WO2020262474A1 - 成型用加飾フィルム、成型物、及びディスプレイ - Google Patents
成型用加飾フィルム、成型物、及びディスプレイ Download PDFInfo
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- WO2020262474A1 WO2020262474A1 PCT/JP2020/024860 JP2020024860W WO2020262474A1 WO 2020262474 A1 WO2020262474 A1 WO 2020262474A1 JP 2020024860 W JP2020024860 W JP 2020024860W WO 2020262474 A1 WO2020262474 A1 WO 2020262474A1
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/416—Reflective
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2451/00—Decorative or ornamental articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
- C09K2019/2078—Ph-COO-Ph-COO-Ph
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Definitions
- This disclosure relates to decorative films for molding, molded products, and displays.
- a transmissive decorative film transparent decorative film
- a scene of the other side can be visually recognized from one side of the decorative film through the decorative film itself, and one side (surface).
- a decorative film that allows a specific display to be visually recognized from the surface and substantially invisible from the other side (back surface).
- it has a circularly polarizing plate, a cholesteric liquid crystal layer arranged on a part of the circularly polarizing plate, a side surface of the cholesteric liquid crystal layer, and a packing layer covering the surface of the circularly polarizing plate on which the cholesteric liquid crystal layer is not formed.
- a transmissive decorative film that can give different visual effects on the observation surface is disclosed (see, for example, JP-A-2018-97327).
- a transparent display device having a light emitting layer sandwiched between a pair of transparent electrodes, capable of displaying images and character information on both sides, and having a transparent background has been attracting attention.
- a transparent display device using an organic EL (Electro-Luinescence) panel has attracted attention (see, for example, Japanese Patent Application Laid-Open No. 2007-071948).
- the transparent display described in JP-A-2007-071948 is transparently visible from one side and not visible from one side.
- the decorative pattern can be seen from the viewpoint of interior design, etc., and as described in Japanese Patent Application Laid-Open No. 2011-045427, it can be used as a mirror for various purposes. The needs for use are also increasing.
- the films described in JP-A-2018-97327, JP-A-2007-071948, and JP-A-2011-045427 have a planar shape and do not mention moldability. Further, it was confirmed by the studies of the present inventors that the color of the film described in JP-A-2007-071948 changes depending on the viewing angle to be visually recognized. From the viewpoint of further enhancing the decorativeness, incorporating into a housing such as a display, and applicability of a three-dimensional (3D) three-dimensional shape to a display surface, it should have moldability into a three-dimensional three-dimensional shape. Is preferable. Further, when visually recognizing the decorative film, it is preferable that the film has a small change in color depending on the viewing angle.
- the problem to be solved by the embodiment of the present disclosure is to obtain a decorative film for molding, a molded product thereof, and a display to which the molded product is applied, which are excellent in the appearance of uniform color regardless of the molding processability and the viewing angle. Is to provide.
- the reflective layer is a layer containing a cholesteric liquid crystal.
- the cholesteric liquid crystal compound is a compound having one ethylenically unsaturated group or one cyclic ether group.
- the reflective layer further comprises any one of (2) to (4) containing a chiral agent containing a polymerizable group, or a chiral agent containing a polymerizable group and a chiral agent having no polymerizable group. Described decorative film for molding.
- the molded product is a display in which the maximum height T2 in the normal direction of the display surface has a relationship of T2> 0.02 ⁇ T1 with respect to the maximum width T1 in the in-plane direction of the display surface of the display display unit.
- a decorative film for molding a molded product thereof, and a display to which the molded product is applied, which are excellent in molding processability and expression of uniform color regardless of a viewing angle. it can.
- FIG. 1 is a schematic plan view of an example of a convex mold of a molding mold composed of a concave mold and a convex mold when viewed from above.
- FIG. 2 is a schematic cross-sectional view schematically showing a cross section cut in a direction parallel to the longitudinal direction in the top view of FIG.
- FIG. 3 is a schematic cross-sectional view schematically showing a cross section cut in a direction parallel to the lateral direction in the top view of FIG.
- FIG. 4 is a schematic plan view of another example of the convex mold of the molded mold composed of the concave mold and the convex mold when viewed from above.
- FIG. 5 is a schematic cross-sectional view schematically showing a cross section 62 obtained by cutting the convex shape of FIG. 4 along a line passing through a circular center in a top view.
- total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition.
- solid content is a component excluding the solvent as described above, and may be, for example, a solid or a liquid at 25 ° C.
- substitution and non-substitution includes those having no substituent as well as those having a substituent.
- alkyl group includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- % by mass and “% by weight” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
- a combination of two or more preferred embodiments is a more preferred embodiment.
- the decorative film for molding (hereinafter, also simply referred to as “decorative film”) according to the present disclosure is provided on a plastic base material (hereinafter, also simply referred to as a base material) and a selective reflection wavelength.
- a reflective layer having a central wavelength in the range of 380 nm or more and 780 nm or less, and a glass transition point of a plastic substrate (hereinafter, may be abbreviated as “Tg”) + 10 ° C.
- Tg glass transition point of a plastic substrate
- the decorative film for molding according to the present disclosure can be used for various purposes, and examples thereof include interior / exterior of displays, interior / exterior of electric appliances, interior / exterior of automobiles, packaging containers, and the like. Above all, it can be suitably used as the interior and exterior of a display, and can be particularly preferably used as a decorative film for molding used for the exterior of a display.
- the elastic modulus of the reflective layer at a temperature of Tg + 10 ° C. is in the range of 0.0001 GPa or more, the self-cohesive force of the reflective layer and the structure of the film are maintained, and the film is stretched following the plastic substrate. Further, it is presumed that when the elastic modulus is 0.5 GPa or less, the flexibility of the reflective layer is maintained, the occurrence of breakage and cracks is suppressed, and the reflective layer can be stretched following the substrate.
- the center wavelength of the selective reflection wavelength in the range of 380 nm or more and 780 nm or less, which is a wavelength visible to human eyes, it is possible to adjust the color change depending on the viewing angle and the visually recognized color itself. It is possible to provide a decorative film with excellent design.
- the decorative film for molding according to the present disclosure has a base material.
- the base material conventionally known base materials can be used without particular limitation as base materials used for molding such as three-dimensional molding and insert molding, and are appropriately selected according to the use of the decorative film, suitability for insert molding, and the like. Just do it.
- the shape and material of the base material are not particularly limited and may be appropriately selected as desired. From the viewpoint of ease of molding (particularly ease of insert molding) and chipping resistance, the base material is preferably a resin base material, and preferably a resin film.
- the base material for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic resin, urethane resin, urethane-acrylic resin, polycarbonate (PC), acrylic-polycarbonate resin, triacetyl cellulose (TAC). , Polyolefin, cycloolefin polymer (COP), acrylic film containing resins such as acrylic nitrile / butadiene / styrene copolymer resin (ABS resin).
- the base material may be a laminated resin base material having two or more layers.
- an acrylic resin / polycarbonate laminated film is preferable.
- the base material may contain additives, if necessary.
- Additives include, for example, mineral oils, hydrocarbons, fatty acids, alcohols, fatty acid esters, fatty acid amides, metal soaps, natural waxes, silicones and other lubricants; magnesium hydroxide, aluminum hydroxide and other inorganic flame retardants; halogen-based, Phosphorus-based organic flame retardants; organic or inorganic fillers such as metal powder, talc, calcium carbonate, potassium titanate, glass fiber, carbon fiber, wood powder; antioxidants, UV inhibitors, lubricants, dispersants, Additives such as coupling agents, foaming agents and colorants, polyesters, polyacetals, polyamides, polyphenylene ethers and the like, and engineering plastics other than the above-mentioned resins can be mentioned.
- a commercially available product may be used as the base material.
- Commercially available products include, for example, Technoroy (registered trademark) series (acrylic resin film or acrylic resin / polycarbonate resin laminated film, manufactured by Sumitomo Chemical Co., Ltd.) ABS film (manufactured by Okamoto Co., Ltd.), ABS sheet (Sekisui Molding Industry (Sekisui Molding Industry)).
- ABS refers to an acrylonitrile / butadiene / styrene copolymer resin.
- the thickness of the base material is determined according to the intended use of the molded product to be produced, the handleability of the film, and the like.
- the thickness is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, further preferably 20 ⁇ m or more, and particularly preferably 50 ⁇ m or more.
- the upper limit is preferably 500 ⁇ m or less, more preferably 450 ⁇ m or less, and particularly preferably 200 ⁇ m or less.
- the decorative film for molding according to the present disclosure has a reflective layer having a central wavelength of selective reflection wavelength in the range of 380 nm or more and 780 nm or less on a plastic base material.
- the reflective layer having the selective reflection wavelength include a cholesteric liquid crystal film, a dielectric multilayer film, and a metal fine particle-containing film, and from the viewpoint of stretchability, a layer containing a cholesteric liquid crystal compound is preferable.
- the elastic modulus of the reflective layer at the glass transition point (Tg) + 10 ° C. of the plastic substrate is 0.00001 GPa or more and 0.5 GPa or less, preferably 0.00005 GPa or more and 0.5 GPa or less. It is more preferably 0.0001 GPa or more and 0.3 GPa or less, particularly preferably 0.0001 GPa or more and 0.1 GPa or less, and most preferably 0.0001 GPa or more and 0.015 GPa or less.
- the elastic modulus of the reflective layer is a value measured by the minute indentation hardness, and can be measured using, for example, Nano Indenter G200 manufactured by Toyo Corporation.
- the reflective layer is preferably a layer containing a cholesteric liquid crystal compound (cholesteric liquid crystal layer).
- the cholesteric liquid crystal layer in the decorative film for molding according to the present disclosure may be on the base material and may not be in direct contact with the base material, for example, on the base material via another layer such as a colored layer described later. You may have it in.
- the decorative film for molding according to the present disclosure is a color change depending on a visible angle by changing at least one selected from the group consisting of the pitch, the refractive index, and the thickness of the spiral structure in the cholesteric liquid crystal layer. And the visible color itself can be adjusted.
- the pitch of the spiral structure can be easily adjusted by changing the amount of the chiral agent added. Specifically, Fujifilm Research Report No. 50 (2005) p. There is a detailed description in 60-63. Further, the pitch of the spiral structure can be adjusted by conditions such as temperature, illuminance, and irradiation time when fixing the cholesteric orientation state.
- the cholesteric liquid crystal layer is preferably a layer obtained by curing the liquid crystal composition.
- the liquid crystal composition in the present disclosure preferably contains at least a cholesteric liquid crystal compound having one ethylenically unsaturated group or one cyclic ether group. "Having one ethylenically unsaturated group or one cyclic ether group” does not mean having either an ethylenically unsaturated group or a cyclic ether group in one molecule, but in one molecule. It means that there is one ethylenically unsaturated group or cyclic ether group contained in.
- the cholesteric liquid crystal layer is more preferably a cured product (cured layer) of a liquid crystal composition containing a cholesteric liquid crystal compound and a photopolymerization initiator. The photopolymerization initiator will be described later.
- the liquid crystal composition preferably contains, for example, a cholesteric liquid crystal compound having one ethylenically unsaturated group or one cyclic ether group in an amount of 25% by mass or more based on the total solid content of the liquid crystal composition.
- the elastic modulus of the reflective layer at the temperature of Tg + 10 ° C. of the plastic base material is in the range of 0.00001 GPa or more and 0.5 GPa or less.
- the liquid crystal composition may further contain other components such as a chiral agent, an orientation control agent, a polymerization initiator, and an orientation aid.
- the cholesteric liquid crystal compound in the present disclosure is preferably a compound having one ethylenically unsaturated group or one cyclic ether group.
- the ethylenically unsaturated group is not particularly limited, and examples thereof include a (meth) acryloxy group, a (meth) acrylamide group, a vinyl group, a vinyl ester group, and a vinyl ether group. Among them, from the viewpoint of reactivity, it is preferably a (meth) acryloxy group, a (meth) acrylamide group, or a vinyl group, and more preferably a (meth) acryloxy group or a (meth) acrylamide group. It is particularly preferably a (meth) acrylamide group.
- the cyclic ether group is not particularly limited, but from the viewpoint of reactivity, it is preferably an epoxy group or an oxetanyl group, and particularly preferably an oxetanyl group.
- the cholesteric liquid crystal compound having one ethylenically unsaturated group or one cyclic ether group has both an ethylenically unsaturated group and a cyclic ether group in one molecule. You may. For example, in the case of a compound having both an ethylenically unsaturated group and a cyclic ether group, whether the number of ethylenically unsaturated groups is one or the number of cyclic ether groups is one. Either. Further, as long as the number of ethylenically unsaturated groups is one, the compound may have, for example, one ethylenically unsaturated group and one or more cyclic ether groups.
- the cholesteric liquid crystal compound having one ethylenically unsaturated group or one cyclic ether group contains a compound having one ethylenically unsaturated group, it contains a radical polymerization initiator from the viewpoint of moldability. Is preferable, and it is more preferable to include a photoradical polymerization initiator.
- the cholesteric liquid crystal compound having one ethylenically unsaturated group or one cyclic ether group contains a compound having one cyclic ether group, it may contain a cationic polymerization initiator from the viewpoint of moldability. It is preferable to include a photocationic polymerization initiator.
- the cholesteric liquid crystal compound having one ethylenically unsaturated group or one cyclic ether group has only one ethylenically unsaturated group and has a cyclic ether group from the viewpoint of moldability.
- the compound preferably has both an ethylenically unsaturated group and a cyclic ether group, and is preferably a compound having one ethylenically unsaturated group and one cyclic ether group. More preferred.
- the cholesteric liquid crystal compound having one ethylenically unsaturated group or one cyclic ether group may be a compound having a liquid crystal structure, and may be a rod-shaped liquid crystal compound or a disk-shaped liquid crystal compound. Good. Above all, a rod-shaped liquid crystal compound is preferable from the viewpoint of easy adjustment of the pitch of the spiral structure in the cholesteric liquid crystal layer, post-molding property, and designability.
- rod-shaped liquid crystal compound examples include azomethine compounds, azoxy compounds, cyanobiphenyl compounds, cyanophenyl ester compounds, benzoic acid ester compounds, cyclohexanecarboxylic acid phenyl ester compounds, cyanophenylcyclohexane compounds, cyano-substituted phenylpyrimidine compounds, and alkoxy-substituted phenylpyrimidine compounds.
- a phenyldioxane compound, a trans compound, or an alkenylcyclohexylbenzonitrile compound is preferably used.
- liquid crystal high molecular weight compounds can be used.
- the cholesteric liquid crystal layer is more preferably a layer formed by polymerizing a rod-shaped liquid crystal compound to fix its orientation.
- rod-shaped liquid crystal compounds include Makromol. Chem., 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. No. 4,683,327, 562,648, 5770107. Specification, International Publication No. 95/22586, 95/24455, 97/00600, 98/23580, 98/52905, JP-A No. 1-272551, No.
- the compound has one ethylenically unsaturated group or one cyclic ether group.
- the rod-shaped liquid crystal compound for example, among those described in JP-A No. 11-513019 and JP-A-2007-279688, it has one ethylenically unsaturated group or one cyclic ether group. Those having can be preferably used.
- disk-shaped liquid crystal compound examples include those described in JP-A-2007-108732 or JP-A-2010-244038, which have one ethylenically unsaturated group or one cyclic ether group. Can be preferably used.
- cholesteric liquid crystal compound having one ethylenically unsaturated group or one cyclic ether group include the compounds shown below, but it goes without saying that the compounds are not limited thereto.
- the liquid crystal composition may contain one type of cholesteric liquid crystal compound having one ethylenically unsaturated group or one type of cyclic ether group, or may contain two or more types.
- the content of the cholesteric liquid crystal compound having one ethylenically unsaturated group or one cyclic ether group is preferably 25% by mass or more based on the total solid content of the liquid crystal composition. When it is 25% by mass or more, a decorative film having excellent moldability can be obtained.
- the content of the cholesteric liquid crystal compound having one ethylenically unsaturated group or one cyclic ether group is preferably 30% by mass or more, preferably 40% by mass or more, from the viewpoint of moldability. It is more preferably 60% by mass or more and 99% by mass or less, and particularly preferably 80% by mass or more and 98% by mass or less.
- the liquid crystal composition includes cholesteric liquid crystal compounds other than cholesteric liquid crystal compounds having one ethylenically unsaturated group or one cyclic ether group (hereinafter, also simply referred to as "other liquid crystal compounds"). It may be included.
- other liquid crystal compounds include cholesteric liquid crystal compounds having no ethylenically unsaturated group and cyclic ether group, and cholesteric liquid crystal compounds having two or more ethylenically unsaturated groups and having no cyclic ether group, 2.
- Examples thereof include cholesteric liquid crystal compounds having one or more cyclic ether groups and no ethylenically unsaturated groups, and cholesteric liquid crystal compounds having two or more ethylenically unsaturated groups and two or more cyclic ether groups. .. Among them, as other liquid crystal compounds, from the viewpoint of moldability, a cholesteric liquid crystal compound having no ethylenically unsaturated group and a cyclic ether group, and having two or more ethylenically unsaturated groups and having a cyclic ether group.
- a cholesteric liquid crystal compound preferably at least one compound selected from the group consisting of a cholesteric liquid crystal compound having two or more cyclic ether groups and no ethylenically unsaturated group, preferably ethylenically unsaturated.
- the compound is at least one selected from the group consisting of cholesteric liquid crystal compounds having no cholesteric liquid crystal compound, and the cholesteric liquid crystal compound having no ethylenically unsaturated group and cyclic ether group, and two ethylenically unsaturated groups. It is particularly preferable that the compound is at least one selected from the group consisting of cholesteric liquid crystal compounds having and not having a cyclic ether group.
- the cholesteric liquid crystal compound having no ethylenically unsaturated group and cyclic ether group is a liquid crystal composition from the viewpoint of setting the elastic modulus of the reflective layer at a temperature of glass transition point (Tg) + 10 ° C. of a plastic substrate to 0.00001 GPa or more. It is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 15% by mass or less, based on the total solid content of the above.
- the cholesteric liquid crystal compound having two ethylenically unsaturated groups and having no cyclic ether group and the cholesteric liquid crystal compound having two cyclic ether groups and having no ethylenically unsaturated group are plastic substrates. From the viewpoint of setting the elastic coefficient of the reflective layer to 0.5 GPa or less at the temperature of the glass transition point (Tg) + 10 ° C., it is preferably 80% by mass or less, preferably 65% by mass, based on the total solid content of the liquid crystal composition. It is more preferably% or less, and particularly preferably 50% by mass or less.
- the cholesteric liquid crystal compound having three or more ethylenically unsaturated groups and having no cyclic ether group, and the cholesteric liquid crystal compound having three cyclic ether groups and having no ethylenically unsaturated group are plastics. From the viewpoint of setting the elastic coefficient of the reflective layer at 0.5 GPa or less at the glass transition point (Tg) of the base material + 10 ° C., it is preferably 50% by mass or less based on the total solid content of the liquid crystal composition. It is more preferably 30% by mass or less, and particularly preferably 10% by mass or less.
- a known cholesteric liquid crystal compound can be used as the other liquid crystal compound.
- the rod-shaped liquid crystal compound in other liquid crystal compounds include Makromol. Chem. , 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. No. 4,683,327, 5,622,648, 5,770,107, International Publication No. 95/22586. , 95/24455, 97/00600, 98/23580, 98/52905, Japanese Patent Application Laid-Open No. 1-272551, 6-16616, 7-110469, 11- The compounds described in JP-A-80081 and JP-A-2001-328973 can be used. Further, as the rod-shaped liquid crystal compound, for example, those described in JP-A No.
- JP-A-2007-108732 or JP-A-2010-244038 can be preferably used.
- the liquid crystal composition may contain other liquid crystal compounds alone or in combination of two or more.
- the content of the other liquid crystal compound is preferably 70% by mass or less, more preferably 60% by mass or less, and 40% by mass or less, based on the total solid content of the liquid crystal composition. Is more preferable, and 30% by mass or less is particularly preferable.
- the lower limit of the content of other liquid crystal compounds is 0% by mass.
- the liquid crystal composition preferably contains a chiral agent (optically active compound) from the viewpoint of ease of forming a cholesteric liquid crystal layer and ease of adjusting the pitch of the spiral structure.
- the chiral agent has a function of inducing a helical structure in the cholesteric liquid crystal layer. Since the chiral agent has a different spiral twisting direction or spiral pitch induced by the liquid crystal compound, it may be selected according to the purpose.
- the chiral agent is not particularly limited, and is known as a compound (for example, Liquid Crystal Device Handbook, Chapter 3, 4-3, TN (twisted nematic), STN (Super-twisted nematic) chiral agent, page 199, Japan Society for the Promotion of Science. (Described in 1989, edited by the 142nd Committee of the Promotion Association), isosorbide, isomannide derivatives and the like can be used.
- the chiral agent generally contains an asymmetric carbon atom, but an axial asymmetric compound or a surface asymmetric compound that does not contain an asymmetric carbon atom can also be used as the chiral agent.
- Examples of the axial asymmetric compound or the surface asymmetric compound preferably include a binaphthyl compound, a helicene compound, or a paracyclophane compound.
- the liquid crystal composition preferably contains a chiral agent having a polymerizable group as the chiral agent, and contains a chiral agent containing a polymerizable group and a chiral agent having no polymerizable group.
- the polymerizable group is not particularly limited as long as it is a polymerizable group, but from the viewpoint of reactivity and moldability, it is preferably an ethylenically unsaturated group or a cyclic ether group, and is ethylenically. It is more preferably an unsaturated group.
- the preferred embodiments of the ethylenically unsaturated group and the cyclic ether group in the chiral agent are the same as the preferred embodiments of the ethylenically unsaturated group and the cyclic ether group in the cholesteric liquid crystal compound described above, respectively.
- the chiral agent has an ethylenically unsaturated group or a cyclic ether group
- the ethylenically unsaturated group or the cyclic ether group contained in the cholesteric liquid crystal compound in the liquid crystal composition is considered from the viewpoint of reactivity and moldability.
- the ether group and the ethylenically unsaturated group or the cyclic ether group contained in the chiral agent are preferably the same type of group (for example, an ethylenically unsaturated group, preferably a (meth) acryloxy group), and the same group is used. More preferably.
- the chiral agent having a polymerizable group is preferably a chiral agent having two or more polymerizable groups from the viewpoint of reactivity and moldability, and has two or more ethylenically unsaturated groups.
- a chiral agent or a chiral agent having two or more cyclic ether groups is more preferable, and a chiral agent having two or more ethylenically unsaturated groups is particularly preferable.
- the chiral agent may be a cholesteric liquid crystal compound.
- a chiral agent capable of changing the spiral pitch of the cholesteric liquid crystal layer in response to light is also preferable to include a "photosensitive chiral agent").
- the photosensitive chiral agent is a compound that can change the structure by absorbing light and change the spiral pitch of the cholesteric liquid crystal layer.
- a compound that causes at least one of a photoisomerization reaction, a photodimerization reaction, and a photodegradation reaction is preferable.
- a compound that causes a photoisomerization reaction is a compound that causes stereoisomerization or structural isomerization by the action of light.
- the photoisomerized compound include an azobenzene compound and a spiropyran compound.
- the compound that causes a photodimerization reaction means a compound that causes an addition reaction between two groups and cyclizes by irradiation with light.
- the photodimerized compound include cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, benzophenone derivatives and the like.
- the light is not particularly limited, and examples thereof include ultraviolet light, visible light, and infrared light.
- a chiral agent represented by the following formula (CH1) is preferably mentioned.
- the chiral agent represented by the following formula (CH1) can change the orientation structure such as the spiral pitch (helical period, twist period) of the cholesteric liquid crystal phase according to the amount of light at the time of light irradiation.
- Ar CH1 and Ar CH2 independently represent an aryl group or a heteroaromatic ring group, and R CH1 and R CH2 independently represent a hydrogen atom or a cyano group, respectively.
- Ar CH1 and Ar CH2 in the formula (CH1) are independently aryl groups.
- the aryl group in Ar CH1 and Ar CH2 of the formula (CH1) may have a substituent, preferably having a total carbon number of 6 to 40, and more preferably a total carbon number of 6 to 30.
- the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a hydroxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carboxy group, a cyano group, or a heterocycle.
- the group is preferable, and a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an acyloxy group, an alkoxycarbonyl group, or an aryloxycarbonyl group is more preferable. It is preferable that R CH1 and R CH2 in the formula (CH1) are independently hydrogen atoms.
- Ar CH1 and Ar CH2 an aryl group represented by the following formula (CH2) or formula (CH3) is preferable.
- R CH3 and R CH4 in the formula (CH2) and the formula (CH3) are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, alkoxy group, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, respectively.
- an acyloxy group is preferable, an alkoxy group, a hydroxy group, or an acyloxy group is more preferable, and an alkoxy group is particularly preferable.
- L CH1 and L CH2 in the formula (CH2) and the formula (CH3) are each independently preferably an alkoxy group having 1 to 10 carbon atoms or a hydroxy group.
- the nCH1 in the formula (CH2) is preferably 0 or 1.
- the nCH2 in the formula (CH3) is preferably 0 or 1.
- the heteroaromatic ring group in Ar CH1 and Ar CH2 of the formula (CH1) may have a substituent, and has a total carbon number of 4 to 40, more preferably a total carbon number of 4 to 30.
- a substituent for example, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, a hydroxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, or a cyano group is preferable.
- a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acyloxy group is more preferable.
- a heteroaromatic ring group a pyridyl group, a pyrimidinyl group, a frill group, or a benzofuranyl group is preferable, and a pyridyl group or a pyrimidinyl group is more preferable.
- the liquid crystal composition may contain one kind of chiral agent alone or two or more kinds.
- the content of the chiral agent can be appropriately selected according to the structure of the cholesteric liquid crystal compound to be used and the desired pitch of the spiral structure, but the ease of forming the cholesteric liquid crystal layer, the ease of adjusting the pitch of the spiral structure, and the ease of adjusting the pitch of the spiral structure, and From the viewpoint of moldability, it is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, and 3% by mass or more, based on the total solid content of the liquid crystal composition. It is particularly preferably 10% by mass or less.
- the content of the chiral agent having a polymerizable group is 0.2 mass by mass with respect to the total solid content of the liquid crystal composition from the viewpoint of moldability. % Or more and 15% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, further preferably 1% by mass or more and 8% by mass or less, and 1.5% by mass or more. It is particularly preferably 5% by mass or less. Further, when the chiral agent having no polymerizable group is contained as the chiral agent, the content of the chiral agent having no polymerizable group is 0, based on the total solid content of the liquid crystal composition, from the viewpoint of moldability.
- the pitch of the spiral structure of the cholesteric liquid crystal in the cholesteric liquid crystal layer, and the selective reflection wavelength and its range described later can be easily determined not only by the type of the liquid crystal compound used but also by adjusting the content of the chiral agent. Can be changed. Although it cannot be said unconditionally, when the content of the chiral agent in the liquid crystal composition is doubled, the pitch may be halved and the center value of the selective reflection wavelength may be halved.
- the liquid crystal composition preferably contains a polymerization initiator, and more preferably contains a photopolymerization initiator.
- the liquid crystal composition preferably contains a radical polymerization initiator from the viewpoint of moldability, and is preferably a photoradical polymerization initiator. It is more preferable to include.
- the liquid crystal composition contains a cholesteric liquid crystal compound having one cyclic ether group
- the liquid crystal composition preferably contains a cationic polymerization initiator, and further contains a photocationic polymerization initiator from the viewpoint of moldability. Is more preferable.
- the liquid crystal composition preferably contains only one of a radical polymerization initiator or a cationic polymerization initiator as the polymerization initiator.
- the polymerization initiator a known polymerization initiator can be used. Further, the polymerization initiator is preferably a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays. Examples of photopolymerization initiators include ⁇ -carbonyl compounds (described in US Pat. No. 2,376,661 and US Pat. No. 2,376,670), acyloin ether compounds (described in US Pat. No. 2,448,828), and ⁇ -hydrogen substitution. Aromatic acidoine compounds (described in US Pat. No. 2,725,512), polynuclear quinone compounds (described in US Pat. Nos.
- Patent No. 35949367 Japanese Patent Laid-Open No. 60-105667, US Pat. No. 4,239,850
- oxadiazole compounds described in US Pat. No. 421,970
- photoradical polymerization initiator and the photocationic polymerization initiator known ones can be used.
- Preferred examples of the photoradical polymerization initiator include ⁇ -hydroxyalkylphenone compounds, ⁇ -aminoalkylphenone compounds, and acylphosphine oxide compounds.
- the photocationic polymerization initiator a known one can be used.
- Preferred examples of the photocationic polymerization initiator include iodonium salt compounds and sulfonium salt compounds.
- the liquid crystal composition may contain one kind of polymerization initiator alone or two or more kinds.
- the content of the polymerization initiator can be appropriately selected according to the structure of the cholesteric liquid crystal compound to be used and the desired pitch of the spiral structure, but the ease of forming the cholesteric liquid crystal layer, the ease of adjusting the pitch of the spiral structure, and the polymerization From the viewpoint of speed and strength of the cholesteric liquid crystal layer, it is preferably 0.05% by mass or more and 10% by mass or less, and 0.05% by mass or more and 5% by mass or less, based on the total solid content of the liquid crystal composition. It is more preferably 0.1% by mass or more and 2% by mass or less, and particularly preferably 0.2% by mass or more and 1% by mass or less.
- the liquid crystal compound may contain a cross-linking agent in order to improve the strength and durability of the cholesteric liquid crystal layer after curing.
- a cross-linking agent one that cures with ultraviolet rays, heat, humidity or the like can be preferably used.
- the cross-linking agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyfunctional acrylate compound such as trimethylolpropane tri (meth) acrylate or pentaerythritol tri (meth) acrylate; glycidyl (meth) acrylate.
- Epoxy compounds such as ethylene glycol diglycidyl ether; 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], azilysin compounds such as 4,4-bis (ethyleneiminocarbonylamino) diphenylmethane; hexa Isocyanate compounds such as methylenediisocyanate and biuret-type isocyanate; polyoxazoline compounds having an oxazoline group in the side chain; alkoxysilane compounds such as vinyltrimethoxysilane and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane. Be done. Further, a known catalyst can be used depending on the reactivity of the cross-linking agent, and the productivity can be improved in addition to the strength and durability of the cholesteric liquid crystal layer.
- the liquid crystal composition may contain one type of cross-linking agent alone or two or more types.
- the content of the cross-linking agent is preferably 1% by mass or more and 20% by mass or less, and 3% by mass or more and 15% by mass, based on the total solid content of the liquid crystal composition. More preferably, it is less than%.
- the liquid crystal composition preferably contains a polyfunctional polymerizable compound, and more preferably contains a polyfunctional polymerizable compound having the same type of polymerizable group.
- the polyfunctional polymerizable compound include cholesteric liquid crystal compounds having two or more ethylenically unsaturated groups and no cyclic ether groups in the above-mentioned compounds, and ethylene having two or more cyclic ether groups.
- Cholesteric liquid crystal compounds having no sex unsaturated groups cholesteric liquid crystal compounds having two or more ethylenically unsaturated groups and two or more cyclic ether groups, chiral agents having two or more polymerizable groups, the above-mentioned cross-linking.
- Agents can be mentioned.
- the polyfunctional polymerizable compound a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and having no cyclic ether group, and having two or more cyclic ether groups and ethylenically unsaturated.
- the liquid crystal composition may contain one kind of polyfunctional polymerizable compound alone or two or more kinds.
- the content of the polyfunctional polymerizable compound is preferably 0.5% by mass or more and 70% by mass or less, and 1% by mass or more and 50% by mass, based on the total solid content of the liquid crystal composition. It is more preferably 1.5% by mass or more and 20% by mass or less, and particularly preferably 2% by mass or more and 10% by mass or less.
- the liquid crystal composition may contain other additives other than those described above, if necessary.
- additives known additives can be used, such as surfactants, polymerization inhibitors, antioxidants, horizontal alignment agents, ultraviolet absorbers, light stabilizers, colorants, metal oxide particles, etc. Can be mentioned.
- the liquid crystal composition may contain a solvent.
- the solvent is not particularly limited and may be appropriately selected depending on the intended purpose, but an organic solvent is preferably used.
- the organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose.
- a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, an alkyl halide solvent, an amide solvent, a sulfoxide solvent or a heterocyclic solvent can be selected. Examples thereof include based solvents, hydrocarbon solvents, ester solvents, ether solvents and the like. These may be used alone or in combination of two or more.
- a ketone solvent is particularly preferable in consideration of the burden on the environment.
- the above-mentioned component may function as a solvent.
- the content of the solvent in the liquid crystal composition is not particularly limited, and may be adjusted to the content of the solvent that can obtain the desired coatability.
- the content of the solid content with respect to the total mass of the liquid crystal composition is not particularly limited, but is preferably 1% by mass to 90% by mass, more preferably 5% by mass to 80% by mass, and 10% by mass. It is particularly preferably% to 80% by mass.
- the solvent content of the liquid crystal composition at the time of curing when forming the cholesteric liquid crystal layer is preferably 5% by mass or less, preferably 3% by mass or less, based on the total solid content of the liquid crystal composition. More preferably, it is more preferably 2% by mass or less, and particularly preferably 1% by mass or less. Further, the content of the solvent in the cholesteric liquid crystal layer obtained by curing the liquid crystal composition is preferably 5% by mass or less, and preferably 3% by mass or less, based on the total mass of the cholesteric liquid crystal layer. More preferably, it is more preferably 2% by mass or less, and particularly preferably 1% by mass or less.
- the liquid crystal composition is applied by using an appropriate method such as a roll coating method, a gravure printing method, or a spin coating method, in which the liquid crystal composition is made into a solution state with a solvent, or a liquid material such as a molten liquid after heating is applied. Can be done with. Further, the coating can be performed by various methods such as a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method. It is also possible to form a coating film by ejecting the liquid crystal composition from a nozzle using an inkjet device.
- the cured cholesteric liquid crystal layer is formed by curing the liquid crystal composition.
- the curing By the curing, the molecular orientation of the liquid crystal compound including the cholesteric liquid crystal compound is maintained and fixed.
- the curing is preferably carried out by a polymerization reaction of a polymerizable group such as an ethylenically unsaturated group or a cyclic ether group contained in the liquid crystal compound.
- the coating film is dried by a known method after the coating of the liquid crystal composition and before the polymerization reaction for curing.
- it may be dried by leaving it, or it may be dried by heating. It is sufficient that the liquid crystal compounds in the liquid crystal composition are oriented after the application and drying of the liquid crystal composition.
- the cholesteric liquid crystal layer has selective reflectivity in a specific wavelength range.
- the "center wavelength of the selective reflection wavelength” is expressed by the following formula when the minimum value and the minimum value of the light transmittance of the target object (member) are Tmin (%). It refers to the average value of two wavelengths showing half-value transmittance [T 1/2 ;%], and having selective reflectivity means having a specific wavelength range satisfying the selective reflection wavelength.
- one of the two wavelengths is the maximum wavelength in the wavelength range including a wavelength shorter than the wavelength indicating Tmin, and the other wavelength of the two wavelengths is longer than the wavelength indicating Tmin.
- the decorative film for molding according to the present disclosure may have two or more cholesteric liquid crystal layers. Further, each of the two or more cholesteric liquid crystal layers may be a layer having the same composition or a layer having a different composition.
- each of the above-mentioned base materials has a cholesteric liquid crystal layer from the viewpoint of suppressing a change in reflectance after molding. Is preferable.
- the thickness of the cholesteric liquid crystal layer is preferably 0.3 ⁇ m or more and 15 ⁇ m or less, more preferably 0.5 ⁇ m or more and 9 ⁇ m or less, and 0.6 ⁇ m or more and 3 ⁇ m from the viewpoint of suppressing the change in reflectance after molding. The following is particularly preferable.
- each cholesteric liquid crystal layer is independently in the above thickness range.
- the decorative film for molding according to the present disclosure may have an orientation layer in contact with the cholesteric liquid crystal layer.
- the alignment layer is used to orient the molecules of the liquid crystal compound in the liquid crystal composition when forming the layer containing the liquid crystal compound.
- the alignment layer is used when forming a layer such as a liquid crystal layer, and the decorative film for molding according to the present disclosure may or may not include the alignment layer.
- the oriented layer can be provided by means such as rubbing treatment of an organic compound (preferably a polymer), oblique vapor deposition of an inorganic compound such as SiO, and formation of a layer having microgrooves. Further, an orientation layer in which an orientation function is generated by applying an electric field, applying a magnetic field, or irradiating light is also known.
- the lower layer can be directly oriented (for example, rubbing) to function as the alignment layer without providing the alignment layer.
- An example of such an underlying base material is polyethylene terephthalate (PET).
- the lower cholesteric liquid crystal layer behaves as an alignment layer, and the liquid crystal compound for producing the upper layer may be oriented.
- the liquid crystal compound in the upper layer can be oriented without providing the alignment layer and without performing a special orientation treatment (for example, rubbing treatment).
- the thickness of the alignment layer is not particularly limited, but is preferably in the range of 0.01 ⁇ m to 10 ⁇ m.
- -Rubbing treatment alignment layer examples include methacrylate-based copolymers, styrene-based copolymers, polyolefins, polyvinyl alcohols, and modified polyvinyl alcohols described in paragraph 0022 of JP-A-8-338913.
- Poly (N-methylolacrylamide), polyester, polyimide, vinyl acetate copolymer, carboxymethyl cellulose, polycarbonate and the like are included.
- a silane coupling agent can be used as a polymer.
- Water-soluble polymers eg, poly (N-methylolacrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol, modified polyvinyl alcohol
- gelatin, polyvinyl alcohol or modified polyvinyl alcohol are more preferred, and polyvinyl alcohol or modified polyvinyl alcohol is particularly preferred. ..
- the liquid crystal composition is applied to the rubbing surface of the alignment layer to orient the molecules of the liquid crystal compound. Then, if necessary, the alignment layer polymer is reacted with the polyfunctional monomer contained in the cholesteric liquid crystal layer, or the alignment layer polymer is crosslinked with a cross-linking agent to form the cholesteric liquid crystal layer. be able to.
- the surface of the alignment layer, the base material, or the other layer to which the liquid crystal composition is applied may be subjected to a rubbing treatment, if necessary.
- the rubbing treatment can be generally carried out by rubbing the surface of the film containing the polymer as a main component with paper or cloth in a certain direction.
- a general method of rubbing processing is described in, for example, "LCD Handbook" (published by Maruzensha, October 30, 2000).
- N represents the number of rubbing
- l represents the contact length of the rubbing roller
- r represents the radius of the roller
- n represents the number of revolutions per minute of the roller
- v represents the stage. Represents the moving speed (speed per second).
- the photo-alignment material used for the photo-alignment layer formed by light irradiation is described in many documents and the like.
- the photocrosslinkable silane derivative described above, the photocrosslinkable polyimide, polyamide, or ester described in Japanese Patent Application Laid-Open No. 2003-520878, Japanese Patent Application Laid-Open No. 2004-522220, and Japanese Patent No. 4162850 are preferable examples. Particularly preferred are azo compounds, photocrosslinkable polyimides, polyamides, or esters.
- the photo-aligned layer formed from the above material is irradiated with linearly polarized light or non-polarized light to produce a photo-aligned layer.
- linearly polarized light irradiation is an operation for causing a photoreaction in a photoaligned material.
- the wavelength of light used varies depending on the photoalignment material used, and is not particularly limited as long as it is a wavelength required for the photoreaction.
- the peak wavelength of the light used for light irradiation is 200 nm to 700 nm, and more preferably, ultraviolet light having a peak wavelength of light of 400 nm or less.
- Light sources used for light irradiation include known light sources such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, carbon arc lamps and other lamps, and various lasers (eg, semiconductor lasers, helium neon). Examples include lasers, argon ion lasers, helium cadmium lasers, YAG (Yttrium Aluminum Garnet) lasers), light emitting diodes, and cathode wire tubes.
- known light sources such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, carbon arc lamps and other lamps, and various lasers (eg, semiconductor lasers, helium neon). Examples include lasers, argon ion lasers, helium cadmium lasers, YAG (Yttrium Aluminum Garnet) lasers), light emitting diodes, and cathode wire tubes.
- a method using a polarizing plate eg, iodine polarizing plate, a two-color dye polarizing plate, a wire grid polarizing plate
- reflection using a prism element eg, Gran Thomson prism
- a Brewster angle A method using a type polarizing element or a method using light emitted from a polarized laser light source can be adopted. Further, only light having a required wavelength may be selectively irradiated by using a filter, a wavelength conversion element, or the like.
- the incident angle of light varies depending on the photoalignment material, but is preferably 0 ° to 90 ° (vertical), more preferably 40 ° to 90 °, with respect to the alignment layer.
- unpolarized light irradiate the non-polarized light diagonally.
- the incident angle is preferably 10 ° to 80 °, more preferably 20 ° to 60 °, and particularly preferably 30 ° to 50 °.
- the irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.
- ⁇ Circular polarizing plate> It is also preferable to arrange a circularly polarizing plate adjacent to the cholesteric liquid crystal layer. By arranging the circular polarizing plate, a transmissive decorative film that can give different visual effects on the observation surface can be obtained.
- the circular polarizing plate transmits circular polarization (left circular polarization) in the direction opposite to the turning direction of the circular polarization reflected by the cholesteric liquid crystal.
- Examples of the circular polarizing plate include those in which a linear polarizing plate and a ⁇ / 4 plate are laminated. As for the configuration in the circular polarizing plate, for example, the ⁇ / 4 plate and the linear polarizing plate are arranged in this order from the cholesteric liquid crystal layer side.
- the linear polarizing plate and the ⁇ / 4 plate transmit the slow axis of the ⁇ / 4 plate and the linear polarizing plate so that the left circularly polarized light is transmitted as linearly polarized light among the light incident from the ⁇ / 4 plate side.
- the decorative film for molding according to the present disclosure may further have a colored layer.
- the position of the colored layer in the decorative film for molding according to the present disclosure is not particularly limited and can be provided at a desired position, but the following two aspects are preferably mentioned.
- the decorative film for molding according to the present disclosure further has a colored layer between the base material and the cholesteric liquid crystal layer.
- the color of the colored layer is not limited and can be appropriately selected depending on the use of the decorative film for molding and the like.
- Examples of the color of the colored layer include black, gray, white, red, orange, yellow, green, blue, and purple. Further, the color of the colored layer may be a metallic color.
- the colored layer preferably contains a resin from the viewpoint of strength and scratch resistance.
- the resin include a binder resin described later.
- the colored layer may be a layer obtained by curing the polymerizable compound, or may be a layer containing the polymerizable compound and the polymerization initiator.
- the polymerizable compound and the polymerization initiator are not particularly limited, and known ones can be used.
- the colorant include pigments and dyes, and pigments are preferable from the viewpoint of durability.
- the colored layer metallic metal particles, pearl pigments and the like can be applied, and methods such as thin film deposition and plating can also be applied.
- the pigment is not limited, and known inorganic pigments, organic pigments and the like can be applied.
- the inorganic pigment include white pigments such as titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide and barium sulfate, carbon black, titanium black, titanium carbon, iron oxide and graphite. Black pigments, iron oxide, barium yellow, cadmium red, chrome yellow and the like.
- the inorganic pigments described in paragraphs 0015 and 0114 of JP-A-2005-7765 can also be applied.
- organic pigments examples include phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, azo pigments such as azo red, azo yellow and azo orange, quinacridone pigments such as quinacridone red, shinkasha red and shinkasha magenta, and perylene red.
- Perylene pigments such as perylene maroon, carbazole violet, anthrapyridine, flavanthron yellow, isoindrin yellow, induslon blue, dibrom anzasron red, anthraquinone red, diketopyrrolopyrrole and the like can be mentioned.
- Specific examples of organic pigments include C.I. I.
- Pigment Red 177, 179, 224, 242, 254, 255, 264 and other red pigments C.I. I. Pigment Yellow 138, 139, 150, 180, 185 and other yellow pigments, C.I. I. Pigment Orange 36, 38, 71 and other orange pigments, C.I. I. Pigment Green Pigment Green 7, 36, 58 and other green pigments, C.I. I. Blue pigments such as Pigment Blue 15: 6, C.I. I. Examples include purple pigments such as Pigment Violet 23.
- the organic pigment described in paragraph 093 of JP2009-256572 can also be applied.
- the pigment may include a pigment having light transmission and light reflection (so-called brilliant pigment).
- the glitter pigment include metal glitter pigments such as aluminum, copper, zinc, iron, nickel, tin, aluminum oxide, and alloys thereof, interfering mica pigments, white mica pigments, graphite pigments, and glass flake pigments. Can be mentioned.
- the glitter pigment may be uncolored or colored. When exposure is performed in the molding of a decorative film for molding, the glitter pigment is preferably used within a range that does not interfere with curing by exposure.
- the colorant may be used alone or in combination of two or more. Further, when two or more kinds of colorants are used, an inorganic pigment and an organic pigment may be combined.
- the content of the colorant in the colored layer is preferably 1% by mass to 50% by mass and 5% by mass to 50% by mass with respect to the total mass of the colored layer from the viewpoint of the development of the desired color and the suitability for molding. % Is more preferable, and 10% by mass to 40% by mass is particularly preferable.
- the colored layer may contain a dispersant.
- the dispersant By including the dispersant, the dispersibility of the colorant in the formed colored layer is improved, and the color of the obtained decorative film can be made uniform.
- the dispersant can be appropriately selected depending on the type, shape and the like of the colorant, and a polymer dispersant is preferable.
- the polymer dispersant include silicone polymers, acrylic polymers, polyester polymers and the like.
- a silicone polymer such as a graft type silicone polymer as a dispersant.
- the weight average molecular weight of the dispersant is preferably 1,000 to 5,000,000, more preferably 2,000 to 3,000,000, and 2,500 to 3,000,000. Is particularly preferred. When the weight average molecular weight is 1,000 or more, the dispersibility of the colorant is further improved.
- dispersant a commercially available product may be used.
- Commercially available products include BASF Japan's EFKA 4300 (acrylic polymer dispersant), Kao Corporation's Homogenol L-18, Homogenol L-95, Homogenol L-100, and Japan Lubrizol Co., Ltd.
- Examples thereof include Solspers 20000, Solspers 24000, DISPERBYK-110, DISPERBYK-164, DISPERBYK-180, DISPERBYK-182 manufactured by Big Chemie Japan Ltd.
- "Homogenol", “Solsperse”, and "DISPERBYK” are all registered trademarks.
- the dispersant may be used alone or in combination of two or more.
- the content of the dispersant in the colored layer is preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the colorant.
- the colored layer preferably contains a binder resin from the viewpoint of proper molding process.
- a binder resin a known resin can be applied without limitation.
- the binder resin is preferably a transparent resin from the viewpoint of obtaining a desired color, and specifically, a resin having a total light transmittance of 80% or more is preferable.
- the total light transmittance can be measured by a spectrophotometer (for example, a spectrophotometer UV-2100 manufactured by Shimadzu Corporation).
- the binder resin is not limited, and a known resin can be applied.
- the binder resin include acrylic resin, silicone resin, polyester, polyurethane, and polyolefin.
- the binder resin may be a homopolymer of a specific monomer or a copolymer of a specific monomer and another monomer.
- the binder resin may be used alone or in combination of two or more.
- the content of the binder resin in the colored layer is preferably 5% by mass to 70% by mass and 10% by mass to 60% by mass with respect to the total mass of the colored layer from the viewpoint of molding processability. Is more preferable, and 20% by mass to 60% by mass is particularly preferable.
- the colored layer may contain additives in addition to the above components, if necessary.
- a known additive can be applied without limitation.
- the additive include the surfactant described in paragraph 0017 of Japanese Patent No. 4502784, paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362, and the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. (Also referred to as a polymerization inhibitor, preferably a phenothiazine.), Additives described in paragraphs 0058 to 0071 of JP-A-2000-310706 can be mentioned.
- a method for forming the colored layer examples include a method using a composition for forming a colored layer, a method of laminating colored films, and the like.
- a method for forming the colored layer a method using a composition for forming a colored layer is preferable.
- a colored layer may be formed by using a commercially available paint such as nax Real series, nax Admira series, nax multi series (manufactured by Nippon Paint Co., Ltd.), and Retan PG series (manufactured by Kansai Paint Co., Ltd.).
- Examples of the method of using the composition for forming a colored layer include a method of applying a composition for forming a colored layer to form a colored layer, a method of printing a composition for forming a colored layer to form a colored layer, and the like.
- Examples of the printing method include screen printing, inkjet printing, flexographic printing, gravure printing, offset printing and the like.
- the composition for forming a colored layer contains a colorant. Further, the composition for forming a colored layer preferably contains an organic solvent, and may contain each of the above components that can be contained in the colored layer.
- the content of each of the above components that can be contained in the composition for forming a colored layer is the amount obtained by replacing "colored layer” with "composition for forming a colored layer” in the description regarding the content of each of the above components in the colored layer. It is preferable to adjust within the range of.
- the organic solvent is not limited, and a known organic solvent can be applied.
- examples of the organic solvent include ester compounds, ether compounds, ketone compounds, aromatic hydrocarbon compounds and the like.
- the organic solvent may be used alone or in combination of two or more.
- the content of the organic solvent in the composition for forming a colored layer is preferably 5% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, based on the total mass of the composition for forming a colored layer.
- Examples of the method for preparing the composition for forming a colored layer include a method of mixing an organic solvent and a component contained in the colored layer such as a colorant.
- a pigment dispersion liquid containing the pigment and the dispersant is used from the viewpoint of further enhancing the uniform dispersibility and dispersion stability of the pigment to form a colored layer. It is preferable to prepare a composition for formation.
- the thickness of the colored layer is not particularly limited, but is preferably 0.5 ⁇ m or more, more preferably 3 ⁇ m or more, and 3 ⁇ m to 50 ⁇ m from the viewpoint of visibility and three-dimensional moldability. Further preferably, it is particularly preferably 3 ⁇ m to 20 ⁇ m. When two or more colored layers are provided, it is preferable that each colored layer is independently in the range of the thickness.
- the decorative film for molding according to the present disclosure may also have a protective layer.
- the protective layer may be a layer having sufficient strength to protect the cholesteric liquid crystal layer or the like, but a resin having excellent durability against light, heat, humidity and the like is preferable. Further, from the viewpoint of visibility and blackening (suppression of reflection by reflected light from the outside, for example, suppression of reflection of fluorescent lamp), the protective layer may have an antireflection ability.
- the protective layer preferably contains a resin from the viewpoint of durability, and is at least one selected from the group consisting of siloxane resin, fluororesin, urethane resin, acrylic resin, ester resin, melamine resin, and olefin resin. It is more preferable to contain a resin, and it is further preferable to contain at least one resin selected from the group consisting of a siloxane resin, a fluororesin, and a urethane resin.
- the fluororesin is not particularly limited, and examples thereof include those described in paragraphs 0076 to 0106 of JP-A-2009-217258 and paragraphs 0083 to 0127 of JP-A-2007-2299999.
- fluororesin examples include a fluoroalkyl resin in which hydrogen in an olefin is replaced with fluorine, and examples thereof include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxyalkano, and perfluoro.
- copolymers such as ethylene propene and ethylene tetrafluoroethylene, or fluororesin dispersions that are water-dispersed by copolymerizing with an emulsifier or a component that enhances affinity with water.
- a fluororesin examples include Lumiflon manufactured by Asahi Glass Co., Ltd., Obbligato, Zeffle manufactured by Daikin Industries, Ltd., Neophron, Teflon manufactured by DuPont (registered trademark), and Kinner manufactured by Arkema Co., Ltd.
- a compound having at least one of a polymerizable functional group and a crosslinkable functional group and containing a fluorine atom may be used, and a perfluoroalkyl (meth) acrylate, a vinyl fluoride monomer, and a fluorine atom may be used.
- Examples thereof include a radically polymerizable monomer such as a vinylidene compound monomer and a cationically polymerizable monomer such as perfluorooxetane.
- fluorine compounds include LINK3A manufactured by Kyoeisha Chemical Co., Ltd., Optool manufactured by Daikin Industries, Ltd., Opstar manufactured by Arakawa Chemical Industries, Ltd., and tetrafluorooxetane manufactured by Daikin Industries, Ltd. ..
- the cholesteric liquid crystal layer it is preferable to have a layer containing an ultraviolet (UV) absorber on the visual side rather than the cholesteric liquid crystal layer.
- the ultraviolet absorber may be contained in the protective layer or the base material, and a layer containing the ultraviolet absorber (ultraviolet absorbing layer) may be separately provided.
- the ultraviolet absorber is a compound having an ultraviolet absorbing property and having a molecular weight of less than 5,000.
- the molecular weight refers to the weight average molecular weight measured by the above method when the ultraviolet absorber has a molecular weight distribution. If it does not have a molecular weight distribution, the molecular weight is measured using electrospray ionization mass spectrometry (ESI-MS).
- ESI-MS electrospray ionization mass spectrometry
- ESI-MS electrospray ionization mass spectrometry
- a compound having a maximum absorption wavelength of 380 nm or less is preferable, and a compound having a maximum absorption wavelength of 250 nm to 380 nm (particularly preferably 270 nm to 380 nm) is more preferable.
- the ultraviolet absorber examples include triazine compounds, benzotriazole compounds, benzophenone compounds, salicylic acid compounds, metal oxide particles and the like. From the viewpoint of ultraviolet absorption performance, the ultraviolet absorber preferably contains a triazine compound or a benzotriazole compound, and more preferably contains a triazine compound. The total content of the triazine compound and the benzotriazole compound in the ultraviolet absorber is preferably 80% by mass or more with respect to the total amount of the ultraviolet absorber.
- the UV absorber is preferably contained in the binder polymer.
- the binder is not particularly limited, but at least one selected from the group consisting of acrylic resin, polyester, polyurethane, polyolefin, siloxane resin, and fluoropolymer is preferable, and the binder is selected from the group consisting of acrylic resin, polyester, polyurethane, and polyolefin. At least one type is more preferable, and acrylic resin is further preferable.
- the thickness of the protective layer is not particularly limited, but is preferably 2 ⁇ m or more, more preferably 4 ⁇ m or more, and further preferably 4 ⁇ m to 50 ⁇ m from the viewpoint of wiping resistance and three-dimensional moldability. It is particularly preferably 4 ⁇ m to 20 ⁇ m.
- the decorative film for molding according to the present disclosure may have an adhesive layer from the viewpoint of easy attachment to other members (preferably other members for molding) and improvement of adhesion between layers. Good.
- the material of the adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a known adhesive or a layer containing an adhesive can be mentioned.
- the pressure-sensitive adhesive examples include an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive.
- the adhesive "Characteristic evaluation of release paper / release film and adhesive tape and its control technology", Information Mechanism, 2004, acrylic adhesive described in Chapter 2, ultraviolet (UV) curable adhesive Agents, silicone adhesives and the like.
- the acrylic pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing a polymer of (meth) acrylic monomer ((meth) acrylic polymer). When a pressure-sensitive adhesive is contained, a pressure-sensitive adhesive may be further contained.
- the adhesive examples include urethane resin adhesives, polyester adhesives, acrylic resin adhesives, ethylene vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, silicone adhesives and the like.
- a urethane resin adhesive or a silicone adhesive is preferable from the viewpoint of higher adhesive strength.
- the method for forming the adhesive layer is not particularly limited, and a protective film on which the adhesive layer is formed is used as a surface of the cholesteric liquid crystal layer of a laminate having the adhesive layer and an adherend (for example, a base material and a cholesteric liquid crystal layer; The same applies hereinafter), a method of laminating the adhesive layer so as to be in contact with the adherend, a method of laminating the adhesive layer alone so as to be in contact with the adherend, a method of applying the above-mentioned adhesive or the composition containing the adhesive onto the adherend, etc. Can be mentioned.
- the laminating method or coating method a method similar to the above-mentioned method of laminating a transparent film or a method of coating a composition for forming a colored layer is preferably mentioned.
- the thickness of the adhesive layer in the decorative film is preferably 5 ⁇ m to 100 ⁇ m in terms of both adhesive strength and handleability.
- the decorative film for molding according to the present disclosure may have other layers other than those described above.
- examples of other layers include a reflective layer, an ultraviolet absorbing layer, a self-repairing layer, an antistatic layer, an antifouling layer, an electromagnetic wave blocking layer, and a conductive layer, which are known layers in a decorative film.
- Other layers in the decorative film for molding according to the present disclosure can be formed by a known method. For example, a method of applying a composition containing the components contained in these layers (composition for layer formation) in layers and drying the composition can be mentioned.
- the decorative film for molding according to the present disclosure may have a cover film as the outermost layer for the purpose of preventing stains and the like.
- a cover film any material having flexibility and good peelability can be used without particular limitation, and examples thereof include a resin film such as a polyethylene film.
- the method of attaching the cover film is not particularly limited, and examples thereof include known attachment methods, such as a method of laminating a cover film on a protective layer.
- the step of preparing the composition for forming a reflective layer may be, for example, a step of preparing a liquid crystal composition containing a liquid crystal compound (preferably a cholesteric liquid crystal compound), and the liquid crystal composition is further a cholesteric liquid crystal having a polymerizable group. It preferably contains a compound and a photopolymerization initiator and has curability.
- a liquid crystal compound preferably a cholesteric liquid crystal compound
- the liquid crystal composition is further a cholesteric liquid crystal having a polymerizable group. It preferably contains a compound and a photopolymerization initiator and has curability.
- the method for producing a decorative film for molding according to the present disclosure preferably includes a step of preparing the liquid crystal composition.
- the composition of each component of the liquid crystal composition in the step of preparing the liquid crystal composition is the same as that of the liquid crystal composition in the decorative film for molding described above, except for the aspects described later.
- the method for producing a decorative film for molding according to the present disclosure preferably includes a step of applying the liquid crystal composition on a plastic base material to form a liquid crystal composition layer.
- the liquid crystal composition layer formed in this step has a central wavelength of selective reflection wavelength in the range of 380 nm or more and 780 nm or less, and the elastic modulus of the reflection layer at a temperature of Tg + 10 ° C. of a plastic substrate is 0.00001 GPa or more and 0. It may be a reflective layer of 5 GPa or less.
- the above-mentioned base material can be preferably used.
- the liquid crystal composition is applied by using a liquid crystal composition in a solution state with a solvent, or a liquid material such as a melt after heating by a roll coating method, a gravure printing method, a spin coating method, or the like. It can be carried out by an appropriate method.
- the liquid crystal composition can be further applied by various methods such as a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method.
- the liquid crystal composition can be applied by ejecting the liquid crystal composition from a nozzle using an inkjet device to form a liquid crystal composition layer.
- the solvent it is preferable to dry the liquid crystal composition layer by a known method after the application of the liquid crystal composition and before the step of forming the cholesteric liquid crystal layer.
- it may be dried by leaving or air-drying, or by heating.
- the amount of the liquid crystal composition to be applied may be appropriately set in consideration of the liquid crystal composition layer after drying. Further, it is preferable that the liquid crystal compounds in the liquid crystal composition are oriented after the liquid crystal composition is applied and dried.
- the method for producing a decorative film for molding according to the present disclosure preferably includes a step of curing the liquid crystal composition layer to form a cholesteric liquid crystal layer.
- the orientation state of the molecules of the liquid crystal compound including the cholesteric liquid crystal compound is maintained and fixed, and the cholesteric liquid crystal layer is formed.
- the reflective layer has a central wavelength of selective reflection wavelength in the range of 380 nm or more and 780 nm or less, and the elastic modulus of the reflective layer at a temperature of Tg + 10 ° C. of the plastic substrate is 0.00001 GPa or more and 0.5 GPa or less.
- a liquid crystal layer is formed.
- the curing of the liquid crystal composition layer is preferably carried out by a polymerization reaction of a polymerizable group such as an ethylenically unsaturated group or a cyclic ether group contained in the compound contained in the liquid crystal compound.
- a polymerizable group such as an ethylenically unsaturated group or a cyclic ether group contained in the compound contained in the liquid crystal compound.
- the curing is preferably performed by exposure.
- the liquid crystal composition layer preferably contains a photopolymerization initiator.
- the light source for exposure it can be appropriately selected and used according to the photopolymerization initiator.
- a light source capable of irradiating light in a wavelength range for example, 365 nm, 405 nm
- specific examples thereof include an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp.
- the exposure amount is not particularly limited and may be appropriately set, is preferably 5mJ / cm 2 ⁇ 2,000mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 1,000mJ / cm 2 ..
- the heating temperature is not particularly limited and may be selected according to the composition of the liquid crystal compound and the liquid crystal composition to be used, and examples thereof include 60 ° C. to 120 ° C.
- the cholesteric liquid crystal layer may be formed by the exposure, but also other layers such as a colored layer may be cured by the exposure as needed.
- the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be preferably used in the present disclosure.
- the heating temperature and the heating time are not particularly limited and may be appropriately selected according to the thermal polymerization initiator and the like to be used.
- the heating temperature is preferably 60 ° C. or higher and 200 ° C. or lower, and the heating time is preferably 5 minutes to 2 hours.
- the heating means is not particularly limited, and known heating means can be used, and examples thereof include a heater, an oven, a hot plate, an infrared lamp, and an infrared laser.
- the method for producing a decorative film for molding according to the present disclosure includes steps other than the above-mentioned steps, for example, a step of forming a colored layer, a step of forming an alignment layer, a step of forming a protective layer, and a step of forming an adhesive layer. Any other step may be included as desired, such as a step of performing.
- the formation of each of the above layers such as a colored layer can be performed by using the above-mentioned method or a known method.
- the molding method according to the present disclosure is a molding method using the decorative film for molding according to the present disclosure, and is preferably a molding method including a step of molding the decorative film for molding according to the present disclosure.
- the molded product according to the present disclosure is a molded product obtained by molding the decorative film for molding according to the present disclosure, and is preferably a molded product manufactured by the molding method according to the present disclosure.
- the molded product according to the present disclosure is
- a molded body obtained by molding a film having a reflective layer having a central wavelength of selective reflection wavelength in the range of 380 nm or more and 780 nm or less on a plastic base material is formed on a display surface of a display display unit. It is preferable to have a step of molding in a range where the maximum height T2 in the normal direction of the display surface satisfies the relationship of T2> 0.02 ⁇ T1 with respect to the maximum width T1 in the in-plane direction.
- the molding method according to the present disclosure more preferably satisfies T2> 0.05 ⁇ T1, and more preferably T2> 0.1 ⁇ T1.
- the molding method according to the present disclosure can obtain a decorative molded body that expresses a uniform color regardless of the viewing angle.
- the effect is particularly obtained when the decorative film has a mirror surface design having an average reflectance of 30% or more in the range of 380 to 780 nm.
- the molding method according to the present disclosure preferably includes a step of molding the decorative film for molding according to the present disclosure. Since the decorative film for molding according to the present disclosure is excellent in molding processability, it can be suitably used for manufacturing a molded product, and for example, at least one kind selected from the group consisting of three-dimensional molding and insert molding. It is particularly suitable when producing a molded product by molding.
- the method for producing the molded product will be described in detail by taking insert molding as an example.
- a molded product in insert molding, can be obtained, for example, by arranging a decorative film for molding in a mold in advance and injection molding a base resin in the mold.
- a molded product in which a decorative film for molding is integrated on the surface of the resin molded product can be obtained.
- the method for producing a molded product is a step of arranging a decorative film for molding in a mold for injection molding and closing the mold, then a step of injecting molten resin into the mold, and further, the injection resin is solidified. Includes the step of taking out when it is done.
- the injection molding mold (that is, the molding mold) used for manufacturing the decorative molded product is a mold having a convex shape (that is, a male mold) and a mold having a concave shape corresponding to the convex shape (that is, a mold).
- a female mold is provided, and the mold is closed after the decorative film for molding is placed on the molding surface which is the inner peripheral surface of the female mold.
- the decorative film for molding is molded (preformed) by using the molding mold for molding. It is also possible to give the decorative film a three-dimensional shape in advance and supply it to the molding die. In addition, when arranging the decorative film for molding in the molding mold, it is necessary to align the decorative film for molding and the molding mold with the decorative film for molding inserted in the molding mold. Become.
- the fixing pin is formed in advance at a position where it fits with the alignment hole. Further, as a method of aligning the decorative film for molding and the molding die with the decorative film for molding inserted in the molding die, there is a method other than the method of inserting the fixing pin into the alignment hole. The following methods can be used.
- the temperature of the molten resin injected into the molding die is set according to the physical characteristics of the resin used.
- the temperature of the molten resin is preferably in the range of 240 ° C. or higher and 260 ° C. or lower.
- the burr and the dummy portion of the molded product are integrated around the decorative portion that is finally the product (molded product).
- the dummy portion there is an insertion hole formed by inserting the fixing pin in the above-mentioned alignment. Therefore, a molded product can be obtained by performing a finishing process for removing the above-mentioned burrs and dummy portions from the intermediate molded product before the finishing process.
- three-dimensional molding is also preferably mentioned.
- thermoforming, vacuum molding, compressed air molding, vacuum pressure air molding and the like are preferably mentioned.
- the method of vacuum forming is not particularly limited, but a method of performing three-dimensional molding in a heated state under vacuum is preferable.
- the vacuum refers to a state in which the room is evacuated to a degree of vacuum of 100 Pa or less.
- the temperature at the time of three-dimensional molding may be appropriately set according to the base material for molding used, but a temperature range of 60 ° C. or higher is preferable, a temperature range of 80 ° C. or higher is more preferable, and a temperature range of 100 ° C. or higher is further preferable. ..
- the upper limit of the temperature at the time of three-dimensional molding is preferably 200 ° C.
- the temperature at the time of three-dimensional molding refers to the temperature of the molding base material used for three-dimensional molding, and is measured by attaching a thermocouple to the surface of the molding base material.
- the transmittance is not particularly limited.
- a base material of 88% or more is preferable, and a base material having a transmittance of 91.5% or more is more preferable.
- Examples of the material of the mold include glass and plastic, and glass, acrylic, and polycarbonate are preferable examples. More preferably, it is glass and acrylic, and acrylic is most preferable.
- the shape is not particularly limited, but a convex shape having a maximum height near the central portion is preferable.
- a lens shape or a pyramid shape can be mentioned.
- a shape having a uniform uneven pattern in the surface is also preferable. Examples include a microlens array structure and a lenticular structure.
- the molding method according to the present disclosure preferably includes a step of curing the protective layer in the molded decorative film for molding.
- the curing method in the step of curing the protective layer is not particularly limited, depending on the presence or absence of the crosslinkable group of the siloxane resin contained in the protective layer, the presence or absence of the ethylenically unsaturated group of the organic resin, and the polymerization initiator.
- the method of curing the protective layer with light or heat is preferable, and the method of curing the protective layer with light is more preferable.
- the exposure in the step of curing the protective layer may be performed from either side of the decorative film for molding, but it is preferably performed from the side of the protective layer.
- a cover film is provided as the outermost layer on the side of the protective layer, exposure may be performed with the cover film held (before the cover film is peeled off).
- the total light transmittance of the cover film is preferably 80% or more, more preferably 90% or more.
- the exposure method for example, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be preferably used in the present disclosure.
- any light source capable of irradiating light in a wavelength range capable of curing the protective layer (for example, 365 nm or 405 nm) can be appropriately selected and used.
- Specific examples thereof include ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.
- the exposure amount is not particularly limited and may be appropriately set, is preferably 5mJ / cm 2 ⁇ 2,000mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 1,000mJ / cm 2 ..
- the protective layer not only the protective layer but also the colored layer may be cured simultaneously or sequentially, if necessary.
- the colored layer contains a polymerizable compound and a photopolymerization initiator.
- a cured colored layer can be obtained by exposing the colored layer containing the polymerizable compound and the photopolymerization initiator.
- the heating temperature and the heating time when curing by heat are not particularly limited, and may be appropriately selected depending on the thermal polymerization initiator and the like to be used.
- the heating temperature is preferably 60 ° C. or higher and 200 ° C. or lower, and the heating time is preferably 5 minutes to 2 hours.
- the heating means is not particularly limited, and known heating means can be used, and examples thereof include a heater, an oven, a hot plate, an infrared lamp, and an infrared laser.
- the use of the molded product obtained as described above is not particularly limited and can be used for various articles, such as display interior / exterior, automobile interior / exterior, electric product interior / exterior, packaging container, and the like. Particularly preferred. Above all, the interior and exterior of the display are preferable, and the exterior of the display is more preferable.
- a molded product obtained by molding the above-mentioned decorative film for molding of the present invention is arranged on a display display unit.
- a molded product of a decorative film for molding having a display display unit, a plastic base material arranged adjacent to the display display unit, and a reflective layer having a central wavelength of selective reflection wavelength in the range of 380 nm or more and 780 nm or less.
- the maximum height (T2) of the display surface in the normal direction is T2> 0.02 ⁇ T1 with respect to the maximum width (T1) of the display surface of the display unit in the in-plane direction.
- a display having the above relationship is preferable.
- ⁇ Formation of alignment layer 1> As a base material, an acrylic film having a thickness of 125 ⁇ m (Technoloy S001 manufactured by Sumika Acrylic Sales Co., Ltd., Tg of the base material was 105 ° C.) was prepared. A coating liquid for forming the alignment layer 1 was applied to one side of this base material with a wire bar coater. Then, it was dried at 80 ° C. for 120 seconds to prepare a base material having an oriented layer 1 having a layer thickness of 1.0 ⁇ m.
- composition of coating liquid for forming alignment layer 1 The following modified polyvinyl alcohol: 28 parts Citric acid ester (AS3, manufactured by Sankyo Chemical Co., Ltd.): 1.2 parts Photopolymerization initiator (Irgacure 2959, manufactured by BASF): 0.84 parts Glutaraldehyde: 2.8 parts Water: 699 parts Methanol: 226 parts
- Modified polyvinyl alcohol (The number at the bottom right of each structural unit represents the molar ratio)
- the components in the composition shown below were stirred and dissolved in a container kept at 25 ° C. to prepare a coating liquid 1 (liquid crystal composition 1) for a cholesteric liquid crystal layer.
- composition of coating liquid 1 for cholesteric liquid crystal layer Methyl ethyl ketone: 150.6 parts The following liquid crystal compound 1 (rod-shaped liquid crystal compound): 93.4 parts Photopolymerization initiator A (IRGACURE 907, manufactured by BASF): 0.50 parts The following chiral agent A: 3.3 parts The following Chiral agent B: 3.3 parts The following surfactant F1: 0.027 parts
- Liquid crystal compound 1 (monofunctional): The following rod-shaped liquid crystal compound.
- the liquid crystal compound 1 is a radical polymerization system, and although it has an oxetanyl group (cationically polymerizable functional group), it is defined as monofunctional because it has one acryloxy group (radical polymerizable group).
- Chiral agent B (0 functional): The following compound.
- Bu in the compound represents an n-butyl group.
- the prepared liquid crystal composition 1 was applied to the surface of the rubbing-treated alignment layer 1 with a wire bar coater and dried at 85 ° C. for 120 seconds to obtain a laminate having a cholesteric liquid crystal layer 1 having a layer thickness of 1.4 ⁇ m.
- Acrylic adhesive liquid (SK Dyne SG-50Y, manufactured by Soken Chemical Co., Ltd.) is applied to the side of the base material on which the cholesteric liquid crystal layer 1 is formed with a comma coater, and dried at 120 ° C. for 2 minutes. An adhesive layer 1 having a layer thickness of 25 ⁇ m was formed. In this way, the laminated body 1 (decorative film for molding 1) was produced.
- FIG. 1 is a schematic plan view of a convex mold of a molding mold composed of a concave mold and a convex mold when viewed from above.
- FIG. 1 is a schematic plan view of a convex mold of a molding mold composed of a concave mold and a convex mold when viewed from above.
- FIG. 2 is a schematic cross-sectional view schematically showing a cross section (cross section in the minor axis direction) 22 cut in a direction parallel to the longitudinal direction in the top view of FIG. 1
- FIG. 3 is a schematic cross section of FIG. 1 in the top view. It is a schematic cross-sectional view which shows typically the cross section (cross section in the long axis direction) 32 cut in the direction parallel to the lateral direction.
- a TOM molding machine NGF-0510-R (manufactured by Fuse Vacuum Co., Ltd.) was used for the compressed air molding process, the molding temperature was 120 ° C., and the draw ratio was 200% at the highest portion.
- An integrated exposure amount of 500 mJ / cm 2 is applied to the surface of the base material in the molded body after the molding process by a light exposure device (nitrogen purge UV irradiator, GS Yuasa Co., Ltd., metal halide lamp, output 120 W / cm). Then, it was cured to obtain a molded body 1.
- the elastic modulus of the cholesteric liquid crystal layer 1 was measured using a nanoindenter G200 manufactured by Toyo Technica.
- the reflectance of the laminate 1 before molding is measured in the wavelength range of 380 nm to 1,100 nm from the normal direction on the adhesive layer 1 side of the laminate 1 using a spectrophotometer V-670 manufactured by JASCO Corporation. Measured at.
- As the reflectance the highest value of the maximum value of the reflection spectrum was adopted, and the reflectance was evaluated according to the following evaluation criteria. As an evaluation result, A, B, C, or D is preferable, A, B or C is more preferable, A or B is further preferable, and A is most preferable.
- ⁇ Evaluation Criteria >> A: The reflectance is 30% or more. B: The reflectance is 20% or more and less than 30%. C: The reflectance is 10% or more and less than 20%. D: The reflectance is 5% or more and less than 10%. E: The reflectance is less than 5%.
- the obtained molded body 1 was visually observed, the cracked state of the liquid crystal layer was observed, and the evaluation was performed according to the following evaluation criteria.
- A, B, C, or D is preferable, A, B or C is more preferable, A or B is further preferable, and A is most preferable.
- the draw ratio a film printed with a grid pattern having a width of 2 mm is TOM-molded into the molds of FIGS. 1 to 3 to prepare a molded body, and the draw ratio of each region of the molded body is set to the grid pattern. It was calculated by the stretch length (comparison of the lengths of the lattice sides before and after molding).
- the film on which the lattice pattern with a width of 2 mm is printed is an acrylic film with a thickness of 125 ⁇ m (Technoloy S001 manufactured by Sumika Acrylic Sales Co., Ltd.) and an inkjet printer (Aquity® LED 1600, manufactured by Fujifilm Co., Ltd.). Printed with black ink.
- the molding process was carried out using a TOM molding machine NGF-0510-R (manufactured by Fuse Vacuum Co., Ltd.) at a molding temperature of 120 ° C.
- Example 2 to 7 and Comparative Examples 1 to 2 Laminates 2 to 7 and C1 to C2 (decorative films for molding 2 to 7 and decorative films for molding 2 to 7) in the same manner as in Example 1 except that the composition of the liquid crystal composition 1 is changed to the composition shown in Table 1 or Table 2.
- C1 to C2) and molded bodies 2 to 7 and C1 to C2 were produced, respectively.
- measurement and evaluation were performed by the same method as in Example 1. The results of measurement and evaluation are summarized in Table 1.
- the reflected color in Table 1 indicates the color visually recognized when the decorative film for molding is visually observed from the base material side.
- the fact that green is the reflected color means that light of about 550 nm is reflected.
- Liquid crystal compound 2 (bifunctional): The following rod-shaped liquid crystal compound (1,4-bis [4- (3-acryloyloxypropoxy) benzoyloxy] -2-methylbenzene, manufactured by Tokyo Chemical Industry Co., Ltd.)
- Liquid crystal compound 3 (0 functional): The following rod-shaped liquid crystal compound
- Liquid crystal compound 4 (tetrafunctional): The following rod-shaped liquid crystal compound
- the moldings 1 to 7 are installed on the display display of iphone8S (manufactured by Apple Inc., space gray surface color, black decoration on the display side) with the concave surface of the molding facing the display display, the display is turned off. In the case of, a bright green reflection color was confirmed in three dimensions. On the other hand, when the display was turned on, the image displayed on the display was clearly visible through the molded body, and its effectiveness as a three-dimensional transmissive decorative film was confirmed.
- iphone8S space gray surface color, black decoration on the display side
- the molding decorative films of Examples 1 to 7 had better moldability than the molding decorative films of Comparative Examples 1 to 2. Further, the decorative films for molding of Examples 1 to 7 have high reflectance, excellent decorativeness, and also have a function as a transmissive decorative film.
- Example 8 to 10 Reference Example 1
- the retardation layer of the quarter wave plate is formed into the cholesteric liquid crystal layer by the method described in paragraph numbers [0170] to [0171] of JP-A-2017-215558.
- an adhesive layer was formed on the retardation layer of the 1/4 wave plate, and the convex shape used for molding was the convex shape 40 (convex shape 40) having the shape shown in FIG. Molds 8 to 10 were produced in the same manner as in Example 1 except that the convex surface 52 of the above was changed to contact). Note that FIG.
- FIG. 4 is a schematic plan view when another example of the convex mold of the molded mold composed of the concave mold and the convex mold is viewed from above
- FIG. 5 is a schematic plan view of the convex mold of FIG. 4 when viewed from above. It is the schematic cross-sectional view which shows typically the cross section 62 cut along the line.
- T1 the maximum width of the display surface of the display display unit in the in-plane direction
- T2 maximum height
- Molds 8 to 10 were installed on the display display portion and the back surface of ELT-24SRound (manufactured by Tedeck, an inorganic EL transparent display) with the concave surface of the molded body facing the display side.
- the visibility of the display side and the back side when the image was displayed on the display was evaluated according to the following evaluation criteria.
- Reference Example 1 a laminate 1 (unmolded product) is attached to the display display portion and the back surface of ELT-24SRound (manufactured by Tedeck Co., Ltd., an inorganic EL transparent display) from the adhesive layer side, and Examples 8 to 10
- the evaluation was performed in the same manner as above. The results are summarized in Table 2.
- B A slight change in color is confirmed between the case of visual recognition from the 0 ° direction and the case of visual recognition from the 45 ° direction.
- C A change in color is confirmed between the case of visual recognition from the 0 ° direction and the case of visual recognition from the 45 ° direction, but the colors are the same.
- D A large change in color is confirmed between the case of visual recognition from the 0 ° direction and the case of visual recognition from the 45 ° direction.
- the decorative films for molding of Examples 8 to 10 are excellent in visibility of the image when viewed from the display surface side of the transparent display, while are low in visibility from the back surface side. , The displayed image was well hidden. In addition, the reflected color of the cholesteric liquid crystal layer was visually recognized as a uniform color from the back side regardless of the angle, demonstrating an excellent function as a decorative film.
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Abstract
Description
(2)反射層が、コレステリック液晶を含む層である(1)に記載の成型用加飾フィルム。
(3)コレステリック液晶化合物は、エチレン性不飽和基が1つであるか、又は環状エーテル基が1つである化合物である(2)に記載の成型用加飾フィルム。
(4)コレステリック液晶化合物が、1つのエチレン性不飽和基と1つの環状エーテル基とを有する化合物である(2)又は(3)に記載の成型用加飾フィルム。
(5)反射層は、更に、重合性基を含むカイラル剤、又は、重合性基を含むカイラル剤及び重合性基を有しないカイラル剤を含む(2)~(4)のいずれか1つに記載の成型用加飾フィルム。
(6)重合性基を含むカイラル剤は、2つ以上の重合性基を有する(5)に記載の成型用加飾フィルム。
(7)コレステリック液晶化合物を含む層が、コレステリック液晶化合物及び光重合開始剤を含む液晶組成物の硬化物である(2)~(6)のいずれか1つに記載の成型用加飾フィルム。
(8)(1)~(7)のいずれか1つに記載の成型用加飾フィルムが成型された成型物。
(9)(8)に記載の成型物がディスプレイ表示部に配置されたディスプレイ。
(10)ディスプレイ表示部と、
ディスプレイ表示部に隣接して配置され、プラスチック基材、及び選択反射波長の中心波長を380nm以上780nm以下の範囲に有する反射層を有する成型用加飾フィルムの成型物と、
を備え、成型物は、ディスプレイ表示部の表示面の面内方向の最大幅T1に対し、表示面の法線方向の最大高さT2が、T2>0.02×T1の関係を有するディスプレイ。
T1/2=100-(100-Tmin)÷2
本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
更に、本明細書において組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する該当する複数の物質の合計量を意味する。
本明細書において「工程」との語は、独立した工程だけでなく、他の工程と明確に区別できない場合であっても工程の所期の目的が達成されれば、本用語に含まれる。
本明細書において「全固形分」とは、組成物の全組成から溶剤を除いた成分の総質量をいう。また、「固形分」とは、上述のように、溶剤を除いた成分であり、例えば、25℃において固体であっても、液体であってもよい。
本明細書における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
また、本開示において、「質量%」と「重量%」とは同義であり、「質量部」と「重量部」とは同義である。
更に、本開示において、2以上の好ましい態様の組み合わせは、より好ましい態様である。
また、本開示における重量平均分子量(Mw)及び数平均分子量(Mn)は、特に断りのない限り、TSKgel GMHxL、TSKgel G4000HxL、TSKgel G2000HxL(何れも東ソー(株)製の商品名)のカラムを使用したゲルパーミエーションクロマトグラフィ(GPC)分析装置により、溶剤THF(テトラヒドロフラン)、示差屈折計により検出し、標準物質としてポリスチレンを用いて換算した分子量である。
以下、本開示を詳細に説明する。
本開示に係る成型用加飾フィルム(以下、単に「加飾フィルム」ともいう。)は、プラスチック基材(以下、単に基材ともいう。)と、プラスチック基材上に設けられ、選択反射波長の中心波長を380nm以上780nm以下の範囲に有する反射層と、を有し、プラスチック基材のガラス転移点(以下、「Tg」と略記することがある。)+10℃の温度における、反射層の弾性率が、0.0001GPa以上0.5GPa以下である加飾フィルムである。
上記構成による優れた効果の作用機構は明確ではないが、以下のように推定している。
一般的に、プラスチックシートの成型加工は、プラスチック基材の「Tg+10℃」以上の温度で行われることが多い。Tg+10℃の温度における反射層の弾性率が0.0001GPa以上の範囲であると、反射層の自己凝集力及び膜の構造が保たれ、プラスチック基材に追随し膜が延伸される。また、弾性率が0.5GPa以下であることにより、反射層の柔軟性が保たれ、破断及びクラックの発生が抑えられ、基材に追随して延伸できると推定される。
本開示に係る成型用加飾フィルムは、基材を有する。
基材は、立体成型、インサート成型等の成型に用いられる基材として従来公知のものが特に制限なく使用でき、加飾フィルムの用途、インサート成型への適性等に応じて、適宜、選択されればよい。
また、基材の形状及び材質は、特に制限はなく、所望に応じ適宜選択すればよい。基材は、成形容易性(特にインサート成型容易性)、及び、チッピング耐性の観点から、樹脂製の基材であることが好ましく、樹脂フィルムであることが好ましい。
中でも、成型加工性、及び、強度の観点から、PET、アクリル樹脂、ウレタン樹脂、ウレタン-アクリル樹脂、PC、アクリル-ポリカーボネート樹脂、及びポリプロピレンよりなる群から選ばれた少なくとも1種の樹脂フィルムであることが好ましく、アクリル樹脂、PC、及び、アクリル-ポリカーボネート樹脂よりなる群から選ばれた少なくとも1種の樹脂フィルムであることがより好ましい。
また、基材としては、2層以上の積層樹脂基材であってもよい。例えば、アクリル樹脂/ポリカーボネート積層フィルムが好ましく挙げられる。
添加物としては、例えば、鉱油、炭化水素、脂肪酸、アルコール、脂肪酸エステル、脂肪酸アミド、金属石けん、天然ワックス、シリコーンなどの潤滑剤;水酸化マグネシウム、水酸化アルミニウム等の無機難燃剤;ハロゲン系、リン系等の有機難燃剤;金属粉、タルク、炭酸カルシウム、チタン酸カリウム、ガラス繊維、カーボン繊維、木粉等の有機又は無機の充填剤;酸化防止剤、紫外線防止剤、滑剤、分散剤、カップリング剤、発泡剤、着色剤等の添加剤、ポリエステル、ポリアセタール、ポリアミド、ポリフェニレンエーテル等であって、上述した樹脂以外のエンジニアリングプラスチックなどが挙げられる。
市販品としては、例えば、テクノロイ(登録商標)シリーズ(アクリル樹脂フィルム又はアクリル樹脂/ポリカーボネート樹脂積層フィルム、住友化学(株)製)ABSフィルム(オカモト(株)製)、ABSシート(積水成型工業(株)製)、テフレックス(登録商標)シリーズ(PETフィルム、帝人フィルムソリューション(株)製)、ルミラー(登録商標)易成型タイプ(PETフィルム、東レ(株)製)、ピュアサーモ(ポリプロピレンフィルム、出光ユニテック(株)製)等を挙げることができる。
ABSは、アクリロニトリル/ブタジエン/スチレン共重合樹脂のことを指す。
本開示に係る成型用加飾フィルムは、プラスチック基材上に、選択反射波長の中心波長を380nm以上780nm以下の範囲に有する反射層を有する。選択反射波長を有する反射層としては、コレステリック液晶膜、誘電体多層膜、金属微粒子含有膜などが挙げられ、延伸性の観点から、コレステリック液晶化合物を含む層であることが好ましい。
反射層は、コレステリック液晶化合物を含む層(コレステリック液晶層)であることが好ましい。
本開示に係る成型用加飾フィルムにおけるコレステリック液晶層は、基材上にあればよく、基材に直接接していなくともよく、例えば、後述する着色層等の他の層を介して基材上に有していてもよい。
コレステリック液晶層は、液晶組成物を硬化してなる層であることが好ましい。
本開示における液晶組成物は、エチレン性不飽和基を1つ有するか、又は環状エーテル基を1つ有するコレステリック液晶化合物を少なくとも含むことが好ましい。「エチレン性不飽和基を1つ有するか、又は環状エーテル基を1つ有する」とは、1分子中にエチレン性不飽和基又は環状エーテル基のいずれかを有するということではなく、1分子中に含まれるエチレン性不飽和基又は環状エーテル基が1つであること意味する。
コレステリック液晶層は、コレステリック液晶化合物及び光重合開始剤を含む液晶組成物の硬化物(硬化層)であることがより好ましい。光重合開始剤については後述する。
本開示におけるコレステリック液晶化合物は、エチレン性不飽和基を1つ有するか、又は環状エーテル基を1つ有する化合物であることが好ましい。
中でも、反応性の観点から、(メタ)アクリロキシ基、(メタ)アクリルアミド基、又は、ビニル基であることが好ましく、(メタ)アクリロキシ基、又は、(メタ)アクリルアミド基であることがより好ましく、(メタ)アクリロキシ基であることが特に好ましい。
更に、成型性観点から、エチレン性不飽和基、及び、環状エーテル基の両方を有する化合物であることが好ましく、1つのエチレン性不飽和基と1つの環状エーテル基とを有する化合物であることがより好ましい。
中でも、コレステリック液晶層における螺旋構造のピッチの調整容易性、並びに、成型後性、意匠性の観点から、棒状液晶化合物であることが好ましい。
上記コレステリック液晶層は、棒状液晶化合物を重合によって配向を固定してなる層であることがより好ましい。
棒状液晶化合物としては、Makromol. Chem., 190巻、2255頁(1989年)、Advanced Materials 5巻、107頁(1993年)、米国特許第4683327号明細書、同5622648号明細書、同5770107号明細書、国際公開第95/22586号、同95/24455号、同97/00600号、同98/23580号、同98/52905号、特開平1-272551号公報、同6-16616号公報、同7-110469号公報、同11-80081号公報、及び、特開2001-328973号公報などに記載の化合物のうち、エチレン性不飽和基を1つ有するか、又は環状エーテル基を1つ有するものを用いることができる。更に、棒状液晶化合物としては、例えば、特表平11-513019号公報や特開2007-279688号公報に記載のもののうち、エチレン性不飽和基を1つ有するか、又は環状エーテル基を1つ有するものを好ましく用いることができる。
エチレン性不飽和基を1つ有するか、又は環状エーテル基を1つ有するコレステリック液晶化合物の含有量は、液晶組成物の全固形分に対し、25質量%以上であることが好ましい。25質量%以上であると、成型性に優れる加飾フィルムが得られる。
また、エチレン性不飽和基を1つ有するか、又は環状エーテル基を1つ有するコレステリック液晶化合物の含有量は、成型性の観点から、30質量%以上であることが好ましく、40質量%以上であることがより好ましく、60質量%以上99質量%以下であることが更に好ましく、80質量%以上98質量%以下であることが特に好ましい。
上記液晶組成物は、エチレン性不飽和基を1つ有するか、又は環状エーテル基を1つ有するコレステリック液晶化合物以外の他のコレステリック液晶化合物(以下、単に「他の液晶化合物」ともいう。)を含んでいてもよい。
他の液晶化合物としては、例えば、エチレン性不飽和基及び環状エーテル基を有しないコレステリック液晶化合物、2つ以上のエチレン性不飽和基を有し、かつ環状エーテル基を有しないコレステリック液晶化合物、2つ以上の環状エーテル基を有し、かつエチレン性不飽和基を有しないコレステリック液晶化合物、及び、2つ以上のエチレン性不飽和基及び2つ以上の環状エーテル基を有するコレステリック液晶化合物が挙げられる。
中でも、他の液晶化合物としては、成型性の観点から、エチレン性不飽和基及び環状エーテル基を有しないコレステリック液晶化合物、2つ以上のエチレン性不飽和基を有し、かつ環状エーテル基を有しないコレステリック液晶化合物、2つ以上の環状エーテル基を有し、かつエチレン性不飽和基を有しないコレステリック液晶化合物よりなる群から選ばれた少なくとも1種の化合物であることが好ましく、エチレン性不飽和基及び環状エーテル基を有しないコレステリック液晶化合物、2つのエチレン性不飽和基を有し、かつ環状エーテル基を有しないコレステリック液晶化合物、2つの環状エーテル基を有し、かつエチレン性不飽和基を有しないコレステリック液晶化合物よりなる群から選ばれた少なくとも1種の化合物であることがより好ましく、エチレン性不飽和基及び環状エーテル基を有しないコレステリック液晶化合物、及び、2つのエチレン性不飽和基を有し、かつ環状エーテル基を有しないコレステリック液晶化合物よりなる群から選ばれた少なくとも1種の化合物であることが特に好ましい。
他の液晶化合物における棒状液晶化合物としては、Makromol. Chem., 190巻、2255頁(1989年)、Advanced Materials 5巻、107頁(1993年)、米国特許第4683327号明細書、同5622648号明細書、同5770107号明細書、国際公開第95/22586号、同95/24455号、同97/00600号、同98/23580号、同98/52905号、特開平1-272551号公報、同6-16616号公報、同7-110469号公報、同11-80081号公報、及び、特開2001-328973号公報などに記載の化合物を用いることができる。更に、棒状液晶化合物としては、例えば、特表平11-513019号公報又は特開2007-279688号公報に記載のものを好ましく用いることができる。
他の液晶化合物における円盤状液晶化合物としては、例えば、特開2007-108732号公報又は特開2010-244038号公報に記載のものを好ましく用いることができる。
他の液晶化合物の含有量は、成型性の観点から、液晶組成物の全固形分に対し、70質量%以下であることが好ましく、60質量%以下であることがより好ましく、40質量%以下であることが更に好ましく、30質量%以下であることが特に好ましい。なお、他の液晶化合物の含有量の下限値は、0質量%である。
上記液晶組成物は、コレステリック液晶層形成の容易性、及び、螺旋構造のピッチの調整容易性の観点から、カイラル剤(光学活性化合物)を含むことが好ましい。
カイラル剤は、コレステリック液晶層における螺旋構造を誘起する機能を有する。
カイラル剤は、液晶化合物によって誘起する螺旋のよじれ方向又は螺旋ピッチが異なるため、目的に応じて選択すればよい。
カイラル剤としては、特に制限はなく、公知の化合物(例えば、液晶デバイスハンドブック、第3章4-3項、TN(twisted nematic)、STN(Super-twisted nematic)用カイラル剤、199頁、日本学術振興会第142委員会編、1989に記載)、イソソルビド、イソマンニド誘導体等を用いることができる。
カイラル剤は、一般に不斉炭素原子を含むが、不斉炭素原子を含まない軸性不斉化合物あるいは面性不斉化合物もカイラル剤として用いることができる。
軸性不斉化合物又は面性不斉化合物の例には、ビナフチル化合物、ヘリセン化合物、又は、パラシクロファン化合物が好ましく挙げられる。
上記重合性基としては、重合可能な基であれば特に制限はないが、反応性、及び、成型性の観点から、エチレン性不飽和基、又は、環状エーテル基であることが好ましく、エチレン性不飽和基であることがより好ましい。
カイラル剤におけるエチレン性不飽和基及び環状エーテル基の好ましい態様は、上述したコレステリック液晶化合物におけるエチレン性不飽和基及び環状エーテル基の好ましい態様とそれぞれ同様である。
また、カイラル剤がエチレン性不飽和基、又は、環状エーテル基を有する場合、反応性、及び、成型性の観点から、上記液晶組成物におけるコレステリック液晶化合物が有するエチレン性不飽和基、又は、環状エーテル基と、カイラル剤が有するエチレン性不飽和基、又は、環状エーテル基とは同種の基(例えば、エチレン性不飽和基、好ましくは(メタ)アクリロキシ基)であることが好ましく、同じ基であることがより好ましい。
更に、重合性基を有するカイラル剤は、反応性、及び、成型性の観点から、2つ以上の重合性基を有するカイラル剤であることが好ましく、2つ以上のエチレン性不飽和基を有するカイラル剤、又は、2つ以上の環状エーテル基を有するカイラル剤であることがより好ましく、2つ以上のエチレン性不飽和基を有するカイラル剤であることが特に好ましい。
また、カイラル剤は、コレステリック液晶化合物であってもよい。
感光性カイラル剤とは、光を吸収することにより構造が変化し、コレステリック液晶層の螺旋ピッチを変化させ得る化合物である。このような化合物としては、光異性化反応、光二量化反応、及び、光分解反応の少なくとも1つを起こす化合物が好ましい。
光異性化反応を起こす化合物とは、光の作用で立体異性化又は構造異性化を起こす化合物をいう。光異性化化合物としては、例えば、アゾベンゼン化合物、スピロピラン化合物などが挙げられる。
また、光二量化反応を起こす化合物とは、光の照射によって、二つの基の間に付加反応を起こして環化する化合物をいう。光二量化化合物としては、例えば、桂皮酸誘導体、クマリン誘導体、カルコン誘導体、ベンゾフェノン誘導体などが挙げられる。
また、上記光としては、特に制限はなく、紫外光、可視光、赤外光等が挙げられる。
式(CH1)のArCH1及びArCH2におけるアリール基は、置換基を有していてもよく、総炭素数6~40であることが好ましく、総炭素数6~30であることがより好ましい。置換基としては、例えば、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アルコキシ基、ヒドロキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、カルボキシ基、シアノ基、又は、複素環基が好ましく、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、ヒドロキシ基、アシルオキシ基、アルコキシカルボニル基、又は、アリールオキシカルボニル基がより好ましい。
式(CH1)におけるRCH1及びRCH2はそれぞれ独立に、水素原子であることが好ましい。
式(CH2)及び式(CH3)におけるLCH1及びLCH2はそれぞれ独立に、炭素数1~10のアルコキシ基、又は、ヒドロキシ基が好ましい。
式(CH2)におけるnCH1は、0又は1が好ましい。
式(CH3)におけるnCH2は、0又は1が好ましい。
複素芳香環基としては、ピリジル基、ピリミジニル基、フリル基、又は、ベンゾフラニル基が好ましく、ピリジル基、又は、ピリミジニル基がより好ましい。
カイラル剤の含有量は、使用するコレステリック液晶化合物の構造や螺旋構造の所望のピッチに応じ適宜選択することができるが、コレステリック液晶層形成の容易性、螺旋構造のピッチの調整容易性、及び、成型性の観点から、上記液晶組成物の全固形分に対し、1質量%以上20質量%以下であることが好ましく、2質量%以上15質量%以下であることがより好ましく、3質量%以上10質量%以下であることが特に好ましい。
また、カイラル剤として重合性基を有するカイラル剤を含有する場合、重合性基を有するカイラル剤の含有量は、成型性の観点から、上記液晶組成物の全固形分に対し、0.2質量%以上15質量%以下であることが好ましく、0.5質量%以上10質量%以下であることがより好ましく、1質量%以上8質量%以下であることが更に好ましく、1.5質量%以上5質量%以下であることが特に好ましい。
更に、カイラル剤として重合性基を有しないカイラル剤を含有する場合、重合性基を有しないカイラル剤の含有量は、成型性の観点から、上記液晶組成物の全固形分に対し、0.2質量%以上20質量%以下であることが好ましく、0.5質量%以上15質量%以下であることがより好ましく、1.5質量%以上10質量%以下であることが特に好ましい。
また、コレステリック液晶層におけるコレステリック液晶の螺旋構造のピッチ、並びに、後述する選択反射波長及びその範囲は、使用する液晶化合物の種類だけでなく、カイラル剤の含有量を調製することによっても、容易に変化させることができる。一概には言えないが、液晶組成物におけるカイラル剤の含有量が2倍になると、上記ピッチが1/2、及び、上記選択反射波長の中心値も1/2となる場合がある。
上記液晶組成物は、重合開始剤を含むことが好ましく、光重合開始剤を含むことがより好ましい。
また、上記液晶組成物がエチレン性不飽和基を1つ有するコレステリック液晶化合物を含む場合、上記液晶組成物は、成型性の観点から、ラジカル重合開始剤を含むことが好ましく、光ラジカル重合開始剤を含むことがより好ましい。
更に、上記液晶組成物が環状エーテル基を1つ有するコレステリック液晶化合物を含む場合、上記液晶組成物は、成型性の観点から、カチオン重合開始剤を含むことが好ましく、光カチオン重合開始剤を含むことがより好ましい。
また、上記液晶組成物は、重合開始剤として、ラジカル重合開始剤、又は、カチオン重合開始剤のどちらか一方のみを含むことが好ましい。
また、重合開始剤は、紫外線照射によって重合反応を開始可能な光重合開始剤であることが好ましい。
光重合開始剤の例としては、α-カルボニル化合物(米国特許第2367661号、同2367670号の各明細書記載)、アシロインエーテル化合物(米国特許第2448828号明細書記載)、α-炭化水素置換芳香族アシロイン化合物(米国特許第2722512号明細書記載)、多核キノン化合物(米国特許第3046127号、同2951758号の各明細書記載)、トリアリールイミダゾールダイマーとp-アミノフェニルケトンとの組み合わせ(米国特許第3549367号明細書記載)、アクリジン化合物及びフェナジン化合物(特開昭60-105667号公報、米国特許第4239850号明細書記載)、オキサジアゾール化合物(米国特許第4212970号明細書記載)等が挙げられる。
光ラジカル重合開始剤としては、α-ヒドロキシアルキルフェノン化合物、α-アミノアルキルフェノン化合物、アシルホスフィンオキサイド化合物等が好ましく挙げられる。
更に、光カチオン重合開始剤としては、公知のものを用いることができる。
光カチオン重合開始剤としては、ヨードニウム塩化合物、スルホニウム塩化合物等が好ましく挙げられる。
重合開始剤の含有量は、使用するコレステリック液晶化合物の構造や螺旋構造の所望のピッチに応じ適宜選択することができるが、コレステリック液晶層形成の容易性、螺旋構造のピッチの調整容易性、重合速度、及び、コレステリック液晶層の強度の観点から、上記液晶組成物の全固形分に対し、0.05質量%以上10質量%以下であることが好ましく、0.05質量%以上5質量%以下であることがより好ましく、0.1質量%以上2質量%以下であることが更に好ましく、0.2質量%以上1質量%以下であることが特に好ましい。
上記液晶化合物は、硬化後のコレステリック液晶層の強度向上及び耐久性向上のため、架橋剤を含んでいてもよい。架橋剤としては、紫外線、熱、湿気等で硬化するものが好適に使用できる。
架橋剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えばトリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート等の多官能アクリレート化合物;グリシジル(メタ)アクリレート、エチレングリコールジグリシジルエーテル等のエポキシ化合物;2,2-ビスヒドロキシメチルブタノール-トリス[3-(1-アジリジニル)プロピオネート]、4,4-ビス(エチレンイミノカルボニルアミノ)ジフェニルメタン等のアジリジン化合物;ヘキサメチレンジイソシアネート、ビウレット型イソシアネート等のイソシアネート化合物;オキサゾリン基を側鎖に有するポリオキサゾリン化合物;ビニルトリメトキシシラン、N-(2-アミノエチル)3-アミノプロピルトリメトキシシラン等のアルコキシシラン化合物などが挙げられる。また、架橋剤の反応性に応じて公知の触媒を用いることができ、コレステリック液晶層の強度及び耐久性向上に加えて生産性を向上させることができる。
架橋剤の含有量は、コレステリック液晶層の強度及び耐久性の観点から、上記液晶組成物の全固形分に対し、1質量%以上20質量%以下であることが好ましく、3質量%以上15質量%以下であることがより好ましい。
上記液晶組成物は、成型性の観点から、多官能重合性化合物を含むことも好ましく、同種の重合性基を有する多官能重合性化合物を含むこともより好ましい。
多官能重合性化合物としては、上述した化合物における、2つ以上のエチレン性不飽和基を有し、かつ環状エーテル基を有しないコレステリック液晶化合物、2つ以上の環状エーテル基を有し、かつエチレン性不飽和基を有しないコレステリック液晶化合物、及び、2つ以上のエチレン性不飽和基及び2つ以上の環状エーテル基を有するコレステリック液晶化合物、2つ以上の重合性基を有するカイラル剤、上記架橋剤が挙げられる。
中でも、多官能重合性化合物としては、2つ以上のエチレン性不飽和基を有し、かつ環状エーテル基を有しないコレステリック液晶化合物、2つ以上の環状エーテル基を有し、かつエチレン性不飽和基を有しないコレステリック液晶化合物、及び、2つ以上の重合性基を有するカイラル剤よりなる群から選ばれた少なくとも1種の化合物を含むことが好ましく、2つ以上の重合性基を有するカイラル剤を含むことがより好ましい。
多官能重合性化合物の含有量は、成型性の観点から、上記液晶組成物の全固形分に対し、0.5質量%以上70質量%以下であることが好ましく、1質量%以上50質量%以下であることがより好ましく、1.5質量%以上20質量%以下であることが更に好ましく、2質量%以上10質量%以下であることが特に好ましい。
上記液晶組成物は、必要に応じて、上述した以外のその他の添加剤を含んでいてもよい。
その他の添加剤としては、公知の添加剤を用いることができ、界面活性剤、重合禁止剤、酸化防止剤、水平配向剤、紫外線吸収剤、光安定化剤、着色剤、金属酸化物粒子等を挙げることができる。
有機溶剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤、アルキルハライド系溶剤、アミド系溶剤、スルホキシド系溶剤、ヘテロ環化合物系溶剤、炭化水素系溶剤、エステル系溶剤、エーテル系溶剤などが挙げられる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。これらの中でも、環境への負荷を考慮した場合にはケトン系溶剤が特に好ましい。また、上述の成分が溶媒として機能していてもよい。
上記液晶組成物の全質量に対する固形分の含有量は、特に制限はないが、1質量%~90質量%であることが好ましく、5質量%~80質量%であることがより好ましく、10質量%~80質量%であることが特に好ましい。
また、上記液晶組成物を硬化してなる上記コレステリック液晶層における溶媒の含有量は、上記コレステリック液晶層の全質量に対し、5質量%以下であることが好ましく、3質量%以下であることがより好ましく、2質量%以下であることが更に好ましく、1質量%以下であることが特に好ましい。
上記液晶組成物の塗布は、上記液晶組成物を溶媒により溶液状態としたもの、又は加熱後の溶融液等の液状物を、ロールコーティング方式、グラビア印刷方式、又はスピンコート方式などの適宜な方式で行うことができる。更に、塗布は、ワイヤーバーコーティング法、押し出しコーティング法、ダイレクトグラビアコーティング法、リバースグラビアコーティング法、ダイコーティング法等の種々の方法によって行うことができる。また、インクジェット装置を用いて、上記液晶組成物をノズルから吐出して、塗布膜を形成することもできる。
硬化は、液晶化合物が有するエチレン性不飽和基又は環状エーテル基等の重合性基の重合反応により実施することが好ましい。
上記液晶組成物の塗布及び乾燥後において、上記液晶組成物中の液晶化合物が配向していればよい。
上記コレステリック液晶層は、特定の波長域に選択反射性を有する。
本明細書において、「選択反射波長の中心波長」とは、対象となる物(部材)における光の透過率の最小値かつ極小値をTmin(%)とした場合、下記の式で表される半値透過率〔T1/2;%〕を示す2つの波長の平均値のことをいい、選択反射性を有するとは、選択反射波長を満たす特定の波長域を有することをいう。但し、上記2つの波長のうち一方の波長は、上記Tminを示す波長よりも短い波長を含む波長域における最大波長とし、上記2つの波長のうち他方の波長は、上記Tminを示す波長よりも長い波長を含む波長域における最小波長とする。
T1/2=100-(100-Tmin)÷2
上記コレステリック液晶層における選択反射波長は、380nm~780nmの範囲に有する層を少なくとも含むが、近赤外光(780nmを超え2,000nm以下)の範囲に有する層を含んでいてもよい。
本開示に係る成型用加飾フィルムは、コレステリック液晶層を2層以上有していてもよい。
また、2層以上の各コレステリック液晶層はそれぞれ、組成が同じ層であっても、異なる層であってもよい。
上記コレステリック液晶層の厚さは、成型後における反射率変化抑制の観点から、0.3μm以上15μm以下であることが好ましく、0.5μm以上9μm以下であることがより好ましく、0.6μm以上3μm以下であることが特に好ましい。
上記コレステリック液晶層を2層以上有する場合は、各コレステリック液晶層がそれぞれ独立に、上記厚さの範囲であることが好ましい。
本開示に係る成型用加飾フィルムは、上記コレステリック液晶層に接する配向層を有していてもよい。配向層は、液晶化合物を含む層の形成の際、液晶組成物中の液晶化合物の分子を配向させるために用いられる。
配向層は、液晶層などの層の形成の際に用いられ、本開示に係る成型用加飾フィルムにおいては、配向層が含まれていてもいなくてもよい。
基材、コレステリック液晶層などの下層の材料によっては、配向層を設けなくても、下層を直接配向処理(例えば、ラビング処理)することで、配向層として機能させることもできる。そのような下層となる基材の一例としては、ポリエチレンテレフタレート(PET)を挙げることができる。
また、コレステリック液晶層の上に直接層を積層する場合、下層のコレステリック液晶層が配向層として振舞い上層の作製のための液晶化合物を配向させることができる場合もある。このような場合、配向層を設けなくても、また、特別な配向処理(例えば、ラビング処理)を実施しなくても上層の液晶化合物を配向することができる。
配向層の厚さは、特に制限はないが、0.01μm~10μmの範囲にあることが好ましい。
ラビング処理配向層に用いることができるポリマーの例には、例えば特開平8-338913号公報の段落0022に記載のメタクリレート系共重合体、スチレン系共重合体、ポリオレフィン、ポリビニルアルコール及び変性ポリビニルアルコール、ポリ(N-メチロールアクリルアミド)、ポリエステル、ポリイミド、酢酸ビニル共重合体、カルボキシメチルセルロース、ポリカーボネート等が含まれる。シランカップリング剤をポリマーとして用いることができる。水溶性ポリマー(例、ポリ(N-メチロールアクリルアミド)、カルボキシメチルセルロース、ゼラチン、ポリビニルアルコール、変性ポリビニルアルコール)が好ましく、ゼラチン、ポリビニルアルコール又は変性ポリビニルアルコールがより好ましく、ポリビニルアルコール又は変性ポリビニルアルコールが特に好ましい。
上記液晶組成物が塗布される、配向層、基材、又は、そのほかの層の表面は、必要に応じてラビング処理をしてもよい。ラビング処理は、一般にはポリマーを主成分とする膜の表面を、紙や布で一定方向に擦ることにより実施することができる。ラビング処理の一般的な方法については、例えば、「液晶便覧」(丸善社発行、平成12年10月30日)に記載されている。
式(A): L=Nl(1+2πrn/60v)
式(A)において、Nはラビング回数を表し、lはラビングローラーの接触長を表し、rはローラーの半径を表し、nはローラーの回転数(rpm;revolutions per minute)を表し、vはステージ移動速度(秒速)を表す。
光照射により形成される光配向層に用いられる光配向材料としては、多数の文献等に記載がある。例えば、特開2006-285197号公報、特開2007-76839号公報、特開2007-138138号公報、特開2007-94071号公報、特開2007-121721号公報、特開2007-140465号公報、特開2007-156439号公報、特開2007-133184号公報、特開2009-109831号公報、特許第3883848号公報、特許第4151746号公報に記載のアゾ化合物、特開2002-229039号公報に記載の芳香族エステル化合物、特開2002-265541号公報、特開2002-317013号公報に記載の光配向性単位を有するマレイミド及び/又はアルケニル置換ナジイミド化合物、特許第4205195号、特許第4205198号公報に記載の光架橋性シラン誘導体、特表2003-520878号公報、特表2004-529220号公報、特許第4162850号公報に記載の光架橋性ポリイミド、ポリアミド、又は、エステルが好ましい例として挙げられる。特に好ましくは、アゾ化合物、光架橋性ポリイミド、ポリアミド、又は、エステルである。
本明細書において、「直線偏光照射」とは、光配向材料に光反応を生じせしめるための操作である。用いる光の波長は、用いる光配向材料により異なり、その光反応に必要な波長であれば特に限定されるものではない。好ましくは、光照射に用いる光のピーク波長が200nm~700nmであり、より好ましくは光のピーク波長が400nm以下の紫外光である。
非偏光を利用する場合には、斜めから非偏光を照射する。その入射角度は、好ましくは10°~80°、より好ましくは20°~60°、特に好ましくは30°~50°である。
照射時間は、好ましくは1分~60分、より好ましくは1分~10分である。
コレステリック液晶層に隣接して、円偏光板を配置することも好ましい。円偏光板を配置することにより、観察面で異なる視覚効果を与え得る透過加飾フィルムが得られる。
円偏光板は、コレステリック液晶によって反射される円偏光の旋回方向とは逆向きの円偏光(左円偏光)を透過する。
円偏光板としては、直線偏光板と、λ/4板とを積層したものが挙げられる。円偏光板中の構成としては、例えば、コレステリック液晶層側から、λ/4板及び直線偏光板がこの順に配置される。直線偏光板とλ/4板とは、λ/4板側から入射した光のうち、左円偏光を直線偏光にして透過するように、λ/4板の遅相軸及び直線偏光板の透過軸を合わせて配置される。より具体的には、通常、λ/4板の遅相軸と直線偏光板の透過軸とのなす角が45°となるように、直線偏光板とλ/4板とは配置される。
本開示に係る成型用加飾フィルムは、着色層を更に有することもできる。本開示に係る成型用加飾フィルムにおける着色層の位置は、特に制限はなく、所望の位置に設けることができるが、下記の2つの態様が好ましく挙げられる。
1つの態様は、意匠性の観点から、本開示に係る成型用加飾フィルムにおいて、上記基材と上記コレステリック液晶層との間に、着色層を更に有することが好ましい。
他の1つの態様は、意匠性、成型加工性及び耐久性の観点から、上記基材を有する側とは反対側の上記コレステリック液晶層上に、着色層を更に有することが好ましい。
重合性化合物及び重合開始剤としては、特に制限はなく、公知のものを用いることができる。
着色剤としては、例えば、顔料、染料等が挙げられ、耐久性の観点から、顔料が好ましい。着色層を金属調とするために、金属粒子、パール顔料等を適用することができ、蒸着、また、メッキ等の方法を適用することもできる。
無機顔料としては、例えば、二酸化チタン、酸化亜鉛、リトポン、軽質炭酸カルシウム、ホワイトカーボン、酸化アルミニウム、水酸化アルミニウム、硫酸バリウム等の白色顔料、カーボンブラック、チタンブラック、チタンカーボン、酸化鉄、黒鉛等の黒色顔料、酸化鉄、バリウムイエロー、カドミウムレッド、クロムイエローなどが挙げられる。
無機顔料としては、特開2005-7765号公報の段落0015及び段落0114に記載の無機顔料を適用することもできる。
有機顔料の具体例としては、C.I.Pigment Red 177、179、224、242、254、255、264等の赤色顔料、C.I.Pigment Yellow 138、139、150、180、185等の黄色顔料、C.I.Pigment Orange 36、38、71等の橙色顔料、C.I.Pigment Green 7、36、58等の緑色顔料、C.I.Pigment Blue 15:6等の青色顔料、C.I.Pigment Violet 23等の紫色顔料が挙げられる。
有機顔料としては、特開2009-256572号公報の段落0093に記載の有機顔料を適用することもできる。
光輝性顔料は、成型用加飾フィルムの成形において露光を行う場合、露光による硬化を妨げない範囲において用いられることが好ましい。
また、2種以上の着色剤を用いる場合、無機顔料と有機顔料とを組み合わせてもよい。
着色層中の着色剤の含有量は、目的とする色の発現及び成形加工適性の観点から、着色層の全質量に対して、1質量%~50質量%が好ましく、5質量%~50質量%がより好ましく、10質量%~40質量%が特に好ましい。
着色層に含まれる着色剤、特に顔料の分散性を向上する観点から、着色層は、分散剤を含有してもよい。分散剤を含むことにより、形成される着色層における着色剤の分散性が向上し、得られる加飾フィルムにおける色の均一化が図れる。
高分子分散剤としては、例えば、シリコーンポリマー、アクリルポリマー、ポリエステルポリマー等が挙げられる。加飾フィルムに耐熱性を付与したい場合には、例えば、分散剤として、グラフト型シリコーンポリマー等のシリコーンポリマーを用いることが好ましい。
着色層中の分散剤の含有量は、着色剤100質量部に対して、1質量部~30質量部であることが好ましい。
着色層は、成形加工適正の観点から、バインダー樹脂を含むことが好ましい。
バインダー樹脂としては、制限されず、公知の樹脂を適用することができる。バインダー樹脂としては、所望の色を得る観点から、透明な樹脂であることが好ましく、具体的には、全光透過率が80%以上の樹脂が好ましい。全光透過率は、分光光度計(例えば、(株)島津製作所製、分光光度計UV-2100)により測定することができる。
着色層中のバインダー樹脂の含有量は、成形加工性の観点から、着色層の全質量に対して、5質量%~70質量%であることが好ましく、10質量%~60質量%であることがより好ましく、20質量%~60質量%であることが特に好ましい。
着色層は、上記の成分以外に、必要に応じて添加剤を含んでいてもよい。添加剤としては、制限されず、公知の添加剤を適用することができる。添加剤としては、例えば、特許第4502784号公報の段落0017、特開2009-237362号公報の段落0060~0071に記載の界面活性剤、特許第4502784号公報の段落0018に記載の熱重合防止剤(重合禁止剤ともいう。好ましくはフェノチアジンが挙げられる。)、特開2000-310706号公報の段落0058~0071に記載の添加剤等が挙げられる。
着色層の形成方法としては、例えば、着色層形成用組成物を用いる方法、着色されたフィルムを貼り合せる方法等が挙げられる。上記の中でも、着色層の形成方法としては、着色層形成用組成物を用いる方法が好ましい。また、naxレアルシリーズ、naxアドミラシリーズ、naxマルチシリーズ(日本ペイント株式会社製)、レタンPGシリーズ(関西ペイント株式会社製)等の市販の塗料を用いて着色層を形成してもよい。
着色層形成用組成物に含まれ得る上記各成分の含有量は、着色層中の上記各成分の含有量に関する記載のうち、「着色層」を「着色層形成用組成物」と読み替えた量の範囲で調節することが好ましい。
着色層形成用組成物中の有機溶媒の含有量は、着色層形成用組成物の全質量に対して、5質量%~90質量%が好ましく、30質量%~70質量%がより好ましい。
上記着色層の厚さは、特に制限はないが、視認性及び立体成型性の観点から、0.5μm以上であることが好ましく、3μm以上であることがより好ましく、3μm~50μmであることが更に好ましく、3μm~20μmであることが特に好ましい。
上記着色層を2層以上有する場合は、各着色層がそれぞれ独立に、上記厚さの範囲であることが好ましい。
本開示に係る成型用加飾フィルムは、保護層を有することもできる。
保護層は、上記コレステリック液晶層等を保護する十分な強度を有する層であればよいが、光、熱、湿度等に対する耐久性に優れる樹脂が好ましい。
また、視認性、及び、黒しまり(外部からの反射光による映り込み抑制性、例えば、蛍光灯の映り込みの抑制)の観点から、反射防止能を有する保護層であってもよい。
フッ素樹脂としては、特に制限ないが、特開2009-217258号公報の段落0076~0106や、特開2007-229999号公報の段落0083~0127に記載のもの等が挙げられる。
フッ素樹脂の例としては、オレフィン中の水素をフッ素に置換したフッ化アルキル樹脂が挙げられ、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニリデン、ポリフッ化ビニルやパーフルオロアルコキシアルカン、パーフルオロエチレンプロペン、エチレンテトラフルオロエチレンなどの共重合体、又は、乳化剤や水との親和性を高める成分と共重合体化して水分散化したフッ素樹脂ディスパージョンなどがある。このようなフッ素樹脂の具体例としては、旭硝子(株)製ルミフロン、オブリガート、ダイキン工業(株)製ゼッフル、ネオフロン、デュポン社製テフロン(登録商標)、アルケマ社カイナーなどが挙げられる。
また、例えば、重合性官能基及び架橋性官能基のうちの少なくとも1つの基を有し、かつフッ素原子を含む化合物を用いてもよく、パーフルオロアルキル(メタ)アクリレート、フッ化ビニルモノマー、フッ化ビニリデンモノマーのようなラジカル重合性のモノマーや、パーフルオロオキセタンのようなカチオン重合性のモノマーなどが挙げられる。このようなフッ素化合物の具体例としては、共栄社化学(株)製LINC3A、ダイキン工業(株)製オプツール、荒川化学工業(株)製オプスター、ダイキン工業(株)製などテトラフルオロオキセタン等が挙げられる。
紫外線吸収剤としては、極大吸収波長を380nm以下に有する化合物が好ましく、極大吸収波長を250nm~380nm(特に好ましくは270nm~380nm)に有する化合物がより好ましい。
紫外線吸収剤としては、例えば、トリアジン化合物、ベンゾトリアゾール化合物、ベンゾフェノン化合物、サリチル酸化合物、金属酸化物粒子などが挙げられる。
紫外線吸収剤は、紫外線吸収性能の観点から、トリアジン化合物又はベンゾトリアゾール化合物を含むことが好ましく、トリアジン化合物を含むことがより好ましい。
紫外線吸収剤におけるトリアジン化合物及びベンゾトリアゾール化合物の総含有量は、紫外線吸収剤の全量に対し、80質量%以上であることが好ましい。
上記保護層の厚さは、特に制限はないが、ふき取り耐性及び立体成型性の観点から、2μm以上であることが好ましく、4μm以上であることがより好ましく、4μm~50μmであることが更に好ましく、4μm~20μmであることが特に好ましい。
本開示に係る成型用加飾フィルムは、他の部材(好ましくは他の成型用部材)への貼り付け容易性、及び、各層間の密着性を高める観点から、粘着層を有していてもよい。
粘着層の材料としては、特に制限はなく、目的に応じて適宜選択することができる
例えば、公知の粘着剤又は接着剤を含む層が挙げられる。
粘着剤の例としては、アクリル系粘着剤、ゴム系粘着剤、シリコーン系粘着剤などが挙げられる。また、粘着剤の例として、「剥離紙・剥離フィルム及び粘着テープの特性評価とその制御技術」、情報機構、2004年、第2章に記載のアクリル系粘着剤、紫外線(UV)硬化型粘着剤、シリコーン粘着剤等が挙げられる。なお、アクリル系粘着剤とは、(メタ)アクリルモノマーの重合体((メタ)アクリルポリマー)を含む粘着剤をいう。
粘着剤を含む場合には、更に、粘着付与剤が含まれていてもよい。
接着剤としては、例えば、ウレタン樹脂接着剤、ポリエステル接着剤、アクリル樹脂接着剤、エチレン酢酸ビニル樹脂接着剤、ポリビニルアルコール接着剤、ポリアミド接着剤、シリコーン接着剤等が挙げられる。接着強度がより高いという観点から、ウレタン樹脂接着剤又はシリコーン接着剤が好ましい。
粘着層の形成方法としては、特に限定されず、粘着層が形成された保護フィルムを、粘着層と被着体(例えば、基材とコレステリック液晶層とを有する積層体のコレステリック液晶層の表面;以下同様。)とが接するようにラミネートする方法、粘着層を単独で被着体に接するようにラミネートする方法、上記粘着剤又は接着剤を含む組成物を被着体上に塗布する方法等が挙げられる。ラミネート方法又は塗布方法としては、上述の透明フィルムのラミネート方法又は着色層形成用組成物の塗布方法と同様の方法が好ましく挙げられる。
本開示に係る成型用加飾フィルムは、上述した以外のその他の層を有していてもよい。
その他の層としては、加飾フィルムにおいて公知の層である、反射層、紫外線吸収層、自己修復層、帯電防止層、防汚層、防電磁波層、導電性層などが挙げられる。
本開示に係る成型用加飾フィルムにおけるその他の層は公知の方法により形成することができる。例えば、これらの層に含まれる成分を含む組成物(層形成用組成物)を層状に付与し、乾燥する方法等が挙げられる。
本開示に係る成型用加飾フィルムは、汚れの防止等を目的として、最外層としてカバーフィルムを有していてもよい。
カバーフィルムとしては、可撓性を有し、剥離性が良好な材料であれば特に制限なく使用され、ポリエチレンフィルム等の樹脂フィルム等が挙げられる。
カバーフィルムの貼り付け方法としては、特に制限されず、公知の貼り付け方法が挙げられ、カバーフィルムを保護層上にラミネートする方法等が挙げられる。
本開示に係る成型用加飾フィルムの製造は、既述の本開示の成型用加飾フィルムを製造することができる方法であれば、特に制限はない。本開示に係る成型用加飾フィルムは、好ましくは、反射層形成用組成物を準備する工程と、選択反射波長の中心波長を380nm以上780nm以下の範囲に有し、プラスチック基材のTg+10℃の温度における反射層の弾性率が0.00001GPa以上0.5GPa以下である反射層を形成する工程と、を有する方法により製造され、より好ましくは、液晶組成物を準備する工程と、液晶組成物をプラスチック基材上に付与して液晶組成物層を形成する工程と、液晶組成物層を硬化してコレステリック液晶層を形成する工程と、を有する方法により製造される。
本開示に係る成型用加飾フィルムの製造方法は、上記液晶組成物を準備する工程を含むことが好ましい。
液晶組成物を準備する工程における液晶組成物の各成分の組成については、後述する態様以外は、上述した成型用加飾フィルムにおける液晶組成物の態様と同様である。
本開示に係る成型用加飾フィルムの製造方法は、上記液晶組成物をプラスチック基材上に付与して液晶組成物層を形成する工程を含むことが好ましい。本工程で形成される液晶組成物層は、選択反射波長の中心波長を380nm以上780nm以下の範囲に有し、プラスチック基材のTg+10℃の温度における反射層の弾性率が0.00001GPa以上0.5GPa以下である反射層であってもよい。
液晶組成物の付与は、上述したように、液晶組成物を溶媒により溶液状態としたもの、又は加熱後の溶融液等の液状物を、ロールコーティング方式、グラビア印刷方式、又はスピンコート方式などの適宜な方式で行うことができる。液晶組成物の付与は、更に、ワイヤーバーコーティング法、押し出しコーティング法、ダイレクトグラビアコーティング法、リバースグラビアコーティング法、ダイコーティング法等の種々の方法によって行うことができる。また、液晶組成物の付与は、インクジェット装置を用いて液晶組成物をノズルから吐出して、液晶組成物層を形成することもできる。
上記溶媒を使用した場合、上記液晶組成物の付与後であって、上記コレステリック液晶層を形成する工程の前に、液晶組成物層を公知の方法により乾燥することが好ましい。例えば、放置又は風乾によって乾燥してもよく、加熱によって乾燥してもよい。
上記液晶組成物の付与量は、乾燥後の液晶組成物層を考慮し、適宜設定すればよい。
また、上記液晶組成物の付与及び乾燥後において、上記液晶組成物中の液晶化合物が配向していることが好ましい。
本開示に係る成型用加飾フィルムの製造方法は、上記液晶組成物層を硬化してコレステリック液晶層を形成する工程を含むことが好ましい。上記硬化により、コレステリック液晶化合物を含む液晶化合物の分子の配向状態を維持して固定して、コレステリック液晶層が形成される。これにより、反射層として、選択反射波長の中心波長を380nm以上780nm以下の範囲に有し、プラスチック基材のTg+10℃の温度における反射層の弾性率が0.00001GPa以上0.5GPa以下であるコレステリック液晶層が形成される。
露光の光源としては、光重合開始剤にあわせ、適宜選定して用いることができる。例えば、波長域の光(例えば、365nm、405nm)を照射できる光源が好ましく挙げられ、具体的には、超高圧水銀灯、高圧水銀灯、メタルハライドランプ等が挙げられる。
露光量としては、特に制限はなく、適宜設定すればよく、5mJ/cm2~2,000mJ/cm2であることが好ましく、10mJ/cm2~1,000mJ/cm2であることがより好ましい。
また、上記露光による硬化の際に、液晶化合物の配列を容易にするため、加熱することが好ましい。加熱温度としては、特に制限はなく、使用する液晶化合物及び液晶組成物の組成に応じて選択すればよく、例えば、60℃~120℃が挙げられる。
また、上記露光により、上記コレステリック液晶層を形成するだけでなく、必要に応じて、着色層等の他の層もあわせて露光による硬化を行ってもよい。
また、露光方法としては、例えば、特開2006-23696号公報の段落0035~0051に記載の方法を本開示においても好適に用いることができる。
本開示に係る成型用加飾フィルムの製造方法は、上述した工程以外の他の工程、例えば、着色層を形成する工程、配向層を形成する工程、保護層を形成する工程、粘着層を形成する工程等、所望に応じ、任意のその他の工程を含んでいてもよい。着色層等の上記各層の形成については、上述した方法、又は、公知の方法を用いて行うことができる。
本開示に係る成型方法は、本開示に係る成型用加飾フィルムを用いる成型方法であり、本開示に係る成型用加飾フィルムを成型する工程を含む成型方法であることが好ましい。
また、本開示に係る成型物は、本開示に係る成型用加飾フィルムを成型してなる成型物であり、本開示に係る成型方法により製造された成型物であることが好ましい。本開示に係る成型物は、
本開示に係る成型方法は、上記関係を有することで、視野角によらず、均一な色味を発現する加飾成型体が得られる。特に、加飾フィルムが、380~780nmの範囲における平均反射率が30%以上の鏡面意匠である場合、特にその効果が得られる。
本開示に係る成型方法は、本開示に係る成型用加飾フィルムを成型する工程を含むことが好ましい。
本開示に係る成型用加飾フィルムは、成型加工性に優れるため、成型物の製造に好適に用いることができ、例えば、立体成型、及び、インサート成型よりなる群から選ばれた少なくとも1種の成型により成型物を製造する際に特に好適である。
以下、インサート成型を例に挙げて成型物の作製方法(成型方法)について詳述する。
成型物の作製方法は、射出成型用の金型内に、成型用加飾フィルムを配置して型閉めを行う工程、その後、溶融樹脂を金型内に射出する工程、更に、射出樹脂が固化したところで取り出す工程を含む。
また、成型金型内に成型用加飾フィルムを配置する際には、成型金型へ成型用加飾フィルムを挿入した状態で、成型用加飾フィルムと成型金型との位置合わせが必要になる。
ここで、位置合わせ穴は、雌型において、成型用加飾フィルムの端部(成型後に三次元形状が付与されない位置)が予め形成されている。
また、成型金型へ成型用加飾フィルムを挿入した状態で、成型用加飾フィルムと成型金型との位置合わせを行う方法としては、位置合わせ穴へ固定ピンを挿入する方法以外にも、以下の方法を用いることが可能である。
例えば、使用する樹脂がアクリル樹脂であれば、溶融樹脂の温度は、240℃以上260℃以下の範囲内とすることが好ましい。
成型用加飾フィルムを挿入した成型金型内に射出した溶融樹脂が固化した後、成型金型を型開きして、成型金型から、固化した溶融樹脂である成型基材に成型用加飾フィルムが固定化された中間加飾成型体を取り出す。
このため、仕上げ加工前の中間成型物から、上記のバリとダミー部分とを取り除く仕上げ加工を施すことにより、成型物を得ることができる。
立体成型は、熱成型、真空成型、圧空成型、真空圧空成型などが好適に挙げられる。
真空成型する方法としては、特に制限されるものではないが、立体成型を、真空下の加熱した状態で行う方法が好ましい。
真空とは、室内を真空引きし、100Pa以下の真空度とした状態を指す。
立体成型する際の温度は、用いる成型用基材に応じ適宜設定すればよいが、60℃以上の温度域が好ましく、80℃以上の温度域がより好ましく、100℃以上の温度域が更に好ましい。立体成型する際の温度の上限は、200℃が好ましい。
立体成型する際の温度とは、立体成型に供される成型用基材の温度を指し、成型用基材の表面に熱電対を付すことで測定される。
例えば、レンズ形状や、ピラミッド形状などがあげられる。また、面内に均一な凹凸パターンを有する形状も好ましい。マイクロレンズアレイ構造や、レンチキュラー構造などが挙げられる。
成型用加飾フィルムが上記保護層を有する場合、本開示に係る成型方法は、成型された上記成型用加飾フィルムにおける上記保護層を硬化する工程を含むことが好ましい。
上記保護層を硬化する工程における硬化方法としては、特に制限はなく、上記保護層に含まれる上記シロキサン樹脂の架橋性基、上記有機樹脂のエチレン性不飽和基の有無、上記重合開始剤に応じて、選択すればよいが、光又は熱により上記保護層を硬化させる方法が好ましく、光により上記保護層を硬化させる方法がより好ましい。
また、上記保護層の側の最外層として、カバーフィルムを有する場合、上記カバーフィルムを有する状態(カバーフィルムの剥離前)で露光を行ってもよい。上記カバーフィルム側から露光が行われる場合、上記カバーフィルムの全光透過率は80%以上であることが好ましく、90%以上であることがより好ましい。
露光方法としては、例えば、特開2006-23696号公報の段落0035~0051に記載の方法を本開示においても好適に用いることができる。
露光の光源としては、上記保護層を硬化しうる波長域の光(例えば、365nm、405nm)を照射できる光源であれば適宜選定して用いることができる。
具体的には、超高圧水銀灯、高圧水銀灯、メタルハライドランプ等が挙げられる。
露光量としては、特に制限はなく、適宜設定すればよく、5mJ/cm2~2,000mJ/cm2であることが好ましく、10mJ/cm2~1,000mJ/cm2であることがより好ましい。
上記着色層を露光する場合、上記着色層は重合性化合物及び光重合開始剤を含むことが好ましい。重合性化合物及び光重合開始剤を含む着色層を露光することにより、硬化した着色層を得ることができる。
本開示に係る成型方法は、上述した工程以外の他の工程、例えば、本開示に係る成型用加飾フィルムを成型用部材に貼り付ける工程、上述したように、成型物からバリを取り除く工程、成型物からダミー部分を取り除く工程等、所望に応じ、任意のその他の工程を含んでいてもよい。
その他の工程は、特に制限はなく、公知の手段及び公知の方法を用いて行うことができる。
本開示のディスプレイは、既述の本発明の成型用加飾フィルムが成型された成型物がディスプレイ表示部に配置されたものである。
中でも、ディスプレイ表示部と、ディスプレイ表示部に隣接して配置され、プラスチック基材、及び選択反射波長の中心波長を380nm以上780nm以下の範囲に有する反射層を有する成型用加飾フィルムの成型物と、を備え、成型物は、ディスプレイ表示部の表示面の面内方向の最大幅(T1)に対し、前記表示面の法線方向の最大高さ(T2)が、T2>0.02×T1の関係を有するディスプレイが好ましい。
基材として、厚さ125μmのアクリルフィルム(住化アクリル販売(株)製、テクノロイS001、基材のTgは105℃であった。)を用意した。この基材の片面に、配向層1形成用塗布液をワイヤーバーコーターで塗布した。その後、80℃で120秒乾燥し、層厚1.0μmの配向層1を有する基材を作製した。
下記の変性ポリビニルアルコール:28部
クエン酸エステル(AS3、三共化学(株)製):1.2部
光重合開始剤(イルガキュア2959、BASF社製):0.84部
グルタルアルデヒド:2.8部
水:699部
メタノール:226部
上記作製した基材の配向膜1の表面に、短辺方向を基準に反時計回りに31.5°回転させた方向にラビング処理(レーヨン布、圧力:0.1kgf(0.98N)、回転数:1,000rpm、搬送速度:10m/min、回数:1往復)を施した。
以下に示す組成中の成分を、25℃に保温された容器中にて撹拌、溶解させ、コレステリック液晶層用塗布液1(液晶組成物1)を調製した。
メチルエチルケトン:150.6部
下記の液晶化合物1(棒状液晶化合物):93.4部
光重合開始剤A(IRGACURE 907、BASF社製):0.50部
下記のカイラル剤A:3.3部
下記のカイラル剤B:3.3部
下記の界面活性剤F1:0.027部
なお、液晶化合物1はラジカル重合系であり、オキセタニル基(カチオン重合性官能基)を有するものの、アクリロキシ基(ラジカル重合性基)が1つであるため単官能と定義する。
基材のコレステリック液晶層1が形成された側に、アクリル系粘着剤液(SKダインSG-50Y、綜研化学(株)製)をコンマコーターで塗布し、120℃で2分乾燥することで、層厚25μmの粘着層1を形成した。このようにして、積層体1(成型用加飾フィルム1)を作製した。
積層体1を、図1~図3に示される形状が模られた凹部分を有する凹型と凹型に組み合わせられる凸型10とからなる成形型を用意した。成形型の凹型における凹部分を有する側に積層体1を配置して凸型10の凸状面12を接触させて圧空成型加工(TOM成型)を施し、成型加工した。
図1は、凹型及び凸型からなる成形型の凸型を上面視した際の概略平面図である。図2は、図1の上面視での長手方向と平行方向に切断した断面(短軸方向の断面)22を模式的に示す概略断面図であり、図3は、図1の上面視での短手方向と平行方向に切断した断面(長軸方向の断面)32を模式的に示す概略断面図である。
以下に示す測定及び評価を行った。測定及び評価の結果をまとめて表1に示す。
コレステリック液晶層1(反射層)の弾性率を、東洋テクニカ社製のナノインデンターG200を用いて測定した。
成型加工前の積層体1の反射率を、日本分光(株)製分光光度計V-670を用い、積層体1の粘着層1の側の法線方向から、波長380nm~1,100nmの範囲で測定した。反射率は、反射スペクトルの極大値のうち最も高いものを採用し、下記の評価基準にしたがって評価した。評価結果としては、A、B、C、又はDが好ましく、A、B又はCがより好ましく、A又はBがさらに好ましく、Aが最も好ましい。
<<評価基準>>
A:反射率が30%以上である。
B:反射率が20%以上30%未満である。
C:反射率が10%以上20%未満である。
D:反射率が5%以上10%未満である。
E:反射率が5%未満である。
得られた成型体1を目視で観察し、液晶層のひび割れ状態を観察し、下記の評価基準にしたがって評価した。評価結果としては、A、B、C、又はDが好ましく、A、B又はCがより好ましく、A又はBがさらに好ましく、Aが最も好ましい。
なお、延伸率は、幅2mmの格子状パターンを印刷したフィルムを、図1~図3の型に、TOM成型加工して成型体を作製し、成型体の各領域の延伸倍率を格子パターンの延伸長さ(成型前後の格子辺の長さ比較)で算出した。幅2mmの格子パターンを印刷したフィルムは、厚さ125μmのアクリルフィルム(住化アクリル販売(株)製、テクノロイS001)に、インクジェットプリンター(Acuity(登録商標)LED 1600、富士フイルム株式会社製)の黒インクを用いて印刷した。成型加工は、TOM成型機NGF-0510-R(布施真空株式会社製)を使用し、成型温度を120℃として行った。
<<評価基準>>
A:延伸率が100%以上の領域も硬化膜に割れが発生していない。
B:延伸率が50%未満の領域は硬化膜に割れが発生していないが、50%以上は割れが発生している
C:延伸率が25%未満の領域は硬化膜に割れが発生していないが、25%以上は割れが発生している
D:延伸率が10%未満の領域は硬化膜に割れが発生していないが、10%以上は割れが発生している
E:延伸率が10%未満の領域でも割れが発生している
液晶組成物1の組成を、表1又は表2に記載の組成に変更した以外は、実施例1と同様にして、積層体2~7及びC1~C2(成型用加飾フィルム2~7及びC1~C2)、及び、成型体2~7及びC1~C2をそれぞれ作製した。
また、実施例1と同様な方法により測定及び評価を行った。測定及び評価の結果を、まとめて表1に示す。
一方、ディスプレイ表示をONにしたところ、ディスプレイに表示されている画像が、成型体越しにはっきりと視認され、立体状の透過加飾フィルムとしての有効性が確認された。
また、実施例1~実施例7の成型用加飾フィルムは、反射率が高く、加飾性に優れ、透過加飾フィルムとしての機能も備えている。
実施例1において、コレステリック液晶層1の形成後、特開2017-215558号公報の段落番号[0170]~[0171]に記載の方法にて、1/4波長板の位相差層をコレステリック液晶層の表面に転写して形成し、その後、1/4波長板の位相差層上に粘着層を形成したこと、及び、成型に用いる凸型を図4に示す形状の凸型40(凸型40の凸状面52を接触)に変更したこと以外は、実施例1と同様にして、成型体8~10を作製した。
なお、図4は、凹型及び凸型からなる成形型の凸型の他の一例を上面視した際の概略平面図であり、図5は、図4の凸型を上面視で円心を通る線に沿って切断した断面62を模式的に示す概略断面図である。図4における、ディスプレイ表示部の表示面の面内方向の最大幅(T1)、及び、ディスプレイ表示部の表示面の法線方向の最大高さ(T2)は、それぞれ表2に記載した通りである。
<<評価基準>>
A:ディスプレイの表示画像がはっきりと視認された。
B:ディスプレイの表示画像がはっきりとは視認されず、コレステリック液晶層の反射色味が強く視認された。
ディスプレイ表示部の表示面の面内方向に対して垂直な方向(表示面の法線方向)を0°とした際、0°及び45°の角度から視認した際の色味の変化(例えば、0°方向で黄色、45°方向で青色等)について評価を行った。評価結果として、A、B、Cであることが好ましく、A、B、Cであることがより好ましく、Aであることが特に好ましい。
<<評価基準>>
A:0°方向から視認した場合と45°方向から視認した場合とでは、色味の変化がほとんどない。
B:0°方向から視認した場合と45°方向から視認した場合とでは、色味の変化がわずかに確認される。
C:0°方向から視認した場合と45°方向から視認した場合とでは、色味の変化が確認されるが、同種の色味である。
D:0°方向から視認した場合と45°方向から視認した場合とでは、大きな色味の変化が確認される。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (10)
- プラスチック基材と、
前記プラスチック基材の上に設けられ、選択反射波長の中心波長を380nm以上780nm以下の範囲に有する反射層と、
を有し、前記プラスチック基材のガラス転移点+10℃の温度における、前記反射層の弾性率が、0.00001GPa以上0.5GPa以下である、成型用加飾フィルム。 - 前記反射層が、コレステリック液晶化合物を含む層である請求項1に記載の成型用加飾フィルム。
- 前記コレステリック液晶化合物は、エチレン性不飽和基が1つであるか、又は環状エーテル基が1つである化合物である請求項2に記載の成型用加飾フィルム。
- 前記コレステリック液晶化合物が、1つのエチレン性不飽和基と1つの環状エーテル基とを有する化合物である請求項2又は請求項3に記載の成型用加飾フィルム。
- 前記反射層は、更に、重合性基を含むカイラル剤、又は、重合性基を含むカイラル剤及び重合性基を有しないカイラル剤を含む請求項2~請求項4のいずれか1項に記載の成型用加飾フィルム。
- 前記重合性基を含むカイラル剤は、2つ以上の重合性基を有する請求項5に記載の成型用加飾フィルム。
- 前記コレステリック液晶化合物を含む層が、コレステリック液晶化合物及び光重合開始剤を含む液晶組成物の硬化物である請求項2~請求項6のいずれか1項に記載の成型用加飾フィルム。
- 請求項1~請求項7のいずれか1項に記載の成型用加飾フィルムが成型された成型物。
- 請求項8に記載の成型物がディスプレイ表示部に配置されたディスプレイ。
- ディスプレイ表示部と、
ディスプレイ表示部に隣接して配置され、プラスチック基材、及び選択反射波長の中心波長を380nm以上780nm以下の範囲に有する反射層を有する成型用加飾フィルムの成型物と、
を備え、前記成型物は、ディスプレイ表示部の表示面の面内方向の最大幅T1に対し、前記表示面の法線方向の最大高さT2が、T2>0.02×T1の関係を有するディスプレイ。
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WO2023163072A1 (ja) * | 2022-02-25 | 2023-08-31 | 富士フイルム株式会社 | 積層体及びその製造方法、加飾フィルム、物品、加飾パネル、並びに、表示装置 |
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