Decorative film and method for manufacturing same, laminate and method for manufacturing same, optical mask-equipped substrate for decorative film manufacturing, molded body, article, and display device

Abstract

An embodiment of the present invention provides a laminate and a method for manufacturing the same including: a step for providing an optical mask layer on a substrate by printing an AM screen-toned first pattern having a screen line count of 250 or less and a halftone dotted region in which the halftone dot area ratio is 0.5% to less than 99.5% using a first ink on the substrate, and printing a second pattern having a semi-translucent solid region having a printed area ratio of 99.5% or greater and a light transmittance of 5% to less than 95% in a position overlapping the halftone dotted region of the first pattern using a second ink; a step for providing a liquid crystal layer including a liquid crystal compound and a photosensitive chiral agent on the reverse side of the substrate from the optical mask layer; and a step for radiating light to the liquid crystal layer via the optical mask layer and causing the photosensitive chiral agent to photoreact. Also provided are a decorative film, an optical mask-equipped substrate for decorative film manufacturing, a molded body, an article, and a display device.

Description

Decorative film and manufacturing method thereof, laminate and manufacturing method thereof, substrate with optical mask for manufacturing decorative film, molded body, article, and display device

[0001] The present disclosure relates to a decorative film and a manufacturing method thereof, a laminate 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.

[0002] In recent years, films for decorating articles have been proposed as an alternative to coating or painting. For example, a technique for obtaining a decorated molded body by placing a film on the surface of a desired resin molded body and coloring the surface of the resin molded body in a desired hue or by providing a desired pattern on the surface of the resin molded body has attracted attention. Alternatively, a decorated molded body can be obtained by placing a decorative film in a mold frame in advance and then introducing a molding resin into the mold frame.

[0003] For example, a technique using cholesteric liquid crystals is known for decorative films. As a specific example, a decorative film for molding is disclosed, which has a cured liquid crystal layer formed on a substrate by curing a liquid crystal layer containing a cholesteric liquid crystal compound and a photoisomerizable compound (for example, Patent Document 1).

[0004] Patent Document 1: International Publication No. 2018 / 230395

[0005] As with the technology described in Patent Document 1, a cholesteric liquid crystal compound and a photosensitive chiral agent are used, and light is irradiated through an optical mask layer having a pattern to cause a photoreaction of the photosensitive chiral agent. This causes the length of the helical pitch of the liquid crystal phase to change depending on the light transmittance of the optical mask layer, and a patterned hue can be expressed by reflecting light of a wavelength corresponding to the helical pitch.

[0006] A patterned optical mask layer can be formed into a long optical mask layer of 100 meters or more by printing using, for example, a wet electrophotographic method, a gravure printing method, or an inkjet rotary printing method. When attempting to form a long decorative film with a patterned hue change using a cholesteric liquid crystal compound, a photosensitive chiral agent, and a long patterned optical mask layer, a hue change similar to the halftone dots of the optical mask layer may appear on the decorative film. This halftone dot-like hue change is visually perceived as a mixture of multiple hues, i.e., a low-saturation hue, and a high-saturation hue cannot be obtained. For example, when a high-resolution printing method such as an inkjet sheet-fed printing method, a laser printer method, or a laser photoplotter method is used to form an optical mask layer with finer halftone dots and then used to form a decorative film, a halftone dot-like hue change does not appear, and a high-saturation hue can be obtained. However, this high-resolution printing method can only produce short optical mask layers of a few meters or less, so it was found that in order to produce a long decorative film, it was necessary to bond together a large number of short optical mask layers, which resulted in poor manufacturing efficiency.

[0007] An embodiment of the present disclosure is to provide a method for manufacturing a multicolored laminate having high saturation and high productivity. Other embodiments of the present disclosure are to provide a multicolored laminate having 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.

[0008] Specific means for solving the problems include the following aspects: <1> A method for producing a laminate, comprising the steps of: printing, on a substrate, using a first ink, a first pattern in an AM screen style with a screen ruling of 250 lines or less, having halftone dot areas with a dot area ratio of 0.5% or more and less than 99.5%, and printing, on a substrate, using a second ink, a second pattern having semi-transparent solid areas with a print area ratio of 99.5% or more and a light transmittance of 5% or more and less than 95%, in a position overlapping with the halftone dot areas of the first pattern, thereby providing an optical mask layer on the substrate; providing, on the side of the substrate opposite the optical mask layer, a liquid crystal layer containing a liquid crystal compound and a photosensitive chiral agent; and irradiating the liquid crystal layer with light through the optical mask layer to photoreact the photosensitive chiral agent. <2> The method for producing a laminate according to <1>, wherein the entire dotted regions of the first pattern overlap with the semi-transparent solid regions of the second pattern, or the second pattern further has an area with a printing area ratio of less than 0.5%, and the entire dotted regions of the first pattern overlap with the semi-transparent solid regions of the second pattern and with an area with a printing area ratio of less than 0.5% of the second pattern. <3> The method for producing a laminate according to <1> or <2>, wherein the entire dotted regions of the first pattern overlap with the semi-transparent solid regions of the second pattern. <4> The method for producing a laminate according to any one of <1> to <3>, wherein the second pattern further has a halftone dot region, the first pattern further has at least one region which is a semi-transparent solid region and a region having a printing area ratio of less than 0.5%, the entire halftone dot region of the second pattern overlaps with at least one region which is a semi-transparent solid region and a region having a printing area ratio of less than 0.5% of the first pattern, and the second pattern is an AM screen-style pattern having a screen ruling of 250 lines or less. <5> The method for producing a laminate according to <4>, wherein the step of providing an optical mask layer on the substrate further comprises printing a pattern different from the first pattern and the second pattern on the substrate, wherein the pattern different from the first pattern and the second pattern has at least one region of a semi-transparent solid region and a region with a printing area ratio of less than 0.5%, and the at least one region of a semi-transparent solid region and a region with a printing area ratio of less than 0.5% of the pattern different from the first pattern and the second pattern overlaps with the entire region of the halftone dot region of the first pattern and the entire region of the halftone dot region of the second pattern.<6> The method for manufacturing a laminate according to <5>, wherein the pattern different from the first pattern and the second pattern further has a halftone dot area and is an AM screen pattern with a screen ruling of 250 lines or less. <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 the plurality of patterns do not overlap each other. <8> The method for manufacturing a laminate according to any one of <1> to <7>. <9> A method for manufacturing a decorative film, comprising, in this order: an optical mask layer, a substrate, and a cholesteric liquid crystal layer containing a liquid crystal compound and a photosensitive chiral agent, wherein the optical mask layer has an AM screen pattern with a screen ruling of 250 lines or less and a halftone dot area ratio of 0.5% or more and less than 99.5%, and the light transmittance of the halftone dots in the halftone dot area is T. Ｄ , the light transmittance of the gap between the halftone dots is T Ａ When this is the case, 5%≦T Ａ <95%, and the light transmittance at the portion of the optical mask layer with the lowest light transmittance is T ｍｉｎ , the light transmittance T at the point with the highest light transmittance ＭＡＸ When this is done, (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ <10> A laminate comprising an optical mask layer, a substrate, and a cholesteric liquid crystal layer containing a liquid crystal compound and a photosensitive chiral agent, in this order, wherein the optical mask layer has a dotted region with an AM screen tone having a screen ruling of 250 lines or less and a dot area ratio of 0.5% or more and less than 99.5%, and the light transmittance of the dots in the dotted region is T Ｄ , the light transmittance of the gap between the halftone dots is T Ａ When this is the case, 5%≦T Ａ < 95% and 1% ≦ T Ａ -T Ｄ <11> A laminate having an area where the dotted area of ​​the optical mask layer is <80.75%. Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ<12> The laminate according to <10>, wherein the optical mask layer has a dotted area (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ <13> The laminate according to <10> or <11>, wherein the optical mask layer has an AM screen tone with a screen ruling of 250 lines or less and a halftone dot area ratio of 0.5% or more and less than 99.5%, and the light transmittance of the halftone dots in the halftone dot area is T Ｄ , the light transmittance of the gap between the halftone dots is T Ａ When 5%≦T Ａ <95%, and the light transmittance at the portion of the optical mask layer having the lowest light transmittance is T ｍｉｎ , the light transmittance T at the point where the light transmittance is highest ＭＡＸ When Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ <14> A substrate with an optical mask for producing a decorative film, the substrate comprising: a substrate; and an optical mask layer, the optical mask layer having an AM screen tone with a screen ruling of 250 lines or less and a halftone dot area ratio of 0.5% or more and less than 99.5%, and the light transmittance of the halftone dots in the halftone dot area is T Ｄ , the light transmittance of the gap between the halftone dots is T Ａ When 5%≦T Ａ < 95% and 1% ≦ T Ａ -T Ｄ <15> A decorative film having a substrate with an optical mask for producing a decorative film, the substrate having a region where the cholesteric pitch maxima are 80.75%. <16> A decorative film having a cholesteric liquid crystal layer, the cholesteric liquid crystal layer having dot regions where the cholesteric pitch maxima are arranged in a dot pattern, the dot regions being divided into unit lattices which are rectangular with the smallest area and have the cholesteric pitch maxima as vertices, and the difference between the maximum value and the minimum value of the cholesteric pitch in each unit lattice is called an intra-lattice pitch difference ΔP Ｓ When this is the case, the above ΔP Ｓ The maximum value of ΔP Ｓ（ＭＡＸ）is the difference between the maximum and minimum values ​​of the cholesteric pitch in the entire cholesteric liquid crystal layer, ΔP ａｌｌ For 0 < ΔP Ｓ（ＭＡＸ） / ΔP ａｌｌ <16> The decorative film according to <15>, wherein the cholesteric liquid crystal layer has a region in which the cholesteric pitch change per 100 μm in an in-plane direction is 13 nm or more. <17> In the cholesteric liquid crystal layer, Ｓ（ＭＡＸ） <18> A decorative film according to <15> or <16>, wherein the cholesteric liquid crystal layer has a dot region in which maximal points of the cholesteric pitch are arranged in a dot pattern, the dot region is divided into unit lattices that are rectangular with the smallest area and whose vertices are the maximal points of the cholesteric pitch, and the difference between the maximum value and the minimum value of the cholesteric pitch in each unit lattice is defined as an intra-lattice pitch difference ΔP Ｓ In the cholesteric liquid crystal layer, the above ΔP Ｓ The maximum value of ΔP Ｓ（ＭＡＸ） <19> In the cholesteric liquid crystal layer, a difference ΔP between the maximum value and the minimum value of the cholesteric pitch in the entire cholesteric liquid crystal layer is ａｌｌ The decorative film according to <15> or <18>, wherein the thickness is 70 nm or more.

[0009] <20> A molded body 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 body according to <20>. <22> The article according to <21>, which is an electronic device. <23> A display device comprising the article according to <22>.

[0010] According to an embodiment of the present disclosure, there is provided a method for manufacturing a multicolored laminate with high saturation and excellent productivity. According to other embodiments of the present disclosure, there are provided a multicolored laminate with high saturation, a decorative film 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.

[0011] FIG. 1 is a diagram showing an 8 cm x 4 cm pattern of an optical mask layer. FIG. 2 is an enlarged view of a 370 μm x 500 μm region of the pattern of FIG. 1, where the light transmittance is controlled to 40%. FIG. 3 is a diagram showing the hue change of an 8 cm x 4 cm cholesteric liquid crystal layer. FIG. 4 is an enlarged view of a 370 μm x 500 μm region of the hue change of the cholesteric liquid crystal layer of FIG. 3. FIG. 5A is a schematic diagram for explaining an example of a first pattern of an optical mask layer implemented by the manufacturing method of the present disclosure. The color density in the diagram indicates a lower light transmittance per 300 μm square, with the closer to black the region, the lower the light transmittance per 300 μm square. FIG. 5B is a schematic diagram for explaining an example of a second pattern of an optical mask layer implemented by the manufacturing method of the present disclosure. The color density in the diagram indicates a lower light transmittance per 300 μm square, with the closer to black the region, the lower the light transmittance per 300 μm square. FIG. 5C is a schematic diagram illustrating an example of an optical mask layer implemented by the manufacturing method of the present disclosure. The color intensity in the diagram indicates a lower light transmittance per 300 μm square, with the darker the area, the lower the light transmittance per 300 μm square. FIG. 5D is a magnified view of a portion of the first pattern in FIG. 5A. FIG. 5E is a magnified view of a portion of the second pattern in FIG. 5B. FIG. 5F is a magnified view of a portion of the optical mask layer in FIG. 5C. FIG. 6 is a schematic view of a manufacturing apparatus implementing an example of a liquid crystal film manufacturing method of the present disclosure. FIG. 7 is a schematic view illustrating an example of a liquid crystal film manufacturing method implemented by the manufacturing apparatus of FIG. 6. FIG. 8 is a view showing a 300 mm x 980 mm pattern of the optical mask layer used in the examples. FIG. 9 is a view showing a 300 mm x 980 mm first pattern of the optical mask layer used in the examples. FIG. 10 is a view showing a 300 mm x 980 mm second pattern of the optical mask layer used in the examples. Fig. 11 is a diagram showing a third pattern of the optical mask layer of 300 mm x 980 mm used in the examples. Fig. 12 is a diagram showing a fourth pattern of the optical mask layer of 300 mm x 980 mm used in the examples. Fig. 13 is a diagram showing a fifth pattern of the optical mask layer of 300 mm x 980 mm used in the examples. Fig. 14 is a diagram showing a sixth pattern of the optical mask layer of 300 mm x 980 mm used in the examples.FIG. 15 is a diagram showing a first pattern of the optical mask layer used in the Examples. FIG. 16 is a diagram showing a second pattern of the optical mask layer used in the Examples. FIG. 17 is a diagram showing a first pattern of the optical mask layer used in the Examples. FIG. 18A is a diagram explaining the first pattern of the optical mask layer used in the Examples. FIG. 18B is a diagram explaining the second pattern of the optical mask layer used in the Examples. FIG. 18C is a diagram explaining the optical mask layer used in the Examples. FIG. 19A is a diagram explaining the first pattern of the optical mask layer used in the Examples. FIG. 19B is a diagram explaining the second pattern of the optical mask layer used in the Examples. FIG. 19C is a diagram explaining the optical mask layer used in the Examples. FIG. 20A is a diagram explaining the first pattern of the optical mask layer used in the Examples. FIG. 20B is a diagram explaining the second pattern of the optical mask layer used in the Examples. FIG. 20C is a diagram explaining the optical mask layer used in the Examples. FIG. 21A is a diagram explaining the first pattern of the optical mask layer used in the Examples. FIG. 21B is a diagram illustrating a second pattern of the optical mask layer used in the examples. FIG. 21C is a diagram illustrating a third pattern of the optical mask layer used in the examples. FIG. 21D is a diagram illustrating the optical mask layer used in the examples. FIG. 22A is a diagram illustrating a first pattern of the optical mask layer used in the examples. FIG. 22B is a diagram illustrating a second pattern of the optical mask layer used in the examples. FIG. 22C is a diagram illustrating a third pattern of the optical mask layer used in the examples. FIG. 22D is a diagram illustrating the optical mask layer used in the examples. FIG. 23 is a diagram illustrating a second pattern of the optical mask layer used in the comparative examples.

[0012] The present disclosure will be described in detail below. The following description of the components may be based on representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.

[0013] In this specification, the term "to" indicating a numerical range is used to mean that the numerical values ​​before and after it are included as the upper and lower limits. In the numerical ranges described in stages in this specification, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this specification, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples.

[0014] Furthermore, in this specification, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition means the total amount of the corresponding substances present in the composition, unless otherwise specified.

[0015] In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

[0016] In this specification, the term "total solid content" refers to the total mass of the components excluding the solvent from the entire composition. As described above, the term "solid content" refers to the components excluding the solvent, and may be, for example, solid or liquid at 25°C.

[0017] In the description of groups (atomic groups) in this specification, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups. For example, the term "alkyl group" encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups).

[0018] In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.

[0019] In the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.

[0020] In the present disclosure, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are molecular weights determined by gel permeation chromatography (GPC) using columns of TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names of Tosoh Corporation), detection with a differential refractometer using THF (tetrahydrofuran) as a solvent, and conversion using polystyrene as a standard substance.

[0021] <Method for manufacturing laminate> A method for manufacturing a laminate according to the present disclosure includes the steps of: printing, on a substrate, a first pattern having an AM (Amplitude Modulation) screen tone with a screen ruling of 250 lines or less, using a first ink, and having dotted regions with a dot area ratio of 0.5% or more and less than 99.5%, and printing, on a substrate, a second pattern having semi-transparent solid regions with a printing area ratio of 99.5% or more and a light transmittance of 5% or more and less than 95%, at a position overlapping the dotted regions of the first pattern, thereby providing an optical mask layer on the substrate; providing, on the opposite side of the substrate from the optical mask layer, a liquid crystal layer containing a liquid crystal compound and a photosensitive chiral agent; and irradiating the liquid crystal layer with light through the optical mask layer to cause a photoreaction of the photosensitive chiral agent.

[0022] A cholesteric liquid crystal layer selectively reflects incident light and exhibits a hue corresponding to the wavelength of the reflected light. The desired hue can be obtained by changing the helical pitch of the cholesteric liquid crystal compound. The helical pitch of the cholesteric liquid crystal compound can be controlled by using a photosensitive chiral agent whose helical induction power increases or decreases through photoreaction and irradiating light through a patterned optical mask layer, thereby producing a hue corresponding to the light transmittance of the pattern. Patterned optical mask layers can be formed to lengths of 100 meters or more by printing using, for example, wet electrophotography, gravure printing, or inkjet rotary printing. However, long optical mask layers have limited resolution and the halftone dots that control light transmittance are coarse. When attempting to form a long cholesteric liquid crystal layer with a patterned hue change using an optical mask layer with coarse halftone dots, a hue change similar in shape to the halftone dots of the optical mask layer may appear in the cholesteric liquid crystal layer. For example, when an attempt is made to form a cholesteric liquid crystal layer of FIG. 3 exhibiting blue-green-red hues using an optical mask layer having an AM screen pattern with a screen ruling of 175 lines, as shown in FIGS. 1 and 2, a dot-like hue change, as shown in FIG. 4, may occur. The dot-like hue change is visually perceived as a mixture of multiple hues, i.e., a low-saturation hue, and a high-saturation hue cannot be obtained. On the other hand, when an optical mask layer with finer dots is formed using a high-resolution printing method, such as an inkjet sheet-fed printing method, a laser printer method, or a laser photoplotter method, and used to form a decorative film, the dot-like hue change does not occur, and a high-saturation hue can be obtained. However, such high-resolution printing methods can only form short optical mask layers of a few meters or less. Therefore, it has been found that forming a long decorative film requires bonding together multiple short optical mask layers, resulting in poor manufacturing efficiency.

[0023] In view of the above phenomenon, the present disclosure has discovered that the difference in light transmittance between the halftone dots and the gaps between the halftone dots in the optical mask layer and the amount of diffusion of the photosensitive chiral agent are factors that cause the appearance of halftone dot-like hue changes and the reduction in saturation. When light is irradiated onto the photosensitive chiral agent in the cholesteric liquid crystal layer through the optical mask layer, the light is blocked in the halftone dot areas and transmitted through the gaps between the halftone dots, resulting in a greater photoreaction of the photosensitive chiral agent in the gaps. In other words, a difference in the helical twisting power of the photosensitive chiral agent occurs depending on the difference in light transmittance between the halftone dot areas and the gaps. The photosensitive chiral agent diffuses within the cholesteric liquid crystal layer depending on the viscosity and temperature. As the photoreacted photosensitive chiral agent and the unreacted photosensitive chiral agent diffuse and mix, the difference in helical twisting power gradually approaches uniformity. However, if the difference in light transmittance is large relative to the amount of diffusion, uniformity does not progress sufficiently, and the difference in helical twisting power remains in the form of halftone dots, appearing as a hue change. Furthermore, the larger the in-plane size of a single halftone dot relative to the in-plane diffusion distance of the photosensitive chiral agent, the greater the amount of diffusion required to uniform the helical twisting power. Therefore, the coarser the halftone dots, the more likely they are to cause a halftone dot-like hue change. Furthermore, it has been found that FM (Frequency Modulation) screen-style halftone dots are a halftone dot method that controls the printing density by the halftone dot density. Therefore, in medium-density printing areas, multiple halftone dots are connected to form a single halftone dot several times larger in the in-plane direction, making halftone dot-like hue changes more likely.

[0024] In contrast, in the manufacturing method disclosed herein, by using an AM screen halftone dot pattern, halftone dots can be evenly spaced, preventing the dots from overlapping at medium densities and suppressing halftone hue changes. Furthermore, by printing semi-transparent solid areas with a print area ratio of 99.5% or more and a light transmittance of 5% to less than 95% in positions overlapping the halftone dot areas of the first pattern, an optical mask layer can be prepared with a controlled difference in light transmittance between the halftone dot areas and the gap areas, allowing for the production of a decorative film with high saturation. Furthermore, by setting the screen ruling to 250 lines or less, a long optical mask layer can be realized, allowing for the efficient production of long decorative films.

[0025] An example of a preferred embodiment of the laminate manufacturing method of the present disclosure will be described below with reference to the drawings. FIG. 6 shows a schematic diagram of an example of a laminate manufacturing apparatus (hereinafter also referred to as a "manufacturing apparatus") for carrying out the laminate manufacturing method of the present disclosure (hereinafter also referred to as the "manufacturing method of the present disclosure"). FIG. 7 shows a schematic diagram for explaining an example of a laminate manufacturing method carried out by the manufacturing apparatus shown in FIG. 6. Note that the drawings in this disclosure are schematic diagrams, and the size of each part, the relationship between the thicknesses of each layer, and the positional relationship do not necessarily correspond to actual ones. The same applies to the following drawings.

[0026] 6 is a manufacturing apparatus 100a that uses a long substrate 12a to manufacture a liquid crystal film by roll-to-roll (hereinafter also referred to as "RtoR") processing. As is well known, RtoR is a manufacturing method in which a long object to be processed is fed from a roll formed by winding the object, processed by film formation or the like while being transported in the longitudinal direction, and the processed object is then wound into a roll again.

[0027] As an example, the manufacturing apparatus 100a includes a feed roller 102, a first conveying section 120, a coating section 150, a second conveying section 122, an exposure section 152, a heating section 154, a curing section 156, a third conveying section 124, and a take-up roller 116. The first conveying section 120, the second conveying section 122, and the third conveying section 124 include conveying rollers and the like, and convey the long workpiece along a predetermined path. In addition to the components shown in the figure, the manufacturing apparatus 100a may also include various components that are provided in known devices that form a film by coating while conveying the long workpiece, such as a pair of conveying rollers, a guide member for the substrate, and various sensors.

[0028] In the manufacturing apparatus 100a, a roll 130 formed by winding a long substrate 12a is loaded onto a delivery roller 102. The substrate 12a is pulled out from the roll 130 and passed through a predetermined path that passes through a first conveying section 120, a coating section 150, a second conveying section 122, an exposure section 152, a heating section 154, a curing section 156, and a third conveying section 124, and reaches a take-up roller 116. In addition, the prepared liquid crystal composition that will become the cholesteric liquid crystal layer is supplied to a coating nozzle 104 of the coating section 150, and coating is performed.

[0029] In the manufacturing apparatus 100a utilizing the roll-to-roll process, the delivery of the substrate 12a from the roll 130 and the winding up of the substrate 12a (laminate film 23d) on which the cholesteric liquid crystal layer 18 has been formed are performed synchronously. As a result, while the long substrate 12a is transported in the longitudinal direction along a predetermined transport path, a liquid crystal composition prepared in the coating unit 150 is applied to the substrate 12a, the coating film is exposed to light in the exposure unit 152, the coating film is heated in the heating unit 154 to align the liquid crystals, and the coating film is cured in the curing unit 156 by ultraviolet irradiation and / or heating, etc., to form the cholesteric liquid crystal layer 18. Furthermore, the long laminate film 23d on which the cholesteric liquid crystal layer 18 has been formed on the substrate 12a is wound into a roll by the winding roller 116 to form the roll 132. 6 and 7, the liquid crystal film of the present disclosure is a laminated film 23d in which a cholesteric liquid crystal layer 18 is laminated on the surface of a substrate 12a. The cholesteric liquid crystal layer 18 may be used in a state where it is laminated on the substrate 12a, or may be peeled off from the substrate 12a.

[0030] In the delivery step shown in FIG. 6, the substrate 12a delivered from the roll 130 is a resin film such as a PET film on which a pattern mask is formed, as shown in S1 of FIG.

[0031] As the resin film forming the base material 12a, various known transparent sheet-like materials that are used as substrates (base materials) can be used. Specific substrates will be described later.

[0032] In the present disclosure, such a film having a layer (film) that exhibits a required function, such as an alignment layer, a protective layer, an adhesive layer, a light-reflecting layer, an anti-reflection layer, a light-shielding layer, a planarizing layer, a buffer layer, a stress relaxation layer, or a release layer, formed on the surface thereof, may be used as the substrate 12a.

[0033] -Step of providing an optical mask layer on a substrate- The manufacturing method disclosed herein includes a step of providing an optical mask layer on a substrate. In the step of providing an optical mask layer on a substrate, two or more printed patterns (hereinafter also referred to as "patterns") are formed, including a first pattern printed using a first ink and a second pattern printed using a second ink. The printed pattern is a pattern formed by disposing ink from a single ink cartridge, ink tank, toner, or similar ink source. For example, in a liquid electrophotographic method, in which ink from two or more colors of toner is disposed on a transfer roll, and then two or more colors of ink are disposed on a substrate in one pass from the transfer roll, the printed pattern is divided for each color and is not affected by the number of times the ink is disposed on the substrate. Furthermore, in a gravure printing method, when one type of ink is used for two or more printing plates, two types of patterns are formed by disposing the ink, and therefore the patterns are divided for each printing plate. Here, the first ink and the second ink each refer to 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. The color and composition of the ink are not particularly limited, and known inks can be used. From the viewpoint of controlling the amount of photoreaction of the photosensitive chiral agent, the ink preferably absorbs or reflects light irradiated in the process of photoreacting the photosensitive chiral agent. Furthermore, when the optical mask layer is a colored layer in the decorative film, it is preferable to form the optical mask layer using inks of various colors as appropriate, depending on the desired design of the decorative film.

[0034] The optical mask layer includes an AM screen-style printing pattern. The AM screen-style printing pattern is a printing method that controls the printing density in a gradational manner by changing the area ratio of halftone dots arranged at equal intervals in the in-plane direction of the screen. The screen ruling indicates the number of halftone dots arranged per inch, and the higher the screen ruling, the higher the resolution and the narrower the spacing between halftone dots.

[0035] The first pattern has a halftone dot area, and the halftone dot area has a dot area ratio of 0.5% or more but less than 99.5%, preferably 5% or more but less than 95%, and more preferably 10% or more but less than 90%. 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 in the above range, the color range exhibited by the decorative film can be widened.

[0036] In order to increase the number of hue change areas in the decorative film and improve the design, the first pattern preferably has two or more halftone dot areas, and more preferably has three or more halftone dot areas. In order to increase the number of colors in the decorative film, it is preferable that these areas each have a different halftone dot area ratio.

[0037] The first pattern may have an area in which the dot area ratio changes in a gradation tone according to the desired hue pattern of the decorative film.

[0038] The dot area ratio of a dotted area is the ratio of the dot area to the unit area, expressed as a percentage. It can be calculated by measuring the size of the dots and the spacing between them using a microscope, and then calculating the dot area per unit grid and the area of ​​the unit grid.

[0039] The first pattern is an AM screen pattern with a screen ruling of 250 lines or less, preferably 230 lines or less, and more preferably 210 lines or less. Since a smaller screen ruling is less likely to cause printing unevenness, setting the screen ruling within the above range is preferable because it can reduce loss due to printing unevenness. Furthermore, from the viewpoint that a smaller screen ruling can increase the printing speed, it is preferable to set the screen ruling within the above range. From the viewpoint of ease of diffusion of the photoreacted photosensitive chiral agent, the screen ruling is preferably 100 lines or more, more preferably 175 lines or more. The first pattern preferably further has at least one region: a semi-transparent solid region and a region with a printing area ratio of less than 0.5%. The semi-transparent solid region refers to a region of the printing pattern with a printing area ratio of 99.5% or more and a light transmittance of 5% to less than 95%, and may be part of an AM screen printing pattern or part of a two-tone printing pattern.

[0040] Furthermore, the semi-transparent solid area is preferably an area of ​​the printed pattern in which the printing area ratio within at least a 300 μm square is 99.5% or more and the light transmittance is 5% or more and less than 95%. The printing area ratio is preferably the printing area ratio within a 300 μm square. The printing area ratio within a 300 μm square is the area ratio of the area of ​​the printed pattern where ink is present within a 300 μm square (a square with each side of 300 μm).

[0041] The light transmittance of the optical mask layer indicates the transmittance of light irradiated in the step of photoreacting the photosensitive chiral agent.

[0042] An area with a print area ratio of less than 0.5% is an area in the print pattern where ink is present at an area ratio of less than 0.5%.

[0043] The second pattern is printed using a second ink in a pattern that overlaps the halftone dotted area 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 but less than 95%. Here, the semi-transparent solid area is the same as the semi-transparent solid area of ​​the first pattern described above. Furthermore, the second pattern is preferably a semi-transparent solid area with a printing area ratio of 99.5% or more within at least a 300 μm square and a light transmittance of 5% or more but less than 95%.

[0044] In order to prevent the halftone dots of the first pattern from interfering with the second pattern and creating a new moiré pattern, it is preferable that the entire halftone dot area of ​​the first pattern overlaps with the semi-transparent solid area of ​​the second pattern, or that the second pattern further has an area with a printing area ratio of less than 0.5% and that the entire halftone dot area of ​​the first pattern overlaps with the semi-transparent solid area and the area with a printing area ratio of less than 0.5% of the second pattern. Here, the area with a printing area ratio of less than 0.5% is the same as the area with a printing area ratio of less than 0.5% of the first pattern described above.

[0045] From the viewpoint of precisely controlling the hue change of the cholesteric liquid crystal layer, it is preferable that the second pattern further has a halftone dotted region, which is the same as the halftone dotted region of the first pattern described above.

[0046] From the viewpoint of suppressing a dot-like hue change in the cholesteric liquid crystal layer by reducing the difference in light transmittance between the dot portions and the gap portions between the dots and by reducing the difference in the reaction amount of the photosensitive chiral agent, it is preferable that the entire dotted region of the first pattern overlaps with the semi-transparent solid region of the second pattern. From the viewpoint of suppressing a dot-like hue change in the cholesteric liquid crystal layer, the difference in light transmittance between the dot portions and the gap portions between the dots is preferably 95% or less, more preferably 60% or less, even more preferably 40% or less, and particularly preferably 30% or less.

[0047] 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, wherein the pattern different from the first pattern and the second pattern has at least one area of ​​a light-transmitting solid area and an area with a printing area ratio of less than 0.5%, and it is preferable that the at least one area of ​​the light-transmitting solid area and an area with a printing area ratio of less than 0.5% of the pattern different from the first pattern and the second pattern overlaps with the entire area of ​​the halftone dot area of ​​the first pattern and the entire area of ​​the halftone dot area of ​​the second pattern.

[0048] From the viewpoint of more precise control of the hue change of the cholesteric liquid crystal layer, it is preferable that the pattern different from the first pattern and the second pattern further has a halftone dotted area. It is preferable that the pattern different from the first pattern and the second pattern is an AM screen pattern with a screen ruling of 250 lines or less. The pattern different from the first pattern and the second pattern is formed by printing a pattern different from the first pattern and the second pattern on the substrate in addition to printing the first pattern and the second pattern.

[0049] Increasing the number of patterns results in a greater number of gradations, thereby reducing the difference in light transmittance between the halftone dots and the gaps. Therefore, the pattern different from the first and second patterns preferably includes multiple patterns, each of which is different from the others. 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 to the substrate. Examples of the medium include a transfer roller made of resin or rubber, known as a blanket. The multiple patterns are preferably formed by printing the first and second patterns and then printing the pattern on the substrate one to five times, or by printing the pattern on the medium one to five times and then transferring the pattern to the substrate. It is more preferable to form the multiple patterns by printing the first and second patterns and then printing three to five times. By printing the first and second patterns and then printing the pattern multiple times, the difference in light transmittance between the halftone dots and the gaps can be more precisely controlled, resulting in better suppression of graininess in the decorative film.

[0050] When halftone dot areas of different patterns overlap, the halftone dots connect to form halftone dots of a larger size, making the graininess more visible. Therefore, it is preferable that the halftone dot areas of the first pattern, the halftone dot areas of the second pattern, and the halftone dot areas of patterns different from the first and second patterns do not overlap, and if there are multiple patterns different from the first and second patterns, it is preferable that the halftone dot areas of each of the multiple patterns do not overlap.

[0051] From the viewpoint of production efficiency, the printing method is preferably a printing method capable of printing long prints of 100 meters or more on a film substrate made of a resin material. Examples include liquid electrophotography, gravure printing, and inkjet rotary printing. From the viewpoint of resolution and registration of multiple printed patterns, liquid electrophotography is more preferable.

[0052] Here, examples of the first and second patterns of the present disclosure will be described using Figures 5A to 5F. Figures 5A to 5C each show the optical mask layer (3) when the first pattern is (1) and the second pattern is (2). Color intensity in the figure indicates a lower light transmittance per 300 μm square, with the darker the area, the lower the light transmittance per 300 μm square. Figures 5D to 5F are enlarged views of portions of the patterns and optical mask layer shown in Figures 5A to 5C, respectively. The first pattern shown in Figure 5D (1) has a dot diameter of 27.8 μm and a dot spacing of 100 μm, so the dot area ratio can be calculated as 24% and is considered to have a dotted area. Furthermore, the second pattern shown in Figure 5E (2) has a printing area ratio of 100% and a semi-transparent solid area with a light transmittance of 50%. As shown in (3) of FIG. 5F, a part of the semi-transparent solid area of ​​the second pattern is formed in a position overlapping with the halftone dot area of ​​the first pattern.

[0053] Preferably, the optical mask layer is in direct contact with the substrate.

[0054] (Substrate) Examples of the substrate include substrates used for molding such as three-dimensional molding and insert molding. From the viewpoints of ease of molding and chipping resistance, the substrate is preferably a resin substrate, and more preferably a resin film.

[0055] Examples of resins include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic resin, urethane resin, urethane-acrylic resin, polycarbonate (PC), acrylic-polycarbonate, polyolefin, triacetyl cellulose (TAC), cycloolefin polymer (COP), and acrylonitrile / butadiene / styrene copolymer (ABS resin).

[0056] From the viewpoint of moldability and strength, the substrate is preferably 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, more 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 most preferably polyethylene terephthalate.

[0057] The substrate may have a single layer structure or a multi-layer structure. A preferred laminate film is, for example, an acrylic resin / polycarbonate resin laminate film.

[0058] The substrate may contain additives as needed, such as lubricants such as mineral oil, hydrocarbons, fatty acids, alcohols, fatty acid esters, fatty acid amides, metal soaps, natural waxes, and silicones, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, halogen-based and phosphorus-based organic flame retardants, organic or inorganic fillers such as metal powder, talc, calcium carbonate, potassium titanate, glass fiber, carbon fiber, and wood flour, additives such as antioxidants, ultraviolet inhibitors, lubricants, dispersants, coupling agents, foaming agents, and colorants, and engineering plastics other than the above-mentioned resins, such as polyolefins, polyesters, polyacetals, polyamides, and polyphenylene ether resins.

[0059] The substrate may be a commercially available product. Examples of commercially available products include the Technoloy (registered trademark) series (acrylic resin film or acrylic resin / polycarbonate resin laminate film, Sumitomo Chemical Co., Ltd.), ABS film (Okamoto Corporation), ABS sheet (Sekisui Seikei Co., Ltd.), Teflex (registered trademark) series (PET film, Teijin Film Solutions Limited), Lumirror (registered trademark) Easy Forming Type (PET film, Toray Industries, Inc.), Purethermo (polypropylene film, Idemitsu Unitech Co., Ltd.), and Cosmoshine (registered trademark) series (PET film, Toyobo Co., Ltd.).

[0060] If the thickness of the substrate is too thin, the supportability may decrease, and bending or the like may occur during transportation. On the other hand, if the thickness is too thick, the flexibility may decrease, making transportation difficult, increasing the size when wound up on a roll, or making it difficult to peel the formed cholesteric liquid crystal layer from the support substrate 12a. From the above viewpoints, the thickness of the substrate is preferably 1 μm or more, more preferably 10 μm or more, even more preferably 20 μm or more, and particularly preferably 50 μm or more. The thickness of the substrate is preferably 500 μm or less, more preferably 450 μm or less, and particularly preferably 200 μm or less.

[0061] (Step of Providing a Liquid Crystal Layer Containing a Liquid Crystal Compound and a Photosensitive Chiral Agent) The manufacturing method of the present disclosure includes a step of providing a liquid crystal layer containing a liquid crystal compound and a photosensitive chiral agent on the side of the substrate opposite the optical mask layer. The liquid crystal layer is preferably a cholesteric liquid crystal layer. As shown in FIG. 6 , the substrate 12a fed from the roll 130 passes through the first conveying section 120 and reaches the coating section 150. In the coating section 150, the substrate 12a is subjected to a coating process. Note that in the example shown in FIG. 6 , during coating in the coating section 150, the liquid crystal composition is applied to the substrate 12a by the coating nozzle 104 while the substrate 12a is wrapped around the backup roller 106. If coating is performed using a method that does not require the backup roller 106, such as bar coating, the backup roller 106 may not be necessary. As shown in S2 in FIG. 7 , in the coating step, 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 substrate 12a to form a coating film 21a. A laminate of the substrate 12a and the coating film 21a is defined as a laminate film 23a. The preferred liquid crystal compound and photosensitive chiral agent are the same as the liquid crystal compound and photosensitive chiral agent contained in the cholesteric liquid crystal layer of the decorative film described below.

[0062] The coating method in the coating step may be a roll coating method, a gravure printing method, or a spin coating method. The composition may be applied by a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, or a die coating method. The composition may be applied using an inkjet device. In a coating method using an inkjet device, the composition may be ejected from a nozzle.

[0063] The coating film 21a is formed on the surface opposite to the optical mask layer, i.e., the optical mask layer is formed on the surface (rear surface) of the base material 12a opposite to the surface on which the coating film 21a is formed.

[0064] -Step of irradiating the liquid crystal layer with light through the optical mask layer to photoreact the photosensitive chiral agent- The manufacturing method disclosed herein includes a step of irradiating the liquid crystal layer with light through the optical mask layer to photoreact the photosensitive chiral agent. As shown in FIG. 6, the laminated film 23a passes through the second conveying section 122 and reaches the exposure section 152. In the exposure section 152, the laminated film 23a is subjected to the irradiation step. As shown by S3 in FIG. 7, in the irradiation step, the exposure device 108 irradiates the wet coating film 21a with light from the substrate 12a side, i.e., through the optical mask layer. The light irradiated by the exposure device 108 is of a wavelength to which the photosensitive chiral agent in the coating film 21a (liquid crystal composition) is photosensitive. Therefore, an exposed coating film 21b is formed by the exposure process. In the exposed coating film 21b, the photosensitive chiral agent is photosensitive, changing its structure and helical twisting force. The laminate of the substrate 12a and the exposed coating film 21b is called a laminate film 23b.

[0065] Here, the exposed coating film 21b is irradiated with light in different doses in different regions, corresponding to the light transmittance of each region of the optical mask layer. The amount of structural change due to photosensitivity of the photosensitive chiral agent varies depending on the dose of irradiation. Therefore, the amount of change in the helical twisting power of the photosensitive chiral agent in the exposed coating film 21b varies depending on the transmittance of the optical mask layer.

[0066] The wavelength of the light used for exposure may be set depending on the type of photosensitive chiral agent, etc. 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.

[0067] Next, as shown in FIG. 6 , the laminated film 23b is transported to the heating section 154. In the heating device 110, the coating film of the laminated film 23b is dried and subjected to an orientation process. As shown in S4 in FIG. 7 , in the orientation process, the heating device 110 heats the exposed coating film 21b, thereby aligning the liquid crystal compound in the coating film 21b. The heating process forms a coating film 21c in which the liquid crystal compound is oriented according to the structure of the chiral agent. As described above, 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 dose. Since the selective reflection wavelength in the cholesteric liquid crystal phase depends on the pitch of the helical structure in the cholesteric liquid crystal phase, regions with different selective reflection wavelengths are formed. A laminate of the substrate 12a and the oriented coating film 21c is the laminated film 23c.

[0068] Next, as shown in FIG. 6, the laminate film 23c is preferably transported to a curing unit 156 and subjected to a curing process. As shown in S5 in FIG. 7, in the curing process, the laminate film 23c is wound around a backup roller 114, and the curing unit 112 cures the aligned coating film 21c to form a cholesteric liquid crystal layer 18. This produces a liquid crystal film having a cholesteric liquid crystal layer 18. The laminate of the substrate 12a and the cholesteric liquid crystal layer 18 forms a laminate film 23d. The coating film 21c can be cured by known curing methods, such as photocuring by irradiation with ultraviolet light or the like, or thermal curing by heating. When curing by light irradiation, it is preferable to irradiate the coating film 21c with light from the side opposite the optical mask layer.

[0069] Next, the produced liquid crystal film (laminated film 23 d ) is preferably passed through the third conveying section 124 and wound into a roll by the winding roller 116 to form a roll 132 .

[0070] The cholesteric liquid crystal layer of the produced liquid crystal film has a structure in which regions with different selective reflection wavelengths are formed according to the transmittance of the optical mask layer, and each region reflects light of the selective reflection wavelength, thereby displaying an image with a corresponding hue.

[0071] Here, in the example shown in Figure 6, the manufactured liquid crystal film is wound into a roll, but this is not limited to this, and the manufactured liquid crystal film may also be configured to have a cutting section that cuts the manufactured liquid crystal film into a predetermined size.

[0072] Furthermore, when the curing method of the coating film in the curing step is photocuring, the wavelength of the light irradiated in the curing step is preferably different from the wavelength of the light irradiated in the step of photoreacting the photosensitive chiral agent, and the wavelength of the light irradiated in the step of photoreacting the photosensitive chiral agent is preferably 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 photosensitive and which does not cleave the polymerization initiator. By differentiating the wavelength of the light irradiated in the curing step and the step of photoreacting the photosensitive chiral agent, it is possible to prevent the coating film from being cured by light irradiation in the step of photoreacting the photosensitive chiral agent, and to achieve a desired change in the pitch of the helical structure of the liquid crystal compound.

[0073] The wavelength of light irradiated in the step of photoreacting the photosensitive chiral agent may be selected based on the type of photosensitive chiral agent to which the photosensitive chiral agent is sensitive. Specifically, the wavelength of light irradiated in the irradiation step is preferably 350 nm to 400 nm. In other words, it is preferable to use a chiral agent that is photosensitive in this wavelength range. Furthermore, the dose of light irradiated in the step of photoreacting the photosensitive chiral agent may be set to an amount that results in a desired selective reflection wavelength based on the type of photosensitive chiral agent, etc.

[0074] The wavelength of the light irradiated in the curing step may be selected depending on the type of polymerization initiator, etc. 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 start the polymerization reaction in this wavelength range. Furthermore, the amount of light irradiated in the curing step may be set depending on the type of polymerization initiator, etc.

[0075] 6, the step of photoreacting the photosensitive chiral agent involves a single light irradiation, but the light irradiation may be performed in two or more separate steps. For example, the step of photoreacting the photosensitive chiral agent may include a first irradiation step and a second irradiation step. By performing the light irradiation in two or more separate steps in the step of photoreacting the photosensitive chiral agent, the structural change of the photosensitive chiral agent due to exposure can be more suitably adjusted, and the desired selective reflection wavelength can be achieved.

[0076] Furthermore, the peak wavelengths of the light irradiated in the first irradiation step and the second irradiation step may be different. By shifting the peak wavelength of the light in the first irradiation step from the peak wavelength of the light to which the photosensitive chiral agent is photosensitive and matching the peak wavelength of the light in the second irradiation step with the peak wavelength of the light to which the photosensitive chiral agent is photosensitive, the amount of light irradiated can be substantially adjusted. Specifically, for example, if the photosensitive chiral agent has an absorption peak at 365 nm and a spectrum with a base in the range of 250 nm to 450 nm, the first irradiation step can be irradiated with light at 265 nm near the base, and the second irradiation step can be irradiated with light at the peak of 365 nm, thereby substantially adjusting the amount of light irradiated.

[0077] In the example shown in FIG. 6 , the cholesteric liquid crystal layer 18 is wound around the roll 132 immediately after formation. However, a process of attaching a protective film or the like to the surface of the cholesteric liquid crystal layer 18 before winding around the roll 132 may be included. Here, in the examples shown in FIGS. 6 and 7 , a single cholesteric liquid crystal layer 18 is formed on the substrate 12 a. However, this is not limited thereto. Two or more cholesteric liquid crystal layers may be formed by performing a combination of the coating process, the irradiation process, the alignment process, and the curing process two or more times. For example, a substrate on which a cholesteric liquid crystal layer having a right-handed helix has been formed may be supplied to the manufacturing apparatus again as a processing object, thereby forming a cholesteric liquid crystal layer having a left-handed helix on the cholesteric liquid crystal layer. Alternatively, the manufacturing apparatus may have two or more combinations of a coating section, an exposure section, a heating section, and a curing section between a feed roller and a take-up roller in the substrate transport direction. By forming two or more cholesteric liquid crystal layers, the hue of the two or more cholesteric liquid crystal layers can be changed using the same optical mask layer, and the patterns of the two or more cholesteric liquid crystal layers can be aligned with high positional accuracy.

[0078] The manufacturing method of the present disclosure may further include a peeling step of peeling the optical mask layer and the substrate 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.).

[0079] <Laminate> A first embodiment of the laminate of the present disclosure includes, in this order, an optical mask layer, a substrate, and a cholesteric liquid crystal layer containing a liquid crystal compound and a photosensitive chiral agent, and the optical mask layer has an AM screen tone with a screen ruling of 250 lines or less and a dotted region with a dot area ratio of 0.5% or more and less than 99.5%. Further, in the first embodiment of the laminate of the present disclosure, the light transmittance of the dots in the dotted region is T Ｄ , the light transmittance of the gap between the halftone dots is T Ａ When this is the case, 5%≦T Ａ <95%, and the light transmittance T at the portion of the optical mask layer with the lowest light transmittance ｍｉｎ , the light transmittance T at the highest pointＭＡＸ When this is done, (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ A second embodiment of the laminate of the present disclosure comprises, in this order, an optical mask layer, a substrate, and a cholesteric liquid crystal layer containing a liquid crystal compound and a photosensitive chiral agent, wherein the optical mask layer has an AM screen tone with a screen ruling of 250 lines or less and a halftone dot area ratio of 0.5% or more and less than 99.5%, and in the halftone dot area, the light transmittance of the halftone dots is T Ｄ , the light transmittance of the gap between the halftone dots is T Ａ When this is the case, 5%≦T Ａ < 95% and 1% ≦ T Ａ -T Ｄ <80.75%.

[0080] In this specification, unless otherwise specified, the term "laminate of the present disclosure" or simply "laminate" refers to both the first embodiment and the second embodiment. In addition, the laminate of the present disclosure is preferably a laminate manufactured by the laminate manufacturing method of the present disclosure.

[0081] (Optical mask layer) The optical mask layer can be produced by the same method as the optical mask layer described above using the laminate production method. The light transmittance of the optical mask layer of the present disclosure indicates the transmittance to light irradiated in the step of photoreacting the photosensitive chiral agent.

[0082] Light transmittance T of the halftone dots in the halftone dot area Ｄ is the ratio of the amount of light that passes through a halftone dot and enters the cholesteric liquid crystal layer to the amount of light that enters the halftone dot, expressed as a percentage. For example, the light transmittance per 10 μmΦ (i.e., within a circle with a diameter of 10 μm) within the halftone dot measured using a microscopic ultraviolet, visible, and near-infrared spectrophotometer MSV-5500 is expressed as T Ｄ The measurement can be performed using a microspectrophotometer whose measurement area is smaller than the dot area. Ａis the ratio, expressed as a percentage, of the amount of light that passes through the gaps and enters the cholesteric liquid crystal layer relative to the amount of light that enters the gaps between the halftone dots. As with the light transmittance of the halftone dots, the light transmittance per 10 μmφ in the gaps 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 μmφ, and can be measured using a microspectrophotometer, for example, by narrowing the measurement position to a location with relatively low transmittance through visual and microscopic observation. The location of the optical mask layer with the highest light transmittance is the location with the highest light transmittance per 10 μmφ, and can be measured using a microspectrophotometer, for example, by narrowing the measurement position to a location with relatively high transmittance through visual and microscopic observation.

[0083] In a first embodiment of the laminate of the present disclosure, the light transmittance of the dots in the dotted area is set to T Ｄ , the light transmittance of the gap between the halftone dots is T Ａ When this is the case, 5%≦T Ａ <95%, and the light transmittance T at the portion of the optical mask layer with the lowest light transmittance ｍｉｎ , the light transmittance T at the highest point ＭＡＸ When this is done, (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ ) is 0.95 or less. Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ ) is 0.95 or less, the difference in the amount of photoreaction of the photosensitive chiral agent between the dot portion and the gap portion can be reduced, the hue change of the cholesteric liquid crystal layer due to the difference in helical induction power can be suppressed, and the saturation can be improved. In a second embodiment of the laminate of the present disclosure, from the viewpoint of improving the saturation of the entire decorative film, in all the dot-painted areas of the optical mask layer, (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ ) is preferably 0.95 or less in all halftone dot areas of the optical mask layer. Ａ -T Ｄ ) / (T ＭＡＸ -Tｍｉｎ ) is preferably 0.50 or less, more preferably 0.30 or less. By setting it in the above range, it is possible to reduce the dot-like hue change of the cholesteric liquid crystal layer and suppress graininess. In the laminate of the present disclosure, from the viewpoint of obtaining a decorative film with abundant color changes by controlling the light transmittance of the dot-painted region, (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ ) is preferably 0.03 or more.

[0084] In a second embodiment of the laminate of the present disclosure, in the dotted area, the light transmittance of the dots is T Ｄ , the light transmittance of the gap between the halftone dots is T Ａ When this is the case, 5%≦T Ａ < 95% and 1% ≦ T Ａ -T Ｄ <80.75%. Ａ -T Ｄ By making T less than 80.75%, the difference in the amount of photoreaction of the photosensitive chiral agent between the dot portion and the gap portion can be reduced, and the change in hue of the cholesteric liquid crystal layer due to the difference in helical twisting power can be suppressed, thereby improving the saturation. Ａ -T Ｄ By making the ratio of the thickness of the laminate to the thickness of the dotted area 1% or more, the light transmittance of the dotted area can be controlled, and a decorative film with a wide range of color variations can be obtained. Ａ -T Ｄ Furthermore, in the laminate of the present disclosure, it is preferable that the T Ａ -T Ｄ is preferably 60% or less, more preferably 50% or less, and particularly preferably 30% or less. Ａ -T Ｄ is preferably 3% or more, and more preferably 5% or more.

[0085] The substrate is the same as the substrate described above in the method for producing the laminate, and the preferred substrates are also the same.

[0086] 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 the liquid crystal compounds and photosensitive chiral agents contained in the cholesteric liquid crystal layer of the decorative film described below. The laminate of the present disclosure is preferably a decorative film.

[0087] <Substrate with optical mask for producing decorative film> A first embodiment of the substrate with optical mask for producing decorative film of the present disclosure includes a substrate and an optical mask layer, the optical mask layer having an AM screen tone with a screen ruling of 250 lines or less and a halftone dot area ratio of 0.5% or more and less than 99.5%, and in the halftone dot area, the light transmittance of the halftone dots is T Ｄ , the light transmittance of the gap between the halftone dots is T Ａ When 5%≦T Ａ <95%, and the light transmittance T at the portion of the optical mask layer with the lowest light transmittance ｍｉｎ , the light transmittance T at the highest point ＭＡＸ When this is done, (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ A second embodiment of the substrate with an optical mask for producing a decorative film of the present disclosure includes a substrate and an optical mask layer, wherein the optical mask layer has an AM screen tone with a screen ruling of 250 lines or less and a halftone dot area ratio of 0.5% or more and less than 99.5%, and in the halftone dot area, the light transmittance of the halftone dots is T Ｄ , the light transmittance of the gap between the halftone dots is T Ａ When 5%≦T Ａ < 95% and 1% ≦ T Ａ -T Ｄ <80.75%.

[0088] In this specification, unless otherwise specified, when referring to a "substrate with an optical mask for producing a decorative film of the present disclosure" or simply to a "substrate with an optical mask for producing a decorative film," this refers to both the first embodiment and the second embodiment.

[0089] The substrate and the optical mask layer included in the substrate with an optical mask for producing a decorative film are the same as the substrate and the optical mask layer of the laminate described above, and the preferred substrate and optical mask layer are also the same. Furthermore, a first embodiment of the substrate with an optical mask for producing a decorative film of the present disclosure corresponds to a first embodiment of the laminate of the present disclosure, and a second embodiment of the substrate with an optical mask for producing a decorative film of the present disclosure corresponds to a second embodiment of the laminate of the present disclosure.

[0090] <Decorative Film> A first embodiment of the decorative film of the present disclosure is a decorative film including a cholesteric liquid crystal layer having a dot region in which cholesteric pitch maximum points are arranged in a dot pattern. When the dot region is divided into unit lattices, which are squares with the smallest area and each having a maximum point as a vertex, the difference between the maximum and minimum values ​​of the cholesteric pitch in each unit lattice is an intra-lattice pitch difference ΔP Ｓ ΔP in the entire halftone dot area Ｓ The maximum value ΔP Ｓ（ＭＡＸ） is the difference ΔP between the maximum and minimum values ​​of the cholesteric pitch in the entire cholesteric liquid crystal layer. ａｌｌ Whereas, ΔP Ｓ（ＭＡＸ） / ΔP ａｌｌ A second embodiment of the decorative film of the present disclosure is a decorative film having a cholesteric liquid crystal layer, the cholesteric liquid crystal layer having dot regions in which maximal points of the cholesteric pitch are arranged in a dot pattern, the dot regions are divided into unit lattices which are rectangles with the smallest area and whose vertices are the maximal points of the cholesteric pitch, and the difference between the maximum value and the minimum value of the cholesteric pitch in each unit lattice is defined as an intra-lattice pitch difference ΔP Ｓ In the cholesteric liquid crystal layer, the ΔP Ｓ The maximum value of ΔP Ｓ（ＭＡＸ） A decorative film having a thickness of less than 33 nm.

[0091] In this specification, unless otherwise specified, when the term "decorative film of the present disclosure" or simply "decorative film" is used, it refers to both the first embodiment and the second embodiment.

[0092] The dotted area is preferably an area in which cholesteric pitch maximum points are arranged at equal intervals of 100 μm or more and less than 300 μm in a dotted pattern. A preferred embodiment of the dotted area is the same as the dotted area, except that it is formed in a cholesteric liquid crystal layer and the following aspects are described below. The method for manufacturing the decorative film of the present disclosure is preferably a method including the method for manufacturing the laminate of the present disclosure. The decorative film of the present disclosure may be the laminate itself manufactured by the method for manufacturing the laminate of the present disclosure, or may be the laminate from which the substrate and optical mask layer have been removed, or the laminate from which the optical mask layer has been removed. For example, the optical mask layer may be a colored layer or the like in the decorative film of the present disclosure.

[0093] A cholesteric liquid crystal layer selectively reflects incident light and exhibits a hue corresponding to the wavelength of the reflected light. The desired hue of the cholesteric liquid crystal layer can be obtained by changing the helical pitch of the cholesteric liquid crystal compound. When a cholesteric liquid crystal layer has multiple cholesteric pitches within a microscopic region of approximately 100 μm square, it reflects light of multiple wavelengths, and the visual reflection spectrum is equivalent to the average of the spectra of the multiple reflected wavelengths. Therefore, compared to when a cholesteric liquid crystal layer has a uniform cholesteric pitch, the half-width of the reflectance peak in the visual reflection spectrum can be increased. An increase or decrease in the half-width of the reflectance peak in the reflection spectrum significantly affects the saturation. For example, if the half-width is wider than the appropriate half-width, the hue approaches white and the saturation decreases. Conversely, if the half-width is narrower than the appropriate half-width, the hue approaches black and the saturation decreases. In the present disclosure, the maximum pitch difference ΔP of the cholesteric pitch within a unit lattice is Ｓ（ＭＡＸ） 0<ΔP Ｓ（ＭＡＸ） / ΔP ａｌｌ It was found that the saturation can be increased by setting the value in the range of ≦0.4.

[0094] However, when a difference in cholesteric pitch is provided within a unit lattice, graininess may be visually perceived. The greater the difference in cholesteric pitch within the unit lattice, the more easily the graininess becomes visible, and the greater the color range of the entire decorative film, the less easily it becomes visible. For example, when a decorative film has a blue-green-red color range (hue angle range 270°), the blue-green-green color difference (hue angle range 45°) due to the difference in cholesteric pitch within the unit lattice is low in visibility. On the other hand, when a decorative film has a blue-green color range (hue angle range 90°), the blue-green-green color difference (hue angle range 45°) within the unit lattice is highly visible. Furthermore, it has been found that arranging the local maxima at equal intervals in an AM screen-like halftone dot pattern is also important for suppressing graininess, as it can suppress an increase in the visual color difference.

[0095] Therefore, in the present disclosure, the maximum value ΔP of the cholesteric pitch difference in the unit cell Ｓ（ＭＡＸ） ΔP with respect to the pitch difference of the cholesteric pitch of the entire decorative film Ｓ（ＭＡＸ） / ΔP ａｌｌ ≦0.4, and further, by arranging the maximum points in an AM screen-style halftone dot pattern at equal intervals of 100 μm or more and less than 300 μm, a multi-color decorative film with high saturation and suppressed graininess can be realized.

[0096] The cholesteric liquid crystal layer preferably has a cholesteric pitch change of 13 nm or more per 100 μm in-plane distance, in order to realize a region with clear boundaries between patterns as a decorative film. When forming a decorative film with a design with clear boundaries between patterns, i.e., a cholesteric liquid crystal layer with a large rate of change in cholesteric pitch per in-plane distance, it is necessary to significantly change the helical induction force of the photosensitive chiral agent or to suppress the diffusion of the photoreacted photosensitive chiral agent in the in-plane direction, which tends to worsen the visibility of the graininess. As in the decorative film of the present disclosure, the pitch difference ΔP in the halftone dotted region Ｓ（ＭＡＸ） ΔP Ｓ（ＭＡＸ） / ΔP ａｌｌBy setting the cholesteric pitch change rate to ≦0.4, it is possible to suppress deterioration of visibility of graininess even with the same cholesteric pitch change rate, and it is possible to achieve both a clear design and suppression of graininess. In addition, in the second embodiment of the decorative film of the present disclosure, from the viewpoint of obtaining high color saturation, suppression of graininess, and a clear design, the intra-lattice pitch difference ΔP Ｓ ΔP in the entire halftone dot area Ｓ The maximum value ΔP Ｓ（ＭＡＸ） is the difference ΔP between the maximum and minimum values ​​of the cholesteric pitch in the entire cholesteric liquid crystal layer. ａｌｌ Whereas, ΔP Ｓ（ＭＡＸ） / ΔP ａｌｌ It is preferred that it is ≦0.4.

[0097] ΔP in the second embodiment of the decorative film of the present disclosure Ｓ（ＭＡＸ） is less than 33 nm, and preferably 13 nm or less. Ｓ（ＭＡＸ） By making ΔP less than 33 nm, the color difference due to the difference in the cholesteric pitch can be reduced, the half-width of the reflectance peak of the visual reflection spectrum can be increased, and the saturation can be improved. Ｓ（ＭＡＸ） By making the thickness less than 13 nm, the visibility of graininess is further reduced and the glossiness is more excellent. Ｓ（ＭＡＸ） is preferably less than 33 nm, and more preferably 13 nm or less. Ｓ（ＭＡＸ） By setting ΔP in the above range, the color difference due to the difference in the cholesteric pitch is reduced, the visibility of graininess is reduced, and the glossiness is more excellent, which is preferable. Ｓ（ＭＡＸ） is preferably 3.3 nm or more from the viewpoint of increasing the half-value width of the reflectance peak of the visual reflection spectrum and improving the saturation.

[0098] ΔP ａｌｌ is preferably 70 nm or more from the viewpoint that the decorative film can express a wide color range from blue to green to red, and is more preferably 100 nm or more from the viewpoint that the decorative film can express the ultraviolet and infrared regions, i.e., colorless. ａｌｌThe upper limit is preferably 200 nm or less, since the color range of the decorative film is sufficient from the ultraviolet region to the infrared region.

[0099] The "reflection center wavelength" is the maximum reflectance value R in the reflection spectrum of light incident on the cholesteric liquid crystal layer. ｍａｘ (%) and half-value reflectance R １／２ The reflectance is the average value obtained by averaging wavelengths showing the reflectance (%). The reflectance is the integral reflectance and is the relative reflectance to a white standard plate. The method for measuring the reflection center wavelength will be described later.

[0100] At least a part of the central reflection wavelength in the gradation region of the cholesteric liquid crystal layer is preferably within the wavelength region of 380 nm to 780 nm.

[0101] "At least a part of the reflection central wavelength is in the wavelength range of 380 nm to 780 nm" means that at least a part of the gradation region of the cholesteric liquid crystal layer has a reflection wavelength range in the visible light region (380 nm to 780 nm). In other words, the cholesteric liquid crystal layer has selective reflectivity with selective reflection wavelengths in the range of 380 nm to 780 nm. The "selective reflection wavelength" is the wavelength at which the minimum value of transmittance in the target object is T ｍ (%), the half-value transmittance (T １／２ , unit: %) means the average value of two wavelengths. Formula: half-value transmittance T １／２ =100-(100-T ｍ ) ÷ 2

[0102] Next, the cholesteric liquid crystal layer constituting the decorative film of the present disclosure will be described.

[0103] (Cholesteric Liquid Crystal Layer) 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; the same applies hereinafter) of a photocurable composition containing the cholesteric liquid crystal compound and a photosensitive chiral agent. The composition is cured, for example, by light or heat.

[0104] Components of the composition or liquid crystal layer before curing that forms the cholesteric liquid crystal layer include, for example, a cholesteric liquid crystal compound, a photosensitive chiral agent, a chiral agent other than the above-mentioned photosensitive chiral agent (including a photoisomerizable compound), a polymerization initiator, a polymerizable monomer, a polyfunctional polymerizable compound, a crosslinking agent, a solvent, and an additive. The components of the composition or liquid crystal layer before curing that form the cholesteric liquid crystal layer preferably contain a cholesteric liquid crystal compound and a photosensitive chiral agent, and more preferably contain a cholesteric liquid crystal compound, a photosensitive chiral agent, and a polymerization initiator. Furthermore, the components of the composition or liquid crystal layer before curing may further contain other components, such as a polymerization initiator, a polymerizable monomer, a polyfunctional polymerizable compound, a crosslinking agent, a solvent, and an additive, as necessary.

[0105] The "cholesteric liquid crystal layer" is a layer having a molecular orientation state specific to cholesteric liquid crystals. 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 a method such as polymerization or crosslinking.

[0106] Specific embodiments of each component used in the cholesteric liquid crystal layer will be described below.

[0107] - Cholesteric Liquid Crystal Compound - 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 containing the cholesteric liquid crystal compound (or a liquid crystal layer when the composition is formed into a liquid crystal layer). The type of cholesteric liquid crystal compound is not limited. The cholesteric liquid crystal compound may be a known cholesteric liquid crystal compound.

[0108] The cholesteric liquid crystal compound preferably has a reactive group. The reactive group is preferably a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group. From the viewpoints of reactivity and ease of fixing the helical pitch, 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 more preferably at least one polymerizable group selected from the group consisting of an acryloyl group and a methacryloyl group.

[0109] 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.

[0110] 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, a hydrogen bond, or polymerization. At least one of the crosslinking mechanisms of the two or more types of reactive groups is preferably polymerization. The crosslinking mechanism preferably includes two or more types of polymerization. Examples of reactive groups used in the above crosslinking mechanisms include a vinyl group, a (meth)acrylic group, an epoxy group, an oxetanyl group, a vinyl ether group, a hydroxy group, a carboxy group, and an amino group.

[0111] A 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. In each stage, the reactive groups react according to the crosslinking mechanism of each stage. An example of a method for crosslinking two or more types of reactive groups in stages is a method of changing the reaction conditions in each stage. Examples of changes in the reaction conditions include the temperature, the wavelength of light (irradiation), and the polymerization mechanism. Utilizing differences in polymerization mechanisms is preferable because it is easy to separate the reactions. The polymerization mechanism is controlled, for example, by the type of polymerization initiator.

[0112] The combination of polymerizable groups is preferably a combination of a radical polymerizable group and a cationically polymerizable group.From the viewpoint of easy control of reactivity, the combination of polymerizable groups is preferably a combination in which the radical polymerizable group is a vinyl group or a (meth)acrylic group and the cationically polymerizable group is an epoxy group, an oxetanyl group, or a vinyl ether group.Furthermore, the polymerizable group is preferably an ethylenically unsaturated group.

[0113] From the viewpoints of stretchability and heat resistance, the cholesteric liquid crystal compound preferably contains a cholesteric liquid crystal compound having one reactive group (preferably a polymerizable group). From the viewpoints of stretchability and heat resistance, the ratio of the content of the cholesteric liquid crystal compound having one reactive group to the total content of the cholesteric liquid crystal compound is preferably 96% by mass to 100% by mass, more preferably 97% by mass to 100% by mass, and more preferably 98% by mass to 100% by mass.

[0114] From the viewpoints of stretchability and heat resistance, the cholesteric liquid crystal compound preferably includes a cholesteric liquid crystal compound having one reactive group and a cholesteric liquid crystal compound having two or more reactive groups. The cholesteric liquid crystal compound more preferably includes a cholesteric liquid crystal compound having one reactive group and a cholesteric liquid crystal compound having two reactive groups. From the viewpoints 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 preferably 0 to 0.05, more preferably 0 to 0.04, and more preferably 0 to 0.02 by mass.

[0115] Specific examples of reactive groups are shown below. However, the reactive groups are not limited to the following specific examples. In the following specific examples, Et represents an ethyl group, and n-Pr represents an n-propyl group.

[0116]

[0117] Examples of cholesteric liquid crystal compounds 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-weight or high-molecular-weight compound. The discotic cholesteric liquid crystal compound may be a low-molecular-weight or high-molecular-weight compound. In this disclosure, the term "polymer" used with respect to cholesteric liquid crystal compounds means a compound having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, by Masao Doi, page 2, Iwanami Shoten, 1992). Two or more rod-shaped cholesteric liquid crystal compounds, two or more 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. Among the two or more cholesteric liquid crystal compounds, it is preferable that at least one cholesteric liquid crystal compound has a reactive group.

[0118] The cholesteric liquid crystal compound is preferably a rod-shaped cholesteric liquid crystal compound. Examples of rod-shaped cholesteric liquid crystal compounds include azomethines, azoxy compounds, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes, and alkenylcyclohexylbenzonitriles. Examples of rod-shaped cholesteric liquid crystal compounds include polymers of rod-shaped cholesteric liquid crystal compounds having reactive groups. Examples of rod-shaped cholesteric liquid crystal compounds include compounds described in JP 2008-281989 A, JP 11-513019 A, and JP 2006-526165 A.

[0119] Specific examples of rod-shaped cholesteric liquid crystal compounds are shown below. However, the rod-shaped cholesteric liquid crystal compounds are not limited to the following specific examples. The compounds shown below can be synthesized, for example, by the method described in JP-A-11-513019.

[0120]

[0121]

[0122]

[0123]

[0124]

[0125] Examples of rod-shaped cholesteric liquid crystal compounds having one polymerizable group include the following compounds: "Me" in the following chemical formula means a methyl group.

[0126]

[0127]

[0128]

[0129]

[0130]

[0131] Examples of discotic cholesteric liquid crystal compounds include the following compounds: (1) benzene derivatives described in the research reports of C. Destrade et al., for example, Mol. Cryst., Vol. 71, p. 111 (1981); (2) truxene derivatives described in the research reports of C. Destrade et al., for example, Mol. Cryst., Vol. 122, p. 141 (1985) and Physicslett, A, Vol. 78, p. 82 (1990); (3) cyclohexane derivatives described in the research reports of B. Kohne et al., for example, Angew. Chem., Vol. 96, p. 70 (1984); (4) cyclohexane derivatives described in the research reports of J. M. Azacrown-based or phenylacetylene-based macrocycles described in the research reports of Lehn et al. (J. Chem. Commun., 1794 (1985)) and J. Zhang et al. (J. Am. Chem. Soc., 116, 2655 (1994))

[0132] Discotic cholesteric liquid crystal compounds include liquid crystal compounds that have a structure in which the above-mentioned various structures form a discoidal mother nucleus at the center of the molecule, and in which groups such as linear alkyl groups, alkoxy groups, and substituted benzoyloxy groups are radially arranged, exhibiting liquid crystallinity and generally referred to as discotic liquid crystals. When aggregates of such compounds are uniformly aligned, negative uniaxiality is exhibited.

[0133] Examples of the discotic cholesteric liquid crystal compound include the compounds described in paragraphs 0061 to 0075 of JP-A No. 2008-281989.

[0134] In the cholesteric liquid crystal layer, the discotic cholesteric liquid crystal compound having a reactive group may be fixed in an alignment state such as horizontal alignment, vertical alignment, tilt alignment, or twist alignment.

[0135] The cholesteric liquid crystal layer or composition may contain one or more cholesteric liquid crystal compounds. The content of the cholesteric liquid crystal compounds relative to the total mass of the solid content of the cholesteric liquid crystal layer or composition is preferably 30% by mass to 99% by mass, more preferably 40% by mass to 99% by mass, even more preferably 60% by mass to 99% by mass, and particularly preferably 70% by mass to 98% by mass.

[0136] - Chiral agent - The cholesteric liquid crystal layer contains a chiral agent (optically active compound), particularly a photosensitive chiral agent. The chiral agent can induce a helical structure in the cholesteric liquid crystal compound. For example, the chiral agent can adjust the helical pitch. The chiral agent includes a photoisomerizable compound, as described below.

[0137] 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 compounds described in Liquid Crystal Device Handbook (Chapter 3, Section 4-3, Chiral Agents for TN and STN, page 199, edited by the 142nd Committee of the Japan Society for the Promotion of Science, 1989), JP-A Nos. 2003-287623, 2002-302487, 2002-80478, 2002-80851, 2010-181852, and 2014-034581.

[0138] The chiral agent preferably has a cinnamoyl group.

[0139] The chiral agent preferably contains an asymmetric carbon atom. However, 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.

[0140] The chiral agent may have a reactive group. The reactive group is preferably a polymerizable group. The polymerizable group is preferably at least one type of 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 even more preferably at least one type of polymerizable group selected from the group consisting of an acryloyl group and a methacryloyl group. The chiral agent may have two or more reactive groups. The chiral agent may have two or more types of reactive groups.

[0141] From the viewpoint of stretchability and heat resistance, the chiral agent preferably contains a chiral agent having one polymerizable group. When the chiral agent contains a chiral agent having one polymerizable group, from the viewpoint of stretchability and heat resistance, the ratio of the content of the chiral agent having one polymerizable group to the content of the chiral agent is preferably more than 0% 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.

[0142] 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. For example, the reaction between the photosensitive chiral agent having a polymerizable group and the cholesteric liquid crystal compound having a polymerizable group can form a polymer having a structural unit derived from the cholesteric liquid crystal compound having a polymerizable group and a structural unit derived from the photosensitive chiral agent having a polymerizable group. 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.

[0143] The chiral agent (optically active compound) may be a cholestetic liquid crystal compound.

[0144] From the viewpoints of ease of forming a cholesteric liquid crystal layer and ease of adjusting the helical pitch, the chiral agent used in the present disclosure includes a photoisomerizable compound (photosensitive chiral agent) that also acts as a chiral agent. Examples of the photoisomerizable compound that also acts as a chiral agent include a compound represented by the formula (CH1) described below.

[0145] Preferred chiral agents include, for example, isosorbide derivatives, isomannide derivatives and binaphthyl derivatives.

[0146] Specific examples of the chiral agent are shown below, but the chiral agent is not limited to the following specific examples.

[0147]

[0148]

[0149]

[0150] In the above chemical formula, n represents an integer of 2 to 12. From the viewpoint of synthesis costs, n is preferably 2 or 4.

[0151] The cholesteric liquid crystal layer or composition may contain one or more chiral dopants. From the viewpoints of ease of forming a cholesteric liquid crystal layer and ease of adjusting the helical pitch, the content of the chiral dopants relative to the total mass of the solid content 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, even more preferably 3% by mass to 9% by mass, and particularly preferably 4% by mass to 8% by mass.

[0152] The content of the chiral dopant having a polymerizable group relative to the total mass of the solid content of the cholesteric liquid crystal layer or composition is preferably 0.2% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass, and even more preferably 1% by mass to 8% by mass. The content of the chiral dopant not having a polymerizable group relative to the total mass of the solid content of the cholesteric liquid crystal layer or composition is preferably 0.2% by mass to 20% by mass, and more preferably 0.5% by mass to 10% by mass.

[0153] The helical pitch and the selective reflection wavelength and their range are adjusted depending on, for example, the type of cholesteric liquid crystal compound as well as the content of the chiral agent. For example, if the content of the chiral agent in the cholesteric liquid crystal layer is doubled, the helical pitch is halved and the center value of the selective reflection wavelength is also halved.

[0154] (Photoisomerizable compound) The cholesteric liquid crystal layer or composition may contain a photoisomerizable compound. The type of the photoisomerizable compound is not limited. The photoisomerizable compound may be a known photoisomerizable compound. From the viewpoints of suppressing changes in reflectance after molding and maintaining the isomerized structure, a compound whose three-dimensional structure changes upon exposure to light is preferred.

[0155] The photoisomerizable compound has a photoisomerizable structure. From the viewpoints of suppressing changes in reflectance after molding, facilitating photoisomerization, and maintaining the isomerized structure, the photoisomerizable compound preferably has a structure whose three-dimensional structure changes upon exposure, more preferably has a di- or more-substituted ethylenically unsaturated bond whose EZ configuration is isomerized upon exposure, and particularly preferably has a di-substituted ethylenically unsaturated bond whose EZ configuration is isomerized upon exposure. Isomerization of the EZ configuration includes cis-trans isomerization. The di-substituted ethylenically unsaturated bond is preferably an ethylenically unsaturated bond substituted with an aromatic group and an ester bond.

[0156] From the viewpoints of suppressing change in reflectance after molding, facilitating photoisomerization, and maintaining the isomerized structure, the photoisomerizable compound preferably has two or more photoisomerizable structures. The number of photoisomerizable structures in the photoisomerizable compound is preferably 2 to 4, and more preferably 2.

[0157] The photoisomerizable compound is preferably a photoisomerizable compound (photosensitive chiral agent) that also functions as a chiral agent, as described above. The photoisomerizable compound that also functions as a chiral agent is preferably a chiral agent having a molar absorption coefficient of 30,000 or more at a wavelength of 313 nm.

[0158] An example of a photoisomerizable compound that also functions as a chiral agent is a compound represented by the following formula (CH1). The compound represented by formula (CH1) can change its orientation structure, such as its helical pitch (twisting power, helical twist angle), depending on the amount of light irradiated with light. The compound represented by formula (CH1) is also a compound in which the EZ configuration of two ethylenically unsaturated bonds can be isomerized by exposure to light.

[0159]

[0160] In formula (CH1), Ar ＣＨ１ and Ar ＣＨ２ each independently represents an aryl group or a heteroaromatic ring group, R ＣＨ１ and R ＣＨ２ each independently represents a hydrogen atom or a cyano group.

[0161] Ar in formula (CH1)ＣＨ１ and Ar ＣＨ２ are each independently preferably an aryl group. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a hydroxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carboxy group, a cyano group, or a heterocyclic group, and more preferably 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. The total number of carbon atoms in the aryl group is preferably 6 to 40, and more preferably 6 to 30.

[0162] Ar ＣＨ１ and Ar ＣＨ２ are each independently an aryl group represented by the following formula (CH2) or (CH3).

[0163]

[0164] In formula (CH2) and formula (CH3), R ＣＨ３ and R ＣＨ４ each independently represents 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, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carboxy group, or a cyano group; L ＣＨ１ and L ＣＨ２ each independently represents 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; and * represents the bonding position with the ethylenically unsaturated bond in formula (CH1).

[0165] R in formula (CH2) and formula (CH3) ＣＨ３ and R ＣＨ４are each independently preferably 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, or an acyloxy group, more preferably an alkoxy group, a hydroxy group, or an acyloxy group, and particularly preferably an alkoxy group.

[0166] L in formula (CH2) and formula (CH3) ＣＨ１ and L ＣＨ２ are preferably each independently an alkoxy group having 1 to 10 carbon atoms or a hydroxy group. nCH1 in formula (CH2) is preferably 0 or 1. nCH2 in formula (CH3) is preferably 0 or 1.

[0167] Ar in formula (CH1) ＣＨ１ and Ar ＣＨ２ The heteroaromatic ring group in formula (I) may have a substituent. Examples of the substituent include, for example, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, a hydroxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and a cyano group, and more preferably a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, and an acyloxy group. The total number of carbon atoms in the heteroaromatic ring group is preferably 4 to 40, and more preferably 4 to 30. Examples of the heteroaromatic ring group include, for example, a pyridyl group, a pyrimidinyl group, a furyl group, and a benzofuranyl group, and more preferably a pyridyl group or a pyrimidinyl group.

[0168] R in formula (CH1) ＣＨ１ and R ＣＨ２ are each preferably independently a hydrogen atom.

[0169] Specific examples of preferred photoisomerizable compounds are shown below. In the following specific examples, Bu represents an n-butyl group. In the following compounds, the configuration of each ethylenically unsaturated bond is the E-form (trans-form), which changes to the Z-form (cis-form) upon exposure.

[0170]

[0171] The cholesteric liquid crystal layer or composition may contain one or more photoisomerizable compounds. The content of the photosensitive chiral agent relative to the total mass of the solid content 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, even more preferably 3% by mass to 9% by mass, and particularly preferably 4% by mass to 8% by mass.

[0172] -Polymerization initiator- The cholesteric liquid crystal layer or composition preferably 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 α-carbonyl compounds (see, for example, U.S. Pat. Nos. 2,367,661 and 2,367,670), acyloin ether compounds (see, for example, U.S. Pat. No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (see, for example, U.S. Pat. No. 2,722,512), polynuclear quinone compounds (see, for example, U.S. Pat. Nos. 3,046,127 and 2,951,758), combinations of triarylimidazole dimers and p-aminophenyl ketones (see, for example, U.S. Pat. No. 3,549,367), acridine compounds and phenazine compounds (see, for example, JP-A-60-105667 and U.S. Pat. No. 4,239,850), and oxadiazole compounds (see, for example, U.S. Pat. No. 4,212,970).

[0173] Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. Preferred examples of the photoradical polymerization initiator include an α-hydroxyalkylphenone compound, an α-aminoalkylphenone compound, an acylphosphine oxide compound, a thioxanthone compound, and an oxime ester compound. Preferred examples of the photocationic polymerization initiator include an iodonium salt compound and a sulfonium salt compound.

[0174] The composition may contain one or more polymerization initiators. From the viewpoints of ease of adjusting the helical pitch, polymerization rate, and strength of the liquid crystal layer after curing, the content of the polymerization initiator relative to the total mass of the solid content of the cholesteric liquid crystal layer or the composition is preferably 0.05 to 10% by mass, more preferably 0.05 to 5% by mass, even more preferably 0.1 to 4% by mass, and particularly preferably 0.2 to 3% by mass.

[0175] -Polymerizable Monomer- 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 a monomer or oligomer having two or more ethylenically unsaturated groups and undergoing addition polymerization upon irradiation with light. Examples of the polymerizable monomer include a compound 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.

[0176] Examples of the polymerizable monomer include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolethane triacrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane diacrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, tri(acryloyloxyethyl)cyanurate, and glycerin tri(meth)acrylate.

[0177] Examples of the polymerizable monomer include compounds formed by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as trimethylolpropane or glycerin, followed by (meth)acrylation.

[0178] Examples of the polymerizable monomer include urethane acrylates described in JP-B Nos. 48-41708, 50-6034, and 51-37193, and examples of the polymerizable monomer include polyester acrylates described in JP-A Nos. 48-64183, 49-43191, and 52-30490.

[0179] Further, examples of the polymerizable monomer include epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid.

[0180] Preferred polymerizable monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Preferred polymerizable monomers include, for example, "Polymerizable Compound B" described in JP-A-11-133600.

[0181] The polymerizable monomer may be a cationically polymerizable monomer, such as the epoxy compounds, vinyl ether compounds, and oxetane compounds described in JP-A Nos. 6-9714, 2001-31892, 2001-40068, 2001-55507, 2001-310938, 2001-310937, and 2001-220526.

[0182] Epoxy compounds include, for example, aromatic epoxides, alicyclic epoxides, and aliphatic epoxides.

[0183] Examples of aromatic epoxides include diglycidyl ethers or polyglycidyl ethers of bisphenol A, diglycidyl ethers or polyglycidyl ethers of alkylene oxide adducts of bisphenol A, diglycidyl ethers or polyglycidyl ethers of hydrogenated bisphenol A, diglycidyl ethers or polyglycidyl ethers of alkylene oxide adducts of hydrogenated bisphenol A, and novolac-type epoxy resins. Examples of alkylene oxides include ethylene oxide and propylene oxide.

[0184] Examples of alicyclic epoxides include cyclohexene oxide-containing compounds or cyclopentene 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).

[0185] 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 (e.g., diglycidyl ethers of ethylene glycol, diglycidyl ethers of propylene glycol, and diglycidyl ethers of 1,6-hexanediol). Examples of aliphatic epoxides include polyglycidyl ethers of polyhydric alcohols (e.g., 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 (e.g., diglycidyl ethers of polyethylene glycol or its alkylene oxide adducts, and diglycidyl ethers of polypropylene glycol or its alkylene oxide adducts). Alkylene oxides include, for example, ethylene oxide and propylene oxide.

[0186] Examples of the cationically polymerizable monomer include monofunctional or bifunctional oxetane monomers. For example, 3-ethyl-3-hydroxymethyloxetane (e.g., OXT101 manufactured by Toagosei Co., Ltd.), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene (e.g., OXT121 manufactured by Toagosei Co., Ltd.), 3-ethyl-3-(phenoxymethyl)oxetane (e.g., OXT211 manufactured by Toagosei Co., Ltd.), di(1-ethyl-3-oxetanyl)methyl ether (e.g., OXT221 manufactured by Toagosei Co., Ltd.), and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (e.g., OXT212 manufactured by Toagosei Co., Ltd.) are preferably used. In particular, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(phenoxymethyl)oxetane, and di(1-ethyl-3-oxetanyl)methyl ether are preferred. Monofunctional or polyfunctional oxetane compounds described in JP-A Nos. 2001-220526 and 2001-310937 may also be used.

[0187] - Polyfunctional Polymerizable Compound - 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, a cholesteric liquid crystal compound having two or more cyclic ether groups and no ethylenically unsaturated group, a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and two or more cyclic ether groups, and a chiral agent and crosslinking agent having two or more polymerizable groups.

[0188] A preferred example of the ethylenically unsaturated group is a (meth)acrylic group. A more preferred example of the ethylenically unsaturated group is a (meth)acryloxy group.

[0189] Preferred examples of the cyclic ether group include an epoxy group and an oxetanyl group, and more preferred examples of the cyclic ether group include an oxetanyl group.

[0190] The polyfunctional polymerizable compound preferably contains at least one compound selected from the group consisting of a cholesteric liquid crystal compound having two or more ethylenically unsaturated groups and no cyclic ether group, a cholesteric liquid crystal compound having two or more cyclic ether groups and no ethylenically unsaturated group, and a chiral agent having two or more polymerizable groups, and more preferably contains a chiral agent having two or more polymerizable groups.

[0191] The composition may contain one or more polyfunctional polymerizable compounds. The content of the polyfunctional polymerizable compounds relative to the total mass of the solid content of the cholesteric liquid crystal layer or the composition is preferably 0.5% by mass to 70% by mass, more preferably 1% by mass to 50% by mass, even more preferably 1.5% by mass to 20% by mass, and particularly preferably 2% by mass to 10% by mass.

[0192] - Crosslinking Agent - The cholesteric liquid crystal layer or composition may contain a crosslinking agent. The crosslinking agent can improve the strength and durability of the liquid crystal layer after curing. 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.

[0193] Examples of the crosslinking agent include polyfunctional acrylate compounds such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; epoxy compounds such as glycidyl (meth)acrylate, ethylene glycol diglycidyl ether and 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate; oxetane compounds such as 2-ethylhexyloxetane and xylylene bisoxetane; aziridine compounds such as 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate] and 4,4-bis(ethyleneiminocarbonylamino)diphenylmethane; isocyanate compounds such as hexamethylene diisocyanate and biuret isocyanate; polyoxazoline compounds having an oxazoline group on the side chain; and alkoxysilane compounds such as vinyltrimethoxysilane and N-(2-aminoethyl)3-aminopropyltrimethoxysilane. A known catalyst may be used depending on the reactivity of the crosslinking agent, which can improve productivity in addition to improving the strength and durability of the liquid crystal layer.

[0194] The cholesteric liquid crystal layer or composition may contain one or more crosslinking agents. The content of the crosslinking agent(s) relative to the total mass of the solid content of the cholesteric liquid crystal layer or composition is preferably 1% by mass to 20% by mass, and more preferably 3% by mass to 15% by mass, from the viewpoint of the strength and durability of the cholesteric liquid crystal layer.

[0195] Additives The cholesteric liquid crystal layer or composition may contain other additives, such as surfactants, polymerization inhibitors, antioxidants, horizontal alignment agents, UV absorbers, light stabilizers, colorants, and metal oxide particles.

[0196] ~Physical Properties of Cholesteric Liquid Crystal Layer~ The color of the cholesteric liquid crystal layer and its change in color depending on the observation angle are adjusted 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, for example, in "Fujifilm Research Report No. 50 (2005) pp. 60-63." The helical pitch may also be adjusted by conditions such as temperature, illuminance, and irradiation time when fixing the cholesteric alignment state.

[0197] From the viewpoint of vividness of reflected color, the thickness of the cholesteric liquid crystal layer is preferably 0.5 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more. From the viewpoint of ease of formation of the cholesteric liquid crystal layer, the thickness of the cholesteric liquid crystal layer is preferably 10 μm or less, more preferably 6 μm or less, and particularly preferably 4 μm or less. From the above viewpoints, the thickness of the cholesteric liquid crystal layer is preferably in the range of 0.5 μm to 10 μm.

[0198] The haze value of the cholesteric liquid crystal layer is preferably 2.0% or less. A haze value of 2.0% or less can improve the transparency of the cholesteric liquid crystal layer. The haze value is more preferably 1.8% or less, even more preferably 1.3% or less, and particularly preferably 1.0% or less. Since a smaller haze is preferable, there is no lower limit for the haze value. If the lower limit for the haze value is set for convenience, it is 0% or more. The haze value is a value measured using a haze meter (for example, NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.) by a method in accordance with JIS K 7105 (1981).

[0199] (Colored layer) 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 colorant. The colored layer may be one layer or two or more layers. The colored layer may also be an optical mask layer in the laminate of the present disclosure.

[0200] In the decorative film, the position of the colored layer is not particularly limited and may be provided at a desired position. For example, the colored layer may be provided on the reflective layer. Furthermore, when the decorative film includes a substrate, the colored layer may be provided on the side of the substrate opposite to the side on which the reflective layer is formed. Alternatively, the decorative film may be obtained by peeling the substrate from a decorative film including the substrate, and the colored layer may be provided on the decorative film after the substrate has been peeled off.

[0201] The color of the colored layer is not particularly limited and can be appropriately selected depending on the application of the decorative film, etc. Examples of the color of the colored layer include black, gray, white, red, orange, yellow, green, blue, purple, brown, etc. The color of the colored layer may also be a metallic color.

[0202] Colorant: The colorant may be a pigment or a dye. From the viewpoint of durability, the colorant is preferably a pigment. To give the colored layer a metallic tone, metal particles, pearl pigments, etc. may be used as the colorant.

[0203] The pigment may be an inorganic pigment or an organic pigment.

[0204] Examples of inorganic pigments include white pigments such as titanium dioxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate; black pigments such as carbon black, titanium black, titanium carbon, iron oxide, and graphite; iron oxide, barium yellow, cadmium red, and chrome yellow.

[0205] Examples of inorganic pigments include those described in paragraphs 0015 and 0114 of JP-A No. 2005-7765.

[0206] Examples of organic pigments 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 pigments such as perylene red and perylene maroon; carbazole violet, anthrapyridine, flavanthrone yellow, isoindoline yellow, industhrone blue, dibromoanzathrone red, anthraquinone red, and diketopyrrolopyrrole.

[0207] Specific examples of organic pigments include red pigments such as C.I. Pigment Red 177, 179, 224, 242, 2515, and 264; yellow pigments such as C.I. Pigment Yellow 138, 139, 150, 180, and 185; orange pigments such as C.I. Pigment Orange 36, 38, and 71; green pigments such as C.I. Pigment Green 7, 36, and 58; blue pigments such as C.I. Pigment Blue 15:6; and purple pigments such as C.I. Pigment Violet 23.

[0208] Examples of the organic pigment include the organic pigments described in paragraph 0093 of JP-A-2009-256572.

[0209] The pigment may be a pigment having light transmitting and reflecting properties (so-called luster pigment). Examples of the luster pigment include metallic luster pigments such as aluminum, copper, zinc, iron, nickel, tin, aluminum oxide, and alloys thereof, interference mica pigments, white mica pigments, graphite pigments, and glass flake pigments. The luster pigment may be uncolored or colored.

[0210] The colorant may be used alone or in combination of two or more. When two or more colorants are used, an inorganic pigment and an organic pigment may be combined.

[0211] From the viewpoint of achieving the desired color, the content of the colorant is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 50% by mass, and particularly preferably 10% by mass to 40% by mass, relative to the total amount of the colored layer.

[0212] - Binder Resin - The colored layer preferably contains a binder resin from the viewpoints of strength, scratch resistance, and moldability. 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. The total light transmittance can be measured using a spectrophotometer (for example, a spectrophotometer "UV-2100" manufactured by Shimadzu Corporation).

[0213] Examples of binder resins include acrylic resins, silicone resins, polyesters, polyurethanes, and polyolefins. The binder resin may be a homopolymer or a copolymer.

[0214] The binder resin may be used alone or in combination of two or more kinds.

[0215] From the viewpoint of molding processability, 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 particularly preferably 20% by mass to 60% by mass, relative to the total amount of the colored layer.

[0216] Dispersant: The colored layer may contain a dispersant to improve the dispersibility of the colorant, particularly the pigment, contained in the colored layer. The inclusion of a dispersant improves the dispersibility of the colorant in the colored layer. This makes it easier to achieve a uniform color in the resulting decorative film.

[0217] The dispersant can be appropriately selected depending on the type, shape, etc. of the colorant, and is preferably a polymer dispersant.

[0218] Examples of polymer dispersants include silicone polymers, acrylic polymers, and polyester polymers. For example, when it is desired to impart heat resistance to the decorative film, the dispersant is preferably a silicone polymer such as a grafted silicone polymer.

[0219] 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 particularly preferably 2,500 to 3,000,000. When the weight-average molecular weight is 1,000 or more, the dispersibility of the colorant is further improved.

[0220] The dispersant may be a commercially available product. Examples of commercially available dispersants include EFKA 4300 (acrylic polymer dispersant) manufactured by BASF Japan Ltd.; Homogenol L-18, Homogenol L-95, and Homogenol L-100 manufactured by Kao Corporation; Solsperse 20000 and Solsperse 24000 manufactured by The Lubrizol Corporation of Japan; and DISPERBYK-110, DISPERBYK-164, DISPERBYK-180, and DISPERBYK-182 manufactured by BYK-Chemie Japan K.K. Note that "Homogenol," "Solsperse," and "DISPERBYK" are all registered trademarks.

[0221] The dispersant may be used alone or in combination of two or more kinds.

[0222] The content of the dispersant is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the colorant.

[0223] -Additives- In addition to the above components, the colored layer may contain additives as needed. The additives are not particularly limited, and examples thereof include the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362, the thermal polymerization inhibitors (also referred to as polymerization inhibitors, a preferred example of which is phenothiazine) described in paragraph 0018 of Japanese Patent No. 4502784, and the additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.

[0224] -Thickness- The thickness of the colored layer is not particularly limited, but from the viewpoints of visibility and three-dimensional formability, it is preferably 0.5 μm or more, more preferably 3 μm or more, even more preferably 3 μm to 50 μm, and particularly preferably 3 μm to 20 μm. When there are two or more colored layers, it is preferable that each colored layer independently has a thickness in the above-mentioned range.

[0225] -Method for forming colored layer- Examples of the method for forming a colored layer include a method using a colored layer-forming composition, a method of laminating a colored film, etc. Among these, the method for forming a colored layer using a colored layer-forming composition is preferred.

[0226] Examples of methods for forming a colored layer using a colored layer-forming composition include a method of forming a colored layer by applying the colored layer-forming composition, and a method of forming a colored layer by printing the colored layer-forming composition. Examples of printing methods include screen printing, inkjet printing, flexographic printing, gravure printing, and offset printing.

[0227] The colored layer-forming composition may contain a colorant and, if necessary, at least one of a binder resin, a dispersant, and an additive. The type of each component may be the same as that described above for the colored layer. The colorant content is preferably 1% to 50% by mass, more preferably 5% to 50% by mass, and particularly preferably 10% to 40% by mass, relative to the total solid content of the colored layer-forming composition. The binder resin content is preferably 5% to 70% by mass, more preferably 10% to 60% by mass, and particularly preferably 20% to 60% by mass, relative to the total solid content of the colored layer-forming composition. The dispersant content is preferably 1 part by mass to 30 parts by mass relative to 100 parts by mass of the colorant.

[0228] The colored layer may be a layer formed by curing a colored layer-forming composition, and for example, a colored layer-forming composition 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.

[0229] The color layer-forming composition may contain an organic solvent to facilitate application. The organic solvent is not particularly limited, and known organic solvents can be used. Examples of the organic solvent 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.

[0230] The content of the organic solvent is preferably 5% by mass to 90% by mass, and more preferably 30% by mass to 70% by mass, based on the total amount of the color layer-forming composition.

[0231] As the colored layer forming composition, for example, commercially available paints such as nax Real series, nax Admira series, and nax Multi series (manufactured by Nippon Paint Co., Ltd.); Retan PG series (manufactured by Kansai Paint Co., Ltd.) may be used.

[0232] The method for preparing the colored layer-forming composition is not particularly limited, and for example, the colored layer-forming composition may be prepared by mixing each component such as a colorant. Furthermore, when the colored layer-forming composition contains a pigment as a colorant, from the viewpoint of further improving the uniform dispersibility and dispersion stability of the pigment, it is preferable to prepare the colored layer-forming composition by previously preparing a pigment dispersion containing a pigment and a dispersant and mixing other components into the pigment dispersion.

[0233] (Alignment Layer) The decorative film may have an alignment layer, which is used to more easily align the molecules of the cholesteric liquid crystal compound in the light-reflecting portion during the formation of the decorative film.

[0234] The alignment layer is provided, for example, by rubbing an organic compound (preferably a polymer), obliquely vapor-depositing an inorganic compound, forming a layer having microgrooves, etc. As the alignment layer, an alignment layer that generates an alignment function by applying an electric field, a magnetic field, or light irradiation is also known.

[0235] The thickness of the alignment layer is not particularly limited, but is preferably 0.01 μm to 10 μm.

[0236] Depending on the type of substrate and underlayer, the underlayer can serve as an alignment layer without providing a separate alignment layer. For example, the substrate can be directly subjected to an alignment treatment (e.g., rubbing treatment) to function as an alignment layer. An example of a substrate that can be directly oriented is a layer made of polyethylene terephthalate (PET), which may be subjected to rubbing treatment as described below.

[0237] As preferred examples, a rubbed alignment layer and a photo-alignment layer will be described below.

[0238] -Rubbing Treatment Alignment Layer- The rubbed alignment layer is formed, for example, by rubbing the surface of the base on which the liquid crystal composition is applied. The rubbing treatment can be carried out, for example, by rubbing the surface of a film containing a polymer as its main component with paper or cloth in a certain direction. General methods for rubbing treatment are described, for example, in "Liquid Crystal Handbook" (published by Maruzensha, October 30, 2000).

[0239] Examples of polymers for alignment layers that form films containing the above-mentioned polymers as the main component include methacrylate copolymers, styrene copolymers, polyolefins, polyvinyl alcohol, modified polyvinyl alcohol, poly(N-methylolacrylamide), polyesters, polyimides, vinyl acetate copolymers, carboxymethyl cellulose, and polycarbonates, as described in paragraph 0022 of JP-A-8-338913. The polymer for alignment layers may also be a silane coupling agent. The polymer for alignment layers is preferably a water-soluble polymer (e.g., poly(N-methylolacrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol, or modified polyvinyl alcohol), more preferably gelatin, polyvinyl alcohol, or modified polyvinyl alcohol, and particularly preferably polyvinyl alcohol or modified polyvinyl alcohol.

[0240] The rubbing density can be changed by the method described in "Liquid Crystal Handbook" (published by Maruzensha). The rubbing density (L) is quantified by the following formula (A): L = Nl (1 + 2πrn / 60v) Formula (A) In formula (A), 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 rotations of the roller (rpm; revolutions per minute), and v is the stage movement speed (per second).

[0241] Methods for increasing the rubbing density include increasing the number of rubbings, increasing the contact length of the rubbing roller, increasing the radius of the roller, increasing the number of roller rotations, and slowing the stage movement speed.Meanwhile, methods for decreasing the rubbing density include decreasing the number of rubbings, shortening the contact length of the rubbing roller, decreasing the radius of the roller, decreasing the number of roller rotations, and increasing the stage movement speed.In addition, the conditions for the rubbing treatment can be found in Japanese Patent No. 4052558.

[0242] -Photo-Alignment Layer- Examples of photo-alignment materials used in the photo-alignment layer formed by light irradiation include azo compounds described in JP-A Nos. 2006-285197, 2007-76839, 2007-138138, 2007-94071, 2007-121721, 2007-140465, 2007-156439, 2007-133184, 2009-109831, Japanese Patent Nos. 3883848 and 4151746; Examples of the photo-alignment material include aromatic ester compounds described in Japanese Patent Application Laid-Open No. 2002-229039, maleimide and / or alkenyl-substituted nadimide compounds having a photo-alignment unit described in Japanese Patent Application Laid-Open Nos. 2002-265541 and 2002-317013, photo-crosslinkable silane derivatives described in Japanese Patent Nos. 4205195 and 4205198, and photo-crosslinkable polyimides, polyamides, or esters described in Japanese Patent Application Laid-Open Nos. 2003-520878, 2004-529220, and Japanese Patent Application Laid-Open No. 4162850. Among these, the photo-alignment material is preferably an azo compound, photo-crosslinkable polyimide, polyamide, or ester.

[0243] A layer formed from a photo-alignment material is exposed to linearly polarized or unpolarized light to produce a photo-alignment layer.

[0244] In the present disclosure, "irradiation with linearly polarized light" refers to 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 the wavelength necessary for the photoreaction. The light used for photoirradiation is preferably light with a peak wavelength of 200 nm to 700 nm, and more preferably ultraviolet light with a peak wavelength of 400 nm or less.

[0245] Examples of light sources used for light irradiation include known light sources, such as lamps such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, and carbon arc lamps, various lasers (e.g., semiconductor lasers, helium-neon lasers, argon ion lasers, helium-cadmium lasers, and YAG lasers), light-emitting diodes, and cathode ray tubes.

[0246] Methods for obtaining linearly polarized light include a method using a polarizing plate (e.g., an iodine polarizing plate, a dichroic dye polarizing plate, or a wire grid polarizing plate), a method using a prism-based element (e.g., a Glan-Thompson prism) or a reflective polarizer utilizing the Brewster angle, and a method using light emitted from a polarized laser light source. Alternatively, a filter or a wavelength conversion element may be used to selectively irradiate only light of a required wavelength.

[0247] When the irradiated light is linearly polarized, the light may be irradiated from the top or bottom surface of the alignment layer in a direction perpendicular to or oblique to the surface of the alignment layer. The incident angle of the light varies depending on the photo-alignment material, but is preferably 0° to 90° (perpendicular) to the alignment layer, and more preferably 40° to 90°.

[0248] When non-polarized light is used, the non-polarized light is irradiated obliquely from the top or bottom surface of the alignment layer. The incident angle is preferably 10° to 80°, more preferably 20° to 60°, and even more preferably 30° to 50°. The irradiation time is preferably 1 minute to 60 minutes, and more preferably 1 minute to 10 minutes.

[0249] (Refractive index adjusting layer) The decorative film preferably further comprises a refractive index adjusting layer, more preferably between the reflective layer and the layer having the concave-convex structure. As the refractive index adjusting layer, a known refractive index adjusting layer can be used.

[0250] Examples of materials contained in the refractive index adjusting layer include resins, polymerizable compounds, metal salts, particles, etc. The method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples include a method using a resin with a predetermined refractive index alone, a method using a polymer and particles, etc. Examples of polymers include the resins already described as components of the layer having the concavo-convex structure B. Examples of polymerizable compounds include the polymerizable compounds and crosslinking agents already described as components of the reflective layer. Examples of particles include metal oxide particles and metal particles. The type of metal oxide particles is not particularly limited, and examples include known metal oxide particles. Metals in metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.

[0251] Specific examples of 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 Among these, at least one metal oxide particle selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferred, for example, from the viewpoint of ease of adjusting the refractive index.

[0252] Commercially available 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 (Nanouse OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.), and zirconium oxide particles (Nanouse OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

[0253] The average primary particle diameter of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, from the viewpoint of the transparency of the cured film. The average primary particle diameter of the particles is calculated by measuring the particle diameters of 200 random particles using an electron microscope and calculating the arithmetic mean of the measurement results. When the shape of the particles is not spherical, the particle diameter is determined as the longest side.

[0254] The particles may be used alone or in combination of two or more kinds.

[0255] 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 even more preferably 40% by mass to 85% by mass, relative to the total mass of the refractive index adjusting layer.

[0256] The difference between the refractive index of the refractive index adjusting layer and the refractive index of the cholesteric liquid crystal layer is preferably 0.10 or less, more preferably 0.05 or less, and particularly preferably 0.005 to 0.03.

[0257] The thickness of the refractive index adjusting layer is not particularly limited, but is preferably 1 μm or more, more preferably 10 μm or more, and even more preferably 20 μm or more. From the same viewpoint, the thickness of the refractive index adjusting layer is preferably 300 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less.

[0258] (Other Layers) The decorative film may have other layers in addition to the cholesteric liquid crystal layer, the substrate, the colored layer (optical mask layer), and the refractive index adjusting layer.

[0259] Other layers include layers known in decorative films, such as a protective layer, an adhesive layer, an easy-adhesion layer, an ultraviolet absorbing layer, a self-repairing layer, an antistatic layer, an antifouling layer, an electromagnetic wave-proof layer, and a conductive layer.

[0260] The other layers can be formed by known methods, such as applying a composition containing the components to be contained in the other layers (layer-forming composition) in the form of a layer and drying it.

[0261] <Molded body, article, display device> The molded body of the present disclosure is obtained by molding the decorative film of the present disclosure. The decorative film of the present disclosure can be used for various purposes, for example, by molding the decorative film and using it as a molded body.

[0262] An article of the present disclosure includes the decorative film of the present disclosure or the molded body of the present disclosure. A 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, and packaging containers, and the article is particularly suitable for use in electronic devices. Examples of electronic devices include displays, smartphones, mobile phones, and tablets, and the like. Among these, the article is particularly suitable for use in ordinary displays or displays in displays of smartphones, home appliances, audio products, computers, in-vehicle products, and the like. Furthermore, when the decorative film of the present disclosure is used in a display device such as a display or smartphone, a retardation film may be provided between the decorative film of the present disclosure and a display member such as a display. Known retardation films can be used.

[0263] The means for molding the laminate of the present disclosure to obtain a molded article is not particularly limited, and may be, for example, a known method such as three-dimensional molding, insert molding, etc. Furthermore, the means for applying the laminate of the present disclosure to an article is also not particularly limited, and a known method may be used as appropriate depending on the type of article.

[0264] Hereinafter, the present disclosure will be described more specifically with reference to examples, but the present disclosure is not limited to the following examples as long as it does not deviate from the gist of the disclosure.

[0265] Example 1 In Example 1, a liquid crystal film was produced using a manufacturing apparatus 100a configured as shown in FIG. 6. [Preparation of Substrate] A polyethylene terephthalate film (thickness 100 μm, width 330 mm, length 2000 m, Cosmoshine A4160, manufactured by Toyobo Co., Ltd.) having an easy-adhesion layer on one side was prepared as the substrate. [Preparation of Substrate with Optical Mask Layer] An optical mask layer was provided by a printing process on the surface of the substrate on which the easy-adhesion layer was formed. Specifically, using a wet electrophotographic printer (Indigo 6900, manufactured by Hewlett-Packard), the pattern shown in FIG. 8 (width 300 mm, length 980 mm) was repeatedly printed continuously for 1500 m in the longitudinal direction of the substrate on the surface on which the easy-adhesion layer was formed of the substrate. The pattern shown in Fig. 8 was formed by superimposing the first pattern shown in Fig. 9 formed with magenta ink, the second pattern shown in Fig. 10 formed with violet ink, the third pattern shown in Fig. 11 formed with yellow ink, the fourth pattern shown in Fig. 12 formed with orange ink, the fifth pattern shown in Fig. 13 formed with cyan ink, and the sixth pattern shown in Fig. 14 formed with black ink. The inks used were HP Indigo electroinks manufactured by Hewlett-Packard, with the standard four colors of magenta, yellow, cyan, and black, and the special color inks of violet and orange, IndiChrome. All of the first to sixth patterns were formed in a 210-line AM screen tone, and the printing area ratio per 300 µm square was controlled. The color intensity in Figures 8 to 14 indicates the printing area ratio per 300 μm square, with the darker areas in the figures indicating a higher printing area ratio per 300 μm square, and the darkest areas indicating a printing area ratio of 100%. Furthermore, the patterns were controlled so that the halftone dot areas of the first to sixth patterns would not overlap each other.

[0266] [Orientation Treatment] The surface of the substrate on which the easy-adhesion layer was not disposed was subjected to a rubbing treatment in a direction rotated 3° counterclockwise from the short side direction. The rubbing treatment conditions are as follows. <<Conditions>> Rubbing cloth: rayon cloth Pressure: 0.1 kgf Rotation speed: 1,000 rpm Transport speed: 10 m / min Number of times: 1

[0267] [Formation of Liquid Crystal Layer (Cholesteric Liquid Crystal Layer)] A liquid crystal composition 1 having the following composition was prepared. —Composition of Liquid Crystal Composition 1—

[0268] The following rod-shaped liquid crystal compound (1): 100 parts by mass

[0269] 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

[0270] Surfactant 1: the following compound

[0271] Surfactant 2: the following compound

[0272] Photosensitive chiral agent (1): the following compound

[0273] Next, the liquid crystal composition 1 prepared above was applied to the rubbed surface of the substrate using a die coater. The application was carried out at room temperature, adjusting the thickness after drying to about 2.5 μm to 4 μm, to form a coating film (liquid crystal material preparation step).

[0274] Next, 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 dose of 25 mJ / cm. ２ The cholesteric liquid crystal layer was irradiated with ultraviolet light (first light) having a wavelength of 365 nm (photoreaction step of the photosensitive chiral agent). Because an optical mask layer with a small difference in light transmittance between the dots and the gaps was used, the difference in the amount of photoreaction of the photosensitive chiral agent in the cholesteric liquid crystal layer between the dots and the gaps was small, and the difference in helical twisting power was also small.

[0275] The substrate on which the coating film of the photosensitive chiral agent had been photoreacted was heated for 1 minute in a hot air drying zone at 60°C. Next, in a low-oxygen atmosphere (oxygen concentration of 500 ppm or less) at room temperature, the heat-treated coating film was irradiated with light (second light) from a metal halide lamp (GS Yuasa Corporation MAL625NAL) from the cholesteric liquid crystal layer side to harden the cholesteric liquid crystal layer, thereby forming a decorative film (hardening step). The irradiation here was at an exposure dose of 800 mJ / cm. ２ The exposure was carried out under the following conditions: Then, the film was taken up by a take-up roller.

[0276] The substrate with the optical mask layer was examined as follows.

[0277] -Printed area ratio per 300 μm square- 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 μm square area, the magnification was adjusted so that the field of view was 400 μm to 2 mm. The area of ​​the printed pattern to be observed within the 300 μm square was calculated from the shape and size, and the area was calculated to be 90,000 μm. ２ The value obtained by dividing by this was taken as the printing area ratio per 300 μm square.

[0278] -Light Transmittance- The transmittance per 10 μmφ of the wavelength of light irradiated in the step of photoreacting the photosensitive chiral agent was measured using a differential microscopic ultraviolet-visible-near-infrared spectrophotometer (MSV-5500, JASCO Corporation).

[0279] -Light transmittance T of halftone dots Ｄ , the light transmittance T of the gap Ａ - Using a differential microscopic ultraviolet-visible-near-infrared spectrophotometer (MSV-5500, JASCO Corporation), the light transmittance per 10 μm diameter within the halftone dot was measured, and T Ｄ Similarly, the light transmittance per 10 μm diameter in the gap was measured, and T Ａ In the optical mask layer, the minimum value of the light transmittance per 10 μmφ was set to T ｍｉｎ , the maximum value is T ＭＡＸ This was the case.

[0280] The decorative film was tested as follows.

[0281] - Cholesteric pitch - A section of the decorative film was prepared using a microtome (RX-860, Yamato Koki Kogyo Co., Ltd.), and the cross section of the cholesteric liquid crystal layer of the section was observed and measured using a scanning electron microscope (SU3800, Hitachi High-Tech Corporation). The difference between the maximum and minimum cholesteric pitches in the entire cholesteric liquid crystal layer was measured as ΔP. ａｌｌ - Pitch difference within the grating ΔP Ｓ - For the cholesteric pitch maximum points arranged at equal intervals, the smallest square among the squares with the maximum points as vertices was taken as the unit lattice. The halftone dotted area was divided into unit lattices, and the difference between the maximum value and the minimum value of the pitch within the unit lattice was taken as the intra-lattice pitch difference ΔP Ｓ The smallest ΔP in the halftone dot area Ｓ For a unit lattice with a large pitch difference, ΔP Ｓ（ＭＡＸ） It was decided.

[0282] As a result of the verification, the prepared substrate with an optical mask layer had an AM screen-style halftone dot area with a screen ruling of 210 lines using yellow ink, and a semi-transparent solid area of ​​300 μm square with a print area ratio of 100% and a light transmittance of 26.4% at a position overlapping the halftone dot area, and the semi-transparent solid area included a pattern using magenta ink and a pattern using violet ink, and thus contained three or more patterns. Ｄ , the light transmittance T of the gap between the halftone dots Ａ , the light transmittance T at the location of the optical mask layer with the lowest light transmittance ｍｉｎ , the light transmittance T at the highest point ＭＡＸ Let (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ ) was 0.28 or less in all regions. Ａ 49% and T Ｄ 27% and T Ａ -T Ｄ The region included areas where the ratio was 22%.

[0283] The resulting decorative film has a pitch difference ΔPａｌｌ is 258 nm, and the maximum value of the pitch difference within the grating is ΔP Ｓ（ＭＡＸ） is 30 nm, and ΔP Ｓ（ＭＡＸ） / ΔP ａｌｌ =0.12. Furthermore, the maximum value of the amount of change in cholesteric pitch per 100 μm of in-plane distance (maximum cholesteric pitch change) was 172 nm.

[0284] (Evaluation 1) In order to eliminate the influence of the optical mask layer, the cholesteric liquid crystal layer of the decorative film obtained in Example 1 above was transferred onto a PET film (A4160, Toyobo Co., Ltd.) via an optical adhesive sheet (G25, Nichiei Shinka Co., Ltd.) to prepare a decorative film for evaluation, and the following evaluations were performed.

[0285] -Reflection saturation c ＊ - The reflection spectrum of the decorative film was measured with 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), with a piece of black drawing paper with a 1 mm square hole set as the measurement window. The reflection spectrum is an integrated reflection spectrum measured with a spectrophotometer equipped with an integrating sphere device through a 1 mm square measurement window, and also shows the relative reflection spectrum with respect to a white standard plate measured through a similar 1 mm square measurement window. The chromaticity L ＊ a ＊ b ＊ Calculate the chromaticity L ＊ a ＊ b ＊ From the following formula, the reflection saturation c ＊ The chromaticity of the reflection was evaluated according to the standard. As a decorative film, "A" or "B" is preferable because the decorative effect is easily visible, and "A" is particularly preferable. ＊ = {(a ＊ ) ２ +(b ＊ ) ２} １／２ <Standard> A: 50≦c ＊ B: 40≦c ＊ <50 C:c ＊ <40

[0286] - Polychromaticity of Decorative Film - The reflection central wavelength of the decorative film was measured as follows. The reflection spectrum was measured with the surface of the decorative film on which the cholesteric liquid crystal layer was formed as the incident surface. The measurement was performed using a spectrophotometer (V-670, JASCO Corporation) and a large integrating sphere device (ILV-471), with a piece of black drawing paper with a 1 mm square hole set as the measurement window. The reflectance was then calculated from the reflection spectrum. The reflectance is the integrated reflectance measured with a spectrophotometer equipped with an integrating sphere device through a 1 mm square measurement window, and indicates the relative reflectance with respect to a white standard plate also measured through a 1 mm square measurement window. Using the obtained reflection spectrum and reflectance, the maximum value R of the integrated reflectance was calculated. ｍａｘ (%) and half-value reflectance R １／２ The wavelengths showing a difference (%) were averaged, and the average wavelength was taken as the central reflection wavelength. The entire decorative film was evaluated, and the polychromaticity of the decorative film was evaluated according to the following criteria. "A" is preferable as a decorative film. <Criteria> A: There are three or more regions with different central reflection wavelengths. B: There are less than three regions with different central reflection wavelengths.

[0287] -Graininess- The resulting decorative film was observed visually in a room using a fluorescent lamp (straight tube, daylight white, manufactured by Panasonic Corporation) and with an optical microscope (Eclipse LV100N POL, manufactured by Nikon Corporation), and the graininess was evaluated according to the following criteria. For reflective decorative films, "AA" to "D" are preferred, "AA" to "C" are more preferred, "AA" to "B" are even more preferred, "AA" or "A" are particularly preferred, and "AA" is most preferred. <Criteria> AA: No graininess is visible when observed visually from a point 5 cm away from the decorative film, and no halftone-like hue change is observed when observed with an optical microscope. A: No graininess is visible when observed visually from a point 5 cm away from the decorative film, and a halftone-like hue change is observed when observed with an optical microscope. B: No granularity is visible when visually observed from a point 10 cm away from the decorative film, but granularity is visible when visually observed from a point 5 cm away. C: No granularity is visible when visually observed from a point 20 cm away from the decorative film, but granularity is visible when visually observed from a point 10 cm away. D: No granularity is visible when visually observed from a point 30 cm away from the decorative film, but granularity is visible when visually observed from a point 20 cm away. E: Granularity is visible when visually observed from a point 30 cm away from the decorative film.

[0288] - Glossiness - The resulting decorative film was measured for its diffuse reflectance spectrum using a spectrophotometer (V-770, JASCO Corporation) and an absolute reflectance measurement unit (ARMV-919, JASCO Corporation) when light was incident at an angle of -15° relative to the normal to the decorative film surface and reflected light was received at an angle of +25°. Furthermore, the specular reflectance spectrum was also measured when light was incident at -5° and received at +5°. The measurement wavelength range was 380 nm to 780 nm. When the average value of the reflectance in the wavelength range of 380 nm to 780 nm is taken as the reflection intensity RI, the reflection intensity RI of the specular reflection is Ｓ The reflection intensity RI of the diffuse reflection Ｄ Contrast RI Ｄ / RI ＳThe glossiness was evaluated according to the following criteria, since the stronger the reflection intensity in the diffusion direction, the lower the glossiness. As a reflective decorative film, "A" to "C" are preferred, "A" or "B" are more preferred, and "A" is particularly preferred. <Criteria> A: RI Ｄ / RI Ｓ ≦0.005 B:0.005<RI Ｄ / RI Ｓ ≦0.020 C:0.020<RI Ｄ / RI Ｓ ≦0.050 D:0.050<RI Ｄ / RI Ｓ

[0289] - Complementary color saturation c ＊ - A laminate was prepared by overlaying the decorative film on a standard white plate, and the surface of the laminate on the decorative film side was used as the incident surface. Using a spectrophotometer (V-770, JASCO Corporation) and an absolute reflectance measurement unit (ARMV-919, JASCO Corporation), the complementary color reflection spectrum was measured at an angle of incidence of -5° and receiving light of +15° relative to the normal to the decorative film surface. Only the standard white plate was measured at the same angle, and the relative reflectance to the standard white plate was calculated from the relative reflectance. The standard white plate was then compared to the (L ＊ , a ＊ , b ＊ ) = (100,0,0) ＊ a ＊ b ＊ and relative saturation c ＊ The higher the complementary color saturation, the more vivid the decorative effect can be visually recognized, which is preferable for a decorative film.

[0290] As a result of the above, in Example 1, a multicolored decorative film having high reflective saturation, little visible graininess, and a glossy appearance could be efficiently produced.

[0291] Comparative Example 1 A decorative film was produced using the same procedures as in Example 1, except that in the process of providing an optical mask layer on a substrate, an inkjet printer (Jet Press 540WV, Fujifilm Corporation) was used, the pattern was formed in an FM screen style rather than an AM screen style, and the print area ratio and light transmittance were controlled by the dot density. Verification and Evaluation 1 were then performed. The results of the verification and evaluation are summarized in Table 1. The prepared optical mask layer had larger dots in the medium density region, where the dots were connected to each other. The resulting decorative film had insufficient cholesteric pitch uniformity in the larger dot regions of the optical mask layer, resulting in dot-like hue changes and non-uniform reflected color. As a result, the resulting decorative film had low saturation, easily visible graininess, and a weak gloss. The reason for the decrease in gloss is thought to be that when the cholesteric pitch is non-uniform, the orientation of the cholesteric liquid crystal becomes tilted depending on the increase or decrease in pitch, and light is reflected in a diffuse direction compared to the intended horizontal orientation.

[0292] Comparative Example 2 A decorative film was produced using the same procedures as in Example 1, except that in the process of providing an optical mask layer on the substrate, a laser photoplotter type printer was used, a pattern was formed on an A3-sized platemaking film (GPR-7S) using a 350-line AM screen tone, and then the pattern-forming surface of the platemaking film was attached to the substrate, and verification and evaluation 1 were then carried out. The results of the verification and evaluation are summarized in Table 1. As a result, a multicolored decorative film with high reflective saturation, little visible graininess, and a glossy appearance could be produced; however, production efficiency was poor because it was necessary to attach the number of A3-sized platemaking films corresponding to the desired length to the substrate.

[0293] (Comparative Example 3) A decorative film was produced in the same manner as in Example 1, except that the first pattern was the pattern without the dotted areas of Figure 15, the second pattern was the pattern of Figure 16, the third to sixth patterns were not formed, and the content of the photosensitive chiral agent was 5.5 parts by mass, and verification and evaluation 1 were also carried out. The results of the verification and evaluation are summarized in Table 1. The resulting decorative film had a limited number of colors because hue control was not performed by the dotted areas of the optical mask layer.

[0294] Comparative Example 4: The first pattern was the pattern without the halftone dotted area shown in FIG. 17, the second pattern was the pattern shown in FIG. 16, the third to sixth patterns were not formed, and the exposure amount of the first light was 13 mJ / cm ２ A decorative film was produced in the same manner as in Example 1, except that the above-mentioned conditions were met, and verification and evaluation 1 were then carried out. The results of the verification and evaluation are summarized in Table 1. The resulting decorative film had a limited number of colors because no hue control was performed using the halftone dotted areas of the optical mask layer.

[0295] (Comparative Example 5) A decorative film was produced using the same procedure as in Example 1, except that the second to sixth patterns were not formed, and further verification and evaluation 1 were carried out. 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 dotted and gap portions, and the resulting decorative film exhibited a dot-like hue change. As a result, the resulting decorative film had low saturation, a readily visible graininess, and a weak glossiness.

[0296] Comparative Example 6: The second pattern was as shown in FIG. 23, the third to sixth patterns were not formed, and the exposure amount of the first light was 13 mJ / cm ２ A decorative film was produced in the same manner as in Example 1, except that the second pattern was changed to the second pattern, and verification and evaluation 1 were carried out. The results of the verification and evaluation are summarized in Table 1. The prepared optical mask layer had a light transmittance T Ａ Since the first pattern had a small control range for the amount of light transmitted, the amount of change in hue of the cholesteric liquid crystal layer was small. As a result, the number of colors of the resulting decorative film was limited.

[0297] (Example 2) A decorative film was produced in the same manner as in Example 1, except that the first pattern was a 10 cm square pattern having a halftone dotted area as shown in (1) of FIG. 18A, the second pattern was a 10 cm square pattern having a semi-transparent solid area as shown in (2) of FIG. 18B, and the third to sixth patterns were not formed. Verification and evaluation 1 were then carried out. The results of the verification and evaluation are summarized in Table 1. The prepared optical mask layer was (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ ) = 0.52, and the region where (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ ) = 0.99. Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ ) = 0.52, the saturation was high, and a multicolored decorative film was efficiently obtained. Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ ) = 0.99, this is presumably because the dots in the overlapping areas of the first and second patterns are connected to form large dots, as shown in (3) of Figure 18C.

[0298] (Example 3) A decorative film was produced in the same manner as in Example 2, except that the first pattern was a 10 cm square pattern having a halftone dotted area as shown in (4) of FIG. 19A, and the second pattern was a 10 cm square pattern having a semi-transparent solid area as shown in (5) of FIG. 19B, and further verification and evaluation 1 were carried out. The results of the verification and evaluation are summarized in Table 1. The prepared optical mask layer was (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ ) = 0.52, and the region where (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ ) = 0.99. Ａ -T Ｄ) / (T ＭＡＸ -T ｍｉｎ ) = 0.52, the saturation was high, and a multicolored decorative film was efficiently obtained. Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ Graininess was visually recognized in the region where the transmittance difference between the halftone dots and the gaps was 0.99. This is because there was a region where the transmittance difference between the halftone dots and the gaps was large.

[0299] (Example 4) A decorative film was produced in the same manner as in Example 3, except that the first pattern was a 10 cm square pattern having a halftone dot area as shown in (7) of FIG. 20A, the second pattern was a 10 cm square pattern having a semi-transparent solid area as shown in (8) of FIG. 20B, and the entire halftone dot area of ​​the first pattern overlapped with the semi-transparent solid area of ​​the second pattern to form an optical mask layer. Verification and evaluation 1 were also carried out. The results of the verification and evaluation are summarized in Table 1. The prepared optical mask layer had a transmittance difference of 0.01 mm (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ ) = 0.52 for all halftone dotted areas. Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ As a result, a multicolored decorative film with high saturation and slightly reduced graininess was efficiently obtained.

[0300] (Example 5) A decorative film was produced in the same manner as in Example 4, except that the first pattern was a 10 cm square pattern having a halftone dotted area as shown in (10) of FIG. 21A, the second pattern was a 10 cm square pattern having a semi-transparent solid area as shown in (11) of FIG. 21B, and the optical mask layer contained three patterns. Verification and evaluation 1 were also carried out. The results of the verification and evaluation are summarized in Table 1. The prepared optical mask layer was (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎAs a result, a multicolor decorative film having a region where the saturation was even higher than in Example 4 and where the visibility of graininess was slightly suppressed was efficiently obtained.

[0301] (Example 6) A decorative film was produced in the same manner as in Example 5, except that the first pattern was a 10 cm square pattern having a halftone dotted area as shown in (14) of Figure 22A, the second pattern was a 10 cm square pattern having a semi-translucent solid area as shown in (15) of Figure 22B, and the third pattern was a 10 cm square pattern having a halftone dotted area as shown in (16) of Figure 22C, and verification and evaluation 1 were also carried out. The results of the verification and evaluation are summarized in Table 1. As a result, a multicolored decorative film with high saturation and slightly reduced visibility of graininess was efficiently produced.

[0302]

[0303] As shown in Table 1, in Examples 1 to 6, multicolored decorative films with high saturation could be produced efficiently.

[0304] (Evaluation 2) In order to eliminate the influence of the optical mask layer, the cholesteric liquid crystal layer of the decorative film obtained in Example 1 was transferred onto a PET film (A4160, Toyobo Co., Ltd.) via an optical adhesive sheet (G25, Nichiei Shinka Co., Ltd.) to prepare a decorative film for evaluation, and the following Evaluation 2 was performed.

[0305] - Boundary Sharpness - For an area of ​​the decorative film where the hue changes in the in-plane direction, the reflection spectrum was measured at two points 100 μm apart using a differential microscopic ultraviolet-visible-near-infrared spectrophotometer (MSV-5500, JASCO Corporation), and the respective reflection central wavelengths were calculated. The greater the change in reflection central wavelength per 100 μm in-plane distance, the sharper the color boundary is visually perceived, and the more distinct the design is perceived. The boundary sharpness was evaluated according to the following criteria. For a decorative film that achieves a distinct design, an "A" rating is preferable. <Criteria> A: The change in reflection central wavelength per 100 μm in-plane distance is 20 nm or more B: The change in reflection central wavelength per 100 μm in-plane distance is less than 20 nm

[0306] -Color range- The reflection center wavelength of the decorative film is the reflection saturation c ＊ The same measurement as in the evaluation of 1) was carried out, and the shortest and longest reflection central wavelengths in the decorative film were calculated. The color range was evaluated from the difference Δλ in the reflection central wavelengths according to the following criteria. The decorative film is preferably rated "A". <Criteria> A: Δλ≧110 nm B: Δλ<110 nm

[0307] The results of the verification and evaluation are summarized in Table 2.

[0308] Example 7 A decorative film was produced using the same procedure as in Example 1, except that in the process of photoreacting the photosensitive chiral agent, ground glass was placed between the light source and the optical mask layer, the first light was diffused, and heating was performed at 85°C between the process of photoreacting the photosensitive chiral agent and the curing process. 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 μm in-plane distance. In Example 7, a decorative film with high color saturation, gloss, and reduced graininess was efficiently produced, but the resulting decorative film had blurred pattern boundaries. A more gradual change in the cholesteric pitch in the in-plane direction suppresses tilt alignment, leading to improved color saturation, but at the same time, the color change in the in-plane direction is also more gradual, resulting in reduced boundary sharpness.

[0309] (Example 8) The first light was applied at an exposure dose of 75 mJ / cm ２ A decorative film was produced in the same manner as in Example 1, except that the conditions were changed to the above, and further verification and evaluation were carried out. The results of the verification and evaluation are summarized in Table 2. The formed cholesteric liquid crystal layer had a maximum intra-lattice pitch difference of 75 nm. As a result, although a multicolored decorative film with high saturation could be efficiently produced, the resulting decorative film had a weak glossiness and was easily visually perceived as grainy. The larger the intra-lattice pitch difference, the greater the angle of the cholesteric liquid crystal orientation, resulting in a tilted orientation and a worsening of the glossiness and graininess.

[0310] (Example 9) The first light was applied at an exposure dose of 10 mJ / cm ２A decorative film was produced using the same procedures as in Example 1, except that the conditions were changed to the above, and further verification and evaluation were carried out. The results of the verification and evaluation are summarized in Table 2. The formed cholesteric liquid crystal layer had a difference between the maximum and minimum values ​​of cholesteric pitch of 65 nm. As a result, although a multicolored decorative film with high saturation, gloss, and reduced graininess could be efficiently produced, the resulting decorative film had a narrow color range, with only a color change from blue to green. The smaller the difference between the maximum and minimum values ​​of cholesteric pitch in the cholesteric liquid crystal layer, the narrower the achievable color range.

[0311] Example 10 The preparation of a substrate, the preparation of a substrate with an optical mask layer, the alignment treatment, and the formation of a liquid crystal layer were carried out in the same manner as in Example 1, except that the following liquid crystal composition 2 was used as the liquid crystal composition, and light (second light) from a metal halide lamp (GS Yuasa Corporation MAL625NAL) was irradiated through a short wavelength cut filter (a glass substrate on which a dielectric multilayer film was vapor-deposited, with a transmittance of 0.1% or less in the wavelength range of 200 nm to 340 nm) in the curing step.

[0312] —Composition of Liquid Crystal Composition 2— Rod-like liquid crystal compound (1): 100 parts by mass Photopolymerization initiator (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.): 1 part by mass Surfactant 1: 0.02 parts by mass Surfactant 2: 0.055 parts by mass Organic solvent 1 (methyl ethyl ketone): 187.4 parts by mass Organic solvent 2 (furfuryl alcohol): 35.7 parts by mass Photosensitive chiral agent (2) (compound having the following structure): 8.3 parts by mass

[0313] Photosensitive chiral agent (2): the following compound

[0314]

[0315] The obtained liquid crystal layer was further subjected to an alignment treatment and a second liquid crystal layer was laminated thereon using a manufacturing apparatus 100a having a configuration as shown in FIG.

[0316] [Alignment Treatment] The liquid crystal layer surface of the decorative film was rubbed in a direction rotated 3° counterclockwise from the short side direction. The rubbing conditions are as follows: <<Conditions>> Rubbing cloth: rayon cloth Pressure: 0.1 kgf Rotation speed: 1,000 rpm Transport speed: 10 m / min Number of times: 1

[0317] [Formation of Liquid Crystal Layer (Cholesteric Liquid Crystal Layer)] Liquid crystal composition 3 having the following composition was prepared.

[0318] —Composition of Liquid Crystal Composition 3— Rod-like 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: 0.05 parts by mass Surfactant 2: 0.055 parts by mass Organic solvent 1 (methyl ethyl ketone): 212.4 parts by mass Organic solvent 2 (furfuryl alcohol): 21 parts by mass Photosensitive chiral agent (3) (compound having the following structure): 13.5 parts by mass

[0319] Photosensitive chiral agent (3): the following compound

[0320] Next, the liquid crystal composition 3 prepared above was applied to the rubbed surface of the substrate using a die coater. The application was carried out at room temperature, adjusting the thickness after drying to about 2.5 to 4 μm, to form a coating film (liquid crystal material preparation step).

[0321] Next, 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 dose of 330 mJ / cm. ２ The cholesteric liquid crystal layer was irradiated with ultraviolet light (first light) having a wavelength of 365 nm (photoreaction step of the photosensitive chiral agent). Because an optical mask layer with a small difference in light transmittance between the dots and the gaps was used, the difference in the amount of photoreaction of the photosensitive chiral agent in the cholesteric liquid crystal layer between the dots and the gaps was small, and the difference in helical twisting power was also small.

[0322] The substrate on which the coating film of the photosensitive chiral agent had been photoreacted was heated for 1 minute in a hot air drying zone at 60°C. Next, in a low-oxygen atmosphere (oxygen concentration 500 ppm or less), the coating film was irradiated with light (second light) from a metal halide lamp (GS Yuasa Corporation MAL625NAL) from the cholesteric liquid crystal layer side at 75°C to harden the cholesteric liquid crystal layer, thereby forming a decorative film (hardening step). The irradiation here was at an exposure dose of 600 mJ / cm. ２ The exposure was carried out under the following conditions: 1. The film was then wound up on a take-up roller. The resulting decorative film was then inspected and evaluated. The results of the inspection and evaluation are summarized in Table 2. As a result, a multicolored decorative film with high saturation, gloss, and reduced graininess was efficiently produced. Furthermore, the resulting decorative film was composed of two cholesteric liquid crystal layers: one with a right-handed helix and one with a left-handed helix. The hues of the two cholesteric liquid crystal layers were changed using the same optical mask layer, resulting in a decorative film in which the patterns of the two cholesteric liquid crystal layers were aligned with high positional precision.

[0323]

[0324] As shown in Table 2, in Examples 7 to 10, multicolored decorative films with high saturation could be produced efficiently.

[0325] (Example 11) After peeling off the protective film on one side of an adhesive sheet (G25, thickness 25 μm, manufactured by Nichiei Shinka Co., Ltd.) having a protective film on both sides of the adhesive layer, a polyethylene terephthalate film (thickness 50 μm, width 330 mm, length 2000 m, Cosmoshine A4360, manufactured by Toyobo Co., Ltd.) containing an easy-adhesion layer on both sides was attached and laminated (temperature: 30 ° C., linear pressure 100 N / cm, conveying speed 0.1 m / min). As a result, a transfer substrate having a protective film, an adhesive layer, and a transfer destination substrate in this order was obtained. After peeling off the protective film from the transfer substrate, an adhesive layer was attached to the liquid crystal layer of the decorative film produced in Example 10 and laminated (temperature: 30 ° C., linear pressure 100 N / cm, conveying speed 0.1 m / min). As a result, a decorative film 2 having a transfer destination substrate, an adhesive layer, a liquid crystal layer, a substrate, and an optical mask layer in this order was obtained. The optical mask layer and the substrate of the decorative film 2 were peeled off to obtain a decorative film 3 having the transfer destination substrate, adhesive layer, and liquid crystal layer in this order.

[0326] <Preparation of Black Pigment Dispersion> Carbon black, a dispersant, a polymer, and a solvent were mixed to obtain the following black pigment dispersion composition, and the mixture was milled using a triple roll mill and a bead mill. The average particle size of the carbon black measured using a Microtrac FRA (Honeywell) was 163 nm.

[0327] -Composition of black pigment dispersion- Resin-coated carbon black prepared according to the description in paragraphs 0036 to 0042 of Japanese Patent No. 5,320,652: 20.0% by mass Dispersant 1 (structure below): 1.0% by mass Polymer (random copolymer of benzyl methacrylate / methacrylic acid = 72 / 28 (molar ratio), weight average molecular weight: 30,000): 6.0% by mass Propylene glycol monomethyl ether acetate: 73.0% by mass

[0328]

[0329] <Composition of Coating Liquid 1 for Forming Colored Layer> Black pigment dispersion: 30 parts by mass Polymerizable compound 1: Urethane acrylate oligomer, CN-996NS, manufactured by Sartomer Japan Co., Ltd.: 25 parts by mass Binder resin 3: Urethane-modified acrylic polymer (containing polyol) 35% by mass ethyl acetate / ethyl methyl ketone / isopropyl alcohol solution: 25 parts by mass Photopolymerization initiator (Irgacure 2959, manufactured by BASF Corporation): 1.0 part by mass Methyl ethyl ketone: 19 parts by mass

[0330] <Formation of Colored Layer> The colored layer forming coating solution 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 surface of the colored layer of the formed laminate was exposed to an exposure dose of 500 mJ / cm ２ The entire surface was exposed to i-line radiation to form a colored layer 1 (black colored layer) having a thickness of 4 μm, thereby forming a decorative film 4. The decorative film 4 has a transfer destination substrate, an adhesive layer, a liquid crystal layer, and a colored layer in this order.

[0331] <Preparation of decorative film for molding> After peeling off the protective film on one side of an adhesive sheet (G25, thickness 25 μm, manufactured by Nichiei Shinka Co., Ltd.), an adhesive layer was attached to the transfer substrate surface of the decorative film 4, thereby obtaining a decorative film for molding having, in this order, the protective film, adhesive layer, transfer substrate, adhesive layer, liquid crystal layer, and colored layer.

[0332] <Preparation of Molded Body> The decorative film for molding was cut into a sheet having a width of 7.5 cm and a length of 17 cm. After peeling off the protective film, the adhesive layer was attached to a glass panel having a thickness of 2 mm, a width of 7.5 cm, and a length of 17 cm to prepare a molded body. When viewed from the glass panel side, the obtained molded body had high reflective saturation, little graininess was visible, and a glossy, multicolored pattern was visible.

[0333] The disclosures of Japanese Patent Application No. 2022-054572, filed March 29, 2022, and Japanese Patent Application No. 2022-093029, filed June 8, 2022, are incorporated herein by reference in their entirety. All publications, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual publication, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. a step of printing, on a substrate, a first pattern having an AM screen tone with a screen ruling of 250 lines or less and a dotted area with a dot area ratio of 0.5% or more and less than 99.5%, using a first ink; and printing, on a substrate, a second pattern having 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%, using a second ink, in a position overlapping with the dotted area of ​​the first pattern, thereby providing an optical mask layer on the substrate; providing a liquid crystal layer containing a liquid crystal compound and a photosensitive chiral agent on the opposite side of the substrate from the optical mask layer; and a step of irradiating the liquid crystal layer with light through the optical mask layer to photoreact the photosensitive chiral agent. A method for manufacturing a laminate.

2. 2. A method for producing a laminate as described in claim 1, wherein the entire dotted area of ​​the first pattern overlaps with the semi-translucent solid area of ​​the second pattern, or the second pattern further has an area with a printing area ratio of less than 0.5%, and the entire dotted area of ​​the first pattern overlaps with the semi-translucent solid area of ​​the second pattern and an area of ​​the second pattern with a printing area ratio of less than 0.5%.

3. 3. The method for producing a laminate according to claim 1, wherein an entire area of ​​the halftone dot region of the first pattern overlaps with a semi-translucent solid region of the second pattern.

4. the second pattern further comprises a halftone dot region; the first pattern further has at least one of a semi-translucent solid region and a region having a print area ratio of less than 0.5%, and the entire area of ​​the halftone dot region of the second pattern overlaps with at least one of the semi-translucent solid region and the region having a print area ratio of less than 0.5% of the first pattern; The method for producing a laminate according to claim 1 or 2, wherein the second pattern is an AM screen pattern having a screen ruling of 250 lines or less.

5. The step of providing an optical mask layer on the substrate further includes printing a pattern on the substrate that is different from the first pattern and the second pattern; the pattern different from the first pattern and the second pattern has at least one region of a semi-translucent solid region and a region having a printing area ratio of less than 0.5%, 5. The method for producing a laminate according to claim 4, wherein at least one of the semi-transparent solid areas and areas with a printing area ratio of less than 0.5% of a pattern different from the first pattern and the second pattern overlaps with the entire area of ​​the dotted area of ​​the first pattern and the entire area of ​​the dotted area of ​​the second pattern.

6. The method for producing a laminate according to claim 5 , wherein the pattern different from the first pattern and the second pattern further has a halftone dotted area and is an AM screen pattern having a screen ruling of 250 lines or less.

7. The method for producing a laminate according to claim 6 , wherein the pattern different from the first pattern and the second pattern is a plurality of patterns, and the halftone dot areas of the plurality of patterns do not overlap each other.

8. A method for producing a decorative film, comprising the method for producing a laminate according to claim 1 or 2.

9. The optical mask layer includes, in this order, an optical mask layer, a substrate, and a cholesteric liquid crystal layer including a liquid crystal compound and a photosensitive chiral agent; the optical mask layer has an AM screen tone with a screen ruling of 250 lines or less and a halftone dot-painted region with a halftone dot area ratio of 0.5% or more and less than 99.5%, In the halftone dot region, the light transmittance of the halftone dots is T Ｄ , the light transmittance of the gap between the halftone dots is T Ａ When 5%≦T Ａ < 95%; and The light transmittance at the portion of the optical mask layer having the lowest light transmittance is T ｍｉｎ , the light transmittance T at the point with the highest light transmittance ＭＡＸ When this is done, (T Ａ -T Ｄ ) / (T ＭＡＸ-T ｍｉｎ ) ≦0.95 Laminate.

10. The optical mask layer includes, in this order, an optical mask layer, a substrate, and a cholesteric liquid crystal layer including a liquid crystal compound and a photosensitive chiral agent; the optical mask layer has an AM screen tone with a screen ruling of 250 lines or less and a halftone dot-painted region with a halftone dot area ratio of 0.5% or more and less than 99.5%, In the halftone dot region, the light transmittance of the halftone dots is T Ｄ , the light transmittance of the gap between the halftone dots is T Ａ When 5%≦T Ａ < 95% and 1% ≦ T Ａ -T Ｄ <80.75% Laminate.

11. For all halftone dot areas of the optical mask layer (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ 11. The laminate according to claim 10, wherein the lamination satisfies 0.

95.

12. For all halftone dot areas of the optical mask layer (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ 12. The laminate according to claim 10 or 11, wherein the ratio of the cross-sectional area to the cross-sectional area of ​​the laminate satisfies 0.

50.

13. a substrate and an optical mask layer; the optical mask layer has an AM screen tone with a screen ruling of 250 lines or less and a halftone dot-painted region with a halftone dot area ratio of 0.5% or more and less than 99.5%, In the halftone dot region, the light transmittance of the halftone dots is T Ｄ , the light transmittance of the gap between the halftone dots is T Ａ When 5%≦T Ａ < 95%; and The light transmittance at the portion of the optical mask layer having the lowest light transmittance is T ｍｉｎ , the light transmittance T at the point where the light transmittance is the highest ＭＡＸ When (T Ａ -T Ｄ ) / (T ＭＡＸ -T ｍｉｎ ) ≦0.95 Substrate with optical mask for manufacturing decorative film.

14. a substrate and an optical mask layer; the optical mask layer has an AM screen tone with a screen ruling of 250 lines or less and a halftone dot-painted region with a halftone dot area ratio of 0.5% or more and less than 99.5%, In the halftone dot region, the light transmittance of the halftone dots is T Ｄ , the light transmittance of the gap between the halftone dots is T Ａ When 5%≦T Ａ < 95% and 1% ≦ T Ａ -T Ｄ <80.75% Substrate with optical mask for manufacturing decorative film.

15. A decorative film having a cholesteric liquid crystal layer, The cholesteric liquid crystal layer is a dot region in which the cholesteric pitch maximum points are arranged in a dot pattern; The halftone dot region is divided into unit lattices, which are rectangular units with the smallest area and whose vertices are the maximum points of the cholesteric pitch, and the difference between the maximum and minimum values ​​of the cholesteric pitch in each unit lattice is defined as the intra-lattice pitch difference ΔP Ｓ When Said ΔP Ｓ The maximum value of ΔP Ｓ（ＭＡＸ） is the difference between the maximum and minimum values ​​of the cholesteric pitch in the entire cholesteric liquid crystal layer, ΔP ａｌｌ For 0 < ΔP Ｓ（ＭＡ Ｘ） / ΔP ａｌｌ ≦0.4 Decorative film.

16. The decorative film according to claim 15 , wherein the cholesteric liquid crystal layer has a region in which a cholesteric pitch change per 100 μm in-plane direction is 13 nm or more.

17. In the cholesteric liquid crystal layer, the ΔP Ｓ（ＭＡＸ） The decorative film according to claim 15 or 16, wherein the average particle diameter is less than 33 nm.

18. A decorative film having a cholesteric liquid crystal layer, The cholesteric liquid crystal layer is a dot region in which the cholesteric pitch maximum points are arranged in a dot pattern; The halftone dot region is divided into unit lattices, which are rectangular units with the smallest area and whose vertices are the maximum points of the cholesteric pitch, and the difference between the maximum and minimum values ​​of the cholesteric pitch in each unit lattice is defined as the intra-lattice pitch difference ΔP Ｓ In the cholesteric liquid crystal layer, the ΔP Ｓ The maximum value of ΔP Ｓ（ＭＡＸ） is less than 33 nm Decorative film.

19. In the cholesteric liquid crystal layer, the difference ΔP between the maximum value and the minimum value of the cholesteric pitch in the entire cholesteric liquid crystal layer ａｌｌ The decorative film according to claim 15 or 18, wherein the thickness of the film is 70 nm or more.

20. A molded article obtained by molding the decorative film according to claim 15.

21. A molded body obtained by molding the decorative film described in claim 18.

22. An article comprising the decorative film according to claim 15 or claim 18 or the molded body according to claim 20 or claim 21.

23. 23. The article of claim 22 which is an electronic device.

24. A display device comprising the article according to claim 23.