Liquid Crystal Film for Three-Dimensional Molding, Three-Dimensional Molded Body, and Method for Manufacturing Three-Dimensional Molded Body

Abstract

To provide a liquid crystal film for three-dimensional molding capable of providing a three-dimensional molded body that offers superior image light reproducibility when irradiated with the image light, and to provide the three-dimensional molded body and a method of manufacturing the three-dimensional molded body.SOLUTION: A liquid crystal film 10 for three-dimensional molding is provided, comprising a base material 1 and a functional layer 2 including a liquid crystal layer formed of a liquid crystal composition and having a rubbing haze variation of 0.80% or less on an outermost surface thereof.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a liquid crystal film for three-dimensional molding, a three-dimensional molded body, and a method for manufacturing a three-dimensional molded body.

Background Art

[0002] A decorated molded body (decorative molded body) obtained by laminating a decorative sheet on the surface of a molded body is used for building members, vehicle interior members, and the like. The decorative sheet used for the decorative molded body is usually a sheet provided with a functional layer on a base material for the purpose of imparting a visible design (for example, Patent Document 1). As a method of using such a decorative sheet, for example, an insert molding method is used in which the decorative sheet is pre-formed three-dimensionally in advance using a vacuum molding die (pre-forming), and the pre-formed sheet is inserted into an injection molding die and a resin in a fluid state is injected into the die to integrally mold the resin and the sheet.

[0003] By the way, in the automatic driving technology of automobiles and devices that provide virtual reality (VR) and augmented reality (AR), various sensing technologies using image sensors have been developed. Such sensing technologies can acquire a lot of information by using not only information that can be recognized by human vision but also polarization and wavelength components (for example, infrared rays) that humans cannot see.

[0004] Against this background, articles having a design using infrared absorbing ink have been proposed as designs that can be recognized only by sensing technology or can be recognized by both sensing technology and vision (for example, Patent Document 2).

[0005] In addition, inside a sensing device and a VR image display device or an AR image display device that can be visually recognized by humans, three-dimensional molded bodies having various functions are incorporated. These three-dimensional molded bodies are provided with various optical functions that cannot be recognized by the naked eye, contributing to the high functionality of sensing devices and image display devices.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] The inventors have invented to utilize a design using polarization as a means for realizing a molded body having a design invisible to the human visual sense, and have considered the degree of freedom in molding and the degree of freedom in optical characteristics that can be imparted, and have studied a three-dimensional molding liquid crystal film including a liquid crystal layer.

[0008] Specifically, the inventors have produced a three-dimensional molding liquid crystal film including a liquid crystal layer for imparting functionality to a three-dimensional molded body applied to a sensing device, a VR image display device, and an AR image display device, and have performed molding by a known molding method such as vacuum molding using a mold or the like, and have studied the reproducibility of image light of the obtained three-dimensional molded body. Note that the reproducibility of image light means whether an image derived from the image light can be reproduced with good reproducibility when the obtained three-dimensional molded body is irradiated with the image light. As a result of the above evaluation, it was found that depending on the type of the three-dimensional molding liquid crystal film, the reproducibility of the above image light may be inferior, and further improvement is required.

[0009] In view of the above circumstances, an object of the present invention is to provide a three-dimensional molding liquid crystal film capable of obtaining a three-dimensional molded body having excellent reproducibility of image light when irradiated with the image light. Another object of the present invention is also to provide a three-dimensional molded body and a method for manufacturing the three-dimensional molded body.

Means for Solving the Problems

[0010] As a result of addressing the above-described problems, the inventors have found that the above problems can be solved by the following configuration. That is, the present invention is as follows.

[0011] (1) A liquid crystal film for three-dimensional molding including a base material and a functional layer, The functional layer includes a liquid crystal layer, and the liquid crystal layer is obtained from a liquid crystal composition, A liquid crystal film for three-dimensional molding in which the change in rubbing haze on the outermost surface of the functional layer is 0.8% or less. (2) The liquid crystal film for three-dimensional molding according to (1), wherein the coefficient of static friction on the outermost surface of the functional layer is less than 1.0. (3) The liquid crystal film for three-dimensional molding according to (1) or (2), wherein the breaking load of the functional layer is 0.10 mN / cm or more. (4) The liquid crystal film for three-dimensional molding according to any one of (1) to (3), wherein a liquid crystal layer is disposed on the outermost surface side of the functional layer. (5) The liquid crystal film for three-dimensional molding according to any one of (1) to (4), wherein the liquid crystal composition is a polymerizable liquid crystal composition. (6) The liquid crystal film for three-dimensional molding according to (5), wherein the polymerizable liquid crystal composition contains a polyfunctional polymerizable liquid crystal compound. (7) The liquid crystal film for three-dimensional molding according to (5), wherein the polymerizable liquid crystal composition contains a non-liquid crystalline polyfunctional polymerizable compound. (8) The liquid crystal film for three-dimensional molding according to (7), wherein the non-liquid crystalline polyfunctional polymerizable compound is an ester compound of urethane polyol and (meth)acrylic acid, or an esterified product of ester polyol and (meth)acrylic acid. (9) The liquid crystal composition contains a polymerizable liquid crystal compound, The polymerizable liquid crystal compound exhibits a smectic phase, and the liquid crystal film for three-dimensional molding according to any one of (1) to (8). (10) A three-dimensional molded body in which the liquid crystal film for three-dimensional molding according to any one of (1) to (9) and a resin base are integrally molded. (11) A step 1 of preliminarily forming the liquid crystal film for three-dimensional molding according to any one of (1) to (9) by a vacuum forming process; A step 2 of inserting the preliminarily formed liquid crystal film for three-dimensional molding into a predetermined position in an injection mold and clamping the mold; A step 3 of injecting a resin in a fluid state into a cavity formed by clamping the injection mold to form a three-dimensional molded body in which the resin and the liquid crystal film for three-dimensional molding are integrated; A method for manufacturing a three-dimensional molded body, including the above steps. (12) The method for manufacturing a three-dimensional molded body according to (11), further including a step 4 of trimming an excess portion of the preliminarily formed liquid crystal film for three-dimensional molding between step 1 and step 2. (13) A method for manufacturing a three-dimensional molded body, including a step of vacuum molding the liquid crystal film for three-dimensional molding according to any one of (1) to (9) to obtain a three-dimensional molded body. (14) A three-dimensional molded body molded using the liquid crystal film for three-dimensional molding according to any one of (1) to (9).

Advantages of the Invention

[0012] According to the present invention, when image light is irradiated, it is possible to provide a liquid crystal film for three-dimensional molding capable of obtaining a three-dimensional molded body with excellent reproducibility of the image light. Further, according to the present invention, it is possible to provide a three-dimensional molded body and a method for manufacturing a three-dimensional molded body.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0014] Hereinafter, embodiments of the present invention will be described in detail. In this specification, a numerical range represented by "~" means a range including the numerical values described before and after it as the lower limit value and the upper limit value. Also, with respect to angles, "orthogonal" and "parallel" mean within a range of exact angles of ±10°, and for angles, "identical" and "different" can be determined based on whether the difference is less than 5°. In this specification, "visible light" refers to light with a wavelength of 380 to 780 nm. Also, in this specification, when there is no particular note regarding the measurement wavelength, the measurement wavelength is 550 nm. Next, the terms used in this specification will be explained.

[0015] <Re(λ), Rth(λ)> The values of the in-plane retardation and the retardation in the thickness direction refer to the values measured using AxoScan OPMF-1 (manufactured by OptoSciences) with light of the measurement wavelength. Specifically, by inputting the average refractive index ((Nx + Ny + Nz) / 3) and the film thickness (d (μm)) into AxoScan OPMF-1, Direction of the slow axis (°) Re(λ) = R0(λ) Rth(λ) = ((nx + ny) / 2 - nz) × d is calculated. Note that R0(λ) is displayed as a numerical value calculated by AxoScan OPMF-1, but it means Re(λ).

[0016] 〔Liquid crystal film for three-dimensional molding〕 The liquid crystal film for three-dimensional molding of the present invention includes at least a substrate and a functional layer, The functional layer includes a liquid crystal layer, and the liquid crystal layer is obtained from a liquid crystal composition, The change in the surface haze of the outermost surface of the functional layer is 0.80% or less. The rubbing haze change referred to here indicates how much the haze of the entire three-dimensional molding liquid crystal film changes before and after rubbing the outermost surface (the surface opposite to the substrate side) of the functional layer of the three-dimensional molding liquid crystal film under specified conditions by a rubbing test. That is, it is the value obtained by subtracting the haze before the rubbing test from the haze after the rubbing test. The above rubbing haze change is preferably 0.75% or less, more preferably 0.70% or less. The lower limit of the above rubbing haze change is not particularly limited, and 0% can be mentioned. As a method for measuring the rubbing haze change, the outermost surface of the functional layer of the three-dimensional molding liquid crystal film is rubbed 50 times back and forth with a load of 500 gf using a surface property measuring instrument ("HEIDON TRIBOGEAR type38" manufactured by Shinto Kagaku Co., Ltd.) and Kanakin No. 3 as a white cotton cloth for friction. Then, the haze change of the three-dimensional molding liquid crystal film (the haze of the three-dimensional molding liquid crystal film after rubbing Kanakin No. 3 - the haze of the three-dimensional molding liquid crystal film before rubbing Kanakin No. 3) before and after the rubbing is measured. For the measurement of haze, a haze meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd. is used. Note that the means for achieving the above rubbing haze change is not particularly limited. For example, a method of using a liquid crystal composition containing a monomer (e.g., a urethane monomer. Specifically, an ester compound of urethane polyol and (meth)acrylic acid, etc.) for strengthening the toughness of the liquid crystal layer, a method of using a liquid crystal composition containing a polymerizable liquid crystal compound showing a smectic phase, and a method of separately providing a surface protection layer on the liquid crystal layer, etc. can be mentioned.

[0017] When the present inventors examined the cause of the poor reproducibility of the image light of the obtained three-dimensional molded body, they found that the cause is that scratches and distortions enter the liquid crystal layer when the three-dimensional molding liquid crystal film is molded with a mold. That is, when the three-dimensional molding liquid crystal film is mounted on or removed from the mold, and during injection molding, scratches and distortions enter the liquid crystal layer due to the stress applied to the film, etc., so that the image light incident on the obtained three-dimensional molded body is scattered, causing image distortion, etc. On the other hand, by enhancing the abrasion resistance of the outermost surface of the functional layer of the liquid crystal film for three-dimensional molding of the present invention, when the liquid crystal film for three-dimensional molding is attached to or removed from a mold, and during injection molding, damage and distortion are suppressed from occurring in the liquid crystal layer due to stress or the like applied to the film, and a molded body that exhibits desired optical properties can be obtained. This liquid crystal film for three-dimensional molding will be described in detail below.

[0018] The liquid crystal film for three-dimensional molding of the present invention includes at least a substrate 1 and a functional layer 2 containing a liquid crystal layer (in FIG. 1, the liquid crystal layer is not shown). Between the substrate and the liquid crystal layer, a surface modification layer such as an easy-adhesion layer for modifying the surface physical properties of the substrate can be included. In this case, the surface modification layer is assumed to be included in the substrate. The functional layer can be formed by sequentially providing each layer constituting the functional layer on the substrate. However, after providing the functional layer on a temporary support, the functional layer may be transferred to the substrate using an adhesive layer or the like. In this case, the adhesive layer is assumed to be included in the functional layer.

[0019] Further, the coefficient of static friction of the outermost surface of the functional layer of the liquid crystal film for three-dimensional molding of the present invention is preferably less than 1.0. When the coefficient of static friction of the outermost surface of the functional layer is within a predetermined range, the local stress generated by the friction between the mold and the functional layer that occurs when the sheet is molded in the mold is reduced, and a molded body with excellent reproducibility of image light can be obtained. The lower limit of the coefficient of static friction of the outermost surface of the functional layer is not particularly limited, but it is often 0.2 or more. The measurement of the coefficient of static friction is carried out using a static friction measuring instrument (manufactured by Toyo Seiki Co., Ltd., friction measuring instrument AN) under the condition of a tilt speed of 1 degree / second.

[0020] Further, the breaking load of the functional layer of the liquid crystal film for three-dimensional molding of the present invention is preferably 0.10 mN / cm or more. By being a functional layer that can withstand a predetermined load, it is possible to prevent cracks from occurring due to deformation during molding. The upper limit of the breaking load of the functional layer is not particularly limited, but it is often 4.0 mN / cm or less. The measurement of the breaking load of the functional layer is carried out by bonding a polyethylene terephthalate film via a UV adhesive to the surface on the functional layer side of a sample having a support and a functional layer disposed on the support, and performing a peeling test by a 90-degree peel test of the polyethylene terephthalate film using a tensilon universal material testing machine, and taking the obtained initial peeling load peak value as the breaking strength of the film. Examples of the support included in the sample having the functional layer used in the above evaluation include a resin sheet and a glass substrate, which will be described later. Note that the above sample may include an alignment layer for aligning the alignment of the liquid crystal layer.

[0021] Hereinafter, the base material constituting the three-dimensional molding liquid crystal film of the present invention and the functional layer including the liquid crystal layer will be described in detail.

[0022] <Base material> The base material is a member that serves as a support for the functional layer. The base material is selected in consideration of the suitability for vacuum molding and the suitability for simultaneous decoration in which a liquid crystal film is placed between molds and injection molding is performed while performing decoration. For example, a resin sheet made of a thermoplastic resin can be mentioned. Examples of the thermoplastic resin generally include acrylic resins, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter referred to as "ABS resins"), vinyl chloride resins, polyester resins, cycloolefin resins, and cellulose ester resins. In addition, as the base material, a single-layer sheet of these resins or a multi-layer sheet made of the same or different resins can be used. From the viewpoint of excellent so-called trimability in which excess portions can be easily removed by hand or the like in the process of obtaining a molded body or a preform for making a molded body from a sheet-like raw material, the base material preferably contains an acrylic resin (particularly a PMMA resin), a polycarbonate resin, or a cellulose ester resin.

[0023] The thickness of the base material is selected according to the molding shape and application, but is usually about 0.02 to 1.0 mm, and generally about 0.03 to 0.5 mm. The substrate may be transparent or opaque. When the three-dimensional molded body is used as an optical member described later, it is preferable to use a transparent substrate. Further, depending on the application, the substrate may be an optical member having polarization selective absorption or polarization selective reflection (so-called polarizing plate), an optical member that reflects light or electromagnetic waves, and a color filter that selectively absorbs light according to wavelength, etc.

[0024] In order to improve the adhesion between the above-mentioned substrate and the layer provided thereon, if desired, the surface of the substrate can be subjected to surface treatments such as saponification method and oxidation method. Further, an easy-adhesion layer can be provided in advance during the manufacture of the substrate. In this case, the easy-adhesion layer shall be included in the substrate. Examples of the above oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone-ultraviolet treatment method, etc. These surface treatments are appropriately selected according to the type of the substrate, but the corona discharge treatment method is preferable from the viewpoints of effect and operability, etc.

[0025] Also, it is preferable that the surface of the substrate opposite to the surface to which the functional layer including the liquid crystal layer is applied is subjected to anti-blocking treatment as necessary. Examples of the anti-blocking treatment include roughening treatment of the substrate surface, treatment of applying a coating layer containing fine particles as an anti-blocking agent, and treatment of adding fine particles as an anti-blocking agent to the substrate in advance, etc. Further, a removable surface protection film may be provided after molding, and the surface protection film may be provided with an anti-blocking function.

[0026] <Functional layer> The functional layer includes at least a liquid crystal layer, and the liquid crystal layer is a layer obtained from a liquid crystal composition. The functional layer may be composed only of the liquid crystal layer, or may be composed of the liquid crystal layer and other layers. The liquid crystal layer and other layers may be sequentially laminated, or may be layers that are integrally formed and distinguished only by the uneven distribution of components. The arrangement position of the liquid crystal layer is not particularly limited, and it may be arranged on the outermost surface side of the functional layer (the surface side opposite to the base material).

[0027] [Liquid crystal layer] The liquid crystal layer included in the present invention is a layer obtained from a liquid crystal composition. More specifically, it may be a layer in which the liquid crystal composition is brought into a predetermined alignment state and then the alignment is fixed by a polymerization reaction or cooling. When a polymerizable liquid crystal composition is used, the components contained in the liquid crystal layer after the polymerization reaction may no longer exhibit liquid crystallinity, but in this specification, these are also included and referred to as the liquid crystal layer.

[0028] The alignment state of the liquid crystal layer can take any alignment, for example, homogeneous alignment, homeotropic alignment, spray alignment, cholesteric alignment, twist alignment, and hybrid alignment, etc. A plurality of alignment states may be laminated or arranged in different states for each region divided in the plane or thickness direction of the layer. The optical properties of the liquid crystal layer can be selected according to the purpose, and functions such as retardation properties such as in-plane retardation and thickness-direction retardation, optical rotation, cholesteric reflectivity, diffraction, and depolarization can be imparted. Also, the liquid crystal layer may be transparent in the visible region or the infrared region, but by adding dichroic dyes or inorganic anisotropic fine particles, light absorption characteristics with anisotropy and wavelength selectivity, and polarized light emission characteristics may be imparted.

[0029] The liquid crystal layer may exhibit uniform optical properties over the entire surface of the liquid crystal film for three-dimensional molding of the present invention, or may be patterned with a plurality of regions exhibiting different optical properties in the plane. The patterning may have a width or period of 5 centimeters to 1 millimeter and constitute a design macroscopically, or may have a width or period of less than 1 millimeter and does not form a design macroscopically but exhibits a specific optical effect due to the patterning.

[0030] [Liquid crystal composition] The liquid crystal layer is formed from a liquid crystal composition containing a liquid crystal compound. The liquid crystal composition may be a liquid crystal composition containing a polymerizable liquid crystal compound that exhibits liquid crystallinity and has a polymerizable group in the molecule, or may be a liquid crystal composition containing a polymeric liquid crystal compound. Further, the liquid crystal composition may contain other polymerizable compounds, an alignment stabilizer, a polymerization initiator, a solvent, and the like. Among these, from the viewpoint of excellent strength, toughness, and heat resistance, it is preferable that the liquid crystal layer is a layer formed from a composition containing a compound having a polymerizable group (so-called polymerizable liquid crystal composition). In the liquid crystal composition, the content of the liquid crystal compound is preferably 75 to 95 parts by mass, more preferably 75 to 90 parts by mass, and still more preferably 80 to 90 parts by mass with respect to 100 parts by mass of the total solid content in the liquid crystal composition. When the content of the liquid crystal compound is within the above range, the optical anisotropy and the alignment property of the liquid crystal are improved, and it becomes easier to obtain desired optical properties. Note that the above solid content means the components excluding the solvent in the liquid crystal composition. Even if the property of the above component is liquid, it is calculated as the solid content.

[0031] (Polymeric liquid crystal compound) Examples of the polymeric liquid crystal compound include thermotropic liquid crystal polymers described in JP-A-2011-237513. Further, the polymeric liquid crystal compound may have a crosslinkable group (for example, an acryloyl group and a methacryloyl group) at the polymer terminal or side chain. The polymeric liquid crystal compound may be a so-called main-chain type liquid crystal polymer containing a mesogen in the polymer main chain, or a side-chain type liquid crystal polymer containing a mesogen in the side chain. From the viewpoint of excellent thermal physical properties such as the glass transition point and various phase transition points of the liquid crystal, and the degree of freedom in designing the optical anisotropy, a side-chain type liquid crystal polymer is preferable as the polymeric liquid crystal compound.

[0032] As the polymeric liquid crystal compound, a polymeric liquid crystal compound containing a repeating unit represented by the following general formula (1) is preferable.

[0033] General formula (1)

[0034]

Chemical formula

[0035] Here, in the above formula (1), R represents a hydrogen atom or a methyl group. L represents a single bond or a divalent linking group. B represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group, an amino group, an oxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfonyl group, a sulfinyl group, a ureido group, or a crosslinkable group. M represents a mesogenic group.

[0036] (Polymerizable liquid crystal compound) The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition has refractive index anisotropy and has a function of imparting desired optical properties by assuming a predetermined alignment state. Examples of the polymerizable liquid crystal compound include materials that exhibit liquid crystal phases such as nematic phase and smectic phase. Also, polymerizable liquid crystal molecules having various structures such as rod-like liquid crystal compounds and disc-like liquid crystal compounds can be used. The wavelength dispersion of the refractive index anisotropy of the polymerizable liquid crystal compound may be either normal wavelength dispersion or inverse wavelength dispersion. The wavelength dispersion of the polymerizable liquid crystal compound referred to here means that in a film in which the polymerizable liquid crystal compound is homogeneously aligned, the relationship between Re(450), Re(550), and Re(650) of the in-plane retardation of the film satisfies the relationship represented by formula (1) or formula (2), which is defined as normal wavelength dispersion, and the case where the relationship represented by formula (3) or formula (4) is satisfied is defined as inverse wavelength dispersion. Re(450) / Re(550) ≧ 1 ···(1) Re(650) / Re(550) ≦ 1 ···(2) Re(450) / Re(550) ≦ 1 ···(3) Re(650) / Re(550) ≧ 1 ···(4)

[0037] As the polymerizable liquid crystal compound used in this embodiment, compounds described in JP-A-8-050206, JP-A-2007-002220, JP-A-2010-244038, JP-A-2008-19240, JP-A-2013-166879, JP-A-2014-078036, JP-A-2014-198813, JP-A-2011-006360, JP-A-2011-006361, JP-A-2011-207765, JP-A-2008-273925, and JP-A-2015-200877 can be used. Further, a plurality of different polymerizable liquid crystal compounds can be mixed and used. The polymerizable liquid crystal compound preferably has two or more polymerizable groups (e.g., acryloyl group) in the molecule. That is, the polymerizable liquid crystal compound is preferably a polyfunctional polymerizable liquid crystal compound having two or more polymerizable groups. When the molecule has two or more polymerizable groups, the crosslinked structure of the polymer obtained from the polymerizable liquid crystal compound becomes tough, and even when rubbing or deformation stress is applied, the liquid crystal layer does not break or deform significantly, and a three-dimensional molding liquid crystal film with few defects such as scratches and distortions can be obtained. Further, as the polymerizable liquid crystal compound, a polymerizable liquid crystal compound showing a smectic phase is preferable. By using a polymerizable liquid crystal compound showing a smectic phase and fixing the liquid crystal layer in the smectic phase, the optical properties of the liquid crystal layer are less likely to change even when heated and stressed during molding, and since the layer structure is dense and strong, a three-dimensional molding liquid crystal film with few defects such as scratches and distortions can be obtained.

[0038] (Other polymerizable compounds) As the polymerizable compound contained in the polymerizable liquid crystal composition, a non-liquid crystalline polyfunctional polymerizable compound is preferable. Examples of non-liquid crystalline polyfunctional polymerizable compounds include ester compounds of known polyhydric alcohols and (meth)acrylic acid. Examples of polyhydric alcohols include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc., and also ester polyols obtained from polyhydric alcohols and polycarboxylic acids, urethane polyols obtained from polyhydric alcohols and polyisocyanates, etc. From the viewpoint of imparting toughness and moldability to the liquid crystal layer, an ester compound of an ester polyol and (meth)acrylic acid, or an ester compound of a urethane polyol and (meth)acrylic acid is preferred. Examples of ester compounds of urethane polyol and (meth)acrylic acid include EBECRYL1290 (manufactured by Daicel Ornex Co., Ltd.), Laromer LR9000 (manufactured by BASF), and EB1290 (manufactured by Daicel Ornex Co., Ltd.) used in the Examples section described later. The number of polymerizable groups in the non-liquid crystalline polyfunctional polymerizable compound is preferably 2 to 8, more preferably 3 to 6.

[0039] (Alignment stabilizer) The liquid crystal composition may contain an alignment stabilizer. By adding an alignment stabilizer, various disturbing factors are suppressed, the alignment of the liquid crystal compound is stabilized, and a liquid crystal layer with less retardation unevenness can be obtained. Also, by appropriately selecting the structure of the alignment stabilizer, the alignment of the liquid crystal layer can be adjusted to any alignment such as horizontal alignment, vertical alignment, hybrid alignment, and cholesteric alignment. From the viewpoint of achieving both alignment stabilization and leveling, as the alignment stabilizer, an acrylic polymer having a fluoroaliphatic group in the side chain (described in paragraphs 0022 to 0063 of JP-A-2008-257205 and paragraphs 0017 to 0124 of JP-A-2006-91732) is preferred. By using an acrylic polymer having a fluoroaliphatic group in the side chain, the coefficient of static friction on the surface of the functional layer including the liquid crystal layer can be reduced.

[0040] (Polymerization initiator) The liquid crystal composition may contain a polymerization initiator. Depending on the polymerizable groups of the polymerizable liquid crystal compounds, various polymerization initiators can be selected. Preferred combinations of the polymerizable liquid crystal compounds and the polymerization initiators include combinations where the polymerizable liquid crystal compounds are (meth)acrylate compounds and the polymerization initiators are radical polymerization initiators. Examples of the polymerization initiators include various well-known polymerization initiators. In order to achieve the desired alignment, it is preferable that the composition has excellent stability over time and deep curability of the coating film. From this perspective, oxime ester compounds (such as those described in U.S. Patent No. 4,255,513 and JP-A-2001-233842), or acylphosphine oxide compounds (such as those described in JP-B-5-029234, JP-A-10-095788, and JP-A-10-029997) are preferable.

[0041] (Solvent) The liquid crystal composition may contain a solvent. Examples of the solvent include various known solvents. When selecting the solvent, it is preferable to select it in view of the solubility of the polymerizable liquid crystal compound and other components, the wettability of the liquid crystal composition to the substrate, surface tension, viscosity, and volatility. The content of the solvent in the liquid crystal composition is preferably 50 to 90% by mass, more preferably 60 to 85% by mass, based on the total amount of the liquid crystal composition.

[0042] (Other components) Other components that the liquid crystal composition may contain include dyes, UV absorbers, and non-polymerizable functional additives. In particular, by using rod-shaped dichroic dyes as the dyes, dichroic absorption characteristics corresponding to the alignment of the liquid crystal can be imparted. By imparting dichroic absorption characteristics to the liquid crystal layer, the liquid crystal layer can be used as an absorption-type polarizer. Examples of the dichroic dyes include azo dyes described in the examples of JP-A-2013-101328.

[0043] {Other layers} Examples of other layers that may be included in the functional layer include, for example, an alignment layer, a surface protection layer, and a coloring layer.

[0044] The alignment layer is formed on a substrate, and the alignment regulating force thereof can align the liquid crystal compounds in the liquid crystal layer formed on the alignment layer. As the alignment layer, various configurations capable of aligning the liquid crystal compounds to form the liquid crystal layer can be applied. For example, a rubbed film of a layer containing an organic compound such as a polymer, an obliquely deposited film of an inorganic compound, a film having microgrooves, and a film formed by accumulating LB (Langmuir-Blodgett) films of organic compounds such as ω-tricosanoic acid, dioctadecylmethylammonium chloride, and methyl stearate can be mentioned. Further, an alignment film in which an alignment function is generated by irradiation with light can also be mentioned.

[0045] As the alignment layer, a layer formed by rubbing the surface of a layer (polymer layer) containing an organic compound such as a polymer is preferable. The rubbing treatment is carried out by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth. As the polymer used for forming the alignment layer, polyimide, polyvinyl alcohol, modified polyvinyl alcohol described in paragraphs 0071 to 0095 of Japanese Patent No. 3907735, or a polymer having a polymerizable group described in Japanese Patent Application Laid-Open No. 9-152509 is preferable.

[0046] In addition, as the alignment layer, a so-called photoalignment layer (photoalignment film) formed by irradiating a photoalignable material with polarized or non-polarized light is also preferable. It is preferable to form a photoalignment layer having an alignment regulating force by a step of irradiating with polarized light from a vertical or oblique direction, or a step of irradiating with non-polarized light from an oblique direction. By using the photoalignment layer, it is possible to align the liquid crystal compounds with excellent symmetry. From the viewpoint of obtaining a three-dimensional molding liquid crystal film with suppressed foreign matter defects and no unevenness, a photoalignment film capable of imparting an alignment regulating force non-contact is preferable.

[0047] The photo-alignment layer can be formed by applying and drying a coating liquid to form a material layer serving as the photo-alignment layer on a long substrate and then irradiating with ultraviolet rays by linearly polarized light. Note that as the material for this photo-alignment layer, various materials applicable to the photo-alignment method can be used. For example, a photo-dimerizable material, particularly a compound containing a cinnamic acid derivative, can be used. Also, a photo-isomerization material such as an azo compound can be preferably used.

[0048] The thickness of the alignment layer is not particularly limited as long as it can exhibit the alignment function, but is preferably 0.01 to 5 μm, more preferably 0.05 to 2 μm, and even more preferably 0.1 to 0.5 μm. When the thickness of the alignment layer is within the above range, excellent alignment control power can be exhibited and the effect of suppressing foreign matter defects is high.

[0049] The substrate and the alignment layer may be separately provided as layers each fulfilling its respective function, or the substrate may also serve as the alignment layer, that is, the surface of the substrate may have alignment control power. Also, when the substrate and the alignment layer are separately provided, the substrate and the alignment layer may be provided in contact with each other, or another layer may be interposed between the substrate and the alignment layer. As means for directly imparting alignment control power without providing an alignment layer on the substrate surface, there are mentioned a method of performing treatments such as rubbing and polarized light irradiation described above on the substrate surface, and a method of stretching the substrate to align the polymer constituting the substrate in a certain direction. When providing an alignment layer on a substrate, examples of the above-mentioned other layers that can be interposed between the substrate and the alignment layer include a barrier layer and an impact relaxation layer, etc., and these are to be included in the functional layer. However, when the functional layer or the liquid crystal layer is formed on a temporary support different from the substrate and then transferred to the substrate to obtain the three-dimensional molding liquid crystal film of the present invention, it is not necessarily limited to the above-mentioned mode.

[0050] The surface protective layer can be provided on the outermost surface side of the functional layer for the purpose of protecting the liquid crystal layer. The liquid crystal layer and the surface protective layer may be in direct contact, or may be laminated via other layers (such as a barrier layer, an impact buffer layer, an easy adhesion layer, etc.). The surface protective layer is preferably a layer obtained from a curable resin composition, and is preferably crosslinked and cured. The thickness of the surface protective layer is appropriately set according to the application. From the viewpoint of achieving both shape followability to the mold and surface protection function, 0.5 to 10 μm is preferable, and 0.7 to 5 μm is more preferable. The surface of the surface protective layer may be imparted with antiglare properties or antiblocking properties within a range that does not affect the optical properties of the liquid crystal layer.

[0051] Examples of the curable resin composition include compositions containing monomers, oligomers, and / or prepolymers containing polymerizable groups such as (meth)acrylic groups, epoxy groups, and oxetanyl groups, and thermally crosslinkable resin compositions such as polyamic acids, polyimide precursors, and melamines. As the curable resin composition containing a (meth)acrylic group as a polymerizable group, a mixture of polycarbonate (meth)acrylate or acrylic silicone (meth)acrylate and a polyfunctional (meth)acrylate is preferable from the viewpoints of excellent abrasion resistance and moldability and effectively protecting the liquid crystal layer. To the curable resin composition, a polymerization initiator, a crosslinking catalyst, a surfactant, an antistatic agent, an antiblocking agent, etc. may be added as necessary. Using a fluorine-based or silicone-based surfactant is preferable as it reduces the coefficient of static friction on the surface of the functional layer. In addition, the curable resin composition may contain the above-mentioned urethane polyol and an ester compound of (meth)acrylic acid.

[0052] The coloring layer can be provided at an arbitrary position for the purpose of additionally imparting a design recognizable by the human visual sense. As the composition constituting the coloring layer, various known compositions applicable to the three-dimensional molding liquid crystal film can be used without limitation. The coloring layer refers not only to a layer having absorption in the visible region, but also to the entire layer capable of imparting a design visually recognizable by humans through reflection or scattering. The thickness of the coloring layer and the degree of coloring are appropriately selected according to the intended use. Also, the above-described surface protective layer and alignment layer may also serve as the coloring layer.

[0053] [Manufacturing Method of Liquid Crystal Film for Three-Dimensional Molding] The manufacturing method of the liquid crystal film for three-dimensional molding of the present invention is not particularly limited, but for example, it can be manufactured by the following method. i) A step of providing an alignment layer on a substrate as necessary or subjecting the substrate to an alignment treatment. ii) A step of applying a polymerizable liquid crystal composition on the alignment layer or the alignment-treated substrate. iii) A step of fixing the coating film of the polymerizable liquid crystal composition by polymerization after bringing it into a predetermined alignment state. iv) A step of providing a surface protective layer as necessary.

[0054] When manufacturing up to steps i) to iii), the functional layer is the liquid crystal layer itself, and when performing up to step iv), the functional layer is composed of the liquid crystal layer and the surface protective layer.

[0055] Also, as another aspect of the manufacturing method of the liquid crystal film for three-dimensional molding of the present invention, a manufacturing method including the following steps can be mentioned. i) A step of providing an alignment layer on a temporary support as necessary or subjecting the temporary support to an alignment treatment. ii) A step of applying a polymerizable liquid crystal composition on the alignment layer or the alignment-treated temporary support. iii) A step of fixing the coating film of the polymerizable liquid crystal composition by polymerization after bringing it into a predetermined alignment state. iv) A step of laminating the liquid crystal layer on a substrate via an adhesive layer and then removing the temporary support.

[0056] When an alignment film is provided in the above step i) and peeling is performed between the temporary support and the alignment film in step iv) to remove the temporary support, the functional layer is composed of an adhesive layer, a liquid crystal layer, and an alignment layer. Further, when the alignment film is not provided in step i) or the alignment layer is removed together with the temporary support in step iv), the functional layer is composed of an adhesive layer and a liquid crystal layer. Further, if necessary, a surface protective layer may be provided after step iv), and in this case, up to the surface protective layer is the functional layer.

[0057] As the coating methods for the liquid crystal layer, the alignment layer, the surface protective layer, and the adhesive layer, known methods can be used. For example, known coating methods such as die coating, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and slide coating can be mentioned.

[0058] The liquid crystal layer as the functional layer may be included only in one layer in the three-dimensional molding liquid crystal film, or may be included in a plurality of layers. When the liquid crystal layer is disposed on the outermost surface side of the functional layer, in the liquid crystal layer disposed on the outermost surface, the change in rubbing haze may be 0.80% or less, the coefficient of static friction of the outermost liquid crystal layer is preferably less than 1.0, and the breaking load of the outermost liquid crystal layer is preferably 0.10 mN / cm or more.

[0059] 〔Three-dimensional molded body〕 The three-dimensional molded body of the present invention is a three-dimensional molded body formed (molded) using the above-described three-dimensional molding liquid crystal film. As an example of the three-dimensional molded body, typically, the three-dimensional molding liquid crystal film of the present invention and the resin base are laminated in this order from the visible side of the three-dimensional molded body. Among them, a three-dimensional molded body in which the three-dimensional molding liquid crystal film and the resin base are integrally molded is preferable. Specific examples of the three-dimensional molded article include automobile bumpers, body panels, headlight covers, bonnet covers, and number plates; interior panels, wall boards, and curved mirrors for automobiles and buildings; housings, exterior parts, switches, keys, key pads, handles, levers, and buttons for electrical appliances, various equipment products, personal computers, mobile phones, and mobile devices in the home appliance and AV equipment categories; cosmetic cases and cases for miscellaneous goods. In addition to these, by applying it to optical components such as plastic lenses, curved window members, front protection plates for curved displays, apertures, and polygon mirrors, excellent optical characteristics can be exhibited.

[0060] As the resin base, a resin corresponding to the application is used, and examples include polyolefin resins such as polyethylene and polypropylene, thermoplastic resins such as ABS resin, styrene resin, polycarbonate resin, acrylic resin, and vinyl chloride resin. Or, thermosetting resins such as urethane resin and epoxy resin may also be used.

[0061] 〔Method for manufacturing a three-dimensional molded article〕 By using the liquid crystal film for three-dimensional molding of the present invention in various injection molding methods such as insert molding method, injection molding simultaneous decoration method, blow molding method, and gas injection molding method, a three-dimensional molded article can be manufactured. The three-dimensional molded article obtained by molding the liquid crystal film for three-dimensional molding of the present invention may be molded using only the liquid crystal film for three-dimensional molding, or may be a three-dimensional molded article in which the liquid crystal film for three-dimensional molding and the resin base are integrally molded as described above. As a preferred embodiment, in the insert molding method, - A step of pre-molding the liquid crystal film for three-dimensional molding of the present invention by a vacuum molding process, - A step of trimming the surplus portion of the pre-molded liquid crystal film for three-dimensional molding as necessary, - A step of inserting the pre-molded liquid crystal film for three-dimensional molding into a predetermined position in an injection mold and clamping the mold. - Injecting a resin in a fluid state into a cavity formed by clamping an injection molding die to form a three-dimensional molded body in which the resin and the liquid crystal film for three-dimensional molding are integrated. Thus, the three-dimensional molded body of the present invention can be obtained.

[0062] Also, as a preferred embodiment, in the TOM (Three-Dimension Overlay Method) molding method, - Contacting the liquid crystal film for three-dimensional molding of the present invention with a resin base via an adhesive. - Deforming the liquid crystal film for three-dimensional molding into the shape of the resin base by vacuum molding. -- Optionally trimming the surplus portion of the liquid crystal film for three-dimensional molding to form a three-dimensional molded body in which the liquid crystal film for three-dimensional molding and the resin base are integrated. Thus, the three-dimensional molded body of the present invention can be obtained.

[0063] Also, as another preferred embodiment, a step of vacuum molding the liquid crystal film for three-dimensional molding of the present invention to obtain a three-dimensional molded body may be carried out to obtain a three-dimensional molded body.

Examples

[0064] Hereinafter, the invention will be described in detail with reference to examples.

[0065] [Example 1] On a commercially available triacetyl cellulose film (manufactured by Fujifilm, trade name: Z-TAC), a coating liquid 1 for an optical alignment film was prepared with reference to the description of Example 3 in JP-A-2012-155308 and applied with a wire bar. The obtained film was dried with warm air at 60 ° C for 60 seconds to produce an alignment film P-1 with a thickness of 300 nm.

[0066] The following polymerizable liquid crystal composition 1 was continuously applied onto the above-described alignment film P-1. The formed coating film was heated at 60 ° C in a heating atmosphere and irradiated with ultraviolet rays at 70 ° C (300 mJ / cm 2The operation of ) was carried out to fix the alignment of the liquid crystal compound and form a retardation film, and the liquid crystal layer 1 was fabricated. The in-plane retardation Re(550) of the liquid crystal layer 1 was 137 nm, and the wavelength dispersibility was normal wavelength dispersibility.

[0067] ――――――――――――――――――――――――――――――――― (Polymerizable liquid crystal composition 1) ――――――――――――――――――――――――――――――――― · 83 parts by mass of the following rod-like liquid crystal compound (M-1) · 15 parts by mass of the following rod-like liquid crystal compound (M-2) · 2 parts by mass of the following rod-like liquid crystal compound (M-3) · The following urethane monomer (EBECRYL1290, manufactured by Daicel Ornex Co., Ltd.) 3.3 parts by mass · The following polymerization initiator (Irgacure OXE01, manufactured by BASF Co., Ltd.) 4 parts by mass · 0.3 parts by mass of the following fluorine-based polymer (M-4) · 0.1 parts by mass of the following fluorine-based polymer (M-5) · Toluene 552 parts by mass · Methyl ethyl ketone (MEK) 138 parts by mass ―――――――――――――――――――――――――――――――――

[0068] Rod-like liquid crystal compound (M-1)

[0069]

Chemical formula

[0070] Rod-like liquid crystal compound (M-2)

[0071]

Chemical formula

[0072] Rod-like liquid crystal compound (M-3)

[0073] [Chemical formula]

[0074] Urethane monomer

[0075] [Chemical formula]

[0076] Polymerization initiator

[0077] [Chemical formula]

[0078] Fluorine-based polymer (M-4)

[0079] [Chemical formula]

[0080] Fluorine-based polymer (M-5)

[0081] [Chemical formula]

[0082] The laminate obtained above was used as the liquid crystal film 1 for three-dimensional molding.

[0083] [Example 2] The polymerizable liquid crystal composition 1 in Example 1 was replaced with the following polymerizable liquid crystal composition 2, the heating temperature of the coating film was changed from 60°C to 90°C, and the exposure amount was 1000 mJ / cm 2 As a result, a liquid crystal film 2 for three-dimensional molding containing the liquid crystal layer 2 as a functional layer was obtained. The in-plane retardation Re(550) of the liquid crystal layer 2 was 137 nm, and the wavelength dispersibility was inverse wavelength dispersibility. Also, the obtained liquid crystal layer exhibited the characteristics of the smectic phase.

[0084] ――――――――――――――――――――――――――――――― (Coincident liquid crystal composition 2) ――――――――――――――――――――――――――――――― 57.5 parts by mass of the following rod-shaped liquid crystal compound (S-1) 30 parts by mass of the following rod-shaped liquid crystal compound (S-2) 12.5 parts by mass of the following rod-shaped liquid crystal compound (L-1) 6.0 parts by mass of a photoinitiator (Irgacure 819, manufactured by BASF) 0.85 parts by mass of the above fluorine-containing compound M-5 600 parts by mass of cyclopentanone ───────────────────────────────

[0085] Rod-shaped liquid crystal compound (S-1)

[0086]

Chemical formula

[0087] Rod-shaped liquid crystal compound (S-2)

[0088]

Chemical formula

[0089] Rod-shaped liquid crystal compound (L-1)

[0090]

Chemical formula

[0091] [Example 3] The polymerizable liquid crystal composition 1 in Example 1 was replaced with the following polymerizable liquid crystal composition 3, and the liquid crystal layer 3 was formed in the same manner as in Example 1 except that the heating temperature of the coating film was changed from 60 °C to 110 °C, and a three-dimensional molding liquid crystal film 3 containing the liquid crystal layer 3 as a functional layer was obtained. The in-plane retardation Re(550) of the liquid crystal layer 3 was 138 nm, and the wavelength dispersibility was inverse wavelength dispersibility.

[0092] ――――――――――――――――――――――――――――――――― (Polymerizable liquid crystal composition 3) ――――――――――――――――――――――――――――――――― · 97 parts by mass of the following rod-like liquid crystal compound (Z-1) · 3 parts by mass of urethane acrylate (「Laromer LR9000」manufactured by BASF) · 3 parts by mass of the following polymerization initiator (Irgacure OXE01, manufactured by BASF) · 0.3 parts by mass of surfactant (「MegaFac 562」manufactured by DIC) · 146 parts by mass of cyclopentanone · 220 parts by mass of 1,3-dioxolane ―――――――――――――――――――――――――――――――――

[0093] Rod-like liquid crystal compound (Z-1)

[0094]

Chemical formula

[0095] [Example 4] The liquid crystal layer 4 was formed in the same manner as in Example 1 except that the polymerizable liquid crystal composition 1 in Example 1 was replaced with the following polymerizable liquid crystal composition 4. The in-plane retardation Re(550) of the liquid crystal layer 4 was 137 nm, and the wavelength dispersibility was normal wavelength dispersibility.

[0096] ――――――――――――――――――――――――――――――――― (Coincidence Liquid Crystal Composition 4) ――――――――――――――――――――――――――――――――― · 83 parts by mass of the above rod-shaped liquid crystal compound (M-1) · 15 parts by mass of the above rod-shaped liquid crystal compound (M-2) · 2 parts by mass of the above rod-shaped liquid crystal compound (M-3) · Photoinitiator (Irgacure OXE01,[[]] manufactured by BASF) 4 parts by mass · 0.3 parts by mass of the above fluorine-based polymer (M-4) · 0.1 parts by mass of the above fluorine-based polymer (M-5) · 552 parts by mass of toluene · 138 parts by mass of methyl ethyl ketone (MEK) ―――――――――――――――――――――――――――――――――

[0097] Furthermore, a composition for forming a surface protective layer having the following composition was applied onto the liquid crystal layer 4, and a surface protective layer was provided by UV exposure (300 mJ / cm 2 ) in a nitrogen atmosphere, thereby obtaining a three-dimensional molding liquid crystal film 4 including a functional layer including the liquid crystal layer 4 and the surface protective layer. The thickness of the surface protective layer was provided to be 1 μm. ―――――――――――――――――――――――――――――――― (Composition for Forming Surface Protective Layer) ―――――――――――――――――――――――――――――――― 97 parts by mass of the above urethane monomer (EBECRYL 1290,[[]] manufactured by Daicel Ornex Co., Ltd.) 1 part by mass of the above fluorine polymer M-5 Photoinitiator (Irgacure 189, 2 parts by mass manufactured by BASF) ――――――――――――――――――――――――――――――――

[0098] [Comparative Example 1] In Comparative Example 4, a liquid crystal film C1 for three-dimensional molding was produced in the same manner as in Example 4, except that the surface protective layer was not provided.

[0099] [Comparative Example 2] In Comparative Example 2, a liquid crystal film C2 for three-dimensional molding was produced in the same manner as in Example 3, except that the addition amount of the urethane monomer (Laromer LR9000) in the polymerizable liquid crystal composition 3 was set to zero.

[0100] [Evaluation of Liquid Crystal Film for Three-Dimensional Molding] The obtained liquid crystal films for three-dimensional molding of Examples and Comparative Examples were evaluated as follows. The results are shown in Table 1. (Change in Rubbing Haze) The surface of the functional layer of the obtained liquid crystal film for three-dimensional molding was measured for the change in haze of the liquid crystal film for three-dimensional molding before and after reciprocating 50 times with a load of 500 gf using a surface property measuring instrument ("HEIDON TRIBOGEAR type38" manufactured by Shinto Kagaku Co., Ltd.) and Kanakin No. 3 as the white cotton cloth for rubbing. For the measurement of haze, a haze meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd. was used. (Coefficient of Static Friction) The surface of the functional layer of the obtained liquid crystal film for three-dimensional molding was measured for the coefficient of static friction of the surface at a tilt speed of 1 degree / second using a static friction measuring instrument (manufactured by Toyo Seiki Seisaku-sho, Ltd., friction measuring instrument AN). (Breaking Strength of Film) In Examples and Comparative Examples, instead of the above-described photo-alignment film, a test sample having a liquid crystal layer provided using an alignment film obtained by rubbing a polyimide film provided on the surface of a glass plate was produced. The test sample had a three-layer structure of a glass plate, an alignment film, and a liquid crystal layer. A polyethylene terephthalate film was bonded to the surface of the test sample (the surface on the liquid crystal layer side) via a UV adhesive, and a peeling test was performed by a 90-degree peel test of the film (polyethylene terephthalate film) using a tensilon universal material testing machine, and the obtained initial peeling load peak value was taken as the breaking strength of the film.

[0101] (Appearance Evaluation, Light Extinction Evaluation, and Trimming Evaluation) A spherical crown-shaped mold with a diameter of 70 mm and a depth of 10 mm was applied with the three-dimensional molding liquid crystal films of each example and comparative example. After heating to 150 °C with an infrared heater, preliminary molding was performed by vacuum molding. The obtained preliminary molded body was visually evaluated. Those with visible defects (including scratches, cracks, cloudiness, etc.) were rated as appearance "B", and those with good appearance were rated as appearance "A". Also, the preliminary molded body was placed between two polarizers arranged in cross Nicol, irradiated with light including 550 nm, and observed from various directions to observe light leakage (although it should originally function as a λ / 4 plate, if there is distortion due to deformation, the extinction position deviates from the original position and light leakage occurs). Those with a predetermined extinction position maintained throughout were rated as extinction "A", those with light leakage observed in less than 10% of the total surface area of the spherical crown were rated as extinction "B", and those with light leakage observed in 10% or more of the total surface area of the spherical crown were rated as extinction "C". Also, the unnecessary portions around the spherical crown were bent by hand to check whether trimming was possible. Those without burrs or cracks and with the unnecessary portions able to be trimmed were rated as trimming "A", and those that could not be removed by hand and those with burrs or cracks on the spherical crown side were rated as trimming "B". The results are shown in Table 1.

[0102] (Evaluation of Three-Dimensional Molded Body) The preliminary molded body obtained in the above (appearance evaluation, extinction evaluation, and trimming evaluation) was set in an injection molding die, and PMMA resin was injection molded into the cavity formed by clamping the injection molding die to obtain a spherical crown-shaped plastic optical member with a resin base thickness of 1 mm, a diameter of 70 mm, and a depth of 10 mm. Similar to the evaluations in the above (appearance evaluation, extinction evaluation, and trimming evaluation), appearance and extinction were confirmed. The results are shown in Table 1.

[0103]

Table 1

[0104] [Example 5] The following polymerizable liquid crystal composition 5 was applied onto a cellulose-based polymer film (TG40, manufactured by Fujifilm Corporation) with a wire bar of #3.5. Subsequently, for drying the solvent of the composition and for the alignment ripening of the liquid crystal compound, after heating with warm air at 40 °C for 60 seconds, under nitrogen purge (oxygen concentration 100 ppm), ultraviolet irradiation (300 mJ / cm 2 ) was carried out at 40 °C to fix the alignment of the liquid crystal compound and form a retardation film, and a liquid crystal layer 5 was produced. Inside the liquid crystal layer 5, the mesogen was vertically aligned, and the three-dimensional refractive index measured with AxoScan OPMF-1 (manufactured by Optoscience) showed the relationship of nx = ny < nz. The in-plane retardation was Re(550) = 1 nm.

[0105] ――――――――――――――――――――――――――――――――― Polymerizable liquid crystal composition 5 ――――――――――――――――――――――――――――――――― 83 parts by mass of the above rod-shaped liquid crystal compound (M-1) 15 parts by mass of the above rod-shaped liquid crystal compound (M-2) 2 parts by mass of the above rod-shaped liquid crystal compound (M-3) The above urethane monomer (EB1290, manufactured by Daicel Ornex Co., Ltd.) 10 parts by mass The above polymerization initiator (Irgacure OXE01, manufactured by BASF) 4 parts by mass 3 parts by mass of the following fluorine-based polymer (M-6) 0.3 parts by mass of the above fluorine-based polymer (M-4) 1.5 parts by mass of the following onium salt compound S01 552 parts by mass of toluene 138 parts by mass of methyl ethyl ketone (MEK) ―――――――――――――――――――――――――――――――――

[0106] Fluorine polymer (M-6)

[0107]

Chemical formula

[0108] Onium salt compound S01

[0109] [Chemical formula]

[0110] [Example 6] A polyethylene terephthalate (PET) film (Cosmoshine A4100 manufactured by Toyobo Co., Ltd.) with an easy adhesion treatment on one side was prepared, and the surface opposite to the side with the easy adhesion treatment of this film was rubbed to obtain a temporary transfer substrate.

[0111] The following polymerizable liquid crystal composition 6 was applied to the rubbed surface of the above-mentioned temporary transfer substrate using a #5 wire bar to form an uncured liquid crystal composition layer on the temporary transfer substrate. Subsequently, the liquid crystal composition layer was dried by heating at 100 °C for 3 minutes in a hot air dryer. Then, ultraviolet rays with an integrated illuminance of 1500 mJ / cm 2 were irradiated to cure the liquid crystal composition layer to form a liquid crystal layer 6. The obtained liquid crystal layer 6 exhibited red due to cholesteric alignment.

[0112] ――――――――――――――――――――――――――――――――― (Polymerizable liquid crystal composition 6) ――――――――――――――――――――――――――――――――― 85.1 parts by mass of the following liquid crystal compound (Z-1) 5.3 parts by mass of the following compound (Z-2) 3.3 parts by mass of urethane acrylate (「Laromer LR9000」, manufactured by BASF) 5.8 parts by mass of a polymerization initiator (Irgacure 379, manufactured by BASF) 0.2 parts by mass of a surfactant (S-420, manufactured by AGC Seimi Chemical Co., Ltd.) 0.8 parts by mass of a chiral agent (LC-756, manufactured by BASF) 51 parts by mass of 1,3 - dioxolane 34 parts by mass of cyclopentanone ―――――――――――――――――――――――――――――――――

[0113] Liquid crystal compound (Z - 1)

[0114]

Chem.

[0115] Compound (Z - 2)

[0116]

Chem.

[0117] [Example 7] The following composition was mixed and stirred at 80 °C for 1 hour to obtain a polymerizable liquid crystal composition 7. The polymerizable liquid crystal composition 7 was applied by the bar coating method (#9, 30 mm / s) on the rubbing surface of the temporary substrate for transfer used in Example 6. After allowing the applied film to stand at 23 °C room temperature for 30 seconds, it was heated and dried in a drying zone at 120 °C for 1 minute to sufficiently remove the solvent, and the polymerizable liquid crystal compound was phase - transferred to the isotropic liquid crystal phase, and then gradually cooled to room temperature to phase - transfer the polymerizable liquid crystal compound to the smectic liquid crystal state. Next, using a UV irradiation device (SPOT CURE SP - 7; manufactured by Ushio Electric Inc.), ultraviolet rays with an exposure amount of 1000 mJ / cm 2 (based on 365 nm) were irradiated from the side of the coated film, and the polymerizable liquid crystal compound contained in the dried film was polymerized while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound, and a liquid crystal layer 7 was formed from the dried film. The obtained liquid crystal layer exhibited polarization - selective absorption, and acted as a polarizer having a transmission axis in the direction consistent with the rubbing direction of the temporary substrate for transfer and an absorption axis in the direction perpendicular to the transmission axis.

[0118] ――――――――――――――――――――――――――――――――― (Polymerizable liquid crystal composition 7) ――――――――――――――――――――――――――――――――― 75 parts by mass of the following liquid crystal compound (Z-3) 25 parts by mass of the following compound (Z-4) 2.5 parts by mass of the following dichroic dye 1 2.5 parts by mass of the following dichroic dye 2 2.5 parts by mass of the following dichroic dye 3 6 parts by mass of a polymerization initiator (Irgacure 369, manufactured by BASF) Surfactant (BYK-361N, manufactured by BYK-Chemie) 1.2 parts by mass 400 parts by mass of toluene ―――――――――――――――――――――――――――――――――

[0119] Liquid crystal compound (Z-3)

[0120]

Chem.

[0121] Compound (Z-4)

[0122]

Chem.

[0123] Dichroic dye 1

[0124]

Chem.

[0125] Dichroic dye 2

[0126]

Chem.

[0127] Dichroic dye 3

[0128] [Chemical]

[0129] [Evaluation of Liquid Crystal Films for Three-Dimensional Molding 2] (Fabrication of Substrate Films for Three-Dimensional Molding by Liquid Crystal Layer Transfer) As a substrate film for three-dimensional molding, a substrate film made of a resin containing a polymer with an alicyclic structure (Zeonoar Film ZF14-100 manufactured by Nippon Zeon Co., Ltd., thickness 100 μm) was prepared, and one side of it was corona-treated. Next, the following composition for forming an adhesive layer was applied onto the corona-treated surface of the substrate film with a #2 wire bar to form a layer of the composition for forming an adhesive layer as an uncured layer. Further, the films manufactured in Examples 5 to 7 were placed on top of this uncured layer so that the liquid crystal layer side was in contact with the uncured layer. Next, lamination was carried out using a pressure roll, and then ultraviolet rays were irradiated from the substrate film side with an integrated illuminance of 800 mJ / cm 2 from a high-pressure mercury lamp. The triacetyl cellulose film or PET film as the temporary support was peeled off from the laminate (including the temporary support) on which the adhesive layer was formed to obtain a liquid crystal film for three-dimensional molding having a layer structure of (liquid crystal layer / adhesive layer / substrate film) (liquid crystal films for three-dimensional molding 5 to 7).

[0130] ――――――――――――――――――――――――――――――――― (Composition for Forming Adhesive Layer) ――――――――――――――――――――――――――――――――― 3,4-Epoxycyclohexylmethyl -3,4-Epoxycyclohexanecarboxylate 40 parts by mass Diglycidyl ether of bisphenol A 60 parts by mass Diphenyl(4-phenylthiophenyl)sulfonium Hexafluoroantimonate (photo cationic polymerization initiator) 4 parts by mass ―――――――――――――――――――――――――――――――――

[0131] (Evaluation 1) Regarding the three-dimensional molding liquid crystal film obtained in the above (production of the base film for three-dimensional molding by liquid crystal layer transfer), the evaluation of the above-described rubbing haze change and static friction coefficient was performed. In addition, a test sample was cut out from the laminate (including the temporary support) before peeling off the triacetyl cellulose film or PET film, which is a temporary support, from the three-dimensional molding liquid crystal film, and a peeling test was performed by a 90-degree peel test of the film (base film) using a tensilon universal material testing machine. The obtained initial peel load peak value was taken as the breaking strength of the film (liquid crystal layer). These results are shown in Table 2.

[0132] (Evaluation 2) Regarding the three-dimensional molding liquid crystal film produced in the above (production of the base film for three-dimensional molding by liquid crystal layer transfer), a preform was produced in the same manner as in the above (appearance evaluation, light extinction evaluation, and trimming evaluation), and appearance, light extinction, and trimming evaluations were performed. The results are shown in Table 2. However, regarding the preform containing the liquid crystal layer of Example 6, white light was irradiated and observed from various directions, and the reflected color tone of the cholesteric layer (if the alignment state is maintained, the facing point of the spherical crown is red, and a gradual color change is observed as the distance from the facing point increases) was observed. Those in which a predetermined color tone change was maintained throughout were designated as color tone "A", those in which a color change inconsistent with less than 10% of the total area of the spherical crown was observed were designated as color tone "B", and those in which a color change inconsistent with 10% or more of the total area of the spherical crown was observed were designated as color tone "C". In addition, for the preform containing the liquid crystal layer of Example 7, a white light source was placed inside the spherical crown, and the light leakage was evaluated by observing through a polarizing plate arranged in a cross-nicol arrangement with the original transmission axis of the liquid crystal layer 7. Those in which a predetermined light extinction position was maintained throughout were designated as light extinction "A", those in which light leakage was observed in less than 10% of the total area of the spherical crown were designated as light extinction "B", and those in which light leakage was observed in 10% or more of the total area of the spherical crown were designated as light extinction "C".

[0133] (Evaluation 3) Regarding the three-dimensional molding liquid crystal film obtained in the above (Evaluation 3), a spherical plastic optical member was obtained in the same manner as in the above (three-dimensional molded body evaluation). Similar to the evaluation in (Evaluation 2), the color tone was confirmed for the appearance and the three-dimensional molded body including the liquid crystal layer of Example 6. The results are shown in Table 2.

[0134] [Table 2]

[0135] [Evaluation of Image Reproducibility] (Examples 8 to 11, Comparative Examples 3 to 4) In the manner described in Example 1 of JP-A-2013-200482, a spherical wire grid polarizer having a diameter of 70 mm and a depth of 10 mm was obtained. On the convex surface side of the obtained spherical wire grid polarizer, the preforms of Examples 1 to 4 and Comparative Examples 1 to 2 were bonded via a UV curable adhesive. The positions were adjusted so that the direction of the transmission axis of the wire grid polarizer and the slow axis of the preforms of Examples 1 to 4 and Comparative Examples 1 to 2 was 45°. The obtained laminate and a separately prepared half mirror having a diameter of 70 mm, a depth of 10 mm, and a thickness of 60 μm (transmittance 50%) were combined in the manner of FIG. 2 (spherical wire grid polarizer 12, preform 14 of Examples 1 to 4 or Comparative Examples 1 to 2, half mirror 16, display surface 18) to produce the lens elements of Examples 8 to 11 and Comparative Examples 3 to 4.

[0136] (Evaluation of Image Reproducibility) A broadband λ / 4 plate was bonded to the display surface of the liquid crystal panel with a polarizer taken out from a smartphone (iPhone (registered trademark) 7, manufactured by Apple Inc.) so that the angle between the transmission axis and the slow axis of the viewing-side polarizer was 45°. With a white and black stripe pattern with a width of 0.5 cm displayed on this liquid crystal panel, the lens element produced above was placed on the display surface. By passing through the lens element, an enlarged image of the white and black stripe pattern was observed. For the enlarged images of the stripe pattern observed from the center line (front) of the lens element and from 10° (diagonal) from the center line of the lens element, the image reproducibility was evaluated as follows. The results are shown in Table 3. A: The boundary of the stripe pattern maintained a straight line, and an enlarged image without distortion was obtained. Also, a decrease in the contrast between white and black was not visually recognizable. B: The boundary of the stripe pattern maintained a straight line, and no distortion was observed, but a decrease in the contrast between white and black was visually recognizable. C: Distortion of the boundary of the stripe pattern was visually recognized, and the image reproducibility was degraded.

[0137] (Example 12) A lens element was obtained in the same manner as in Example 8, except that the above-described wire grid polarizer, the preform of Example 1, and the preform of Example 5 were stacked in this order to form a three-layer structure, and (evaluation of image reproducibility) was carried out in the same manner as in Example 8. The evaluation results of the obtained lens element are shown in Table 3.

[0138] (Example 13) A lens element was obtained in the same manner as in Example 8, except that the preform of Example 6 and the preform of Example 5 were stacked in this order, and (evaluation of image reproducibility) was carried out in the same manner as in Example 8. The evaluation results of the obtained lens element are shown in Table 3.

[0139] (Examples 14 and 15) A preform produced in Example 7 was further laminated with an adhesive on the concave side of the lens element produced in Example 8 and the lens element produced in Example 12. For the obtained lens elements (Examples 14 and 15), (evaluation of image reproducibility) was carried out in the same manner as in Example 8. The evaluation results of the obtained lens element are shown in Table 3.

[0140]

Table 3

[0141] As shown in the above table, it was confirmed that the liquid crystal film for three-dimensional molding of the present invention exhibits a desired effect (excellent reproducibility of image light when the image light is irradiated). From the comparison of Examples 8 to 11, it was confirmed that when the rubbing haze change is 0.70% or less (Examples 8, 9, 11), the effect is more excellent. In addition, from the comparison of Examples 12 to 15, it was also confirmed that when the rubbing haze change is 0.70% or less, the effect is more excellent. In addition, in Example 12, a liquid crystal layer 5 which is a C plate, and in Examples 14 and 15, a liquid crystal layer 7 which functions as an absorption type polarizer are further provided, and it was confirmed that the image reproducibility in the "oblique" column is further improved.

Explanation of reference numerals

[0142] 1 Substrate 2 Functional layer 10 Liquid crystal film for three-dimensional molding 12 Wire grid polarizer 14 Preform 16 Half mirror 18 Display surface

Claims

1. A step of pre-forming a liquid crystal film for three-dimensional molding including a base material and a functional layer; A step of bonding a resin base and the pre-formed liquid crystal film for three-dimensional molding via an adhesive; A method for manufacturing a three-dimensional molded body, comprising: The functional layer includes a liquid crystal layer, and the liquid crystal layer is obtained from a liquid crystal composition; The change in the surface haze of the outermost surface of the functional layer is 0.8% or less; The liquid crystal composition contains a non-liquid crystal polyfunctional polymerizable compound, or the liquid crystal composition contains a polymerizable liquid crystal compound exhibiting a smectic phase, or the functional layer includes a surface protection layer on the liquid crystal layer; The non-liquid crystal polyfunctional polymerizable compound is an ester compound of urethane polyol and (meth)acrylic acid; The surface protection layer is a crosslinked and cured layer obtained from a curable resin composition containing an ester compound of urethane polyol and (meth)acrylic acid; The change in the surface haze is the change in haze before and after reciprocating 50 times with a load of 500 gf using Kanakin No. 3 as a white cotton cloth for friction on the outermost surface of the functional layer using a surface property measuring instrument, for a method for manufacturing a three-dimensional molded body.

2. The method for manufacturing a three-dimensional molded body according to Claim 1, wherein the wavelength dispersibility of the liquid crystal layer is inverse wavelength dispersibility.

3. The method for manufacturing a three-dimensional molded body according to Claim 1 or 2, wherein the three-dimensional molded body further includes a polarizer.

4. The method for manufacturing a three-dimensional molded body according to Claim 3, wherein the angle formed by the transmission axis of the polarizer and the slow axis of the functional layer is 45°.

5. The method for manufacturing a three-dimensional molded body according to any one of Claims 1 to 4, wherein the liquid crystal layer is disposed on the outermost surface side of the functional layer.

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