Classifications

• • 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
  • C09K19/38—Polymers
  • C09K19/3833—Polymers with mesogenic groups in the side chain
  • C09K19/3842—Polyvinyl derivatives
  • C09K19/3852—Poly(meth)acrylate derivatives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • 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
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • 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
  • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
• • 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
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/023—Optical properties
• • 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
  • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M1/00—Inking and printing with a printer's forme
  • B41M1/26—Printing on other surfaces than ordinary paper
  • B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
  • B41M3/008—Sequential or multiple printing, e.g. on previously printed background; Mirror printing; Recto-verso printing; using a combination of different printing techniques; Printing of patterns visible in reflection and by transparency; by superposing printed artifacts
• • 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
  • C09K19/38—Polymers
• • 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
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
• • 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
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/58—Dopants or charge transfer agents
  • C09K19/586—Optically active dopants; chiral dopants
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements

Definitions

• the present disclosure relates to a decorative film and a method for manufacturing the same, a laminate and a method for manufacturing the same, a substrate with an optical mask for manufacturing a decorative film, a molded body, an article, and a display device.
• films for decorating articles have been proposed as an alternative material to coating or painting.
• the technology that can be obtained is attracting attention.
• the decorated molded body can also be obtained by placing a decorative film in a mold in advance and introducing a molding resin into the mold.
• a technique using cholesteric liquid crystal is known.
• a decorative film for molding has a cured liquid crystal layer formed by curing a liquid crystal layer containing a cholesteric liquid crystal compound and a photoisomerizable compound on a base material (for example, Patent Document 1). .
• Patent Document 1 International Publication No. 2018/230395
• a cholesteric liquid crystal compound and a photosensitive chiral agent are used, and by irradiating light through an optical mask layer having a pattern and photoreacting the photosensitive chiral agent, the light of the optical mask layer is
• the length of the helical pitch of the liquid crystal phase changes depending on the transmittance, and a hue can be developed in a pattern by reflecting light of a wavelength corresponding to the helical pitch.
• the optical mask layer having a pattern can be printed using, for example, a wet electrophotographic method, a gravure printing method, or an inkjet rotary printing method to form a long optical mask layer of 100 meters or more.
• a wet electrophotographic method a gravure printing method
• an inkjet rotary printing method to form a long optical mask layer of 100 meters or more.
• the halftone dots of the optical mask layer A similar shape of hue change may appear on the decorative film.
• This dot-like hue change is visually recognized as a hue in which a plurality of hues are mixed, that is, a hue with low saturation, and a hue with high saturation cannot be obtained.
• Embodiments of the present disclosure provide a method for manufacturing a multicolored laminate with high saturation and high productivity.
• Other embodiments of the present disclosure provide a highly saturated and multicolored laminate, a decorative film and its manufacturing method, a substrate with an optical mask for manufacturing a decorative film, a molded body, an article, and a display device.
• Our goal is to provide the following.
• An AM screen tone with a screen line count of 250 lines or less which has a halftone dot area with a halftone dot area ratio of 0.5% or more and less than 99.5% on the base material using the first ink. and using a second ink to print a printed area ratio of 99.5% or more and a light transmittance of 5% or more at a position overlapping with the halftone dot area of the first pattern.
• a method for producing a laminate comprising the steps of: providing a liquid crystal layer containing a photosensitive chiral agent; and irradiating the liquid crystal layer with light through an optical mask layer to photoreact the photosensitive chiral agent.
• the entire halftone area of the first pattern overlaps with the semi-transparent solid area of the second pattern, or the second pattern further covers an area with a printing area ratio of less than 0.5%.
• ⁇ 1> A method for manufacturing the laminate described above.
• ⁇ 3> The method for manufacturing a laminate according to ⁇ 1> or ⁇ 2>, wherein the entire halftone dot area of the first pattern overlaps the semi-transparent solid area of the second pattern.
• the second pattern further has a halftone area
• the first pattern further has at least one area of a semi-transparent solid area and an area with a printing area ratio of less than 0.5%, and the entire halftone area of the second pattern is covered by the first pattern.
• the step of providing an optical mask layer on the base material further includes printing a pattern different from the first pattern and the second pattern on the base material, A pattern different from the pattern has at least one area of a semi-transparent solid area and an area with a printing area ratio of less than 0.5%, and the pattern is different from the first pattern and the second pattern.
• ⁇ 7> The method for manufacturing a laminate according to ⁇ 6>, wherein the pattern different from the first pattern and the second pattern is a plurality of patterns, and the halftone dot areas of each of the plurality of patterns do not overlap with each other.
• the optical mask layer includes an optical mask layer, a base material, and a cholesteric liquid crystal layer containing a liquid crystal compound and a photosensitive chiral agent in this order, and the optical mask layer has an AM screen style with a screen frequency of 250 lines or less, and It has a halftone dot coating area with a halftone dot area ratio of 0.5% or more and less than 99.5%, and in the halftone dot coating area, the light transmittance of the halftone dot is T D and the light transmittance of the gap between the halftone dots is When T A is 5% ⁇ TA ⁇ 95%, and the light transmittance at the lowest light transmittance point of the optical mask layer is T min , and the light transmittance at the highest light transmittance point is T min A laminate having a region where (T A - T D )/(T MAX -
• the optical mask layer includes an optical mask layer, a base material, and a cholesteric liquid crystal layer containing a liquid crystal compound and a photosensitive chiral agent in this order, and the optical mask layer has an AM screen style with a screen frequency of 250 lines or less, and , has a halftone dot coating area with a halftone dot area ratio of 0.5% or more and less than 99.5%, and in the above halftone dot coating area, the light transmittance of the halftone dot is T D , and the light transmission of the gap between the halftone dots is T A A laminate having a region where 5% ⁇ T A ⁇ 95% and 1% ⁇ T A -T D ⁇ 80.75%.
• the laminate according to ⁇ 10> which satisfies (T A - T D )/(T MAX - T min ) ⁇ 0.95 for all halftone dot areas of the optical mask layer.
• the laminate according to ⁇ 10> or ⁇ 11> which satisfies (T A - T D )/(T MAX - T min ) ⁇ 0.50 for all halftone dot areas of the optical mask layer.
• the optical mask layer includes a base material and an optical mask layer, and the optical mask layer has an AM screen tone with a screen line count of 250 lines or less and a halftone dot area ratio of 0.5% or more and less than 99.5%.
• the optical mask layer includes a base material and an optical mask layer, and the optical mask layer has an AM screen tone with a screen line count of 250 lines or less and a halftone dot area ratio of 0.5% or more and less than 99.5%.
• a base material with an optical mask for producing a decorative film which has a region where 1% ⁇ T A ⁇ T D ⁇ 80.75%.
• a decorative film having a cholesteric liquid crystal layer wherein the cholesteric liquid crystal layer has a halftone dot area in which maximum points of cholesteric pitch are arranged in a halftone pattern, and the cholesteric pitch of the halftone dot area is
• the cholesteric pitch of the halftone dot area is
• a decorative film ⁇ 16> The decorative film according to ⁇ 15>, wherein the cholesteric liquid crystal layer has a region in which the cholesteric pitch change per 100 ⁇ m in-plane distance is 13 nm or more.
• a decorative film having a cholesteric liquid crystal layer wherein the cholesteric liquid crystal layer has a halftone dot area in which maximum points of cholesteric pitch are arranged in a halftone pattern, and the cholesteric pitch of the halftone dot area is
• the cholesteric liquid crystal layer when the cholesteric liquid crystal layer is divided into unit cells, which are rectangles with the smallest area with maximum points as vertices, and the difference between the maximum and minimum values of cholesteric pitch in each unit cell is defined as the intra-lattice pitch difference ⁇ PS .
• a decorative film in which the maximum value of ⁇ P S (MAX) is less than 33 nm.
• ⁇ 20> A molded article obtained by molding the decorative film according to ⁇ 15> or ⁇ 18>.
• ⁇ 21> An article comprising the decorative film according to ⁇ 15> or ⁇ 18> or the molded article according to ⁇ 20>.
• ⁇ 22> The article according to ⁇ 21>, which is an electronic device.
• ⁇ 23> A display device comprising the article according to ⁇ 22>.
• a method for manufacturing a multicolored laminate with excellent productivity and high chroma is provided.
• a multicolored laminate with high saturation, a decorative film and a manufacturing method thereof, a substrate with an optical mask for manufacturing a decorative film, a molded body, an article, and a display device are provided. provided.
• FIG. 1 is a diagram showing a pattern of an 8 cm ⁇ 4 cm optical mask layer.
• FIG. 2 is an enlarged view of a 370 ⁇ m ⁇ 500 ⁇ m area of the pattern shown in FIG. 1 where the light transmittance is controlled to 40%.
• FIG. 3 is a diagram showing the hue change of a cholesteric liquid crystal layer of 8 cm x 4 cm.
• FIG. 4 is an enlarged view showing a 370 ⁇ m ⁇ 500 ⁇ m area of the hue change of the cholesteric liquid crystal layer shown in FIG.
• FIG. 5A is a schematic diagram for explaining an example of the first pattern of the optical mask layer implemented by the manufacturing method of the present disclosure.
• FIG. 5B is a schematic diagram for explaining an example of the second pattern of the optical mask layer implemented by the manufacturing method of the present disclosure.
• the darkness of the color in the figure indicates the low light transmittance per 300 ⁇ m square, and the closer the area is to black, the lower the light transmittance per 300 ⁇ m square.
• FIG. 5C is a schematic diagram for explaining an example of an optical mask layer implemented by the manufacturing method of the present disclosure.
• FIG. 5D is an enlarged view of a part of the first pattern in FIG. 5A.
• FIG. 5E is an enlarged view of a part of the second pattern in FIG. 5B.
• FIG. 5F is an enlarged view of a portion of the optical mask layer of FIG. 5C.
• FIG. 6 is a diagram schematically showing a manufacturing apparatus that implements an example of the method for manufacturing a liquid crystal film of the present disclosure.
• FIG. 7 is a schematic diagram for explaining an example of a method for manufacturing a liquid crystal film carried out by the manufacturing apparatus shown in FIG. FIG.
• FIG. 8 is a diagram showing a 300 mm x 980 mm pattern of the optical mask layer used in the example.
• FIG. 9 is a diagram showing a first pattern of 300 mm x 980 mm of the optical mask layer used in the example.
• FIG. 10 is a diagram showing a second pattern of 300 mm x 980 mm of the optical mask layer used in the example.
• FIG. 11 is a diagram showing a third pattern of 300 mm x 980 mm of the optical mask layer used in the example.
• FIG. 12 is a diagram showing a fourth pattern of 300 mm x 980 mm of the optical mask layer used in the example.
• FIG. 13 is a diagram showing a fifth pattern of 300 mm x 980 mm of the optical mask layer used in the example.
• FIG. 9 is a diagram showing a first pattern of 300 mm x 980 mm of the optical mask layer used in the example.
• FIG. 10 is a diagram showing a second pattern of 300 mm x
• FIG. 14 is a diagram showing a sixth pattern of 300 mm x 980 mm of the optical mask layer used in the example.
• FIG. 15 is a diagram showing the first pattern of the optical mask layer used in Examples.
• FIG. 16 is a diagram showing a second pattern of the optical mask layer used in Examples.
• FIG. 17 is a diagram showing the first pattern of the optical mask layer used in Examples.
• FIG. 18A is a diagram illustrating the first pattern of the optical mask layer used in Examples.
• FIG. 18B is a diagram illustrating a second pattern of the optical mask layer used in Examples.
• FIG. 18C is a diagram illustrating the optical mask layer used in Examples.
• FIG. 19A is a diagram illustrating the first pattern of the optical mask layer used in Examples.
• FIG. 19A is a diagram illustrating the first pattern of the optical mask layer used in Examples.
• FIG. 19B is a diagram illustrating a second pattern of the optical mask layer used in Examples.
• FIG. 19C is a diagram illustrating the optical mask layer used in Examples.
• FIG. 20A is a diagram illustrating the first pattern of the optical mask layer used in Examples.
• FIG. 20B is a diagram illustrating a second pattern of the optical mask layer used in Examples.
• FIG. 20C is a diagram illustrating the optical mask layer used in Examples.
• FIG. 21A is a diagram illustrating the first pattern of the optical mask layer used in Examples.
• FIG. 21B is a diagram illustrating a second pattern of the optical mask layer used in Examples.
• FIG. 21C is a diagram illustrating the third pattern of the optical mask layer used in Examples.
• FIG. 21D is a diagram illustrating the optical mask layer used in Examples.
• FIG. 21A is a diagram illustrating the first pattern of the optical mask layer used in Examples.
• FIG. 21B is a diagram illustrating a second pattern of the optical mask layer used in Examples.
• FIG. 22A is a diagram illustrating the first pattern of the optical mask layer used in Examples.
• FIG. 22B is a diagram illustrating a second pattern of the optical mask layer used in Examples.
• FIG. 22C is a diagram illustrating a third pattern of the optical mask layer used in Examples.
• FIG. 22D is a diagram illustrating the optical mask layer used in Examples.
• FIG. 23 is a diagram showing a second pattern of the optical mask layer used in the comparative example.
• ⁇ indicating a numerical range is used to include the numerical values written before and after it as the lower limit and upper limit.
• the upper limit value or lower limit value described in one numerical range may be replaced with the upper limit value or lower limit value of another numerical range described step by step. good.
• the upper limit or lower limit of the numerical range may be replaced with the value shown in the Examples.
• the amount of each component in the composition is the same as the amount of each component present in the composition, unless otherwise specified. means the total amount of
• process is used not only to refer to an independent process but also to include any process that achieves its intended purpose even if it cannot be clearly distinguished from other processes. .
• total solid content refers to the total mass of the components excluding the solvent from the entire composition of the composition. Further, as described above, the “solid content” refers to components excluding the solvent, and may be solid or liquid at 25° C., for example.
• 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).
• mass % and weight % have the same meaning, and “mass parts” and “weight parts” have the same meaning.
• weight average molecular weight (Mw) and number average molecular weight (Mn) are expressed using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all brand names manufactured by Tosoh Corporation).
• the molecular weight was detected using a gel permeation chromatography (GPC) analyzer using THF (tetrahydrofuran) as a solvent and a differential refractometer, and was calculated using polystyrene as a standard substance.
• GPC gel permeation chromatography
• a method for producing a laminate of the present disclosure includes a screen line number having a halftone dot area having a halftone dot area ratio of 0.5% or more and less than 99.5% on a base material using a first ink.
• AM Amplitude Modulation
• the method includes a step of irradiating the liquid crystal layer with light through the optical mask layer to cause the photosensitive chiral agent to undergo a photoreaction.
• the cholesteric liquid crystal layer wavelength-selectively reflects incident light and exhibits a hue depending on the wavelength of the reflected light.
• a desired hue exhibited by the cholesteric liquid crystal layer can be obtained by changing the helical pitch of the cholesteric liquid crystal compound.
• the helical pitch of a cholesteric liquid crystal compound can be controlled by using a photosensitive chiral agent whose helical inducing force increases or decreases by photoreaction and by irradiating light through a patterned optical mask layer.
• a hue can be expressed.
• the optical mask layer having a pattern can be printed using, for example, a wet electrophotographic method, a gravure printing method, or an inkjet rotary printing method to form a long optical mask layer of 100 meters or more.
• the optical mask layer has limited resolution, and the halftone dots that control light transmittance are coarse.
• a hue change in a shape similar to the halftone dots of the optical mask layer appears in the cholesteric liquid crystal layer.
• a dot-like hue change as shown in FIG. 4 may appear.
• a dot-like hue change is visually recognized as a hue in which a plurality of hues are mixed, that is, a hue with low saturation, and a hue with high saturation cannot be obtained.
• a high-definition printing method such as an inkjet sheet-fed printing method, a laser printer method, or a laser photoplotter method, and used for forming a decorative film.
• no dot-like hue changes appear, and hues with high saturation are obtained.
• high-definition printing methods can only form short optical mask layers of several meters or less, so in order to form a long decorative film, it is necessary to bond many short optical mask layers together. It was found that there was a problem with poor manufacturing efficiency.
• the light transmittance difference between the halftone dots of the optical mask layer and the gap between the halftone dots and the amount of diffusion of the photosensitive chiral agent cause a halftone-like hue change to appear, and the color is
• this is a contributing factor to the decrease in
• the photosensitive chiral agent in the cholesteric liquid crystal layer is irradiated with light through the optical mask layer, the light is blocked at the halftone dots and transmitted through the gaps between the halftone dots.
• the photoreaction of the photosensitive chiral agent proceeds to a large extent.
• a difference in helical inducing force of the photosensitive chiral agent occurs depending on a difference in light transmittance between the halftone dot area and the gap area. Since the photosensitive chiral agent diffuses within the cholesteric liquid crystal layer depending on the viscosity and temperature, the helical inducing force is increased by the progress of diffusion mixing of the photosensitive chiral agent and the unreacted photosensitive chiral agent. The difference gradually approaches uniformity, but if the difference in light transmittance is large relative to the amount of diffusion, the uniformity does not proceed sufficiently, and the difference in helical induced force remains in the form of dots, appearing as a change in hue. .
• the halftone dots can be arranged at equal intervals, and the series of halftone dots can be prevented at medium density. It is possible to suppress the change in color hue. Furthermore, by printing a semi-transparent solid area with a print area ratio of 99.5% or more and a light transmittance of 5% or more and less than 95% at a position overlapping with the halftone dot area of the first pattern, the halftone area It is possible to prepare an optical mask layer in which the difference in light transmittance between the mask layer and the gap portion is controlled, and a decorative film with high color saturation can be manufactured. Further, by setting the number of screen lines to 250 lines or less, a long optical mask layer can be realized, and a long decorative film can be efficiently produced.
• FIG. 6 is a schematic diagram of an example of a laminate manufacturing apparatus (hereinafter also referred to as "manufacturing apparatus") that implements the laminate manufacturing method of the present disclosure (hereinafter also referred to as “manufacturing method of the present disclosure”). shows.
• FIG. 7 shows a schematic diagram for explaining an example of a method for manufacturing a laminate carried out by the manufacturing apparatus shown in FIG. 6. Note that the figures in this disclosure are schematic diagrams, and the sizes of each part, the relationship between the thicknesses of each layer, and the positional relationship do not necessarily match the actual ones. The same applies to the figures below.
• a manufacturing apparatus 100a shown in FIG. 6 manufactures a liquid crystal film by roll-to-roll (hereinafter also referred to as "RtoR") using a long base material 12a.
• RtoR refers to the process of sending out a long workpiece from a roll that is wound around the workpiece, performing processes such as film formation while conveying it in the longitudinal direction, and discarding the processed workpiece. This is a manufacturing method in which the product is wound again into a roll.
• the manufacturing apparatus 100a includes a feed roller 102, a first conveyance section 120, a coating section 150, a second conveyance section 122, an exposure section 152, a heating section 154, a curing section 156, and a third conveyance section. 124 and a take-up roller 116.
• the first transport section 120, the second transport section 122, and the third transport section 124 have transport rollers and the like, and transport a long workpiece along a predetermined path.
• the manufacturing apparatus 100a includes a pair of transport rollers, a guide member for the base material, various sensors, and other known equipment that performs film formation by coating while transporting a long workpiece. It may also include various members.
• a roll 130 formed by winding a long base material 12a is loaded onto a delivery roller 102.
• the base material 12a is pulled out from the roll 130, passes through the first conveyance section 120, the coating section 150, the second conveyance section 122, the exposure section 152, the heating section 154, the curing section 156, and the third conveyance section 124, and then is transferred to the winding roller. 116 through a predetermined route. Further, the prepared liquid crystal composition that will become the cholesteric liquid crystal layer is supplied to the coating nozzle 104 of the coating section 150, and coating is performed.
• the feeding of the base material 12a from the roll 130 and the winding up of the base material 12a (laminated film 23d) on which the cholesteric liquid crystal layer 18 is formed are performed in synchronization.
• the liquid crystal composition prepared in the application section 150 is applied to the base material 12a, and the coated film is exposed in the exposure section 152.
• the coating film is heated in the heating section 154 to orient the liquid crystal, and the coating film is cured by ultraviolet irradiation and/or heating in the curing section 156 to form the cholesteric liquid crystal layer 18.
• a liquid crystal film is a film-like material having a cholesteric liquid crystal layer, and in the examples shown in FIGS. is the liquid crystal film of the present disclosure.
• the cholesteric liquid crystal layer 18 may be used while being laminated on the base material 12a, or may be used after being peeled off from the base material 12a.
• the base material 12a sent out from the roll 130 is a resin film such as a PET film on which a pattern mask is formed, as shown in S1 in FIG.
• the resin film forming the base material 12a various known transparent sheet-like materials used as a substrate (base material) can be used. A specific substrate will be described later.
• an alignment layer on the surface of such a film, an alignment layer, a protective layer, an adhesive layer, a light reflection layer, an antireflection layer, a light shielding layer, a flattening layer, a buffer layer, a stress relaxation layer, a release layer, etc.
• a material on which a layer (film) that exhibits a necessary function may be used as the base material 12a.
• the manufacturing method of the present disclosure includes the step of providing an optical mask layer on a base material.
• two or more printed patterns (hereinafter also referred to as patterns) including a first pattern printed using a first ink and a second pattern printed using a second ink are formed. ).
• a printed pattern is a pattern formed by disposing ink from a single ink cartridge, ink tank, toner, or similar ink source. For example, in the case of a wet electrophotographic method, ink is placed on a transfer roll from toner of two or more colors, and then two or more colors of ink are placed from the transfer roll onto the substrate at one time.
• the printed pattern is divided by color and is not affected by the number of times it is placed on the substrate. Furthermore, in the gravure printing method, when one type of ink is used for two or more printing plates, two types of patterns are formed depending on the arrangement of the inks, so the patterns are classified for each printing plate.
• the first ink and the second ink are each ink of one color, and the first ink and the second ink may be the same or different.
• the ink may be an oil-based ink, a water-based ink, or an ultraviolet curable (UV) ink. Further, the color and composition of the ink are not particularly limited, and known ones can be used.
• the ink preferably absorbs or reflects the light irradiated in the step of photoreacting the photosensitive chiral agent. Furthermore, when the optical mask layer is used as a colored layer in a decorative film, it is preferable to form the optical mask layer using appropriately multicolored inks depending on the desired design of the decorative film.
• the optical mask layer includes an AM screen-like printed pattern.
• the AM screen-like printing pattern is a printing method in which the print density is controlled in a gradation manner by changing the area ratio of halftone dots arranged at equal intervals in the in-plane direction.
• the number of screen lines indicates the number of halftone dots lined up per inch, and the higher the number of screen lines, the higher the resolution and the narrower the interval between the halftone dots.
• the first pattern has a halftone dot area, and the halftone area ratio of the halftone area is 0.5% or more and less than 99.5%, preferably 5% or more and less than 95%, and 10% or more and less than 90%. More preferably less than Since the hue exhibited by the decorative film changes depending on the halftone dot area ratio of the halftone dot area, by setting the halftone dot area ratio within the above range, it is possible to widen the color range exhibited by the decorative film.
• the first pattern preferably has two or more halftone dot areas, and more preferably three or more areas, from the viewpoint of increasing the number of hue change areas of the decorative film and improving the design. From the viewpoint of increasing the number of colors in the decorative film, these locations preferably have different dot area ratios.
• the first pattern may have a region in which the dot area ratio changes in a gradation style depending on the desired hue pattern of the decorative film.
• the halftone dot area ratio of the halftone dot area is the ratio of the halftone dot area per unit area expressed as a percentage. It can be measured by measuring the size of halftone dots and the interval between halftone dots using a microscope, and calculating from the halftone dot area per unit grid and the area of the unit grid.
• the first pattern is an AM screen style pattern with a screen line count of 250 lines or less, preferably a screen line count of 230 lines or less, and more preferably a screen line count of 210 lines or less. Since the smaller the number of screen lines, the less likely printing unevenness will occur, it is preferable to set the number of screen lines within the above range, since it is possible to reduce loss due to uneven printing. Furthermore, from the viewpoint that the smaller the number of screen lines, the faster the printing speed can be, it is preferable to set the number of screen lines within the above range.
• the number of screen lines is preferably 100 lines or more, and more preferably 175 lines or more, from the viewpoint of ease of diffusion of the photosensitive chiral agent that has undergone photoreaction.
• the first pattern further includes at least one of a semi-transparent solid area and an area with a printing area ratio of less than 0.5%.
• the semi-transparent solid area refers to the area in the printed pattern where the printing area ratio is 99.5% or more and the light transmittance is 5% or more and less than 95%, and it is an AM screen-like printed pattern. or a part of a two-tone printed pattern.
• the semi-transparent solid area is preferably an area in which the printed area ratio within at least 300 ⁇ m square of the printed pattern is 99.5% or more, and the light transmittance is 5% or more and less than 95%.
• the printed area ratio is preferably the printed area ratio within 300 ⁇ m square.
• the printing area ratio within 300 ⁇ m square is the area ratio of the area where ink exists within 300 ⁇ m square (a square of 300 ⁇ m on a side) of the printed pattern.
• the light transmittance of the optical mask layer indicates the transmittance of light irradiated in the step of photoreacting the photosensitive chiral agent.
• the area with a printed area ratio of less than 0.5% is an area in the printed pattern where the area ratio of the area where ink exists is less than 0.5%.
• a second pattern is printed using a second ink in a pattern that overlaps the halftone areas of the first pattern.
• the second pattern has a semi-transparent solid area with a printing area ratio of 99.5% or more and a light transmittance of 5% or more and less than 95%.
• the semi-transparent solid area is the same as the semi-transparent solid area of the first pattern described above.
• the second pattern is preferably a semi-transparent solid area having a printing area ratio of 99.5% or more within at least 300 ⁇ m square and a light transmittance of 5% or more and less than 95%.
• the entire halftone dot area of the first pattern is half of the second pattern.
• the second pattern overlaps with the transparent solid area, or the second pattern has an area with a printing area ratio of less than 0.5%, and the entire halftone area of the first pattern overlaps with the semi-transparent area of the second pattern. It is preferable to overlap with the light solid coating area and the area with a printing area ratio of less than 0.5%.
• the area where the printing area ratio is less than 0.5% is the same as the area where the printing area ratio is less than 0.5% of the first pattern described above.
• the second pattern further has a halftone dot area.
• the halftone dot painting area is the same as the halftone dot painting area of the first pattern described above.
• the entire halftone dot area of the first pattern overlaps the semi-transparent solid area of the second pattern.
• the difference in light transmittance between the halftone dots and the gap between the halftone dots is preferably 95% or less, more preferably 60% or less, and 40% or less, from the viewpoint of suppressing the halftone hue change of the cholesteric liquid crystal layer. is more preferable, and 30% or less is particularly preferable.
• the step of providing an optical mask layer on the substrate further includes printing a pattern different from the first pattern and the second pattern on the substrate, and the first pattern and the second pattern are different from each other.
• the different pattern has at least one area of a transparent solid area and an area with a printing area ratio of less than 0.5%, and the transparent solid area has a pattern different from the first pattern and the second pattern.
• at least one of the areas with a printing area ratio of less than 0.5% overlaps the entire halftone dot area of the first pattern and the entire halftone dot area of the second pattern.
• the pattern different from the first pattern and the second pattern further has a halftone dot area.
• the pattern different from the first pattern and the second pattern is preferably an AM screen-like pattern with a screen line count of 250 lines or less.
• a pattern that is different from the first pattern and the second pattern is a pattern that is different from the first pattern and the second pattern in addition to printing the first pattern and printing the second pattern. is formed by printing on a substrate.
• a pattern different from the first pattern and the second pattern is made of multiple patterns.
• the plurality of patterns include different patterns.
• the multiple patterns are formed by printing the pattern multiple times on the substrate, or by printing the pattern multiple times on a medium and then transferring the pattern from the medium onto the substrate. Examples of the medium include a resin or rubber transfer roller called a blanket.
• the pattern may be printed 1 to 5 times on the base material, or the pattern may be printed 1 to 5 times on the medium.
• the pattern is preferably formed by transferring the pattern onto the substrate after printing five times, and printing is performed three to five times in addition to printing the first pattern and printing the second pattern. It is more preferable that it be formed by.
• the halftone dots When the halftone dot areas of different patterns overlap, the halftone dots connect with each other, forming halftone dots of slightly larger size, and the graininess becomes more visible. It is preferable that the halftone dot area of the second pattern and the halftone dot area of a pattern different from the first pattern and the second pattern do not overlap. In the case of patterns, it is preferable that the halftone areas of the plurality of patterns do not overlap.
• the printing method is preferably a printing method that can print a long length of 100 meters or more on a film base material made of a resin material.
• Examples include a wet electrophotographic method, a gravure printing method, or an inkjet rotary printing method. From the viewpoint of resolution and registration of multiple printed patterns, a wet electrophotographic method is more preferable.
• FIGS. 5A to 5F each show the optical mask layer in (3) when the first pattern is (1) and the second pattern is (2).
• the darkness of the color in the figure indicates the low light transmittance per 300 ⁇ m square, and the closer the area is to black, the lower the light transmittance per 300 ⁇ m square.
• 5D to 5F are enlarged views showing a portion of the pattern and optical mask layer of FIGS. 5A to 5C, respectively.
• the second pattern shown in FIG. 5E (2) has a semi-transparent solid area with a printing area ratio of 100% and a light transmittance of 50%.
• a part of the semi-transparent solid area of the second pattern is formed at a position overlapping with the halftone area of the first pattern.
• the optical mask layer is in direct contact with the base material.
• Base material examples include base materials used for molding such as three-dimensional molding and insert molding. From the viewpoint of moldability and chipping resistance, the base material is preferably a resin base material, and preferably a resin film.
• the resin examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic resin, urethane resin, urethane-acrylic resin, polycarbonate (PC), acrylic-polycarbonate, polyolefin, triacetylcellulose (TAC), and cycloolefin.
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• acrylic resin acrylic resin
• urethane resin urethane resin
• urethane-acrylic resin polycarbonate
• PC acrylic-polycarbonate
• polyolefin polyolefin
• TAC triacetylcellulose
• cycloolefin examples include polymers (COP) and acrylonitrile/butadiene/styrene copolymers (ABS resins).
• the base material is a resin film containing at least one resin selected from the group consisting of polyethylene terephthalate, acrylic resin, urethane resin, urethane-acrylic resin, polycarbonate, acrylic-polycarbonate, and polypropylene. It is preferably a resin film containing at least one resin selected from the group consisting of polyethylene terephthalate, acrylic resin, polycarbonate, and acrylic-polycarbonate resin, and polyethylene terephthalate is most preferred.
• the base material may have a single-layer structure or a multi-layer structure.
• a preferred laminated film includes, for example, an acrylic resin/polycarbonate resin laminated film.
• the base material may contain additives if necessary.
• additives include mineral oils, hydrocarbons, fatty acids, alcohols, fatty acid esters, fatty acid amides, metal soaps, natural waxes, lubricants such as silicones, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, halogens, Organic flame retardants such as phosphorus, metal powder, talc, calcium carbonate, potassium titanate, organic or inorganic fillers such as glass fiber, carbon fiber, wood flour, antioxidants, ultraviolet inhibitors, lubricants, dispersants, Examples include additives such as coupling agents, foaming agents, and colorants, polyolefins, polyesters, polyacetals, polyamides, polyphenylene ether resins, and engineering plastics other than the above-mentioned resins.
• the base material may be a commercially available product.
• Commercially available products include, for example, the Technoloy (registered trademark) series (acrylic resin film or acrylic resin/polycarbonate resin laminate film, Sumitomo Chemical Co., Ltd.), ABS film (Okamoto Co., Ltd.), ABS sheet (Sekisui Molding Industry Co., Ltd.), Flex (registered trademark) series (PET film, Teijin Film Solutions Co., Ltd.), Lumirror (registered trademark) easy molding type (PET film, Toray Industries, Inc.), Pure Thermo (polypropylene film, Idemitsu Unitec Co., Ltd.), Cosmoshine (registered) Trademark) series (PET film, Toyobo Co., Ltd.).
• the thickness of the base material is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, even more preferably 20 ⁇ m or more, and particularly preferably 50 ⁇ m or more.
• the thickness of the base material is preferably 500 ⁇ m or less, more preferably 450 ⁇ m or less, and particularly preferably 200 ⁇ m or less.
• the manufacturing method of the present disclosure includes the step of providing a liquid crystal layer containing a liquid crystal compound and a photosensitive chiral agent on the opposite side of the base material from the optical mask layer.
• the liquid crystal layer is a cholesteric liquid crystal layer.
• the base material 12a sent out from the roll 130 passes through the first conveyance section 120 and reaches the application section 150.
• a coating process is performed on the base material 12a in the coating section 150.
• the liquid crystal composition is applied to the substrate 12a by the coating nozzle 104 while being wound around the backup roller 106.
• the backup roller 106 When coating is performed by a method that allows coating without the backup roller 106, such as bar coating, the backup roller 106 may be omitted.
• the coating nozzle 104 in FIG. 6 applies a liquid crystal composition containing a cholesteric liquid crystal compound and a photosensitive chiral agent to the surface of the base material 12a to form a coating film 21a.
• a laminate of the base material 12a and the coating film 21a is referred to as a laminate film 23a.
• Preferred liquid crystal compounds and photosensitive chiral agents are the same as those contained in the cholesteric liquid crystal layer of the decorative film described below.
• the coating method in the coating step may be a roll coating method, a gravure printing method, or a spin coating method.
• Application of the composition may be performed by wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating or die coating.
• Application of the composition may be performed using an inkjet device.
• the composition In the coating method using an inkjet device, the composition may be ejected from a nozzle.
• the coating film 21a is formed on the surface opposite to the optical mask layer. That is, the optical mask layer is formed on the surface (back surface) of the base material 12a opposite to the surface on which the coating film 21a is formed.
• the manufacturing method of the present disclosure includes a step of irradiating the liquid crystal layer with light through an optical mask layer to cause the photosensitive chiral agent to undergo a photoreaction.
• the laminated film 23a passes through the second transport section 122 and reaches the exposure section 152.
• the laminated film 23a is subjected to an irradiation process.
• the exposure device 108 irradiates the undried coating film 21a with light from the base material 12a side, that is, through the optical mask layer.
• the light emitted by the exposure device 108 has a wavelength to which the photosensitive chiral agent in the coating film 21a (liquid crystal composition) is sensitive. Therefore, the exposed coating film 21b is formed by the exposure process. In the exposed coating film 21b, the photosensitive chiral agent is exposed to light, its structure changes, and the helical inducing force changes.
• a laminate of the base material 12a and the exposed coating film 21b is referred to as a laminate film 23b.
• the exposed coating film 21b is irradiated with a different amount of light for each region, corresponding to the light transmittance of each region of the optical mask layer.
• the amount of structural change of the photosensitive chiral agent due to exposure to light varies depending on the amount of irradiation. Therefore, in the exposed coating film 21b, the amount of change in the helical inducing force of the photosensitive chiral agent differs from region to region depending on the transmittance of the optical mask layer.
• the wavelength of light used for exposure may be set depending on the type of photosensitive chiral agent, etc. Further, the amount of light irradiation may also be set depending on the type of photosensitive chiral agent, the light transmittance of the pattern mask, etc.
• the laminated film 23b is conveyed and reaches the heating section 154.
• the coating film of the laminated film 23b is dried and subjected to an orientation treatment.
• the exposed coating film 21b is heated by the heating device 110, thereby aligning the liquid crystal compound in the coating film 21b.
• the heat treatment forms a coating film 21c in which the liquid crystal compound is oriented according to the structure of the chiral agent.
• the coating film 21c has a structure in which the length of the helical pitch of the cholesteric liquid crystal phase varies depending on the exposure amount.
• a laminate of the base material 12a and the oriented coating film 21c is referred to as a laminate film 23c.
• the laminated film 23c is preferably transported to a curing section 156, where it is subjected to a curing process.
• the curing section 112 cures the oriented coating film 21c while the laminated film 23c is wound around the backup roller 114 to form the cholesteric liquid crystal layer 18.
• a liquid crystal film having a cholesteric liquid crystal layer 18 is produced.
• a laminate of the base material 12a and the cholesteric liquid crystal layer 18 is referred to as a laminate film 23d.
• a method for curing the coating film 21c known curing methods such as photocuring by irradiation with light such as ultraviolet rays, thermal curing by heating, etc. can be used.
• light irradiation it is preferable to irradiate the coating film 21c with light from the side opposite to the optical mask layer.
• the produced liquid crystal film passes through the third conveying section 124 and is wound into a roll by a winding roller 116 to form a roll 132.
• the cholesteric liquid crystal layer of the fabricated liquid crystal film has a structure in which regions with different selective reflection wavelengths are formed depending on the transmittance of the optical mask layer, so each region reflects light with a selective reflection wavelength. An image with a corresponding hue can be displayed.
• the fabricated liquid crystal film is wound into a roll, but the structure is not limited to this. It is good also as a structure which has.
• the wavelength of the light irradiated in the curing process is different from the wavelength of the light irradiated in the process of photoreacting the photosensitive chiral agent. More preferably, the wavelength of the light irradiated in the step of photoreacting the photosensitive chiral agent is longer than the wavelength of the light irradiated in the curing step. Specifically, the wavelength of the light irradiated in the step of photoreacting the photosensitive chiral agent is preferably a wavelength to which the photosensitive chiral agent is sensitive and a wavelength at which the polymerization initiator is not cleaved.
• the amount of change in the pitch of the helical structure of the liquid crystal compound can be set to a desired amount of change.
• the wavelength of the light irradiated in the step of photoreacting the photosensitive chiral agent may be selected from the wavelength to which the photosensitive chiral agent is sensitive, depending on the type of the photosensitive chiral agent.
• the wavelength of the light irradiated in the irradiation step is preferably 350 nm to 400 nm. That is, it is preferable to use a chiral agent that is sensitive to this wavelength range.
• the amount of light irradiated in the step of photoreacting the photosensitive chiral agent may be set to the amount that results in a desired selective reflection wavelength depending on the type of the photosensitive chiral agent and the like.
• the wavelength of light irradiated in the curing step may be selected depending on the type of polymerization initiator and the like. Specifically, the wavelength of the light irradiated in the curing step is preferably 300 nm to 350 nm. That is, it is preferable to use a polymerization initiator that can initiate a polymerization reaction within this wavelength range. Further, the amount of light irradiated in the curing step may be set depending on the type of polymerization initiator and the like.
• the light irradiation is performed once in the step of photoreacting the photosensitive chiral agent, but the light irradiation may be performed in two or more parts.
• the step of photoreacting the photosensitive chiral agent may include a first irradiation step and a second irradiation step.
• the peak wavelength of the irradiated light may be different.
• the peak wavelength of light in the first irradiation step is shifted from the peak wavelength of light to which the photosensitive chiral agent is sensitive, and the peak wavelength of light in the second irradiation step is coincident with the peak wavelength of light to which the photosensitive chiral agent is sensitive. By doing so, the amount of light irradiation can be substantially adjusted.
• the amount of light irradiation can be substantially adjusted by irradiating light with a peak wavelength of 365 nm.
• the cholesteric liquid crystal layer 18 is wound onto the roll 132 immediately after being formed, but before being wound onto the roll 132, a protective film or the like is pasted on the surface of the cholesteric liquid crystal layer 18. It may also include a step of.
• one layer of cholesteric liquid crystal layer 18 is formed on the base material 12a, but the structure is not limited to this, and the coating process, irradiation process, alignment process, It is also possible to perform a combination of curing steps two or more times to form two or more cholesteric liquid crystal layers.
• the manufacturing apparatus may be configured to have two or more combinations of an application section, an exposure section, a heating section, and a curing section between the feed-out roller and the take-up roller in the transport direction of the base material.
• the manufacturing method of the present disclosure may further include a peeling step of peeling the optical mask layer and the base material from the laminate.
• the peeling step can be performed, for example, by transferring the liquid crystal layer to another film via an adhesive sheet (G25, Nichiei Shinka Co., Ltd.).
• a first embodiment of the laminate of the present disclosure includes, in this order, an optical mask layer, a base material, and a cholesteric liquid crystal layer containing a liquid crystal compound and a photosensitive chiral agent, and the optical mask layer has a screen frequency It has an AM screen tone of 250 lines or less and a halftone dot area with a halftone dot area ratio of 0.5% or more and less than 99.5%.
• a second embodiment of the laminate of the present disclosure includes, in this order, an optical mask layer, a base material, and a cholesteric liquid crystal layer containing a liquid crystal compound and a photosensitive chiral agent, and the optical mask layer has a screen line. It has an AM screen tone of several 250 lines or less and a halftone dot coating area with a halftone dot area ratio of 0.5% or more and less than 99.5%, and in the above halftone dot coating area, the light transmittance of the halftone dot is T D , has a region where 5% ⁇ TA ⁇ 95% and 1% ⁇ TA - T D ⁇ 80.75%, where T A is the light transmittance of the gap between halftone dots. .
• the laminate of the present disclosure is preferably a laminate manufactured by the method of manufacturing a laminate of the present disclosure.
• optical mask layer can be produced in the same manner as the optical mask layer described above in the method for producing a laminate.
• the light transmittance in the optical mask layer of the present disclosure indicates the transmittance to light irradiated in the step of photoreacting the photosensitive chiral agent.
• the light transmittance TD of a halftone dot in a halftone dot coating area is expressed as a percentage of the amount of light that has passed through the halftone dot and entered the cholesteric liquid crystal layer relative to the amount of light that has entered the halftone dot.
• the measurement area is smaller than the halftone dot area, so that T D is the light transmittance per 10 ⁇ m ⁇ (in other words, within a circle with a diameter of 10 ⁇ m) within the halftone dot measured using a microscopic UV-visible near-infrared spectrophotometer MSV-5500. Can be measured with a small microspectrophotometer.
• the light transmittance TA of the gap between halftone dots is expressed as a percentage of the amount of light that has passed through the gap and entered the cholesteric liquid crystal layer relative to the amount of light that has entered the gap between halftone dots. Similar to the light transmittance at a point, the light transmittance per 10 ⁇ m ⁇ in the gap can be measured using a microspectrophotometer.
• the location of the optical mask layer with the lowest light transmittance is the location with the lowest light transmittance per 10 ⁇ m ⁇ , and for example, after narrowing down the measurement positions to locations with relatively low transmittance by visual observation and microscopic observation. , which can be measured by a microspectrophotometer.
• the location of the optical mask layer with the highest light transmittance is the location with the highest light transmittance per 10 ⁇ m ⁇ .For example, after narrowing down the measurement positions to locations with relatively high transmittance by visual observation and microscopic observation, , which can be measured by a microspectrophotometer.
• (T A - T D )/(T MAX - T min ) By setting (T A - T D )/(T MAX - T min ) to 0.95 or less, the difference in the amount of photoreaction of the photosensitive chiral agent between the halftone dot area and the gap area can be reduced, and the helical inducing force can be reduced. It is possible to suppress hue changes in the cholesteric liquid crystal layer due to differences and improve saturation.
• (T A - T D )/(T MAX - T min ) is preferably 0.95 or less.
• (T A - T D )/(T MAX - T min ) is preferably 0.50 or less, and 0.30 in all halftone areas of the optical mask layer. It is more preferable that it is the following. By setting it within the above range, it is possible to reduce the dot-like hue change of the cholesteric liquid crystal layer, and to suppress the graininess.
• (T A - T D )/(T MAX - T min ) is 0.03 from the viewpoint of obtaining a decorative film with rich color changes by controlling the light transmittance of the halftone dot coating area. It is preferable that it is above.
• T A - T D By setting T A - T D to 1% or more, the light transmittance of the halftone dot area can be controlled, and a decorative film with rich color changes can be obtained.
• T A - T D is preferably 60% or less, and preferably 50% or less, from the viewpoint of reducing the dot-like hue change of the cholesteric liquid crystal layer and suppressing the graininess. It is more preferable that it is, and it is especially preferable that it is 30% or less.
• T A - T D is preferably 3% or more, more preferably 5% or more.
• the base material is the same as the base material described above in the method for producing a laminate, and the preferred base material is also the same.
• the liquid crystal layer contains a liquid crystal compound and a photosensitive chiral agent, and preferred liquid crystal compounds and photosensitive chiral agents are the same as those contained in the cholesteric liquid crystal layer of the decorative film described below.
• the laminate of the present disclosure is preferably a decorative film.
• a first embodiment of the base material with an optical mask for manufacturing a decorative film of the present disclosure includes a base material and an optical mask layer, and the optical mask layer has an AM screen style with a screen line count of 250 lines or less, and , has a halftone dot coating area with a halftone dot area ratio of 0.5% or more and less than 99.5%, and in the above halftone dot coating area, the light transmittance of the halftone dot is T D , and the light transmission of the gap between the halftone dots is When the ratio is T A , 5% ⁇ TA ⁇ 95%, and the light transmittance T min at the lowest light transmittance point of the optical mask layer and the light transmittance T at the highest light transmittance point.
• a second embodiment of the base material with an optical mask for producing a decorative film of the present disclosure includes a base material and an optical mask layer, and the optical mask layer has an AM screen style with a screen line count of 250 lines or less, and has a halftone dot coating area with a halftone dot area ratio of 0.5% or more and less than 99.5%;
• T A is the transmittance, there is a region where 5% ⁇ TA ⁇ 95% and 1% ⁇ T A -T D ⁇ 80.75%.
• base material with an optical mask for producing a decorative film of the present disclosure or simply “base material with an optical mask for producing a decorative film” refers to the first embodiment described above. and the second embodiment described above.
• the base material and the optical mask layer included in the base material with an optical mask for producing a decorative film are the same as the base material and the optical mask layer of the above-mentioned laminate, and the preferred base material and optical mask layer are also the same.
• the first embodiment of the base material with an optical mask for producing a decorative film of the present disclosure corresponds to the first embodiment of the laminate of the present disclosure
• the base material with an optical mask for producing a decorative film of the present disclosure corresponds to the first embodiment of the laminate of the present disclosure
• the second embodiment of the material corresponds to the second embodiment of the laminate of the present disclosure.
• a first embodiment of the decorative film of the present disclosure is a decorative film including a cholesteric liquid crystal layer having a halftone dot area in which maximum points of cholesteric pitch are arranged in a halftone dot shape. Then, when the halftone dot area is divided into unit grids, which are rectangles with the smallest area with maximum points as vertices, the intra-grid pitch difference ⁇ P S is the difference between the maximum and minimum cholesteric pitch values in each unit grid. , the maximum value ⁇ P S (MAX) of ⁇ P S in the entire halftone coating area is ⁇ P S (MAX) / ⁇ P all ⁇ 0.4.
• a second embodiment of the decorative film of the present disclosure is a decorative film having a cholesteric liquid crystal layer, wherein the cholesteric liquid crystal layer has a halftone dot area in which maximum points of cholesteric pitch are arranged in a halftone shape. Then, the above halftone dot area is divided into unit grids, which are rectangles with the smallest area, with the maximum point of cholesteric pitch as the apex, and the difference between the maximum and minimum values of cholesteric pitch in each unit grid is calculated as the intra-grid pitch difference.
• a decorative film in which, in the cholesteric liquid crystal layer, a maximum value of ⁇ P S (MAX), where ⁇ P S is less than 33 nm.
• the above-mentioned halftone dot region is preferably a region in which maximum points of cholesteric pitch are arranged in a halftone dot shape at regular intervals of 100 ⁇ m or more and less than 300 ⁇ m. Further, a preferable aspect of the above-mentioned halftone dot area is the same as the above-mentioned halftone dot area except that it is formed in a cholesteric liquid crystal layer and the aspect described below.
• the method for producing a decorative film of the present disclosure preferably includes the method for producing a laminate of the present disclosure. Further, the decorative film of the present disclosure may be the laminate itself produced by the method of producing a laminate of the present disclosure, or may be a laminate obtained by removing the base material and the optical mask layer from the laminate. Alternatively, the optical mask layer may be removed from the above laminate. For example, the optical mask layer can also be a colored layer or the like in the decorative film of the present disclosure.
• the cholesteric liquid crystal layer wavelength-selectively reflects incident light and exhibits a hue depending on the wavelength of the reflected light.
• a desired hue exhibited by the cholesteric liquid crystal layer can be obtained by changing the helical pitch of the cholesteric liquid crystal compound.
• the cholesteric liquid crystal layer has a plurality of cholesteric pitches within a small area of about 100 ⁇ m square, it reflects light of a plurality of wavelengths, and the visually recognized reflection spectrum is equivalent to the average of the spectrum of the plurality of reflected wavelengths. Therefore, compared to the case where the cholesteric pitch is uniform, the half width of the reflectance peak of the visually recognized reflection spectrum can be increased.
• the saturation can be increased by setting the maximum pitch difference ⁇ P S (MAX) of the cholesteric pitch within the unit cell within the range of 0 ⁇ P S (MAX) / ⁇ P all ⁇ 0.4.
• the decorative film has a color range of, for example, blue to green (hue angle range of 90°)
• the color difference between blue-green and green (hue angle range of 45°) within the unit grid is highly visible.
• arranging the maximum points at equal intervals in the form of AM screen-like halftone dots is also important for suppressing graininess, since it can suppress an increase in visual color difference.
• the maximum value ⁇ P S (MAX) of the cholesteric pitch difference in the unit cell is set as ⁇ P S (MAX) / ⁇ P all ⁇ 0.4 with respect to the pitch difference of the cholesteric pitch of the entire decorative film. Furthermore, by arranging the maximum points in an AM screen-like halftone dot shape at equal intervals of 100 ⁇ m or more and less than 300 ⁇ m, a multicolored decorative film with high saturation and suppressed graininess can be realized.
• the cholesteric liquid crystal layer has a cholesteric pitch change of 13 nm or more per 100 ⁇ m in-plane distance, since it is possible to realize a region with sharp boundaries between patterns as a decorative film.
• a decorative film with a design with sharp boundaries between patterns that is, a cholesteric liquid crystal layer with a large rate of change in cholesteric pitch per distance in the in-plane direction
• the helical inducing force of the photosensitive chiral agent is greatly changed, or Since it is necessary to suppress the in-plane diffusion of the photosensitive chiral agent that has undergone photoreaction, the visibility of graininess tends to deteriorate.
• the change rate of cholesteric pitch is the same. Also, it is possible to suppress deterioration of visibility due to graininess, and achieve both a clear design and suppression of graininess.
• the difference between the maximum and minimum values of cholesteric pitch in each unit cell is for a certain intra-lattice pitch difference ⁇ P S , the maximum value ⁇ P S (MAX) of ⁇ P S in the entire halftone area is the difference ⁇ P all between the maximum and minimum cholesteric pitch values in the entire cholesteric liquid crystal layer. , ⁇ P S (MAX) / ⁇ P all ⁇ 0.4.
• ⁇ P S (MAX) in the second embodiment of the decorative film of the present disclosure is less than 33 nm, preferably 13 nm or less.
• ⁇ P S (MAX) By setting ⁇ P S (MAX) to less than 33 nm, it is possible to reduce the color difference due to the difference in cholesteric pitch, increase the half-width of the reflectance peak of the visible reflection spectrum, and improve the saturation.
• ⁇ PS (MAX) is less than 13 nm, the visibility of graininess is further reduced and the glossiness is more excellent.
• ⁇ P S (MAX) in the first embodiment of the decorative film of the present disclosure is preferably less than 33 nm, more preferably 13 nm or less.
• ⁇ P S (MAX) By setting ⁇ P S (MAX) within the above range, the color difference due to the difference in cholesteric pitch is reduced, the visibility of graininess is reduced, and the gloss is more excellent, which is preferable. Further, ⁇ P S (MAX) in the decorative film of the present disclosure is preferably 3.3 nm or more from the viewpoint of increasing the half width of the reflectance peak of the visually recognized reflection spectrum and improving the saturation.
• ⁇ P all is set to 70 from the viewpoint that the decorative film can express a wide color range from blue to green to red. It is preferably at least 100 nm, and more preferably at least 100 nm, since it can be expressed in the ultraviolet and infrared regions, ie, colorless.
• the upper limit of ⁇ P all is preferably 200 nm or less since the color range for the decorative film is sufficient from the ultraviolet to infrared ranges.
• Reflectance center wavelength is the average of the wavelength showing the maximum value of reflectance R max (%) and the wavelength showing half-maximum reflectance R 1/2 (%) in the reflection spectrum of light incident on the cholesteric liquid crystal layer. refers to the average value.
• the reflectance is an integral reflectance and a relative reflectance with respect to a white standard plate. A method for measuring the reflection center wavelength will be described later.
• At least a part of the reflection center wavelength in the gradation region of the cholesteric liquid crystal layer is preferably within the wavelength range of 380 nm to 780 nm.
• At least a part of the reflection center wavelength is in the wavelength range of 380 nm to 780 nm means that at least part of the gradation area of the cholesteric liquid crystal layer has a reflection wavelength range in the visible light range (380 nm to 780 nm). are doing. That is, it has a selective reflection property in which a selective reflection wavelength exists in a region of 380 nm to 780 nm.
• the cholesteric liquid crystal layer is a layer containing at least a cholesteric liquid crystal compound.
• the cholesteric liquid crystal layer is preferably a cured product (cured layer; hereinafter the same) of a photocurable composition containing a cholesteric liquid crystal compound and a photosensitive chiral agent.
• the composition is cured, for example, by light or heat.
• composition before curing that forms the cholesteric liquid crystal layer or the components of the liquid crystal layer examples include a cholesteric liquid crystal compound, a photosensitive chiral agent, a chiral agent other than the above-mentioned photosensitive chiral agent (including a photoisomerizable compound), and a polymerization initiator. agents, polymerizable monomers, polyfunctional polymerizable compounds, crosslinking agents, solvents, and additives.
• the composition before curing that forms the cholesteric liquid crystal layer or the components of the liquid crystal layer preferably contains a cholesteric liquid crystal compound and a photosensitive chiral agent, and preferably contains a cholesteric liquid crystal compound, a photosensitive chiral agent, and a polymerization initiator.
• compositions or liquid crystal layer before curing As a component of the composition or liquid crystal layer before curing, other components such as a polymerization initiator, a polymerizable monomer, a polyfunctional polymerizable compound, a crosslinking agent, a solvent, and an additive may be added as necessary. May contain.
• “Cholesteric liquid crystal layer” is a layer having a molecular orientation state unique to cholesteric liquid crystal.
• the orientation state may include an orientation state that reflects right-handed circularly polarized light, an orientation state that reflects left-handed circularly polarized light, or both.
• the orientation state may be fixed by methods such as polymerization and crosslinking.
• the cholesteric liquid crystal layer contains at least a cholesteric liquid crystal compound.
• the cholesteric liquid crystal layer may be a layer formed by curing a composition (or a liquid crystal layer when the composition is molded into a liquid crystal layer) containing a cholesteric liquid crystal compound.
• the type of cholesteric liquid crystal compound is not limited.
• the cholesteric liquid crystal compound may be a known cholesteric liquid crystal compound.
• the cholesteric liquid crystal compound has a reactive group.
• the reactive group is preferably a polymerizable group.
• the polymerizable group include radically polymerizable groups and cationic polymerizable groups.
• the cholesteric liquid crystal compound preferably has a radically polymerizable group.
• the radically polymerizable group is preferably at least one polymerizable group selected from the group consisting of a vinyl group, an acryloyl group, and a methacryloyl group, and at least one type selected from the group consisting of an acryloyl group and a methacryloyl group. More preferably, it is a polymerizable group.
• the cholesteric liquid crystal compound may have two or more reactive groups.
• the cholesteric liquid crystal compound may have two or more types of reactive groups.
• the cholesteric liquid crystal compound may be a cholesteric liquid crystal compound having two or more types of reactive groups with different crosslinking mechanisms.
• the crosslinking mechanism may be a condensation reaction, hydrogen bonding or polymerization. At least one of the crosslinking mechanisms of two or more types of reactive groups is preferably polymerization.
• the crosslinking mechanism preferably includes two or more types of polymerization. Examples of the reactive groups utilized in the above-mentioned crosslinking mechanism include vinyl groups, (meth)acrylic groups, epoxy groups, oxetanyl groups, vinyl ether groups, hydroxy groups, carboxy groups, and amino groups.
• the cholesteric liquid crystal compound having two or more types of reactive groups with different crosslinking mechanisms may be a compound that can be crosslinked in stages. At each stage, reactive groups react according to the crosslinking mechanism at each stage. Examples of methods for stepwise crosslinking of two or more types of reactive groups include a method of changing reaction conditions in each step. Examples of changes in reaction conditions include temperature, wavelength of light (irradiation), and polymerization mechanism. It is preferable to utilize differences in polymerization mechanisms from the viewpoint of easy separation of reactions.
• the polymerization mechanism is controlled, for example, by the type of polymerization initiator.
• the combination of polymerizable groups a combination of a radically polymerizable group and a cationic polymerizable group is preferred.
• the combination of polymerizable groups is such that the radically polymerizable group is a vinyl group or (meth)acrylic group, and the cationically polymerizable group is an epoxy group, oxetanyl group, or vinyl ether group. It is preferable that there be.
• the polymerizable group an ethylenically unsaturated group is preferable.
• the cholesteric liquid crystal compound preferably contains a cholesteric liquid crystal compound having one reactive group (preferably a polymerizable group).
• the ratio of the content of the cholesteric liquid crystal compound having one reactive group to the content of the cholesteric liquid crystal compound is preferably 96% by mass to 100% by mass, and preferably 97% by mass to It is more preferably 100% by mass, and preferably 98% to 100% by mass.
• the cholesteric liquid crystal compound preferably contains a cholesteric liquid crystal compound having one reactive group and a cholesteric liquid crystal compound having two or more reactive groups. More preferably, the cholesteric liquid crystal compound includes a cholesteric liquid crystal compound having one reactive group and a cholesteric liquid crystal compound having two reactive groups. From the viewpoint of stretchability and heat resistance, the ratio of the content of the cholesteric liquid crystal compound having two or more reactive groups to the content of the cholesteric liquid crystal compound having one reactive group is 0 to 0 on a mass basis. It is preferably .05, more preferably 0 to 0.04, and preferably 0 to 0.02.
• reactive groups are shown below. However, the reactive group is not limited to the specific examples below.
• Et represents an ethyl group
• n-Pr represents an n-propyl group.
• cholesteric liquid crystal compounds examples include rod-shaped cholesteric liquid crystal compounds and discotic cholesteric liquid crystal compounds.
• the rod-shaped cholesteric liquid crystal compound may be a low-molecular type or a high-molecular type compound.
• the discotic cholesteric liquid crystal compound may be a low-molecular type or a high-molecular type compound.
• the term "polymer” used with respect to cholesteric liquid crystal compounds means a compound with a degree of polymerization of 100 or more (Polymer Physics/Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992 ).
• Two or more types of rod-shaped cholesteric liquid crystal compounds, two or more types of discotic liquid crystal compounds, or a mixture of a rod-shaped cholesteric liquid crystal compound and a discotic cholesteric liquid crystal compound may be used.
• the cholesteric liquid crystal compound is preferably a rod-shaped cholesteric liquid crystal compound.
• rod-shaped cholesteric liquid crystal compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, and alkoxy-substituted phenyls.
• Examples include pyrimidines, phenyldioxanes, tolans and alkenylcyclohexylbenzonitrile.
• rod-shaped cholesteric liquid crystal compound examples include polymers of rod-shaped cholesteric liquid crystal compounds having reactive groups.
• examples of the rod-shaped cholesteric liquid crystal compound include compounds described in JP-A No. 2008-281989, Japanese Patent Publication No. 11-513019, and Japanese Patent Application Publication No. 2006-526165.
• rod-shaped cholesteric liquid crystal compounds are shown below.
• the rod-shaped cholesteric liquid crystal compound is not limited to the following specific examples.
• the compounds shown below are synthesized, for example, by the method described in Japanese Patent Publication No. 11-513019.
• rod-shaped cholesteric liquid crystal compound having one polymerizable group examples include the following compounds.
• "Me” shown in the chemical formula below means a methyl group.
• discotic cholesteric liquid crystal compounds include the following compounds.
• a discotic cholesteric liquid crystal compound has a structure in which the various structures described above are used as a disc-shaped core at the center of the molecule, and groups such as linear alkyl groups, alkoxy groups, and substituted benzoyloxy groups are arranged in a radial manner. It includes liquid crystal compounds that exhibit liquid crystal properties and are generally called discotic liquid crystals. When an aggregate of such compounds is uniformly oriented, negative uniaxiality appears.
• discotic cholesteric liquid crystal compounds include compounds described in paragraphs 0061 to 0075 of JP-A No. 2008-281989.
• the discotic cholesteric liquid crystal compound having a reactive group may be fixed in an orientation state such as horizontal orientation, vertical orientation, tilted orientation, or twisted orientation.
• the cholesteric liquid crystal layer or composition may contain one or more cholesteric liquid crystal compounds.
• the content ratio of the cholesteric liquid crystal compound to the total solid mass of the cholesteric liquid crystal layer or composition is preferably 30% to 99% by mass, more preferably 40% to 99% by mass, It is more preferably 60% by mass to 99% by mass, and particularly preferably 70% by mass to 98% by mass.
• the cholesteric liquid crystal layer contains a chiral agent (optically active compound), in particular a photosensitive chiral agent.
• Chiral agents can induce a helical structure in cholesteric liquid crystal compounds.
• chiral agents can adjust helical pitch.
• Chiral agents include photoisomerizable compounds, as described below.
• the type of chiral agent is not limited.
• the chiral agent may be a known chiral agent.
• the chiral agent may be selected depending on the desired helical structure.
• Examples of chiral agents include, for example, Liquid Crystal Device Handbook (Chapter 3, Section 4-3, Chiral Agents for TN and STN, p. 199, edited by the 142nd Committee of the Japan Society for the Promotion of Science, 1989), Japanese Patent Application Publication No. 2003-287623, Examples include compounds described in JP 2002-302487, JP 2002-80478, JP 2002-80851, JP 2010-181852, and JP 2014-034581.
• the chiral agent has a cinnamoyl group.
• the chiral agent preferably contains an asymmetric carbon atom.
• the chiral agent may be an axially asymmetric compound or a planar asymmetric compound that does not contain an asymmetric carbon atom.
• Examples of the axially asymmetric compound and the planar asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof.
• the chiral agent may have a reactive group.
• the reactive group is preferably a polymerizable group.
• the polymerizable group is preferably at least one polymerizable group selected from the group consisting of an ethylenically unsaturated group, an epoxy group, and an aziridinyl group, more preferably an ethylenically unsaturated group, and an acryloyl group. It is more preferably at least one polymerizable group selected from the group consisting of and methacryloyl group.
• a chiral agent may have two or more reactive groups.
• the chiral agent may have two or more types of reactive groups.
• the chiral agent preferably contains a chiral agent having one polymerizable group.
• the ratio of the content of the chiral agent having one polymerizable group to the content of the chiral agent is 0% by mass. It is preferably greater than 50% by mass, more preferably 50% by mass or more, and even more preferably 70% by mass or more. The upper limit may be 100% by mass.
• the ratio of the content of the chiral agent having one polymerizable group to the content of the chiral agent may be 0% by mass to 100% by mass.
• the composition for the cholesteric liquid crystal layer preferably contains a cholesteric liquid crystal compound having a polymerizable group and a photosensitive chiral agent having a polymerizable group.
• the reaction between a photosensitive chiral agent having a polymerizable group and a cholesteric liquid crystal compound having a polymerizable group is a reaction between a structural unit derived from a cholesteric liquid crystal compound having a polymerizable group and a photosensitive chiral agent having a polymerizable group. It is possible to form a polymer having structural units derived from.
• the type of polymerizable group in the photosensitive chiral agent is preferably the same as the type of polymerizable group in the cholesteric liquid crystal compound.
• the chiral agent may be a cholestic liquid crystal compound.
• the chiral agent used in the present disclosure includes a photoisomerizable compound (photosensitive chiral agent) that also acts as a chiral agent.
• photoisomerizable compound photosensitive chiral agent
• examples of the photoisomerizable compound that also acts as a chiral agent include a compound represented by the below-mentioned formula (CH1).
• Preferred chiral agents include, for example, isosorbide derivatives, isomannide derivatives, and binaphthyl derivatives.
• chiral agents are shown below. However, the chiral agent is not limited to the specific examples below.
• n represents an integer of 2 to 12. From the viewpoint of synthesis cost, n is preferably 2 or 4.
• the cholesteric liquid crystal layer or composition may contain one or more chiral agents.
• the content ratio of the chiral agent to the total solid mass of the cholesteric liquid crystal layer or composition is 1% by mass to 20% by mass from the viewpoint of ease of forming the cholesteric liquid crystal layer and ease of adjusting the helical pitch. It is preferably 2% by mass to 10% by mass, even more preferably 3% by mass to 9% by mass, and particularly preferably 4% by mass to 8% by mass.
• the content ratio of the chiral agent having a polymerizable group to the total solid mass of the cholesteric liquid crystal layer or composition is preferably 0.2% by mass to 15% by mass, and preferably 0.5% by mass to 10% by mass. It is more preferably 1% by mass to 8% by mass. Further, the content ratio of the chiral agent having no polymerizable group to the total solid mass of the cholesteric liquid crystal layer or composition is preferably 0.2% by mass to 20% by mass, and 0.5% by mass. % to 10% by mass is more preferable.
• the helical pitch, the selective reflection wavelength, and its range are adjusted, for example, depending on not only the type of cholesteric liquid crystal compound but also the content of the chiral agent. For example, when the content of the chiral agent in the cholesteric liquid crystal layer is doubled, the helical pitch becomes 1/2, and the central value of the selective reflection wavelength also becomes 1/2.
• the cholesteric liquid crystal layer or composition may include a photoisomerizable compound.
• the type of photoisomerizable compound is not limited.
• the photoisomerizable compound may be a known photoisomerizable compound. From the viewpoint of suppressing changes in reflectance after molding and maintaining the isomerized structure, compounds whose steric structure changes upon exposure to light are preferred.
• a photoisomerizable compound has a photoisomerizable structure.
• the photoisomerizable compound preferably has a structure whose steric structure changes upon exposure, and the EZ configuration changes to isomerism upon exposure. It is more preferable to have a di-substituted or more ethylenically unsaturated bond whose EZ configuration is isomerized by exposure to light. Isomerization of the EZ configuration includes cis-trans isomerization.
• the disubstituted ethylenically unsaturated bond is preferably an ethylenically unsaturated bond substituted with an aromatic group and an ester bond.
• the photoisomerizable compound has two or more photoisomerizable structures from the viewpoint of suppressing changes in reflectance after molding, ease of photoisomerization, and maintainability of the isomerization structure.
• the number of photoisomerizable structures in the photoisomerizable compound is preferably two to four, more preferably two.
• the photoisomerizable compound is preferably a photoisomerizable compound (photosensitive chiral agent) that also acts as a chiral agent as described above.
• the photoisomerizable compound that also acts as a chiral agent is preferably a chiral agent having a molar extinction coefficient of 30,000 or more at a wavelength of 313 nm.
• Examples of the photoisomerizable compound that also acts as a chiral agent include a compound represented by the following formula (CH1).
• the compound represented by formula (CH1) can change the orientation structure such as the helical pitch (twisting force, helical twist angle) depending on the amount of light at the time of light irradiation.
• the compound represented by formula (CH1) is a compound in which the EZ configuration in two ethylenically unsaturated bonds can be isomerized by exposure to light.
• Ar CH1 and Ar CH2 each independently represent an aryl group or a heteroaromatic ring group
• R CH1 and R CH2 each independently represent a hydrogen atom or a cyano group
• Ar CH1 and Ar CH2 in formula (CH1) are each independently preferably an aryl group.
• the aryl group may have a substituent.
• substituents 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 heterocyclic group.
• 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 are more preferable.
• the total number of carbon atoms in the aryl group is preferably 6 to 40, more preferably 6 to 30.
• Ar CH1 and Ar CH2 are each independently an aryl group represented by the following formula (CH2) or the following formula (CH3).
• R CH3 and R CH4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, a hydroxy group, an acyl group.
• L CH1 and L CH2 each independently represent a halogen atom, an alkyl group, an alkoxy group, or a hydroxy group
• nCH1 represents an integer of 0 to 4
• nCH2 represents an integer of 0 to 6
• * represents the bonding position with the ethylenically unsaturated bond in formula (CH1).
• R CH3 and R CH4 in formula (CH2) and formula (CH3) each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, Alternatively, it is preferably an acyloxy group, more preferably an alkoxy group, a hydroxy group, or an acyloxy group, and particularly preferably an alkoxy group.
• L CH1 and L CH2 in formulas (CH2) and (CH3) are each independently preferably an alkoxy group having 1 to 10 carbon atoms or a hydroxy group. It is preferable that nCH1 in formula (CH2) is 0 or 1. It is preferable that nCH2 in formula (CH3) is 0 or 1.
• the heteroaromatic ring group in Ar CH1 and Ar CH2 in formula (CH1) may have a substituent.
• Preferred examples of the substituent include 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. More preferred are a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acyloxy group.
• the total number of carbon atoms in the heteroaromatic ring group is preferably 4 to 40, more preferably 4 to 30.
• the heteroaromatic group is preferably a pyridyl group, a pyrimidinyl group, a furyl group, or a benzofuranyl group, and more preferably a pyridyl group or a pyrimidinyl group.
• R CH1 and R CH2 in formula (CH1) are each independently preferably a hydrogen atom.
• Bu represents an n-butyl group.
• E form trans form
• Z form cis form
• the cholesteric liquid crystal layer or composition may contain one or more photoisomerizable compounds.
• the content ratio of the photosensitive chiral agent to the total solid mass of the cholesteric liquid crystal layer or composition is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 10% by mass. It is preferably 3% by mass to 9% by mass, more preferably 4% to 8% by mass.
• the cholesteric liquid crystal layer or composition contains a polymerization initiator.
• the type of polymerization initiator is not limited.
• the polymerization initiator may be a known polymerization initiator.
• the polymerization initiator is preferably a photopolymerization initiator.
• Examples of the photopolymerization initiator include ⁇ -carbonyl compounds (see, for example, US Pat. No. 2,367,661 and US Pat. No. 2,367,670), and acyloin ether compounds (see, for example, US Pat. No. 2,448,828). , ⁇ -hydrocarbon-substituted aromatic acyloin compounds (see, for example, US Pat. No.
• photopolymerization initiators include radical photopolymerization initiators and cationic photopolymerization initiators.
• Preferred photoradical polymerization initiators include, for example, ⁇ -hydroxyalkylphenone compounds, ⁇ -aminoalkylphenone compounds, acylphosphine oxide compounds, thioxanthone compounds, and oxime ester compounds.
• Preferred photocationic polymerization initiators include iodonium salt compounds and sulfonium salt compounds.
• the composition may contain one or more polymerization initiators.
• the content ratio of the polymerization initiator to the total solid mass of the cholesteric liquid crystal layer or composition is 0.05 from the viewpoint of ease of adjusting the helical pitch, polymerization rate, and strength of the liquid crystal layer after curing. It is preferably from 0.05% to 5% by mass, even more preferably from 0.1% to 4% by mass, and even more preferably from 0.2% by mass to 10% by mass. Particularly preferred is 3% by mass.
• the composition for the cholesteric liquid crystal layer may contain a polymerizable monomer.
• the polymerizable monomer can promote crosslinking of the cholesteric liquid crystal compound.
• Examples of the polymerizable monomer include monomers or oligomers that have two or more ethylenically unsaturated groups and undergo addition polymerization upon irradiation with light.
• Examples of the polymerizable monomer include compounds having an ethylenically unsaturated group.
• Examples of the polymerizable monomer include monofunctional acrylates, monofunctional methacrylates, polyfunctional acrylates, and polyfunctional methacrylates.
• Examples of the polymerizable monomer include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl(meth)acrylate.
• polymerizable monomers examples include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolethane triacrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane diacrylate, and neopentyl glycol di(meth)acrylate.
• meth)acrylate pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate (acryloyloxypropyl) ether, tri(acryloyloxyethyl)isocyanurate, tri(acryloyloxyethyl)cyanurate and glycerin tri(meth)acrylate.
• polymerizable monomer examples include compounds formed by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as trimethylolpropane or glycerin, followed by (meth)acrylation.
• Examples of the polymerizable monomer include urethane acrylates described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Application Laid-Open No. 51-37193.
• Examples of polymerizable monomers include polyester acrylates described in JP-A-48-64183, JP-B-49-43191, and JP-B-52-30490.
• examples of polymerizable monomers include epoxy acrylates, which are reaction products of epoxy resin and (meth)acrylic acid.
• Preferred polymerizable monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate.
• a preferable polymerizable monomer for example, "polymerizable compound B" described in JP-A-11-133600 can be mentioned.
• the polymerizable monomer may be a cationically polymerizable monomer.
• the cationic polymerizable monomer include JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, and JP-A-2001-310.
• examples thereof include epoxy compounds, vinyl ether compounds, and oxetane compounds described in JP-A No. 938, JP-A No. 2001-310937, and JP-A No. 2001-220526.
• epoxy compounds include aromatic epoxides, alicyclic epoxides, and aliphatic epoxides.
• Aromatic epoxides include diglycidyl ether or polyglycidyl ether of bisphenol A, diglycidyl ether or polyglycidyl ether of alkylene oxide adducts of bisphenol A, diglycidyl ether or polyglycidyl ether of hydrogenated bisphenol A, hydrogenated bisphenol A Diglycidyl ethers or polyglycidyl ethers of alkylene oxide adducts and novolac type epoxy resins are mentioned.
• alkylene oxide include ethylene oxide and propylene oxide.
• alicyclic epoxides examples include cyclohexene oxide-containing compounds obtained by epoxidizing a compound having a cycloalkane ring (e.g., cyclohexene and cyclopentene rings) with an oxidizing agent (e.g., hydrogen peroxide and peracid). Or a cyclopentene oxide-containing compound may be mentioned.
• Examples of aliphatic epoxides include diglycidyl ethers or polyglycidyl ethers of aliphatic polyhydric alcohols and diglycidyl ethers or polyglycidyl ethers of alkylene oxide adducts of aliphatic polyhydric alcohols.
• Examples of aliphatic epoxides include diglycidyl ethers of alkylene glycols (eg, diglycidyl ethers of ethylene glycol, diglycidyl ethers of propylene glycol, and diglycidyl ethers of 1,6-hexanediol).
• aliphatic epoxides examples include polyglycidyl ethers of polyhydric alcohols (eg, diglycidyl ethers or polyglycidyl ethers of glycerin and diglycidyl ethers or polyglycidyl ethers of alkylene oxide adducts of glycerin).
• examples of aliphatic epoxides include diglycidyl ethers of polyalkylene glycols (eg, diglycidyl ethers of polyethylene glycol or its alkylene oxide adducts, and diglycidyl ethers of polypropylene glycols or its alkylene oxide adducts).
• alkylene oxide examples include ethylene oxide and propylene oxide.
• Examples of cationically polymerizable monomers include monofunctional or bifunctional oxetane monomers.
• 3-ethyl-3-hydroxymethyloxetane for example, OXT101 manufactured by Toagosei Co., Ltd.
• 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene for example, OXT121 manufactured by Toagosei Co., Ltd.
• 3-ethyl-3-(phenoxymethyl)oxetane for example, OXT211 manufactured by Toagosei Co., Ltd.
• di(1-ethyl-3-oxetanyl) methyl ether for example, OXT221 manufactured by Toagosei Co., Ltd.
• 3-ethyl -3-(2-ethylhexyloxymethyl)oxetane for example, OXT212 manufactured by Toagosei Co., Ltd.
• 3-ethyl-3-hydroxymethyloxetane 3-ethyl-3-(phenoxymethyl)oxetane and di(1-ethyl-3-oxetanyl)methyl ether.
• Monofunctional or polyfunctional oxetane compounds described in JP-A No. 2001-220526 and JP-A No. 2001-310937 may be used.
• the composition for the cholesteric liquid crystal layer may contain a polyfunctional polymerizable compound.
• the polyfunctional polymerizable compound can contribute to suppressing changes in reflectance after molding.
• Examples of the polyfunctional polymerizable compound include a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and no cyclic ether group, and a cholesteric liquid crystal compound having two or more cyclic ether groups and having no cyclic ether group.
• Examples include cholesteric liquid crystal compounds having no unsaturated groups, cholesteric liquid crystal compounds having two or more ethylenically unsaturated groups and two or more cyclic ether groups, chiral agents and crosslinking agents having two or more polymerizable groups. It will be done.
• Preferred ethylenically unsaturated groups include, for example, (meth)acrylic groups.
• a more preferable ethylenically unsaturated group is, for example, a (meth)acryloxy group.
• Preferred cyclic ether groups include, for example, epoxy groups and oxetanyl groups.
• a more preferable cyclic ether group includes, for example, an oxetanyl group.
• the polyfunctional polymerizable compound includes a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and no cyclic ether group, and a cholesteric liquid crystal compound having two or more cyclic ether groups and having no ethylenically unsaturated group. It is preferable to contain at least one compound selected from the group consisting of a cholesteric liquid crystal compound that does not have a cholesteric liquid crystal compound and a chiral agent that has two or more polymerizable groups, and preferably contains a chiral agent that has two or more polymerizable groups. is more preferable.
• the composition may contain one or more polyfunctional polymerizable compounds.
• the content ratio of the polyfunctional polymerizable compound to the total solid mass of the cholesteric liquid crystal layer or composition is preferably 0.5% by mass to 70% by mass, and 1% by mass to 50% by mass. It is more preferably 1.5% by mass to 20% by mass, and particularly preferably 2% by mass to 10% by mass.
• the cholesteric liquid crystal layer or composition may include a crosslinking agent.
• the crosslinking agent can improve the strength and durability of the cured liquid crystal layer.
• the type of crosslinking agent is not limited.
• the crosslinking agent may be a known crosslinking agent.
• the crosslinking agent is preferably a compound that is cured by ultraviolet light, heat, or moisture.
• crosslinking agents include polyfunctional acrylate compounds such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; glycidyl(meth)acrylate, ethylene glycol diglycidyl ether, and 3',4'-epoxycyclohexyl.
• Epoxy compounds such as methyl 3,4-epoxycyclohexanecarboxylate; Oxetane compounds such as 2-ethylhexyloxetane and xylylene bisoxetane; 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate], 4 , 4-bis(ethyleneiminocarbonylamino)diphenylmethane; isocyanate compounds such as hexamethylene diisocyanate, biuret-type isocyanate; polyoxazoline compounds having an oxazoline group in the side chain; vinyltrimethoxysilane, N-(2-amino Examples include alkoxysilane compounds such as (ethyl)3-aminopropyltrimethoxysilane.
• a known catalyst may be used depending on the reactivity of the crosslinking agent. The use of a catalyst can improve productivity in addition to improving the strength and durability of the liquid crystal layer.
• the cholesteric liquid crystal layer or composition may contain one or more crosslinking agents.
• the content ratio of the crosslinking agent to the total solid mass of the cholesteric liquid crystal layer or composition is preferably 1% by mass to 20% by mass, from the viewpoint of the strength and durability of the cholesteric liquid crystal layer, and 3% by mass. % to 15% by mass is more preferable.
• the cholesteric liquid crystal layer or composition may contain other additives.
• Other additives include, for example, surfactants, polymerization inhibitors, antioxidants, horizontal alignment agents, ultraviolet absorbers, light stabilizers, colorants, and metal oxide particles.
• the color of the cholesteric liquid crystal layer and the change in color depending on the viewing angle are adjusted, for example, by at least one selected from the group consisting of helical pitch, refractive index, and thickness.
• the helical pitch can be adjusted by, for example, the content of the chiral agent. Details are described in, for example, "Fujifilm Research Report No. 50 (2005), pages 60-63.”
• the helical pitch may be adjusted by conditions such as temperature, illumination intensity, and irradiation time when fixing the cholesteric alignment state.
• the thickness of the cholesteric liquid crystal layer is preferably 0.5 ⁇ m or more, more preferably 2 ⁇ m or more, and even more preferably 3 ⁇ m or more from the viewpoint of the vividness of the reflected color. Further, from the viewpoint of ease of forming the cholesteric liquid crystal layer, the thickness of the cholesteric liquid crystal layer is preferably 10 ⁇ m or less, preferably 6 ⁇ m or less, and particularly preferably 4 ⁇ m or less. From the above viewpoint, the thickness of the cholesteric liquid crystal layer is preferably in the range of 0.5 ⁇ m to 10 ⁇ m or less.
• the haze value of the cholesteric liquid crystal layer is preferably 2.0% or less. When the haze value is 2.0% or less, the transparency of the cholesteric liquid crystal layer can be improved.
• the haze value is more preferably 1.8% or less, further preferably 1.3% or less, and particularly preferably 1.0% or less. Since a smaller haze is more preferable, the lower limit of the haze value is not limited. If the lower limit of the haze value is set for convenience, it is 0% or more.
• the haze value is a value measured by a method according to JIS K 7105 (1981) using a haze meter (for example, NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.).
• the decorative film may include a colored layer. This makes it easier to obtain a desired design.
• the colored layer is a layer containing a coloring agent.
• the number of colored layers may be one layer, or two or more layers. Further, the colored layer may be an optical mask layer in the laminate of the present disclosure.
• the position of the colored layer is not particularly limited, and may be provided at any desired position.
• a colored layer may be provided on the reflective layer.
• the decorative film when the decorative film includes a base material, it may be provided on the side opposite to the side on which the reflective layer of the base material is formed. It may be used as a decorative film and provided on the decorative film after peeling off the base material.
• the color of the colored layer is not particularly limited, and can be appropriately selected depending on the use of the decorative film.
• Examples of the color of the colored layer include black, gray, white, red, orange, yellow, green, blue, purple, and brown.
• the color of the colored layer may be a metallic color.
• the colorant may be a pigment or a dye. From the viewpoint of durability, the colorant is preferably a pigment. In order to give the colored layer a metallic tone, metal particles, pearl pigments, etc. may be used as the coloring agent.
• the pigment may be an inorganic pigment or an organic pigment.
• inorganic pigments examples 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, graphite, etc. black pigments; iron oxide, barium yellow, cadmium red, and chrome yellow.
• inorganic pigments examples include the inorganic pigments described in paragraphs 0015 and 0114 of JP-A No. 2005-7765.
• 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; perylene red, Perylene pigments such as perylene maroon; carbazole violet, anthrapyridine, flavanthrone yellow, isoindoline yellow, induthrone blue, dibrom anthathurone red, anthraquinone red, and diketopyrrolopyrrole.
• 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
• perylene red Perylene pigments such as perylene maroon
• organic pigments include C.I. I. Pigment Red 177, 179, 224, 242, 2515, 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 7, 36, 58 and other green pigments; C.I. I. Pigment Blue 15:6 and other blue pigments; and C.I. I. Examples include purple pigments such as Pigment Violet 23.
• organic pigments examples include organic pigments described in paragraph 0093 of JP-A No. 2009-256572.
• the pigment may be a pigment that has light transmittance and light reflectivity (so-called glitter pigment).
• bright pigments include metal bright pigments of aluminum, copper, zinc, iron, nickel, tin, aluminum oxide, and alloys thereof, interference mica pigments, white mica pigments, graphite pigments, and glass flake pigments. can be mentioned.
• the glitter pigment may be uncolored or colored.
• One type of colorant may be used alone, or two or more types may be used in combination.
• an inorganic pigment and an organic pigment may be combined.
• the content of the colorant is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 50% by mass, based on the total amount of the colored layer. , 10% by mass to 40% by mass is particularly preferred.
• the colored layer preferably contains a binder resin from the viewpoints of strength, scratch resistance, and suitability for molding.
• the type of binder resin is not particularly limited. From the viewpoint of obtaining a desired color, the binder resin is preferably a transparent resin, and specifically, a resin having a total light transmittance of 80% or more is preferable. The total light transmittance can be measured with a spectrophotometer (eg, spectrophotometer "UV-2100" manufactured by Shimadzu Corporation).
• binder resin examples include acrylic resin, silicone resin, polyester, polyurethane, and polyolefin.
• the binder resin may be a homopolymer or a copolymer.
• binder resin One type of binder resin may be used alone, or two or more types may be used in combination.
• the content of the binder resin is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and 20% by mass, based on the total amount of the colored layer. Particularly preferred is % by weight to 60% by weight.
• the colored layer may contain a dispersant.
• a dispersant included, the dispersibility of the colorant in the colored layer is improved. Therefore, the color of the obtained decorative film can be more easily made uniform.
• the dispersant can be appropriately selected depending on the type, shape, etc. of the colorant, and is preferably a polymer dispersant.
• polymeric dispersants examples include silicone polymers, acrylic polymers, and polyester polymers.
• the dispersant when it is desired to impart heat resistance to the decorative film, is preferably a silicone polymer such as a graft type silicone polymer.
• 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 more preferably 2,500 to 3,000,000. It is particularly preferable. When the weight average molecular weight is 1,000 or more, the dispersibility of the colorant is further improved.
• the dispersant may be a commercially available product.
• Commercially available dispersants include EFKA 4300 (acrylic polymer dispersant) manufactured by BASF Japan; homogenol L-18, homogenol L-95, and homogenol L-100 manufactured by Kao; and homogenol L-100 manufactured by Japan Lubrizol. , Solsperse 20000, and Solsperses 24000; and DISPERBYK-110, DISPERBYK-164, DISPERBYK-180, and DISPERBYK-182 manufactured by BYK Chemie Japan. Note that "Homogenol,” “Solsperse,” and “DISPERBYK” are all registered trademarks.
• One type of dispersant may be used alone, or two or more types may be used in combination.
• the content of the dispersant is preferably 1 part by mass to 30 parts by mass based on 100 parts by mass of the colorant.
• the colored layer may contain additives, if necessary, in addition to the above-mentioned components.
• the additive is not particularly limited, and for example, the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP2009-237362; and the surfactants described in paragraph 0018 of Japanese Patent No. 4502784.
• Thermal polymerization inhibitors also referred to as polymerization inhibitors; preferred examples include phenothiazine
• the thickness of the colored layer is not particularly limited, but from the viewpoint of visibility and three-dimensional moldability, it is preferably 0.5 ⁇ m or more, more preferably 3 ⁇ m or more, and even more preferably 3 ⁇ m to 50 ⁇ m. , 3 ⁇ m to 20 ⁇ m is particularly preferred.
• each colored layer independently has a thickness within the above range.
• the 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.
• the method of forming the colored layer is preferably a method using a composition for forming a colored layer.
• a method of forming a colored layer using a colored layer forming composition includes a method of coating a colored layer forming composition to form a colored layer, for example, a method of forming a colored layer by printing a colored layer forming composition.
• Examples include a method of forming.
• Examples of printing methods include screen printing, inkjet printing, flexo printing, gravure printing, and offset printing.
• the composition for forming a colored layer may contain a colorant and, if necessary, at least one of a binder resin, a dispersant, and an additive.
• the types of each component may be those described above for the colored layer.
• the content of the coloring agent is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 50% by mass, and 10% by mass based on the total solid content of the composition for forming a colored layer. % to 40% by weight is particularly preferred.
• the content of the binder resin is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and 20% by mass based on the total solid content of the composition for forming a colored layer. % to 60% by weight is particularly preferred.
• the content of the dispersant is preferably 1 part by mass to 30 parts by mass based on 100 parts by mass of the colorant.
• the colored layer may be a layer formed by curing a composition for forming a colored layer, for example, a composition for forming a colored layer containing a polymerizable compound and a polymerization initiator may be used.
• the polymerizable compound and polymerization initiator are not particularly limited, and known polymerizable compounds and known polymerization initiators may be used.
• One type of polymerizable compound may be used alone, or two or more types may be used in combination.
• One type of polymerization initiator may be used alone, or two or more types may be used in combination.
• the composition for forming a colored layer may contain an organic solvent from the viewpoint of making coating easier.
• the organic solvent is not particularly limited, and any known organic solvent can be used. Examples of organic solvents include alcohols, esters, ethers, ketones, and aromatic hydrocarbons. One type of organic solvent may be used alone, or two or more types may be used in combination.
• the content of the organic solvent is preferably 5% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, based on the total amount of the composition for forming a colored layer.
• composition for forming a colored layer commercially available paints such as NAX Real series, NAX Admira series, and NAX Multi series (manufactured by Nippon Paint Co., Ltd.); Rethan PG series (manufactured by Kansai Paint Co., Ltd.) may be used.
• the method for preparing the composition for forming a colored layer is not particularly limited, and for example, the composition for forming a colored layer may be prepared by mixing each component such as a coloring agent.
• the composition for forming a colored layer contains a pigment as a coloring agent, from the viewpoint of further increasing the uniform dispersibility and dispersion stability of the pigment, a pigment dispersion containing the pigment and a dispersant is prepared in advance, and the pigment dispersion is prepared in advance. It is preferable to prepare a composition for forming a colored layer by mixing other components with the above composition.
• the decorative film may have an alignment layer.
• the alignment layer is used to more easily align the molecules of the cholesteric liquid crystal compound in the light reflecting portion when forming the decorative film.
• the alignment layer is provided by, for example, rubbing treatment with an organic compound (preferably a polymer), oblique vapor deposition of an inorganic compound, formation of a layer having microgrooves, or the like.
• an alignment layer an alignment layer in which an alignment function is produced by application of an electric field, a magnetic field, or light irradiation is also known.
• the thickness of the alignment layer is not particularly limited, but is preferably 0.01 ⁇ m to 10 ⁇ m.
• the underlayer can be used as an alignment layer without providing a separate alignment layer.
• alignment treatment for example, rubbing treatment
• it can be made to function as an alignment layer.
• An example of a base material that can be directly aligned is a layer made of polyethylene terephthalate (PET), which may be subjected to a rubbing process as described below.
• the rubbing treatment alignment layer is formed, for example, by performing a rubbing treatment on the surface of the base to which the liquid crystal composition is applied.
• the rubbing treatment can be performed, for example, by rubbing the surface of a film containing a polymer as a main component in a certain direction with paper or cloth.
• a general method of rubbing treatment is described, for example, in "Liquid Crystal Handbook" (published by Maruzensha, October 30, 2000).
• Examples of polymers for the alignment layer forming a film mainly composed of the above-mentioned polymers include methacrylate copolymers, styrene copolymers, polyolefins, and the like described in paragraph 0022 of JP-A-8-338913.
• Examples include polyvinyl alcohol, modified polyvinyl alcohol, poly(N-methylolacrylamide), polyester, polyimide, vinyl acetate copolymer, carboxymethyl cellulose, and polycarbonate.
• the polymer for alignment layer may be a silane coupling agent.
• the alignment layer polymer is preferably a water-soluble polymer (for example, poly(N-methylolacrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol, or modified polyvinyl alcohol), more preferably gelatin, polyvinyl alcohol, or modified polyvinyl alcohol, and polyvinyl alcohol. or modified polyvinyl alcohol is particularly preferred.
• the rubbing density (L) is quantified by the following formula (A).
• Formula (A) L Nl(1+2 ⁇ rn/60v)
• N is the number of rubbings
• l is the contact length of the rubbing roller
• r is the radius of the roller
• n is the number of revolutions per minute (rpm) of the roller
• v is the stage movement speed (per second).
• Methods for increasing the rubbing density include increasing the number of times of rubbing, increasing the contact length of the rubbing roller, increasing the radius of the roller, increasing the number of rotations of the roller, and decreasing the stage movement speed. can be mentioned.
• methods for lowering the rubbing density include reducing the number of rubbings, shortening the contact length of the rubbing roller, decreasing the radius of the roller, decreasing the number of rotations of the roller, and increasing the stage movement speed.
• One method is to do so.
• the description in Japanese Patent No. 4052558 can also be referred to as the conditions for the rubbing process.
• Examples of the photo-alignment material used in the photo-alignment layer formed by light irradiation include JP-A Nos. 2006-285197, 2007-76839, 2007-138138, and 2007-94071. Publications, JP 2007-121721, JP 2007-140465, JP 2007-156439, JP 2007-133184, JP 2009-109831, Japanese Patent No. 3883848, and patents Azo compound described in JP-A No. 4151746; aromatic ester compound described in JP-A No. 2002-229039; photo-alignable unit described in JP-A No. 2002-265541 and JP-A No. 2002-317013.
• Maleimide and/or alkenyl-substituted nadimide compounds include photocrosslinkable silane derivatives described in Japanese Patent No. 4205195 and Japanese Patent No. 4205198; and Japanese Patent Application Publication No. 2003-520878, Japanese Patent No. 2004-529220, and Japanese Patent No. 4162850 Examples include photocrosslinkable polyimides, polyamides, and esters described in the above publication.
• the photo-alignment material is preferably an azo compound, photo-crosslinkable polyimide, polyamide, or ester.
• a layer formed from a photo-alignment material is irradiated with linearly polarized light or non-polarized light to produce a photo-alignment layer.
• linearly polarized light irradiation is an operation for causing a photoreaction in a photoalignment material.
• the wavelength of the light used varies depending on the photoalignment material used, and is not particularly limited as long as it is a wavelength necessary for the photoreaction.
• the light used for light irradiation is preferably light with a peak wavelength of 200 nm to 700 nm, more preferably ultraviolet light with a peak wavelength of 400 nm or less.
• the 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 various lasers (for example, semiconductor lasers, (helium neon laser, argon ion laser, helium cadmium laser, or YAG laser), light emitting diodes, and cathode ray tubes.
• known light sources such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury-xenon lamps, carbon arc lamps, and various lasers (for example, semiconductor lasers, (helium neon laser, argon ion laser, helium cadmium laser, or YAG laser), light emitting diodes, and cathode ray tubes.
• lasers for example, semiconductor lasers, (helium neon laser, argon ion laser, helium cadmium laser, or YAG laser
• Methods for obtaining linearly polarized light include methods using a polarizing plate (for example, an iodine polarizing plate, a dichroic dye polarizing plate, or a wire grid polarizing plate), a method using a prism-based element (for example, a Glan-Thompson prism), or a method using a Brewster angle.
• a polarizing plate for example, an iodine polarizing plate, a dichroic dye polarizing plate, or a wire grid polarizing plate
• a prism-based element for example, a Glan-Thompson prism
• a Brewster angle for example, a a Brewster angle
• Examples include a method using a reflective polarizer and a method using light emitted from a polarized laser light source.
• only light of a required wavelength may be selectively irradiated using a filter, a wavelength conversion element, or the like.
• the irradiated light is linearly polarized light
• a method of irradiating the light from the top or back surface of the alignment layer in a direction perpendicular to or oblique to the surface of the alignment layer can be mentioned.
• the incident angle of light varies depending on the photo-alignment material, but is preferably 0° to 90° (perpendicular), more preferably 40° to 90°, with respect to the alignment layer.
• the non-polarized light When using non-polarized light, the non-polarized light is irradiated obliquely from the top or back surface of the alignment layer.
• the angle of incidence is preferably 10° to 80°, more preferably 20° to 60°, even more preferably 30° to 50°.
• the irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.
• the decorative film preferably further includes a refractive index adjusting layer, more preferably between the reflective layer and the layer having the uneven structure.
• a refractive index adjusting layer can be used as the refractive index adjusting layer.
• Examples of materials included in the refractive index adjusting layer include resins, polymerizable compounds, metal salts, particles, and the like.
• the method of controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a polymer and particles, and the like.
• Examples of the polymer include the resins already described as components of the layer having the uneven structure B.
• Examples of the polymerizable compound include the polymerizable compounds and crosslinking agents already described as components of the reflective layer.
• Examples of the particles include metal oxide particles and metal particles.
• the type of metal oxide particles is not particularly limited, and examples thereof include known metal oxide particles. Metals in the metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.
• the metal oxide particles include zirconium oxide particles (ZrO 2 particles), Nb 2 O 5 particles, titanium oxide particles (TiO 2 particles), silicon dioxide particles (SiO 2 particles), and composites thereof. At least one kind selected from the group consisting of particles is preferable. Among these, as the metal oxide particles, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable, for example, because the refractive index can be easily adjusted.
• metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74), Calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F75), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F76), zirconium oxide particles (Nano Youth OZ-S30M, Nissan and zirconium oxide particles (Nano Teen OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).
• the average primary particle diameter of the particles is, for example, preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, from the viewpoint of transparency of the cured film.
• the average primary particle diameter of the particles is calculated by measuring the particle diameter of 200 arbitrary particles using an electron microscope and taking the arithmetic average of the measurement results. In addition, when the shape of the particle is not spherical, the longest side is taken as the particle diameter.
• the particles may be used alone or in combination of two or more.
• the content of particles in the refractive index adjusting layer is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and 40% by mass, based on the total mass of the refractive index adjusting layer. % to 85% by mass is more preferable.
• the difference between the refractive index of the refractive index adjustment layer and the refractive index of the cholesteric liquid crystal layer is preferably 0.10 or less, more preferably 0.05 or less, and 0.005 to 0.03. It is particularly preferable.
• the thickness of the refractive index adjusting layer is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 20 ⁇ m or more. Moreover, from the same viewpoint, the thickness of the refractive index adjusting layer is preferably 300 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 50 ⁇ m or less.
• the decorative film may have layers other than the cholesteric liquid crystal layer, the base material, the colored layer (optical mask layer), and the refractive index adjustment layer.
• a protective layer includes a protective layer, an adhesive layer, an easy-to-adhesion layer, an ultraviolet absorbing layer, a self-healing layer, an antistatic layer, an antifouling layer, an electromagnetic wave prevention layer, a conductive layer, etc., which are known layers in decorative films. can be mentioned.
• compositions layer-forming composition
• a composition layer-forming composition
• these layers are applied in a layered manner and then dried.
• the molded article of the present disclosure is formed by molding the decorative film of the present disclosure.
• the decorative film of the present disclosure can be used for various purposes, and for example, the decorative film can be molded and used as a molded product.
• the article of the present disclosure includes the decorative film of the present disclosure or the molded article of the present disclosure.
• the display device of the present disclosure includes the article of the present disclosure.
• Examples of the article of the present disclosure include electronic devices such as smartphones, mobile phones, and tablets, automobiles, electrical appliances, packaging containers, and the like, and the article can be particularly preferably used for electronic devices.
• display devices such as a display, a smartphone, a mobile phone, and a tablet are more preferably mentioned. Among these, it can be particularly suitably used for ordinary displays or displays in display devices such as smartphones, home appliances, audio products, computers, and in-vehicle products.
• a retardation film may be provided between the decorative film of the present disclosure and a display member such as a display.
• a retardation film known ones can be used.
• the means for molding the laminate of the present disclosure to obtain a molded body is not particularly limited, and may be, for example, a known method such as three-dimensional molding or insert molding. Furthermore, the means for applying the laminate of the present disclosure to an article is not particularly limited, and any known method may be used as appropriate depending on the type of article.
• Example 1 As Example 1, a liquid crystal film was manufactured using a manufacturing apparatus 100a configured as shown in FIG.
• base material As a base material, a polyethylene terephthalate film (thickness 100 ⁇ m, width 330 mm, length 2000 m, Cosmoshine A4160, manufactured by Toyobo Co., Ltd.) containing an easily adhesive layer on one side was prepared.
• base material with optical mask layer An optical mask layer was provided on the surface of the base material on which the easy-adhesion layer was formed by printing. Specifically, using a wet electrophotographic printing machine (Indigo 6900, manufactured by Hewlett-Packard), the pattern shown in FIG.
• the patterns shown in FIG. 8 are the first pattern shown in FIG. 9 formed with magenta ink, the second pattern shown in FIG. 10 formed with violet ink, and the second pattern shown in FIG. 11 formed with yellow ink.
• a fourth pattern shown in FIG. 12 formed with orange ink
• a fifth pattern shown in FIG. 13 formed with cyan ink
• a sixth pattern shown in FIG. 14 formed with black ink. It was formed by superimposing the pattern.
• the color inks used were standard four colors of magenta, yellow, cyan, and black, and IndiChrome special color inks of violet and orange, manufactured by Hewlett-Packard under the trade name of HP Indigo Electro Ink.
• the first to sixth patterns were all formed in a 210-line AM screen pattern, and the printing area ratio per 300 ⁇ m square was controlled.
• the density of the colors in Figures 8 to 14 indicates the high printing area ratio per 300 ⁇ m square, and the darker the area in the figure, the higher the printing area ratio per 300 ⁇ m square, and the area shown in the darkest color indicates that the printing area ratio is 100%.
• the patterns were controlled so that the halftone areas of the first to sixth patterns did not overlap with each other.
• Liquid crystal composition 1 having the composition described below was prepared. -Composition of liquid crystal composition 1-
• the following rod-shaped liquid crystal compound (1) 100 parts by mass
• Photopolymerization initiator (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.): 4 parts by mass Surfactant 1 (compound having the following structure): 0.05 parts by mass Surfactant 2 (compound having the following structure): 0.055 parts by mass Organic solvent 1 (methyl ethyl ketone): 187 parts by mass Organic solvent 2 (furfuryl alcohol): 36 parts by mass Photosensitive chiral agent (1) (compound having the following structure): 8 parts by mass
• Surfactant 1 The following compound
• Surfactant 2 The following compound
• Photosensitive chiral agent (1) the following compound
• liquid crystal composition 1 prepared above was applied onto the rubbed surface of the base material using a die coater.
• the coating was adjusted so that the thickness after drying was approximately 2.5 ⁇ m to 4 ⁇ m, and was carried out at room temperature to form a coating film (liquid crystal material preparation step).
• the coating film was irradiated with UV (Ultra Violet)-LED (manufactured by CCS) at room temperature through an optical mask layer at an illuminance of 50 mW and an exposure amount of 25 mJ/cm 2 . light) was irradiated onto the cholesteric liquid crystal layer (photoreaction process of photosensitive chiral agent). Since we used an optical mask layer with a small difference in light transmittance between the halftone dots and the gaps, the amount of photoreaction of the photosensitive chiral agent in the cholesteric liquid crystal layer has a small difference between the halftone dots and the gaps, and the helical induction The difference in power is also small.
• the base material on which the coating film after the photoreaction process of the photosensitive chiral agent was laminated was heated for 1 minute in a hot air drying zone at 60°C.
• the coated film after heat treatment is irradiated with light (second light) from a metal halide lamp (GS Yuasa Co., Ltd. MAL625NAL) from the cholesteric liquid crystal layer side at room temperature in a low oxygen atmosphere (oxygen concentration 500 ppm or less).
• the cholesteric liquid crystal layer was cured to form a decorative film (curing step).
• the irradiation here was performed under an exposure condition of an exposure amount of 800 mJ/cm 2 . After that, it was wound up with a winding roller.
• the base material with an optical mask layer was verified as follows.
• the substrate with the optical mask layer was observed from the surface of the optical mask layer using an optical microscope (Eclipse LV100N POL, Nikon Corporation). In order to observe a 300 ⁇ m square area, the magnification was adjusted so that the field of view ranged from 400 ⁇ m to 2 mm. The area of the printed pattern to be observed included within a 300 ⁇ m square was calculated from the shape and size, and the value divided by 90,000 ⁇ m 2 was taken as the printed area ratio per 300 ⁇ m square.
• the transmittance per 10 ⁇ m ⁇ was measured using a differential microscopy ultraviolet visible near infrared spectrophotometer (MSV-5500, JASCO Corporation).
• the decorative film was verified as follows.
• -Cholesteric pitch- A section of the decorative film was prepared using a microtome (RX-860, Daiwa Koki Kogyo Co., Ltd.), and the cross section of the cholesteric liquid crystal layer of the section was observed using a scanning electron microscope (SU3800, Hitachi High-Tech Corporation). I measured it. The difference obtained by subtracting the minimum value from the maximum value of the cholesteric pitch in the entire cholesteric liquid crystal layer was defined as ⁇ P all .
• ⁇ P all Intra-grid pitch difference ⁇ P S - Regarding the maximal points of cholesteric pitch arranged at equal intervals, a rectangle with the smallest area among the rectangles having the maximal points as vertices was used as a unit cell.
• the halftone dot painting area was divided into unit grids, and the difference obtained by subtracting the minimum pitch from the maximum value of the pitch within the unit grid was defined as the intra-grid pitch difference ⁇ PS .
• the intra-lattice pitch difference was defined as ⁇ P S (MAX) .
• the prepared substrate with an optical mask layer had an AM screen halftone dot coating area with a screen line count of 210 using yellow ink, and a 300 ⁇ m square printing area ratio of 100 at a position overlapping the halftone dot coating area. % and a light transmittance of 26.4%, and the semi-transparent solid area included a magenta ink pattern and a violet ink pattern, and included three or more patterns. . Furthermore, the light transmittance T D of the halftone dots, the light transmittance T A of the gap between the halftone dots, the light transmittance T min at the lowest light transmittance point of the optical mask layer, and the light transmittance at the highest light transmittance point.
• An optical mask layer was formed in which (T A - T D )/(T MAX - T min ) was 0.28 or less in all regions. Further, this optical mask layer included a region where T A was 49%, T D was 27%, and T A -T D was 22%.
• the pitch difference ⁇ P all in the entire cholesteric liquid crystal layer was 258 nm
• the maximum value ⁇ P S (MAX) of the pitch difference in the lattice was 30 nm
• ⁇ P S (MAX) / ⁇ P all 0.12. Met.
• the maximum value of the amount of change in cholesteric pitch per 100 ⁇ m in-plane distance was 172 nm.
• the cholesteric liquid crystal layer was attached to a PET film (A4160, Toyobo Co., Ltd.) via an optical adhesive sheet (G25, Nichiei Shinka Co., Ltd.). Co., Ltd.) to produce a decorative film for evaluation, and the following evaluations were performed.
• the reflection spectrum of the decorative film was measured using the surface on which the cholesteric liquid crystal layer was formed as the incident surface.
• the measurement was carried out using a spectrophotometer (V-670, JASCO Corporation) and a large integrating sphere device (ILV-471), using black drawing paper with a 1 mm square hole as a measurement window.
• the reflection spectrum is an integrated reflection spectrum measured with a spectrophotometer equipped with an integrating sphere device using a 1 mm square measurement window, and a relative reflection spectrum with respect to a white standard plate similarly measured using a 1 mm square measurement window. shows.
• the reflection center wavelength of the decorative film was measured as follows.
• the reflection spectrum of the decorative film was measured using the surface on which the cholesteric liquid crystal layer was formed as the incident surface.
• the measurement was carried out using a spectrophotometer (V-670, JASCO Corporation) and a large integrating sphere device (ILV-471), using black drawing paper with a 1 mm square hole as a measurement window.
• the reflectance was determined from the reflection spectrum. Reflectance is an integrated reflectance measured with a spectrophotometer equipped with an integrating sphere device using a 1 mm square measurement window, and is a relative reflectance with respect to a white standard plate similarly measured using a 1 mm square measurement window. shows.
• the obtained decorative film was visually observed indoors using a fluorescent lamp (straight tube, daylight white, manufactured by Panasonic Corporation) and observed using an optical microscope (Eclipse LV100N POL, Nikon Corporation).
• the graininess was evaluated according to the following criteria.
• As the reflective decorative film "AA” to “D” are preferable, “AA” to “C” are more preferable, “AA” to “B” are even more preferable, and “AA” or “A” is particularly preferable. , “AA” are most preferred.
• A No graininess is observed when visually observed from a point 5 cm away from the decorative film, and a dot-like hue change is observed when observed using an optical microscope.
• B No graininess is observed when visually observed from a point 10 cm away from the decorative film, and graininess is observed when visually observed from a point 5cm away from the decorative film.
• C No graininess is observed when visually observed from a point 20 cm away from the decorative film, and graininess is observed when visually observed from a point 10cm away from the decorative film.
• D No graininess is observed when visually observed from a point 30 cm away from the decorative film, and graininess is observed when visually observed from a point 20cm away from the decorative film.
• E Graininess is visible when visually observed from a point 30 cm away from the decorative film.
• the obtained decorative film was measured using a spectrophotometer (V-770, JASCO Corporation) and an absolute reflectance measurement unit (ARMV-919, JASCO Corporation) with respect to the vertical line on the surface of the decorative film.
• the diffuse reflection spectrum was measured when light was incident at an angle of -15° and reflected light was received at an angle of +25°. Furthermore, the specular reflection spectrum at -5° incidence and +5° reception was also measured.
• the measurement wavelength range was 380 nm to 780 nm.
• the contrast RI D /RI S of the reflection intensity RI D of the diffuse reflection with respect to the reflection intensity RI S of the specular reflection was calculated. Since the stronger the reflection intensity in the diffusion direction, the lower the glossiness, the glossiness was evaluated according to the following criteria.
• the reflective decorative film "A" to “C” are preferable, “A” or “B” is more preferable, and “A” is particularly preferable.
• Example 1 it was possible to efficiently produce a multicolored decorative film with high reflective saturation, less visible graininess, and a glossy appearance.
• the printing machine In the process of forming an optical mask layer on the base material, the printing machine is an inkjet type (Jet Pr). ess 540WV, Fuji Film Corporation), and the pattern is F instead of AM screen style.
• a decorative film was produced in the same manner as in Example 1, except that it was formed into an M screen pattern and the printing area ratio and light transmittance were controlled by the density of halftone dots, and further verification and evaluation 1 were conducted. .
• the results of the verification and evaluation are summarized in Table 1.
• slightly larger halftone dots were formed in which halftone dots were connected to each other in the medium concentration region.
• the cholesteric pitch did not become sufficiently uniform in the areas where the halftone dots of the optical mask layer were large, resulting in a halftone hue change and non-uniform reflection color. .
• the obtained decorative film had low chroma, graininess was easily visible, and gloss was weak.
• the reason for the decrease in gloss is that when the cholesteric pitch is non-uniform, the alignment of the cholesteric liquid crystal becomes a tilted alignment as the pitch increases or decreases, and light is reflected in a diffused direction compared to the desired horizontal alignment. Guessed.
• Example 2 In the process of forming an optical mask layer on the base material, a laser photoplotter type printing machine is used to form a pattern on an A3 size plate making film (GPR-7S) using a 350-line AM screen tone.
• a decorative film was produced in the same manner as in Example 1, except that the pattern-forming surface was bonded so as to be in contact with the base material, and further verification and evaluation 1 were conducted. The results of the verification and evaluation are summarized in Table 1. As a result, we were able to produce a multicolored decorative film with high reflective saturation, less visible graininess, and a glossy appearance. Production efficiency was poor because it was necessary to laminate the number of sheets according to the number of sheets.
• the first pattern is the pattern shown in FIG. 15 that does not have the halftone dot area
• the second pattern is the pattern shown in FIG. 16
• the third to sixth patterns are not formed
• the content of the photosensitive chiral agent is A decorative film was produced in the same manner as in Example 1, except that the amount was 5.5 parts by mass, and further verification and evaluation 1 were conducted. The results of the verification and evaluation are summarized in Table 1.
• the obtained decorative film had a small number of colors because the hue was not controlled by the dot-coated areas of the optical mask layer.
• the first pattern is the pattern shown in FIG. 17 without the halftone area
• the second pattern is the pattern shown in FIG. 16
• the third to sixth patterns are not formed
• the exposure amount of the first light is 13 mJ/
• a decorative film was produced in the same manner as in Example 1, except that the film was set to cm 2 , and further verification and evaluation 1 were performed. The results of the verification and evaluation are summarized in Table 1.
• the obtained decorative film had a small number of colors because the hue was not controlled by the dot-coated areas of the optical mask layer.
• Example 5 A decorative film was produced in the same manner as in Example 1, except that the second to sixth patterns were not formed, and further verification and evaluation 1 were conducted. The results of the verification and evaluation are summarized in Table 1.
• the prepared optical mask layer had a large difference in light transmittance between the halftone dots and the gap, and the obtained decorative film had a halftone dot-like hue change. As a result, the obtained decorative film had low chroma, graininess was easily visible, and gloss was weak.
• Example 2 The first pattern is a 10 cm square pattern with a halftone dot area shown in (1) of FIG. 18A, and the second pattern is a 10 cm square pattern with a semi-transparent solid area shown in (2) of FIG. 18B.
• a decorative film was produced in the same manner as in Example 1, except that the third to sixth patterns were not formed, and further verification and evaluation 1 were conducted. The results of the verification and evaluation are summarized in Table 1.
• the first pattern is a 10 cm square pattern with a halftone dot area shown in (4) of FIG. 19A
• the second pattern is a 10 cm square pattern with a semi-transparent solid area shown in (5) of FIG. 19B.
• a decorative film was produced in the same manner as in Example 2, except for the pattern, and further verification and evaluation 1 were conducted. The results of the verification and evaluation are summarized in Table 1.
• Example 4 The first pattern is a 10 cm square pattern with a halftone dot area shown in (7) of FIG. 20A, and the second pattern is a 10 cm square pattern with a semi-transparent solid area shown in (8) of FIG. 20B. Decoration was carried out in the same manner as in Example 3, except that the entire halftone dot area of the first pattern was an optical mask layer that overlapped with the semi-transparent solid area of the second pattern. A film was produced, and further verification and evaluation 1 were conducted. The results of the verification and evaluation are summarized in Table 1.
• the first pattern is a 10 cm square pattern with a halftone dot area shown in (10) of FIG. 21A
• the second pattern is a 10 cm square pattern with a semi-transparent solid area shown in (11) of FIG. 21B.
• a decorative film was prepared in the same manner as in Example 4, except that the optical mask layer included three patterns, and further verification and evaluation 1 were conducted. The results of the verification and evaluation are summarized in Table 1.
• Example 6 The first pattern is a 10 cm square pattern with a halftone dot area shown in (14) in Figure 22A, and the second pattern is a 10 cm square pattern with a semi-transparent solid area shown in (15) in Figure 22B.
• a decorative film was produced in the same manner as in Example 5, except that the third pattern was a 10 cm square pattern with a halftone dot area shown in (16) of FIG. 22C, Furthermore, verification and evaluation 1 were conducted. The results of the verification and evaluation are summarized in Table 1. As a result, a multicolored decorative film with high chroma and slightly suppressed visibility of graininess was efficiently obtained.
• the reflection center wavelength of the decorative film is measured in the same way as the evaluation of reflection saturation c * , and the shortest reflection center wavelength and longest reflection center wavelength in the decoration film are calculated, and the difference between the reflection center wavelengths is calculated.
• the color range was evaluated from ⁇ according to the following criteria. As a decorative film, it is preferable that it is "A". ⁇ Standards> A: ⁇ 110nm B: ⁇ 110nm
• Example 7 In the step of photoreacting the photosensitive chiral agent, ground glass is installed between the light source and the optical mask layer to make the first light diffused light, and the step of photoreacting the photosensitive chiral agent, A decorated film was produced in the same manner as in Example 1, except that the heating performed during the curing step was 85° C., and further verification and evaluation were performed. The results of the verification and evaluation are summarized in Table 2.
• the formed cholesteric liquid crystal layer had a maximum cholesteric pitch change of 10 nm per 100 ⁇ m in-plane distance.
• Example 7 although it was possible to efficiently produce a decorative film with high chroma, gloss, and suppressed graininess, the pattern boundaries of the obtained decorative film were blurred.
• Example 8 A decorative film was produced in the same manner as in Example 1, except that the first light was set to an exposure amount of 75 mJ/cm 2 , and further verification and evaluation were performed. The results of the verification and evaluation are summarized in Table 2.
• the cholesteric liquid crystal layer thus formed had a maximum intra-lattice pitch difference of 75 nm. As a result, although it was possible to efficiently produce a multicolored decorative film with high saturation, the resulting decorative film had weak gloss and graininess that was easily visible. The larger the intra-lattice pitch difference, the more the cholesteric liquid crystal will be aligned at a larger angle, resulting in worse gloss and graininess.
• Example 9 A decorative film was produced in the same manner as in Example 1, except that the first light was set to an exposure amount of 10 mJ/cm 2 , and further verification and evaluation were performed. The results of the verification and evaluation are summarized in Table 2.
• the difference between the maximum value and the minimum value of cholesteric pitch was 65 nm.
• the resulting decorative film had a narrow color range, with colors ranging from blue to green. There was only change. The smaller the difference between the maximum and minimum values of the cholesteric pitch in the cholesteric liquid crystal layer, the narrower the color range that can be achieved.
• Example 10 The following liquid crystal composition 2 was used as the liquid crystal composition, and in the curing process, a short wavelength cut filter (a dielectric multilayer film was deposited on a glass substrate, and the transmittance in the wavelength range of 200 nm to 340 nm was 0.1% or less) )
• a short wavelength cut filter a dielectric multilayer film was deposited on a glass substrate, and the transmittance in the wavelength range of 200 nm to 340 nm was 0.1% or less
• Preparation of the substrate and preparation of the substrate with an optical mask layer were performed in the same manner as in Example 1, except that the light (second light) of a metal halide lamp (GS Yuasa Co., Ltd. MAL625NAL) was irradiated through the preparation, alignment treatment, and formation of a liquid crystal layer.
• a metal halide lamp GS Yuasa Co., Ltd. MAL625NAL
• Photosensitive chiral agent (2) the following compound
• the obtained liquid crystal layer was further subjected to an alignment treatment and a second liquid crystal layer was laminated using a manufacturing apparatus 100a configured as shown in FIG.
• Liquid crystal composition 3 having the composition described below was prepared.
• Photosensitive chiral agent (3) the following compound
• liquid crystal composition 3 prepared above was applied onto the rubbed surface of the base material using a die coater.
• the coating was adjusted so that the thickness after drying was approximately 2.5 to 4 ⁇ m, and was carried out at room temperature to form a coating film (liquid crystal material preparation step).
• the coating film was irradiated with UV (Ultra Violet)-LED (manufactured by CCS) at room temperature through an optical mask layer at an illuminance of 50 mW and an exposure amount of 330 mJ/cm 2 . light) was irradiated onto the cholesteric liquid crystal layer (photoreaction process of photosensitive chiral agent). Since we used an optical mask layer with a small difference in light transmittance between the halftone dots and the gaps, the amount of photoreaction of the photosensitive chiral agent in the cholesteric liquid crystal layer has a small difference between the halftone dots and the gaps, and the helical induction The difference in power is also small.
• the base material on which the coating film after the photoreaction process of the photosensitive chiral agent was laminated was heated for 1 minute in a hot air drying zone at 60°C.
• the coating film is irradiated with light (second light) from a metal halide lamp (GS Yuasa Co., Ltd. MAL625NAL) from the cholesteric liquid crystal layer side in a low oxygen atmosphere (oxygen concentration 500 ppm or less) at 75°C.
• the liquid crystal layer was cured to form a decorative film (curing process).
• the irradiation here was performed under an exposure condition of an exposure amount of 600 mJ/cm 2 . After that, it was wound up with a winding roller. The obtained decorative film was verified and evaluated.
• the results of the verification and evaluation are summarized in Table 2.
• the obtained decorative film has a structure in which two cholesteric liquid crystal layers are formed, a cholesteric liquid crystal layer having a right-handed helix and a cholesteric liquid crystal layer having a left-handed helix, and the same optical mask layer Since the hue of the two cholesteric liquid crystal layers was changed using the method, a decorative film in which the patterns of the two cholesteric liquid crystal layers were aligned with high positional accuracy was obtained.
• Example 11 After peeling off the protective film on one side of an adhesive sheet (G25, thickness 25 ⁇ m, manufactured by Nichiei Shinka Co., Ltd.) that has protective films on both sides of the adhesive layer, a polyethylene terephthalate film (thickness 50 ⁇ m, width 330 mm, length 2000 m, Cosmoshine A4360, manufactured by Toyobo Co., Ltd.) and laminated (temperature: 30° C., linear pressure 100 N/cm, conveyance speed 0.1 m/min). Thereby, a transfer base material having a protective film, an adhesive layer, and a transfer destination base material in this order was obtained.
• an adhesive layer was attached to the liquid crystal layer of the decorative film prepared in Example 10 and laminated (temperature: 30°C, linear pressure 100 N/cm, conveyance speed 0.1 m). / minute). Thereby, a decorative film 2 having a transfer destination base material, an adhesive layer, a liquid crystal layer, a base material, and an optical mask layer in this order was obtained. The optical mask layer and base material of the decorative film 2 were peeled off to obtain a decorative film 3 having a transfer destination base material, an adhesive layer, and a liquid crystal layer in this order.
• Carbon black, a dispersant, a polymer, and a solvent were mixed to have the following composition of a black pigment dispersion, and a black pigment dispersion was obtained using a three-roll and bead mill.
• the average particle diameter of carbon black measured using Microtrac FRA (Honeywell) was 163 nm.
• the colored layer forming coating liquid 1 was applied onto the liquid crystal layer of the decorative film 3 using a die coater, and dried at 100° C. for 10 minutes. The entire surface of the colored layer of the formed laminate is exposed to light at an exposure dose of 500 mJ/cm 2 (i-line) to form colored layer 1 (black colored layer) with a layer thickness of 4 ⁇ m.
• a decorative film 4 was formed.
• the decorative film 4 includes a transfer destination base material, an adhesive layer, a liquid crystal layer, and a colored layer in this order.
• the decorative film for molding was cut into a sheet with a width of 7.5 cm and a length of 17 cm, and after peeling off the protective film, an adhesive layer was attached to a glass panel with a thickness of 2 mm, a width of 7.5 cm, and a length of 17 cm. A molded body was produced. When the obtained molded product was visually observed from the glass panel side, it had high reflective saturation, graininess was hardly visible, and a multicolored pattern with a glossy appearance was visible.

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