JP2011128498A - Laminated body and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated body which has improved solvent resistance and water resistance, and also to provide a method of manufacturing the laminated body. <P>SOLUTION: The laminated body includes a uniaxially-oriented transparent base material. The transparent resin layer and a polymer liquid crystal layer. The transparent resin layer includes a face (a) which is made contact to the polymer liquid crystal layer, the face (a) has a liquid crystal alignment formed by the translation of a mold surface, the polymer liquid crystal layer is a polymer liquid crystal layer formed by the polymerization of the liquid crystal monomer aligned in contact with the face (a) or the cross-link of a cross-linkable polymer liquid crystal aligned in contact with the face (a), the optical axis of the uniaxially-oriented transparent base material and the alignment direction of the polymer liquid crystal of the polymer liquid crystal layer are different from each other. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a laminate and a method for producing the same.

  Several techniques have been disclosed for the laminate. For example, Patent Document 1 discloses a substantially visible light substantially composed of a liquid crystalline compound on a retardation film having a retardation value of substantially a half wavelength of visible light formed by stretching a transparent polymer film. A composite retardation plate in which a birefringent layer having a retardation value of ¼ wavelength is formed is disclosed. Patent Document 2 includes a liquid crystalline compound on a retardation film having a retardation value of ¼ wavelength or ½ wavelength of visible light obtained by stretching a transparent polymer film. A composite in which a birefringent layer having a retardation value of substantially a quarter wavelength of visible light and at least one birefringent layer having a retardation value of a half wavelength of visible light is formed. A phase difference plate is disclosed.

  In these retardation plates, an alignment film is used to align the liquid crystal. A polyimide-based alignment film is well known as the alignment film. However, since a polyimide-based alignment film is formed using an organic solvent, when applied to a uniaxially stretched film having generally low solvent resistance, the retardation of the uniaxially stretched film changes. Therefore, an alignment film made of a water-soluble material such as PVA (polyvinyl alcohol) is used, but there are problems in the water resistance and optical characteristics of the laminate. Further, since the rubbing technique is used, there are problems such as alignment defects due to foreign matters such as dust.

  Also, some techniques have been disclosed regarding the liquid crystal alignment method or the liquid crystal molecular alignment method. For example, Patent Document 3 discloses a liquid crystal alignment method characterized by aligning a liquid crystal sandwiched between substrates by adhering a uniaxial member to at least one substrate and removing it later. The liquid crystal alignment method, wherein the uniaxial member is brought into close contact with an organic film, and the uniaxial member is a member subjected to a rubbing treatment. And a liquid crystal device manufactured using the above-mentioned liquid crystal alignment method are disclosed.

  Further, for example, in Patent Document 4, in a liquid crystal molecular alignment method in which liquid crystal molecular alignment is performed without directly rubbing the substrate, (a) a substrate and a member having liquid crystal molecular alignment are made of acrylate (methacrylate). And (b) from the upper surface and / or the lower surface of the member having liquid crystal molecular orientation, so that the system energy ray curable resin composition is sandwiched in contact with the surface having liquid crystal molecular orientation of the member. A method of aligning liquid crystal molecules, a step of irradiating energy rays, and a step of (c) peeling a member having liquid crystal molecular alignment and aligning liquid crystal molecules, and extending a member having liquid crystal molecular alignment The liquid crystal molecular alignment method, which is a resin film, a rubbing resin film, or a resin film that has been irradiated with linearly polarized light to have anisotropy on the surface, has an acrylate (meth) Acrylate) type energy ray curable resin laminate having a liquid crystal molecular orientation transfer layer, etc., it is disclosed.

JP 2002-372622 A JP 2002-372623 A JP-A-6-43458 JP-A-8-313910

  An object of the present invention is to provide a laminate having improved solvent resistance and water resistance and a method for producing the same.

  The laminate according to one embodiment of the present invention is a laminate including a uniaxially oriented transparent base material, a transparent resin layer, and a polymer liquid crystal layer, and the transparent resin layer is in contact with the polymer liquid crystal layer ( a), the surface (a) is a surface having liquid crystal alignment formed by transfer of the mold surface, and the polymer liquid crystal layer is a liquid crystalline monomer aligned in contact with the surface (a) Or a polymer liquid crystal layer formed by crosslinking of a crosslinkable polymer liquid crystal aligned in contact with the surface (a), the optical axis of the uniaxially oriented transparent substrate, and the polymer liquid crystal layer The orientation direction of the polymer liquid crystal is different.

  The manufacturing method of the laminated body which concerns on 1 aspect of this invention is a manufacturing method of the laminated body which has a uniaxially oriented transparent base material, a transparent resin layer, and a polymer liquid crystal layer, Comprising: (1) Said uniaxially oriented A step of forming a layer of a curable resin composition on one surface of a transparent substrate, and (2) pressing a mold having a reverse pattern of a pattern for aligning liquid crystal on the surface of the layer of the curable resin composition. (3) a step of curing the curable resin composition into a transparent resin in a state where the layer of the curable resin composition and the surface of the mold are in contact with each other; and (4) the mold. Peeling and forming a transparent resin layer having a surface (a) having liquid crystal orientation; and (5) forming a liquid crystalline monomer layer on the surface (a) to form the liquid crystalline monomer. Align the liquid crystalline monomer in a state where the liquid crystalline monomer is aligned. Or forming a cross-linkable polymer liquid crystal layer by forming a cross-linkable polymer liquid crystal layer, aligning the cross-linkable polymer liquid crystal, and cross-linking the cross-linkable polymer liquid crystal; and The direction of the optical axis of the uniaxially oriented transparent base material is different from the orientation direction of the surface (a).

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the laminated body which aimed at the improvement of solvent resistance and water resistance, and its manufacturing method.

It is a figure which represents roughly an example of the manufacturing method of the laminated body 10 which concerns on one Embodiment of this invention. It is a disassembled perspective view showing the laminated body 10 which concerns on one Embodiment of this invention.

Next, embodiments of the present invention will be described with reference to the accompanying drawings.
Drawing 1 is a figure showing an example of a manufacturing method of a layered product concerning one embodiment of the present invention. FIG. 2 is an exploded perspective view showing the laminate 10 manufactured by the manufacturing method of FIG. The laminate 10 functions as a wave plate (for example, a half-wave plate or a quarter-wave plate), and converts the polarization state of light (for example, from linearly polarized light (circularly polarized light) to circularly polarized light (linearly polarized light). Conversion). The laminate 10 is configured by laminating a uniaxially oriented transparent base material 11 (hereinafter simply referred to as a uniaxially oriented base material), a transparent resin layer 12, and a polymer liquid crystal layer 13 in that order.

  The uniaxially oriented base material 11 and the polymer liquid crystal layer 13 have optical anisotropy about the directions A1 and A2, respectively, and function as wave plates. By laminating a plurality of wave plates, it is possible to widen the wave plate. As a result, for example, linearly polarized light (circularly polarized light) can be converted to circularly polarized light (linearly polarized light) in a wide wavelength range from about 400 nm (blue) to about 800 nm (red). As an example, the retardation is (a) a combination of a uniaxially oriented substrate 11 having a quarter wavelength (λ / 4) and a polymer liquid crystal layer 13 having a half wavelength (λ / 2), or (b) λ / By combining the two uniaxially oriented base materials 11 and the λ / 4 polymer liquid crystal layer 13, a broadband quarter-wave plate can be obtained. At this time, the angle θ between the directions A1 and A2 is preferably, for example, 60 ° ± 10 ° (50 ° to 70 °), and more preferably 60 ° ± 5 ° (55 ° to 65 °).

  The transparent resin layer 12 has a pattern G for imparting anisotropy to the polymer liquid crystal layer 13. As will be described later, the polymer liquid crystal in the polymer liquid crystal layer 13 is aligned along the pattern G. That is, the direction of the pattern G corresponds to the alignment direction A2 of the polymer liquid crystal layer 13. As will be described later, the pattern G is, for example, an aggregate of substantially groove-shaped patterns, and the polymer liquid crystal is aligned along the substantially groove-shaped.

  As shown in FIG. 1, the laminated body 10 is manufactured as follows. That is, a layer 121 of curable resin is formed on the uniaxially oriented substrate 11 (FIG. 1A). A mold M having a reverse pattern of the pattern G on its surface is pressed against the surface of the curable resin layer 121. Next, in a state where the layer 121 of the curable resin is in contact with the surface of the mold M, the curable resin is cured to form the transparent resin 12 (FIGS. 1B to 1D). Thereafter, a polymer liquid crystal layer 13 is formed on the transparent resin layer 12 (FIG. 1E). The details will be described below.

A. Preparation of Uniaxially Oriented Substrate 11 The uniaxially oriented substrate 11 has an optical axis in the direction A1 as described above, and the retardation value is controlled.

  The uniaxially oriented substrate 11 is preferably made of a polymer film. The polymer film is formed from a polymer that can impart optical anisotropy. Examples of such a polymer include polyolefin (eg, polyethylene, polypropylene, cyclopolyolefin, norbornene polymer), polycarbonate, polyvinyl chloride, polystyrene, polyacrylonitrile, polysulfone, polyarylate, polyvinyl alcohol, and cellulose ester. Further, homopolymers and copolymers of acrylic monomers (acrylic acid esters, acrylic acid, etc.) and methacrylic monomers (methacrylic acid esters, methacrylic acid, etc.) are also included. A mixture of these polymers can also be used.

  The polymer film is preferably produced by a solvent cast method or a melt extrusion method in order to reduce unevenness in birefringence. In addition, the thickness of the polymer film is preferably 20 to 500 μm, more preferably 50 to 200 μm, and more preferably 50 to 100 μm, from the relationship between the need for thinning the wave plate and the mechanical strength of the film. Most preferably it is.

  The optical anisotropy of the uniaxially oriented substrate 11 is preferably obtained by stretching a polymer film or the like. The stretching is preferably uniaxial stretching. Uniaxial stretching is preferably longitudinal uniaxial stretching using a difference in peripheral speed between two or more rolls or tenter stretching in which both sides of a polymer film are gripped and stretched in the width direction.

  When targeting retardation of λ / 2, for example, the retardation value of the uniaxially oriented substrate 11 at a specific wavelength (λ) of 550 nm is preferably 240 to 290 nm, and more preferably 250 to 280 nm. . When targeting λ / 4, for example, the retardation value of the uniaxially oriented substrate 11 at a specific wavelength (λ) of 550 nm is preferably 110 to 145 nm, and more preferably 120 to 140 nm. In addition, you may satisfy the optical conditions of the uniaxially oriented base material 11 whole using two or more polymer films.

  The uniaxially oriented substrate 11 preferably has a small retardation wavelength dependency. For example, it is preferable that the ratio R450 / R550 between the retardation value R450 at 450 nm and the retardation value R550 at 550 nm is small (as close to 1 as possible).

  In addition, as the uniaxially oriented substrate 11, a commercially available film can be used. For example, as a cyclopolyolefin resin film, ZEONOR (manufactured by ZEON Corporation), ARTON (manufactured by JSR Corporation), ESINA (manufactured by Sekisui Chemical Co., Ltd.), F1 film (manufactured by Gunze Corporation), etc. can be used. . As the polycarbonate resin film, Pure Ace (manufactured by Teijin Chemicals Ltd.) can be used.

B. Formation of resin layer 12 (see FIGS. 1A to 1D)
A transparent resin layer 12 having a pattern G for aligning liquid crystals is formed on the uniaxially oriented substrate 11. This process can be divided into the following (1) to (4).

(1) Formation of layer 121 of curable resin composition on uniaxially oriented substrate 11 (see FIG. 1A)
A layer 121 of a curable resin composition (for example, an ultraviolet curable resin composition) is provided on the uniaxially oriented substrate 11. For example, a curable resin is applied to the uniaxially oriented substrate 11. Examples of this 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.

  The viscosity of the curable resin composition at 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 layer 121 of the curable resin composition having a smooth surface can be more easily formed by means such as spin coating. In addition, the viscosity of the curable resin composition is measured at a temperature of 25 ° C. using a rotary viscometer. The viscosity can be adjusted by diluting the curable resin composition with a solvent.

  The curable resin composition preferably includes a polymerizable compound having a plurality of polymerizable groups. In this case, the layer of the curable resin composition can be more easily cured to a desired hardness.

  The curable resin composition is preferably a photocurable resin composition. The photocurable resin composition is preferably a composition comprising a compound having an addition polymerizable unsaturated group (for example, a functional ultraviolet 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. For example, the photopolymerizable composition contains 99% by mass to 90% by mass of a photopolymerizable compound and 1% by mass to 10% by mass of a photopolymerization initiator.

  Here, the photopolymerizable monomer as the photopolymerizable compound is preferably a monomer having an acryloyl group or a methacryloyl group, a monomer having a vinyl group, a monomer having an allyl group, or a monomer having a cyclic ether group, and more preferably. Is a monomer having an acryloyl group or a methacryloyl group.

  Further, the number of polymerizable groups in the photopolymerizable monomer is preferably 1 or more and 6 or less, more preferably 2 or 3, and particularly preferably 2. When the number of polymerizable groups in the photopolymerizable monomer is 2, the polymerization shrinkage when this monomer is polymerized is not so large. For this reason, the transfer accuracy of the pattern of the mold M onto the transparent resin layer 12 is improved.

  The ratio of the photopolymerizable monomer having two or more polymerizable groups in the photopolymerizable monomer contained in the photopolymerizable composition is preferably 30% by mass or more. In this case, a transparent resin layer 12 (polymer) having good solvent resistance and / or heat resistance is obtained. Then, a transparent resin layer 12 having a pattern G for aligning liquid crystals on the surface thereof, a solution containing a liquid crystalline monomer described later, a solution containing a crosslinkable polymer liquid crystal (hereinafter collectively referred to as a polymerizable liquid crystal material solution). Can be reduced or prevented from dissolving the transparent resin layer 12 in the polymerizable liquid crystal material solution. Furthermore, when the polymerizable liquid crystal material solution is heated to control the alignment of the liquid crystal, the change in the state of the transparent resin layer 12 can be reduced or prevented.

  Here, the photopolymerizable monomer is preferably acrylic acid (methacrylic acid), acrylate (methacrylate), acrylamide (methacrylamide), vinyl ether, vinyl ester, allyl ether, allyl ester, or a styrenic compound, and particularly preferably. Is acrylate (methacrylate).

  Specific examples of the acrylate (methacrylate) include (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), tetrahydrofurfuryl acrylate (methacrylate), allyl acrylate (methacrylate), 2-hydroxyethyl acrylate (methacrylate), 2-hydroxypropyl acrylate (methacrylate), N N-diethylaminoethyl acrylate (methacrylate) N, N-dimethylaminoethyl acrylate (methacrylate), dimethylaminoethyl acrylate (methacrylate), methyladamantyl acrylate (methacrylate), ethyladamantyl acrylate (methacrylate), hydroxyadamantyl acrylate (methacrylate), adamantyl acrylate (methacrylate), isobornyl Monoacrylate (methacrylate) such as acrylate (methacrylate), (B) 1,3-butanediol diacrylate (methacrylate), 1,4-butanediol diacrylate (methacrylate), 1,6-hexanediol diacrylate (methacrylate) ), Diethylene glycol diacrylate (methacrylate), triethylene glycol diacrylate ( Acrylate), tetraethylene glycol diacrylate (methacrylate), neopentyl glycol diacrylate (methacrylate), polyoxyethylene glycol diacrylate (methacrylate), diacrylate (methacrylate) such as tripropylene glycol diacrylate (methacrylate), (C ) Trimethylolpropane triacrylate (methacrylate), triacrylate (methacrylate) such as pentaaerythritol triacrylate (methacrylate), (D) having four or more polymerizable groups such as dipentaerythritol hexaacrylate (methacrylate) An acrylate (methacrylate) is mentioned.

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

  Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl cyclohexanecarboxylate, vinyl benzoate and the like.

  Examples of allyl ether include alkyl allyl ether (ethyl allyl ether, propyl allyl ether, (iso) butyl allyl ether, cyclohexyl allyl ether, etc.) and the like.

  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.

  In order for the polymerized cured product (transparent resin layer 12) of the photopolymerizable compound obtained by curing the photopolymerizable composition to have high tensile strength, the photopolymerizable monomer is preferably Acrylate (methacrylate) having two or more polymerizable groups. Specifically, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, diethylene glycol Examples include diacrylate, neopentyl glycol diacrylate, polyoxyethylene glycol diacrylate, and tripropylene glycol diacrylate.

  The molecular weight of the photopolymerizable monomer is preferably 100 or more and 800 or less, more preferably 200 or more and 600 or less. One type of photopolymerizable monomer may be used alone, or two or more types of photopolymerizable monomers may be used in combination.

  The proportion of the photopolymerizable monomer in the photopolymerizable composition is preferably 90% by mass or more and 99% by mass or less with respect to the total amount of the photopolymerizable monomer and the photopolymerization initiator. If the ratio of the photopolymerizable monomer in the photopolymerizable composition is 90% by mass or more, it is possible to reduce the residue of the photopolymerization initiator and reduce deterioration of the physical properties of the polymer of the photopolymerizable compound. Or it becomes possible to prevent. On the other hand, if the ratio of the photopolymerizable monomer in the photopolymerizable composition is 99% by mass or less, the photopolymerizable monomer can be polymerized more easily, that is, a photopolymerizable compound polymer. It becomes possible to form more easily. As a result, an operation such as heating is not required for the photopolymerizable composition.

  On the other hand, as the photopolymerization initiator, (A) acetophenone photopolymerization initiator, (B) benzoin photopolymerization initiator, (C) benzophenone photopolymerization initiator, (D) thioxanthone photopolymerization initiator, ( E) Photopolymerization initiators containing fluorine atoms such as perfluoro (tert-butyl peroxide), perfluorobenzoyl peroxide, (F) α-acyloxime ester, benzyl- (o-ethoxycarbonyl) -α-monooxime, acylphosphine Other photopolymerization initiations such as oxide, glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylthiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxypivalate Agent Can be mentioned.

  Here, the ratio of the photopolymerization initiator in the photopolymerizable composition is 1% by mass or more and 10% by mass or less with respect to the total amount of the photopolymerizable monomer and the photopolymerization initiator. When the ratio of the photopolymerization initiator in the photopolymerizable composition is 1% by mass or more, the photopolymerizable monomer is more easily polymerized, that is, the polymer of the photopolymerizable compound is more It can be easily formed. As a result, it is not required to perform an operation such as heating on the photopolymerizable composition. If the ratio of the photopolymerization initiator in the photopolymerizable composition is 10% by mass or less, it becomes possible to reduce the residue of the photopolymerization initiator and reduce deterioration of physical properties of the polymer of the photopolymerizable compound or It becomes possible to prevent.

  The curable resin composition may contain a surfactant. The surfactant makes it easy to peel the mold M from the transparent resin layer 12. The surfactant preferably includes a compound having a fluoroalkyl group (which may have an etheric oxygen atom), a silicone chain, or a long-chain alkyl group having 4 to 24 carbon atoms, more preferably a fluoroalkyl group. A compound having 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 long-chain 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, octadecyl group and the like. Can be mentioned. The long chain alkyl group having 4 to 24 carbon atoms may be a linear group or a branched group.

  The amount of the surfactant contained in the curable resin composition is determined by the peelability of the mold M from the transparent resin layer 12 and the applicability of the polymerizable liquid crystal material solution to the surface of the transparent resin layer 12. Generally, when the amount of the surfactant contained in the curable resin composition is increased, the peelability of the mold M from the transparent resin layer 12 is improved. On the other hand, the surfactant may not be completely compatible with the resin of the transparent resin layer 12, or the polymerizable liquid crystal material solution applied to the surface of the transparent resin layer 12 may be repelled. Further, the adhesion between the transparent resin layer 12 and the polymer liquid crystal layer 13 may be lowered. When the surfactant is not present at all in the curable resin composition or the amount thereof is small, there is not much problem with the applicability of the polymerizable liquid crystalline material solution to the surface of the transparent resin layer 12. On the other hand, it may be difficult to peel the mold M from the transparent resin layer 12.

(2) The mold M is pressed against the layer of the curable resin composition (see FIG. 1B).
Next, the mold M which has the reverse pattern of the pattern G for aligning a liquid crystal on the surface is pressed to the layer 121 of the said curable resin composition.

  When the curable resin composition contains a photopolymerizable compound, the mold M is preferably made of a light transmissive material. In this case, the composition can be polymerized and cured by irradiating the curable resin composition with light through the mold M.

  Such light transmissive materials include glass, polyethylene-terephthalate (PET), polycarbonate (PC), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), cycloolefin polymer (COP), and transparent fluororesin. Etc.

  The pattern of the mold M can be formed by, for example, a rubbing process. The pattern G can be formed on the curable resin composition layer 121 with high accuracy. That is, the transparent resin layer 12 capable of bringing a small tilt angle to the liquid crystal can be formed regardless of the conditions of the rubbing treatment and the type of the mold M (rubbed resin layer). As a result, the angle dependency of the optical characteristics of the polymer liquid crystal layer 13 can be reduced.

The pattern G for aligning the liquid crystal and the inverted pattern thereof preferably have a shape that does not diffract or reflect visible light, and is generally an aggregate of substantially groove-shaped patterns. The anchoring force in the pattern G increases as the groove depth increases and the groove interval decreases. The anchoring force of the pattern G is generally 1 × 10 ⁻⁵ J / m ² or more, preferably 5 × 10 ⁻⁵ J / m ² or more. When the anchoring force of the pattern G is 1 × 10 ⁻⁵ J / m ² or more, the polymer liquid crystal layer 13 having high uniaxial orientation and low haze can be obtained.
In the present invention, as the mold M, a commercially available substrate with an alignment film subjected to rubbing treatment or a rubbing treated resin film (such as PET film) can be used.

  As described above, when the viscosity of the photopolymerizable composition at 25 ° C. is 1 to 2000 mPa · s, pattern transfer at room temperature is preferable. In this case, the viscosity of the curable resin composition is in an appropriate range, and an increase in thickness unevenness of the curable resin composition layer 121 is suppressed during pattern transfer.

(3) Curing of curable resin composition layer 121 (see FIG. 1C)
The curable resin composition layer 121 is cured to obtain the transparent resin layer 12. The transparent resin layer 12 having the pattern G can be easily formed by curing the curable resin composition in a state where the mold M is pressed against the surface of the curable resin composition layer 121.

  For example, ultraviolet light (for example, high-pressure mercury lamp (frequency: 1.5 kHz to 2.0 kHz, main wavelength light: 255 nm, 315 nm, 365 nm, irradiation energy at 365 nm: 1000 mJ)) is applied to the curable resin composition layer 121. Curing is achieved by irradiation.

  Here, the thickness of the transparent resin layer 12 is preferably 3 μm or more and 30 μm or less, and more preferably 10 μm or more and 20 μm or less. If the thickness of the transparent resin layer 12 is 3 μm or more, the strength of the transparent resin layer 12 is not too small. If the thickness of the transparent resin layer 12 is 30 μm or less, the transmittance of the transparent resin layer 12 is not too low, and the angle dependency of the transmittance can be reduced.

  The transmittance of the polymerized cured product of the photopolymerizable compound 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, sufficient photopolymerization or photocuring of the curable resin composition layer 121 by ultraviolet rays can be performed, and the yellowness in the finally obtained laminate 10 can be reduced, which is preferable.

  The tensile strength of the transparent resin layer 12 is preferably 30 MPa or more. When the tensile strength is 30 MPa or more, the mechanical strength of the transparent resin layer 12 is increased, and a laminate that is strong against bending is obtained.

  Moreover, the contact angle of water with respect to the transparent resin layer 12 (polymerized cured product of a photopolymerizable compound) is preferably 50 ° or more and 90 ° or less, and more preferably 60 ° or more and 80 ° or less. If the contact angle is 50 ° or more, the mold M can be more easily peeled from the transparent resin layer 12. On the other hand, when the contact angle is 90 ° or less, the repelling of the polymerizable liquid crystal material solution can be reduced or prevented when the polymerizable liquid crystal material solution is applied to the transparent resin layer 12. As a result, it is possible to reduce or prevent deterioration in adhesion between the transparent resin layer 12 and the polymer liquid crystal layer 13. In addition, the contact angle of water with respect to the polymerization hardened | cured material of a photopolymerizable compound is measured using a contact angle measuring apparatus according to JISK6768.

  Further, the haze value of the transparent resin layer 12 is preferably 0.5 or less, and more preferably 0.1 or less. If the haze value of the transparent resin layer 12 is 0.5 or less, the haze value of the laminate 10 can be reduced.

  Moreover, the retardation value of the transparent resin layer 12 is preferably 3 nm or less, and more preferably 1 nm or less. If the retardation value of the transparent resin layer 12 is 3 nm or less, the retardation value of the laminate 10 can be controlled more easily, and the ellipticity of the laminate 10 can be improved.

(4) Separation (peeling) of the mold M (see FIG. 1D).
The mold M is separated (peeled) from the transparent resin layer 12. As a result, a transparent resin layer 12 having a surface (a) having liquid crystal orientation is formed. The surface (a) has a pattern G for aligning the polymer liquid crystal in the direction A2. As described above, the direction A2 can be determined by the pattern G, that is, the orientation of the polymer liquid crystal can be controlled.

  As mentioned above, although formation of the transparent resin layer 12 which has a surface (a) was described referring FIG. 1, the formation method of the transparent resin layer 12 is not limited to this. For example, the uniaxially oriented base material 11 and a mold M having a reverse pattern of the pattern G for aligning liquid crystals are brought close to or in contact with each other so that the reverse pattern of the mold M is on the uniaxially oriented base material 11 side. . Next, the curable resin composition is filled between the substrate 11 and the mold M, and the curable resin composition is irradiated with light in a state in which the substrate 11 and the mold M are close to or in contact with each other. The composition is cured to obtain a cured product. Then, the transparent resin layer 12 may be formed by peeling the mold M.

C. Formation of polymer liquid crystal layer 13 (see FIG. 1E).
A polymer liquid crystal layer 13 is formed on the transparent resin layer 12 having the surface (a). As described above, the polymer liquid crystal layer 13 has optical anisotropy. The polymer liquid crystal layer 13 can be formed by the following procedures (1) to (3).

(1) Formation of polymerizable liquid crystalline material layer on transparent resin layer 12 A layer containing a polymerizable liquid crystalline material (polymerizable liquid crystalline material layer) is formed on the transparent resin layer 12 having the surface (a).

  Here, the wavelength dispersion of the retardation value of the polymerizable liquid crystalline material is preferably small. For example, the ratio Re450 / 550 of the retardation value of the polymerizable liquid crystal material at a wavelength of 450 nm to the retardation value of the polymerizable liquid crystal material at a wavelength of 550 nm is preferably small. When this ratio is small, it becomes possible to obtain the laminated body 10 with a favorable ellipticity.

  Further, when the birefringence Δn of the polymerizable liquid crystalline material is large, the thickness of the polymer liquid crystal layer 13 can be reduced, but the retardation wavelength dispersion tends to increase. Therefore, a polymerizable liquid crystalline material having a birefringence index Δn as large as possible within the preferable range of retardation dispersion is preferable.

  The transmittance of the polymer liquid crystal having a thickness of 200 μm with respect to the ultraviolet ray having a wavelength of 360 nm is preferably 92% or more. When the transmittance is 92% or more, the polymerizable liquid crystalline material can be sufficiently photopolymerized or photocured by ultraviolet rays, and the yellowness of the finally obtained laminate 10 can be reduced.

  This polymerizable liquid crystal material is a material having a polymerizable group and a mesogenic group, and includes, for example, a liquid crystal monomer, a liquid crystal polymer, or a liquid crystal copolymer having a polymerizable group.

The polymerizable group is preferably an acryloyl group or methacryloyl group that can be polymerized and cured by light, a vinyl group, an allyl group, or a cyclic ether group, and more preferably an acryloyl group (CH ₂ ═CHCOO—) or a methacryloyl group ( CH ₂ = a _C (CH 3) COO-).

The mesogenic group contributes to the anisotropy of the polymerizable liquid crystalline material. The mesogenic group is preferably a cyclic group containing at least one of an alicyclic hydrocarbon ring, an aromatic hydrocarbon ring and a heterocyclic ring. Moreover, the rings contained in the mesogenic group may be directly bonded to each other or indirectly bonded via a linking group.
The ring group contained in the mesogenic group may be the same kind or a different kind of combination. The number of cyclic groups is particularly preferably 2 or more and 4 or less, particularly preferably 2 or 3. If the number of ring groups is 2 or more, liquid crystallinity is exhibited. When the number of ring groups is 4 or less, the melting point of the liquid crystalline monomer is lowered. For this reason, crystal precipitation is suppressed in the step of polymerizing and curing the polymerizable liquid crystalline material, and the haze of the polymer liquid crystal layer 13 can be reduced.

As the polymerizable liquid crystal material, the following materials are preferable.
(A) a liquid crystalline monomer having a polymerizable group and a mesogenic group,
(B) A polymer in which a crosslinkable group is introduced into a polymer of a compound having an addition polymerizable unsaturated group and a mesogenic group.
The addition polymerizable unsaturated group is a group containing an ethylenic double bond, and includes an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group, and an acryloyl group or a methacryloyl group is preferable.
The crosslinkable group may be the same group as the polymerizable group (such as an acryloyl group that can be polymerized and cured by light), and the preferred embodiment is the same as the polymerizable group.

More specifically, the following materials are preferable as the polymerizable liquid crystal material.
(A1) A liquid crystalline monomer having at least two polymerizable groups selected from an acryloyloxy group and a methacryloyloxy group, and a mesogenic group.
(B1) A polymer in which at least one crosslinkable group selected from an acryloyloxy group and a methacryloyloxy group is introduced into a polymer of a compound having an addition polymerizable unsaturated group and a mesogen group.

The liquid crystalline monomer (a) preferably has a plurality of polymerizable groups. That is, it is preferably a crosslinkable liquid crystalline monomer. In this case, the polymerizable liquid crystal material can be more easily cured to a desired hardness.
When the polymer liquid crystal of (b) is cross-linked, crystallization can be suppressed as compared with the case of the cross-linkable liquid crystal monomer, so that it is easy to produce a film having high transparency.

Examples of the liquid crystalline monomer having a crosslinkable group and two or more ring groups include the following liquid crystalline monomer (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)
However, the symbols in the formulas have the following meanings.
R ¹ and R ² are each an independent hydrogen atom or methyl group.
m1, m2: An integer of 0 to 12 independent of each other.
n1: 0 when m1 is 0, 1 when m1 is an integer of 1-12.
n2: 0 when m2 is 0, 1 when m2 is an integer of 1-12.
X, Y: each independently a single bond, “—COO—”, “—OCO—”, or “—CO—”.
M: A mesogenic group in which two or more ring groups are bonded directly or via a linking group.
As m1 and m2, it is preferable that it is an integer of 1-12 each independently, and it is especially preferable that it is an integer of 2-6.

Specific examples of the liquid crystalline monomer (A) include the following compounds.
^{_{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≡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.
^{_{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.
However, the symbols in the formulas have the following meanings.
R ¹ and R ² are each an independent hydrogen atom or methyl group,
s, t: independent integers of 1 to 12,
Z ¹ and Z ² are each an independent single bond, “—COO—”, “—OCO—”, or “—CO—”.
Ph: 1,4-phenylene group (however, it may be substituted with a methyl group or a methoxy group).

  Examples of the polymer liquid crystal having a crosslinkable group include the polymer liquid crystal (B-2) described in the examples.

  Two or more polymerizable liquid crystal materials can be used in combination. In the case of using two or more kinds in combination, the combination and the mixing ratio are preferably set as appropriate depending on the application and required characteristics.

  The polymerizable liquid crystalline material can contain a polymerization initiator and a surfactant. As the polymerization initiator, the same material as the photopolymerization initiator in the curable resin composition can be used. As described later, the surfactant contributes to the alignment of the polymerizable liquid crystalline material along the surface of the transparent resin layer 12. As the surfactant, the same material as the surfactant in the curable resin composition can be used. The amount of the surfactant contained in the polymerizable liquid crystalline material is set in a range that appropriately controls the alignment of the polymerizable liquid crystalline material.

(2) Alignment of polymerizable liquid crystalline material The polymerizable liquid crystalline material in the polymerizable liquid crystalline material layer is aligned. For example, by heating the polymerizable liquid crystalline material and keeping it in the liquid crystal temperature range, the liquid crystal monomer or the polymer liquid crystal having a crosslinkable group is aligned in the direction A2 corresponding to the pattern G. At this time, by interposing the surfactant between the atmosphere and the polymerizable liquid crystal material, the liquid crystal monomer or the polymer liquid crystal having a crosslinkable group is easily aligned horizontally with respect to the surface of the transparent resin layer 12. .

(3) Polymerization of polymerizable liquid crystal material Polymer liquid crystal material 13 is obtained by polymerizing the aligned polymerizable liquid crystal material. For example, the polymerizable liquid crystalline material is polymerized, cured, or crosslinked by irradiating the polymerizable liquid crystalline material layer with ultraviolet rays. Here, in order to improve the reaction rate of the polymerizable liquid crystalline material, it is preferable to irradiate the polymerizable liquid crystalline material with light in a nitrogen atmosphere. The reaction rate of this polymerized group is preferably 70% or more. When the reaction rate of the polymer is high, the solvent resistance and heat resistance of the polymer liquid crystal layer 13 can be improved.

  As described above, the laminate 10 is produced. The transparent resin layer 12 and the polymer liquid crystal layer 13 of the laminate 10 are formed by polymerization and have solvent resistance and water resistance. For this reason, even when the solvent resistance of the uniaxially oriented substrate 11 is relatively weak, the transparent resin layer 12 and the polymer liquid crystal layer 13 protect the uniaxially oriented substrate 11 and the laminate 10 as a whole. Solvent resistance and water resistance can be secured. Moreover, the wavelength characteristic of the laminated body 10 as a whole can be improved by making the optical axis of the uniaxially oriented substrate 11 and the alignment direction of the liquid crystal of the polymer liquid crystal layer 13 different from each other.

Next, examples of the present invention will be specifically described.
[Synthesis Example 1] Synthesis of Polymer Liquid Crystal (B-1) As described below, a liquid crystal monomer (P6OCB, P6BCOH) was polymerized to synthesize a polymer liquid crystal (B-1).

  Note that x (here, 50) in the polymer liquid crystal (B-1) is a liquid crystal monomer (P6BCOH) relative to the total number of units of the liquid crystal monomer (P6OCB) and the number of units of the liquid crystal monomer (P6BCOH). ) Represents the ratio (molar ratio) of the number of units.

  2.0 g liquid crystalline monomer (P6OCB), 2.0 g liquid crystalline monomer (P6BCOH), 40 mg polymerization initiator (trade name “V40” manufactured by Wako Pure Chemical Industries, Ltd.), 120 mg 1-dodecanethiol (chain transfer agent) and 4.8 g of N, N-dimethylformamide were added, and after the air in the screw cap test tube was replaced with nitrogen, the screw cap test tube was sealed. The screw mouth test tube was stirred and shaken in an 80 ° C. constant temperature bath for 18 hours to polymerize the liquid crystalline monomer.

  The polymerized product was washed in methanol to remove unreacted liquid crystalline monomer, and then a solution obtained by dissolving in tetrahydrofuran was added dropwise to methanol to purify the product by reprecipitation. Thereafter, the product was dried in a vacuum dryer at 40 ° C. for 2 hours to obtain 3.70 g (yield 92%) of a white polymer liquid crystal (B-1).

Table 1 shows the number average molecular weight (Mn), melting point (Tm), glass transition point (Tg), clearing point (Tc), and polymer purity of the polymer liquid crystal (B-1) obtained in Synthesis Example 1.

Synthesis Example 2 Synthesis Example of Crosslinkable Polymer Liquid Crystal (B-2) Using the polymer liquid crystal (B-1) obtained in Synthesis Example 1, a crosslinkable polymer liquid crystal (B-2) was obtained. .

  In a 200 mL three-necked flask, 3.5 g of polymer liquid crystal (B-1), 3.35 g (12.9 mmol) of 4- (4-acryloxy-butyloxy) benzoic acid (manufactured by SYNTON, ST1680), 2 .58 g (21.4 mmol) of dicyclohexylcarbodiimide, 0.466 g (3.82 mmol) of 1,4-dimethylaminopyridine and 200 ml of dichloromethane were added, and the contents were stirred at room temperature overnight.

  The obtained reaction solution was filtered, and the filtrate was dropped into hexane and stirred for 10 minutes, and then the polymer was taken out. Furthermore, this polymer was dissolved in tetrahydrofuran, and the obtained solution was dropped into methanol to perform reprecipitation purification of the polymer. Thereafter, the polymer was dried in a vacuum dryer at room temperature for 2 hours to obtain 3.2 g (yield 90%) of a white crosslinkable polymer liquid crystal (B-2).

  Table 2 shows the number average molecular weight (Mn), melting point (Tm), glass transition point (Tg), clearing point (Tc), and polymer purity of the crosslinkable polymer liquid crystal (B-2) obtained in Synthesis Example 4. Show.

[Preparation Example of Polymer Liquid Crystal Solution and Liquid Crystalline Monomer Solution]
[Preparation Example 2-1]
635 parts by mass of cyclohexanone, 100 parts by mass of a crosslinkable polymer liquid crystal (B-2), 1 part by mass of a polymerization initiator (trade name “Irgacure 127” manufactured by Ciba Specialty Chemicals), 0.2 mass Part of a surfactant (S420, manufactured by Seimi Chemical Co., Ltd.) was mixed, and the resulting mixture was filtered using a PTFE filter having a pore diameter of 0.5 μm to obtain a crosslinkable polymer liquid crystal solution (b-2-1). Got. The surfactant is used for controlling the horizontal alignment of the polymer liquid crystal.

[Preparation Example 2-2]
In the same manner as in Preparation Example 2-1, a crosslinkable polymer liquid crystal solution (b-2-2) was obtained except that 325 parts by mass of cyclohexanone was used according to the ratio shown in Table 3.

[Preparation Example 3-1]
Similarly, according to the ratio shown in Table 3, a crosslinkable liquid crystal monomer solution (c-1) was prepared. Here, in the crosslinkable liquid crystal monomer solution (c-1), 0.2 parts by mass of a surfactant (Seimi Chemical Co., Ltd.) with respect to 100 parts by mass of the crosslinkable liquid crystal monomer (LC242 manufactured by BASF). Made by S420). This liquid crystalline monomer LC242 has a structure corresponding to the liquid crystalline monomer (A) described above.

[Preparation Example 3-2]
In the same manner as in Preparation Example 3-1, a crosslinkable liquid crystalline monomer solution (c-2) was obtained in accordance with the ratio shown in Table 3 except that 280 parts by mass of toluene was used.

[Preparation of photocurable 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 photocurable monomer composition. The viscosity of this composition was 20 mPa · sec.

[Uniaxially oriented substrate]
The uniaxially oriented base material used in the present example is shown below.
ZEONOR ZM14-275 [Re (550) = 275 nm] (Material: COP (cyclic polyolefin), manufactured by Nippon Zeon Co., Ltd.)
ZEONOR ZM16-138 [Re (550) = 138 nm] (Material: COP, manufactured by Nippon Zeon)
Pure Ace T-138 [Re (550) = 138 nm] (Material: PC (polycarbonate), manufactured by Teijin Chemicals Ltd.)
Pure Ace T-270 [Re (550) = 270 nm] (Material: PC, manufactured by Teijin Chemicals Ltd.)

[Example 1]
By sequentially performing the following steps [a], [b], and [c], the orientation axis control layer (transparent resin layer 12) and the horizontal are formed on the uniaxially oriented substrate (uniaxially oriented substrate 11). A liquid crystal laminate (laminate 10) having an oriented polymer liquid crystal layer (polymer liquid crystal layer 13) was obtained.

[A] Production of UV curable resin layer (curable resin layer 121) A photocurable monomer composition was spun onto the surface of ZEONOR ZM14-275 [Re (550) = 275 nm], which is a uniaxially oriented substrate. The ultraviolet curable resin layer was produced by coating by a coating method.

[B] Preparation of orientation axis control layer (transparent resin layer 12) The rubbing-treated PET substrate was pressed onto the surface of the ultraviolet curable resin layer obtained in step [a]. In step [b], the arrangement of the PET substrate with respect to the uniaxially oriented substrate was adjusted so that the angle formed by the optical axis of the uniaxially oriented substrate and the rubbing direction of the PET substrate was 60 degrees.

  Next, the ultraviolet curable resin layer is cured by irradiating the ultraviolet curable resin layer with ultraviolet light having a strength of 700 mJ at room temperature while keeping the PET substrate pressed against the surface of the ultraviolet curable resin layer. It was. Next, the PET substrate was peeled from the cured product of the ultraviolet curable resin to produce an orientation axis control layer to which the rubbing groove of the PET substrate was transferred. The film thickness of the orientation axis control layer was 8.5 μm.

[C] Production of Polymer Liquid Crystal Layer (Polymer Liquid Crystal Layer 13) The crosslinkable liquid crystal monomer solution (c-1) was applied onto the alignment axis control layer by spin coating and dried at 50 ° C. for 10 minutes. Then, the alignment treatment of the crosslinkable liquid crystalline monomer LC242 contained in the crosslinkable liquid crystalline monomer solution (c-1) was performed by maintaining at 100 ° C. for 3 minutes. By performing this alignment treatment, the crosslinkable liquid crystalline monomer LC242 was aligned horizontally with respect to the surface of the uniaxially oriented substrate on the alignment axis control layer.

Thereafter, ultraviolet light having an illuminance of 260 mW / cm ² was irradiated for 3 minutes at room temperature in a nitrogen atmosphere to perform photopolymerization (crosslinking) of the crosslinkable liquid crystalline monomer LC242, thereby producing a crosslinked polymer liquid crystal layer.

  Thus, by performing the operations of steps [a], [b], and [c], the alignment axis control layer and the horizontally aligned polymer liquid crystal layer are laminated in this order on the uniaxially oriented substrate. A liquid crystal laminated film 1 was obtained.

[Example 2]
Using ZEONOR ZM16-138 [Re (550) = 138 nm] as a uniaxially oriented substrate, in step [c], a crosslinkable liquid crystalline monomer solution (c−) was used instead of the crosslinkable liquid crystalline monomer solution (c-1). A liquid crystal laminated film 2 was produced in the same manner as in Example 1 except that 2) was used.

[Example 3]
A liquid crystal laminated film 3 was produced in the same manner as in Example 1 except that Pure Ace T-270 [Re (550) = 270 nm] was used as the uniaxially oriented substrate.

[Example 4]
Pure ace T-138 [Re (550) = 138 nm] was used as the uniaxially oriented substrate, and in step [c], a crosslinkable liquid crystalline monomer solution (c) was used instead of the crosslinkable liquid crystalline monomer solution (c-1). A liquid crystal laminated film 4 was produced in the same manner as in Example 1 except that -2) was used.

[Example 5]
Pure ace T-270 [Re (550) = 270 nm] was used as the uniaxially oriented substrate, and in step [c], a crosslinkable polymer liquid crystal solution (b) was used instead of the crosslinkable liquid crystal monomer solution (c-1). A liquid crystal laminated film 5 was produced in the same manner as in Example 1 except that 2-1) was used.

[Example 6]
Pure ace T-138 [Re (550) = 138 nm] was used as the uniaxially oriented substrate, and in step [c], a crosslinkable polymer liquid crystal solution (b) was used instead of the crosslinkable liquid crystal monomer solution (c-1). A liquid crystal laminated film 6 was produced in the same manner as in Example 1 except that 2-2) was used.

  Tables 4 and 5 show the film thickness, retardation value, haze value, and the like of the liquid crystal laminated films 1 to 6 obtained in Examples 1 to 6.

[Evaluation as a broadband wavelength plate]
The retardation values and ellipticities at wavelengths of 450 nm, 550 nm, and 650 nm of the liquid crystal laminated films 1 to 6 obtained in Examples 1 to 6 were measured. The results are shown in Table 6.

  As a result, the ellipticity of the liquid crystal laminated films 1 to 6 at a wavelength of 450 to 650 nm was 0.85 or more, and the liquid crystal laminated films 1 to 6 were confirmed to function as a broadband quarter wavelength plate.

[High temperature and high humidity test]
A high temperature and high humidity test was performed on the liquid crystal laminated films 1 to 6. Even after 1000 hours had passed after placing in an oven set at 60 ° C. and 90% RH, no significant change in haze value, retardation value, or ellipticity was observed in any of the liquid crystal laminated films.

  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, and these embodiments and examples may be modified or changed without departing from the scope of the present invention. .

DESCRIPTION OF SYMBOLS 10 ... Laminated body, 11 ... Uniaxial orientation base material, 12 ... Transparent resin layer, 13 ... Polymer liquid crystal layer, 121 ... Curable resin composition layer, M ... Mold

Claims (10)

A laminate comprising a uniaxially oriented transparent substrate, a transparent resin layer, and a polymer liquid crystal layer,
The transparent resin layer has a surface (a) in contact with the polymer liquid crystal layer, and the surface (a) is a surface having liquid crystal orientation formed by transfer of a mold surface,
The polymer liquid crystal layer is formed by polymerizing a liquid crystalline monomer aligned in contact with the surface (a) or by crosslinking a crosslinkable polymer liquid crystal aligned in contact with the surface (a). And
The laminate, wherein the optical axis of the uniaxially oriented transparent substrate is different from the alignment direction of the polymer liquid crystal of the polymer liquid crystal layer.   The said transparent resin layer is a transparent resin layer which consists of hardened | cured material of a photocurable resin composition, The said surface (a) hardens the photocurable resin composition in the state which contact | connected the mold surface which has liquid crystal orientation. The laminate according to claim 1, wherein the laminate is a surface formed by doing.   The laminate according to claim 1 or 2, wherein the liquid crystalline monomer is a compound having two or more of at least one polymerizable group selected from an acryloyl group and a methacryloyl group and a mesogenic group.   The crosslinkable polymer liquid crystal is a polymer liquid crystal in which at least one crosslinkable group selected from an acryloyl group and a methacryloyl group is introduced into a polymer of a compound having an addition polymerizable unsaturated group and a mesogen group. The laminate according to claim 1 or 2. A method for producing a laminate having a uniaxially oriented transparent substrate, a transparent resin layer, and a polymer liquid crystal layer,
(1) forming a curable resin composition layer on one surface of the uniaxially oriented transparent substrate;
(2) A mold having on its surface a reverse pattern of a pattern for aligning liquid crystals in an alignment direction different from the optical axis direction of the uniaxially oriented transparent substrate is pressed on the layer of the curable resin composition. Process,
(3) In the state where the layer of the curable resin composition is in contact with the surface of the mold, the step of curing the curable resin composition to make a transparent resin;
(4) peeling the mold and forming a transparent resin layer having a surface (a) having liquid crystal alignment in the alignment direction;
(5) By forming a liquid crystalline monomer layer on the surface (a), aligning the liquid crystalline monomer in the alignment direction, and polymerizing the liquid crystalline monomer in a state where the liquid crystalline monomer is aligned. Or forming a polymer liquid crystal layer by forming a crosslinkable polymer liquid crystal layer, aligning the crosslinkable polymer liquid crystal in the alignment direction, and crosslinking the crosslinkable polymer liquid crystal; Have
The method for producing a laminate, wherein the direction of the optical axis of the uniaxially oriented transparent substrate is different from the orientation direction of the surface (a).   The manufacturing method according to claim 5, wherein the curable resin composition is a photocurable resin composition.   The production method according to claim 5 or 6, wherein the liquid crystalline monomer is a compound having two or more of at least one polymerizable group selected from an acryloyl group and a methacryloyl group, and a mesogenic group.   The crosslinkable polymer liquid crystal is a polymer liquid crystal in which at least one crosslinkable group selected from an acryloyl group and a methacryloyl group is introduced into a polymer of a compound having an addition polymerizable unsaturated group and a mesogen group. The manufacturing method of Claim 5 or 6.   The manufacturing method in any one of Claims 5-8 whose angle which the optical axis of the said uniaxially oriented transparent base material and the orientation direction of the said surface (a) make is 50 degrees or more and 70 degrees or less.   The wavelength plate which consists of a laminated body in any one of Claims 1-4.

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