liquid crystal device 40 shown in FIG. 4 is a liquid crystal display device, and includes a VA (vertical alignment) liquid crystal cell 41. In addition, the liquid crystal device 40 includes a polarizing plate 42 as two polarizers, and the two polarizing plates 42 are arranged so that the polarization axes of the two polarizing plates 42 are orthogonal to each other. . In the liquid crystal device 40, the optical compensation element 30 and the VA liquid crystal cell 41 are provided between two polarizing plates 42.

  Here, the VA liquid crystal cell 41 includes a nematic liquid crystal layer containing substantially rod-like nematic liquid crystal molecules, two transparent electrodes for applying a voltage to the nematic liquid crystal layer, for example, a direction perpendicular to the surfaces of the two transparent electrodes. Has an alignment film for aligning the major axis of the substantially rod-like nematic liquid crystal molecules. That is, in the VA liquid crystal cell 41, when no voltage is applied to the nematic liquid crystal layer, the major axes of the rod-like nematic liquid crystal molecules are aligned in a direction perpendicular to the surfaces of the two transparent electrodes. On the other hand, when a voltage is applied to the nematic liquid crystal layer, the major axes of the substantially rod-like nematic liquid crystal molecules are aligned in a horizontal direction with respect to the surfaces of the two transparent electrodes. Thus, in the VA liquid crystal cell 41, the orientation of the nematic liquid crystal molecules varies by switching (turning on / off) the voltage applied to the nematic liquid crystal layer.

  Here, when no voltage is applied to the nematic liquid crystal layer, the polarized light incident in the direction perpendicular to the surfaces of the two transparent electrodes and passing through one polarizing plate 42 is perpendicular to the surfaces of the two transparent electrodes. Is transmitted through a nematic liquid crystal layer containing substantially rod-shaped nematic liquid crystal molecules oriented in the direction of. At this time, the refractive index (refractive index in the x direction and y direction perpendicular to the z direction) of the nematic liquid crystal layer in a plane perpendicular to the traveling direction (z direction) of the polarized light that has passed through one polarizing plate 42 is: Since it is generally isotropic, the polarized light that has passed through one polarizing plate 42 passes through the VA liquid crystal cell 41 without substantially changing the vibration plane of the polarized light. Then, the polarized light that has passed through the VA liquid crystal cell 41 is blocked by the other polarizing plate 42 having a polarization axis orthogonal to the polarization axis of the one polarizing plate 42. That is, since the light incident on the liquid crystal device 40 is substantially blocked, the liquid crystal device 40 looks dark.

  On the other hand, when a voltage is applied to the nematic liquid crystal layer, the polarized light that has passed through one polarizing plate 42 is nematic liquid crystal containing approximately rod-shaped nematic liquid crystal molecules that are horizontal and oriented in a specific direction on the surfaces of the two transparent electrodes. Permeate the layer. At this time, the refractive index (refractive index in the x direction and y direction perpendicular to the z direction) of the nematic liquid crystal layer in a plane perpendicular to the traveling direction (z direction) of the polarized light that has passed through one polarizing plate 42 is: Since it has anisotropy in a specific direction, when the polarized light passing through one polarizing plate 42 passes through the VA liquid crystal cell 41, the vibration plane of the polarized light is rotated by nematic liquid crystal molecules. A part of the polarized light that has passed through the VA liquid crystal cell 41 passes through the other polarizing plate 42 without being blocked by the other polarizing plate 42 having a polarization axis orthogonal to the polarization axis of the one polarizing plate 42. . That is, a part of the light incident on the liquid crystal device 40 passes through the liquid crystal device 40, so that the liquid crystal device 40 looks bright.

  By the way, when no voltage is applied to the nematic liquid crystal layer, the polarized light incident in a direction oblique to the normal line of the surfaces of the two transparent electrodes and passed through one polarizing plate 42 is included in the nematic liquid crystal layer. Since the shape of the liquid crystal molecules is approximately rod-shaped, the refractive index of the nematic liquid crystal layer in the plane perpendicular to the direction of travel of polarized light that has passed through one polarizing plate 42 has anisotropy. For this reason, when polarized light incident in a direction oblique to the normal line of the surface of the two transparent electrodes and passed through one polarizing plate 42 passes through the VA liquid crystal cell 41, the plane of vibration of the polarized light is nematic. Rotated by liquid crystal molecules. A part of the polarized light incident in a direction oblique to the normal line of the surface of the two transparent electrodes and passed through the VA liquid crystal cell 41 passes through the other polarizing plate 42. That is, part of the light incident on the liquid crystal device 40 obliquely passes through the liquid crystal device 40, so that the liquid crystal device 40 does not look sufficiently dark.

  Here, the liquid crystal device 40 shown in FIG. 4 includes the layer 17 having a liquid crystal alignment surface and the optically anisotropic resin layer 16 included in the optical compensation element 30. In the liquid crystal device 40, the optically anisotropic resin layer 16 included in the optical compensation element 30 has a spiral axis of the cholesteric liquid crystalline polymer in a direction perpendicular to the surfaces of the two transparent electrodes of the VA liquid crystal cell 41. It is provided so as to be oriented. Here, when no voltage is applied to the nematic liquid crystal layer in the VA liquid crystal cell 41, the anisotropy of the refractive index of the nematic liquid crystal layer containing approximately rod-shaped nematic liquid crystal molecules aligned in the direction perpendicular to the surfaces of the two transparent electrodes. Is at least partially compensated by the anisotropy of the refractive index of the optically anisotropic resin layer 16 having a helical axis oriented in a direction perpendicular to the surfaces of the two transparent electrodes of the VA liquid crystal cell 41. For this reason, when the polarized light incident in a direction oblique to the normal line of the surface of the two transparent electrodes and passed through one polarizing plate 42 passes through the VA liquid crystal cell 41, the polarization vibration plane rotates. It can be reduced or prevented. As a result, the polarized light incident in a direction oblique to the normal line of the surface of the two transparent electrodes and passed through one polarizing plate 42 is also more efficiently blocked by the other polarizing plate 42. Become. That is, the light incident obliquely on the liquid crystal device 40 is also more effectively blocked, so that the liquid crystal device 40 appears sufficiently dark.

  Further, in the optical compensation element 30 included in the liquid crystal device 40, the optically anisotropic resin layer 16 is provided on the layer 17 having the liquid crystal alignment surface. The tilt of the cholesteric liquid crystal with respect to the layer 17 having the surface is reduced or prevented. For this reason, the asymmetry of the retardation of the optical compensation element 30 with respect to vision is reduced or prevented. As a result, when no voltage is applied to the nematic liquid crystal layer in the VA liquid crystal cell 41, the refractive index anisotropy of the nematic liquid crystal layer containing approximately rod-shaped nematic liquid crystal molecules aligned in a direction perpendicular to the surfaces of the two transparent electrodes. By the anisotropy of the refractive index of the optically anisotropic resin layer 16 in which the tilt is reduced or prevented (in other words, the refraction of the optical compensation element 30 in which the asymmetry of retardation with respect to vision is reduced or prevented). The rate anisotropy) makes it possible to compensate more effectively.

  Further, in the liquid crystal device shown in FIG. 4, one optical compensation element 30 is provided on one side of the VA liquid crystal cell 41, but two optical compensation elements 30 may be provided on both sides of the VA liquid crystal cell 41. . In this case, the liquid crystal device 40 can be more easily manufactured by sandwiching the VA liquid crystal cell 41 between two pairs of one polarizing plate 42 and one optical compensation element 30.

  In this way, the liquid crystal device 40 shown in FIG. 4 further includes the optical compensation element 30 as shown in FIG. 3, and thus provides the liquid crystal device 40 in which fluctuations in optical characteristics with respect to vision are reduced or prevented. It becomes possible to do.

  Further, in the liquid crystal device 40 shown in FIG. 4, the two polarizing plates 42 may be made of a stretched resin. In this case, each of the two polarizing plates 42 has refractive index anisotropy. In the liquid crystal device 40 shown in FIG. 4, when the resin layer 17 having a liquid crystal alignment surface included in the optical compensation element 30 has structural birefringence, the refractive index of at least one of the two polarizing plates 42 is reduced. Anisotropy can be compensated by the structural birefringence of the resin layer 17 having a liquid crystal orientation surface.

  That is, when the resin layer 17 having the liquid crystal alignment surface has structural birefringence, the refractive index anisotropy variation of the nematic liquid crystal layer of the VA liquid crystal cell 41 with respect to vision and the two polarizing plates 42 The anisotropy of at least one refractive index is caused by the optically anisotropic resin layer 16 and the resin layer 17 having a liquid crystal orientation surface, that is, two layers (optically anisotropic resin included in the optical compensation element 30). The layer 16 and the resin layer 17) having a liquid crystal aligning surface allow at least partial compensation. As a result, the thickness of the optical compensation element 30 in the liquid crystal device 40 can be reduced.

  Next, examples of the present invention will be specifically described. The liquid crystal monomer and the chiral monomer used in this example are both bifunctional monomers.

[Preparation example of liquid crystalline monomer solution]
[Preparation Example 1]
According to the ratio shown in Table 1, a liquid crystalline monomer solution (c-1) was prepared. Here, in the liquid crystal monomer solution (c-1), a chiral monomer (CNL-713 manufactured by ADEKA) (HTP: 29.75) is added to 85 parts by mass of the liquid crystal monomer (PLC-7285 manufactured by ADEKA). 2) 15 parts by mass, 4 parts by mass of a photoinitiator (ADEKA 1919), 0.2 parts by mass of a surfactant (Seimi Chemical Co., S420), and 300 parts by mass of toluene were added. .

[Preparation Example 2]
A liquid crystalline monomer solution (c-2) was obtained in the same manner as in Preparation Example 1 according to the ratio shown in Table 1, except that CNL-716 (HTP: 25.8) manufactured by ADEKA was used as the chiral monomer.

[Preparation Example 3]
8 parts by mass of chiral monomer (LC-756 manufactured by BASF) (HTP: 54.8) and 92% by mass of liquid crystalline monomer (LC-242 manufactured by BASF) and a photopolymerization initiator (BASF) Using 4 parts by mass of Ir184), a liquid crystal monomer solution (c-3) was obtained in the same manner as in Preparation Example 1 according to the ratio shown in Table 1.

［光重合性モノマー組成物の調製］
［調製例４］
撹拌機及び冷却管を装着した３００ｍＬの４つ口フラスコに、６５ｇのビスフェノールＡ型エポキシアクリレート（新中村化学工業社製、ＮＫ オリゴ ＥＡ−１０２０）、３５ｇのヘキサンジアクリレート（新中村化学工業社製、ＮＫ エステル Ａ−ＨＤＮ）、５．０ｇの光重合開始剤（チバスペシャリティーケミカルズ社製、ＩＲＧＡＣＵＲＥ１８４）、１．５ｇの界面活性剤（セイミケミカル社製、Ｓ４２０）、１．０ｇの重合禁止剤（和光純薬社製、Ｑ１３０１）、及び１００ｇのトルエンを投入した。フラスコの内部を常温に保ち、遮光した状態で、１時間撹拌して、光重合性モノマー組成物を得た。この組成物の２５℃における粘度は、２０ｍＰａ・秒であった。

[Preparation of Photopolymerizable Monomer Composition]
[Preparation Example 4]
In a 300 mL four-necked flask equipped with a stirrer and a condenser, 65 g of bisphenol A type epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Oligo EA-1020), 35 g of hexane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) NK ester A-HDN), 5.0 g photopolymerization initiator (manufactured by Ciba Specialty Chemicals, IRGACURE 184), 1.5 g surfactant (manufactured by Seimi Chemical Co., S420), 1.0 g polymerization inhibitor (Wako Pure Chemical Industries, Q1301) and 100 g of toluene were added. The inside of the flask was kept at room temperature and stirred for 1 hour in a light-shielded state to obtain a photopolymerizable monomer composition. The viscosity of this composition at 25 ° C. was 20 mPa · sec.

[Example 1]
By sequentially performing the following steps [a], [b], and [c], the laminate 10 having the resin layer 17 having the liquid crystal orientation surface and the optically anisotropic resin layer 16 on the transparent substrate. Got.

[A] Production of first liquid composition layer 12 The photopolymerizable monomer composition (first liquid composition) obtained in Preparation Example 4 was applied to the surface of a transparent glass substrate by spin coating. A first liquid composition layer was prepared.

[B] Production of Resin Layer 17 Having Liquid Crystal Orientation Surface The rubbing-treated PET substrate was pressed onto the first liquid composition layer obtained in step [a]. In step [b], the arrangement of the PET substrate relative to the transparent substrate was adjusted so that the side of the transparent substrate and the rubbing direction of the PET substrate were substantially horizontal.

  Next, the first liquid composition is cured by irradiating ultraviolet rays having an intensity of 700 mJ at room temperature while keeping the PET substrate pressed against the first liquid composition layer. A layer was formed. Next, the PET substrate is peeled from the cured resin layer to expose the surface that is in contact with the PET substrate to form a liquid crystal alignment surface, and a resin having a liquid crystal alignment surface composed of the cured resin A layer was made. The thickness of the resin layer having the liquid crystal orientation surface was 8.5 μm.

[C] Production of optically anisotropic resin layer 16 The second liquid composition (liquid crystalline monomer solution (c-1)) was applied to the surface of a resin layer having a liquid crystal orientation surface by spin coating, and 70 ° C. For 3 minutes. By performing this treatment, the liquid crystalline monomer and the chiral monomer contained in the second liquid composition have a helical axis perpendicular to the surface of the transparent substrate on the layer having the liquid crystal orientation surface. Cholesteric orientation.

Then, the optically anisotropic resin layer was produced by irradiating ultraviolet rays with an illuminance of 260 mW / cm ² at room temperature for 3 minutes in a nitrogen atmosphere to perform photopolymerization (crosslinking) of the liquid crystalline monomer composition.

  Thus, by performing the operations of steps [a], [b], and [c], a resin layer having a liquid crystal orientation surface and an optically anisotropic resin layer are laminated in this order on the transparent substrate. Thus obtained laminate 1 was obtained.

[Example 2]
A laminate 2 was produced in the same manner as in Example 1 except that in the step [c], the liquid crystalline monomer solution (c-2) was used instead of the liquid crystalline monomer solution (c-1).

[Example 3]
A laminate 3 was produced in the same manner as in Example 1 except that the liquid crystalline monomer solution (c-3) was used in place of the liquid crystalline monomer solution (c-1) in the step [c].

[Example 4]
A laminate 4 was produced in the same manner as the laminate 3 except that the mold A was used instead of the rubbed PET substrate in the step [b]. Here, the mold A had a rectangular pattern as shown in FIG. For mold A, P, L, and H shown in FIG. 2 were 150 nm, 100 nm, and 200 nm, respectively.

  Tables 4 and 5 show the film thickness, haze value, retardation value (R0, R + 30, R-30) and the like of the laminates 1 to 4 obtained in Examples 1 to 4, respectively.

  R0 is a retardation value when light having a wavelength of 589 nm is vertically incident on the sample. R + 30 is a retardation value when light having a wavelength of 589 nm is incident on the sample from a direction inclined at an angle of 30 ° with respect to the vertical. R-30 is a retardation value when light having a wavelength of 589 nm is incident on the sample obliquely from the vertical (however, from the opposite side to R + 30) from a direction inclined by 30 °.

その結果、波長５８９ｎｍにおける積層体１〜３のＲ０が１以下であり、かつＲ＋３０およびＲ−３０が２５±１であり、積層体１〜３は、光学補償板として機能することが確認された。

As a result, it was confirmed that R0 of the laminated bodies 1 to 3 at a wavelength of 589 nm was 1 or less, R + 30 and R-30 were 25 ± 1, and the laminated bodies 1 to 3 functioned as optical compensation plates. .

  Moreover, R0 of the laminated body 4 in wavelength 589nm is 5 +/- 1 and R + 30 and R-30 are 25 +/- 1 and it was confirmed that the laminated body 4 functions as an optical compensator.

[High temperature and high humidity test]
The laminates 1 to 4 were subjected to a high temperature and high humidity test. Even after 1000 hours had passed after placing in an oven set at 60 ° C. and 90% RH, no significant change in haze value or retardation value was observed in any of the laminates.

  The embodiments and examples of the present invention have been specifically described above with reference to the drawings. However, the present invention is not limited to any of these embodiments and examples. The embodiments can be modified, changed or combined without departing from the scope of the invention.

DESCRIPTION OF SYMBOLS 10 Laminated body 11 Base material 12 Layer of 1st composition 13 Mold 14 Layer of cured resin 17 Resin layer which has liquid crystal aligning surface 15 Layer of 2nd liquid composition 16 Optical anisotropic resin layer 30 Optical compensation element 31 Glass substrate 32 Horizontal alignment liquid crystal layer 40 Liquid crystal device 41 VA liquid crystal cell 42 Polarizing plate

Claims (11)

In a method for producing a laminate including a resin layer having a liquid crystal orientation surface and an optically anisotropic resin layer,
Providing a layer of a first curable liquid composition on the substrate;
Pressing a mold having a reversal pattern of liquid crystal alignment pattern against the first liquid composition layer;
Forming a cured resin layer by polymerizing and curing the first liquid composition in a state in which the mold is pressed against the first liquid composition layer;
By removing the mold from the cured resin layer, the surface that is in contact with the mold is exposed to form the liquid crystal aligning surface, and the resin layer having the liquid crystal aligning surface is made of the cured resin. To get the
Providing a layer of a cholesteric liquid crystallinity and polymerization curable second liquid composition containing a liquid crystal monomer and a chiral monomer on the liquid crystal orientation surface of the resin layer;
Aligning the second liquid composition on the liquid crystal aligning surface; and
A method for producing a laminate, comprising polymerizing and curing the second liquid composition in the oriented state to obtain an optically anisotropic resin layer. In the method for producing the laminate according to claim 1,
The method for producing a laminate, wherein the cured resin has an isotropic refractive index. In the method for producing the laminate according to claim 1 or 2,
The method for producing a laminate, wherein the liquid crystalline monomer includes a liquid crystalline monomer having two or more polymerizable functional groups. In the method for producing a laminate according to any one of claims 1 to 3,
The method for producing a laminate, wherein the chiral monomer includes a chiral monomer having two or more polymerizable functional groups. In the method for producing a laminate according to any one of claims 1 to 4,
The method for producing a laminate, wherein the chiral monomer has a helical induction force of 20 or more. In the method for producing a laminate according to any one of claims 1 to 5,
The method for producing a laminate, wherein the resin layer having a liquid crystal alignment surface has structural birefringence given by a pattern for aligning the liquid crystal polymer.   It manufactures by the method of manufacturing the laminated body as described in any one of Claim 1-6, The laminated body characterized by the above-mentioned.   Polymerization of a resin layer having a liquid crystal orientation surface formed by transfer with a mold, and a liquid composition having a cholesteric liquid crystallinity and polymerization curability, which is oriented on the liquid crystal orientation surface and polymerized and cured in the orientation state. A laminated body comprising an optically anisotropic resin layer made of a cured product. The laminate according to claim 8, wherein
A laminate having structural birefringence given by the shape of the liquid crystal orientation surface, the refractive index of the resin layer having the liquid crystal orientation surface, and the refractive index of the optically anisotropic resin layer. In an optical compensation element for optically compensating at least a part of the anisotropy of the refractive index of an element having an anisotropy of refractive index,
An optical compensation element comprising the laminate according to any one of claims 7 to 9. In a liquid crystal device including a layer containing a liquid crystal,
A liquid crystal device further comprising the optical compensation element according to claim 10.

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