Image recording material, method for manufacturing image recording material, and decorative molded body

Abstract

An image recording object and an application thereof, the image recording object including a substrate and an ink jet image disposed on the substrate, the ink jet image including a cholesteric liquid crystal layer, the cholesteric liquid crystal layer having a stripe pattern of bright portions and dark portions observed by a scanning electron microscope in a cross section in a thickness direction of the ink jet image, at least a part of the line representing the bright part or the dark part is a wavy line.

Description

Technical Field

[0001] The present invention relates to an image recorded article, a method for producing the image recorded article, and a decorative molded body. Background Art

[0002] In recent years, an image recording method using ink containing a liquid crystal compound has been proposed. Cholesteric liquid crystals produced by adding a chiral agent to a liquid crystal compound have special light reflectivity and a characteristic that the color tone changes depending on the viewing angle. If an ink containing a liquid crystal compound is used, it is possible to record special images that cannot be observed in other image recording materials. Therefore, it is expected to be used as a component for building materials such as glass decorative films, special decoration of items such as packaging materials, and application in security printing.

[0003] For example, Japanese Patent Publication No. 2016-114661 discloses a method for manufacturing an optical component, which includes a step of forming dots composed of a liquid crystal material having a cholesteric structure on a substrate surface, and the formation of the dots includes a step of spraying a liquid crystal composition containing a liquid crystal compound and a chiral agent on the substrate, and the spraying is performed twice or more on each dot. International Publication No. 2020 / 194831 discloses an ink set for inkjet recording, which includes: a base ink containing at least one polymerizable compound selected from the group consisting of a monofunctional polymerizable compound and a bifunctional polymerizable compound; and an image recording ink containing a polymerizable liquid crystal compound and a chiral compound. Summary of the invention

[0004] Technical issues to be solved by the invention

[0005] However, there is a desire to obtain an image having both good color development and three-dimensional effect using an ink containing a liquid crystal compound.

[0006] The present invention has been made in view of such circumstances, and an object of one embodiment of the present invention is to provide an image recorded article having an image with excellent color development and a three-dimensional effect, a method for producing the image recorded article, and a decorative molded article.

[0007] Means for solving technical problems

[0008] The present invention includes the following aspects.

[0009] <1>

[0010] An image recorded material comprises a substrate and an inkjet image arranged on the substrate.

[0011] The inkjet image contains a cholesteric liquid crystal layer,

[0012] The cholesteric liquid crystal layer has a striped pattern of light and dark portions observed with a scanning electron microscope in a cross section along the thickness direction of the inkjet image.

[0013] At least a part of the line indicating the bright part or the dark part is a wavy line.

[0014] <2>

[0015] The image recorded material according to <1>, wherein

[0016] The period length of the wave of the line indicating the bright portion or the dark portion is 5 μm to 125 μm.

[0017] <3>

[0018] The image recorded material according to <1> or <2>, wherein:

[0019] The maximum value of the amplitude of the line representing the bright part or the dark part in the direction perpendicular to the virtual straight line representing the line representing the bright part or the dark part is 100 nm to 1000 nm.

[0020] <4>

[0021] The image recorded material according to any one of <1> to <3>, wherein

[0022] When the angle between an imaginary straight line representing a bright portion or a dark portion and the main surface of the substrate is defined as the orientation angle,

[0023] The cholesteric liquid crystal layer includes a region having an alignment angle of 5° or more.

[0024] <5>

[0025] The image recorded article according to any one of <1> to <4>, which is a decorative board.

[0026] <6>

[0027] The image recorded article according to any one of <1> to <5>, wherein

[0028] A base layer is disposed between the substrate and the inkjet image.

[0029] <7>

[0030] A method for producing an image record, comprising:

[0031] A step of preparing ink, wherein the ink contains a solvent having a boiling point of 100° C. or higher and lower than 300° C., a polymerizable liquid crystal compound, a chiral compound, a polymerization initiator, and a surfactant;

[0032] The process of heating the substrate to above 45°C;

[0033] The process of applying ink to the heated substrate by inkjet recording;

[0034] A step of heating the applied ink; and

[0035] A step of irradiating the applied ink with active energy rays.

[0036] <8>

[0037] The method for producing an image recorded material according to <7>, wherein:

[0038] In the process of preparing ink, two or more inks are prepared.

[0039] In the step of applying ink, a mixed region in which two or more types of ink are mixed is formed in at least a portion of the substrate by applying ink.

[0040] When two or more inks are respectively formed into ink films, the color difference between the two ink films is 25 or more.

[0041] <9>

[0042] The image recording method according to <7> or <8>, wherein:

[0043] In the process of applying ink, the ink is applied using a multipass method.

[0044] <10>

[0045] The method for producing an image recorded material according to any one of <7> to <9>, wherein:

[0046] Using mercury lamp to irradiate active energy rays,

[0047] The content of the polymerization initiator is 6 to 15 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0048] <11>

[0049] A decorative molded article comprising the molded article of the image recorded article according to <5>.

[0050] Effects of the Invention

[0051] According to one embodiment of the present invention, there are provided an image recorded article having an image with excellent color development and a three-dimensional effect, a method for producing the image recorded article, and a decorated molded article. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1The figure is a schematic diagram showing a stripe pattern of bright areas 14 and dark areas 16 observed by SEM in a cross section of an image recorded material 100 in which an inkjet image 12 is arranged on a substrate 10 .

[0053] Figure 2 The figure is a schematic diagram showing a stripe pattern of bright areas 24 and dark areas 26 observed by SEM in a cross section of an image recorded material 200 in which an inkjet image 22 is arranged on a substrate 20 , and is a diagram for explaining an orientation angle. DETAILED DESCRIPTION

[0054] Hereinafter, the image recorded article and the method for producing the image recorded article of the present invention will be described in detail.

[0055] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the minimum value and the maximum value, respectively.

[0056] In the numerical ranges recorded in stages in this specification, the upper limit or lower limit recorded in a certain numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical ranges recorded in this specification, the upper limit or lower limit recorded in a certain numerical range can also be replaced by the value shown in the embodiment.

[0057] In the present 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 plurality of substances present in the composition unless otherwise specified.

[0058] Furthermore, in the present specification, a combination of two or more preferred aspects is a more preferred aspect.

[0059] Furthermore, in the present specification, the term "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0060] In the present specification, "(meth)acrylate" means acrylate or methacrylate.

[0061] In this specification, "image" refers to the entire film, and "image recording" refers to the formation of an image (ie, film). Furthermore, the concept of "image" in this specification also includes a solid image.

[0062] [Visual Records]

[0063] The image recorded material of the present invention comprises a substrate and an inkjet image recorded on the substrate, the inkjet image comprises a cholesteric liquid crystal layer, the cholesteric liquid crystal layer has a striped pattern of light and dark portions observed using a scanning electron microscope (hereinafter referred to as "SEM") in a cross section along the thickness direction of the inkjet image, and at least a portion of the lines representing the light or dark portions are wavy lines.

[0064] The image recorded material of the present invention has an image with excellent color development and a three-dimensional effect. Although the reason for obtaining such an image is not clear, the present inventors speculate as follows.

[0065] In the image recorded material of the present invention, in the stripe pattern of the bright and dark parts observed by SEM in the image cross section, since the lines representing the bright or dark parts are wavy lines, when the light is incident from the normal direction of the image, a part of the incident light is reflected in the direction (oblique direction) at an angle θ (<90°) relative to the normal direction. If it is reflected not only in the normal direction but also in the oblique direction, the visual recognition from the oblique direction is improved and the color rendering is excellent. In addition, the incident light is reflected in various directions, and the brightness changes locally, so that the three-dimensional sense of the image can be obtained.

[0066] On the other hand, Japanese Patent Application Laid-Open No. 2016-114661 only discloses that the image recording ink is provided in a dotted form, and does not contain any description focusing on color development and three-dimensional effect.

[0067] Furthermore, International Publication No. 2020 / 194831 discloses color rendering properties, but there is no record focusing on three-dimensional effect.

[0068] Furthermore, in the method described in Japanese Patent Publication No. 2016-114661, a reflective layer is formed parallel to the ink film. Therefore, even if the same image is recorded to increase the color density, it is difficult to form a wavy reflective surface or an inclined reflective surface. If the reflective layer is flat relative to the ink film, the regular reflection component is the main component and the diffuse reflection component is small. In the case of such a reflective characteristic, when viewed from the regular reflection direction, the gloss and color are strongly felt, but when viewed from the other direction, the brightness is lacking.

[0069] Hereinafter, each structure in the image recorded material of the present invention will be described in detail.

[0070] <Base material>

[0071] The image recorded article of the present invention comprises a substrate.

[0072] The substrate is not particularly limited, and any substrate can be selected. The substrate may be any of an ink-absorbing substrate, an ink-low-absorbing substrate, and an ink-non-absorbing substrate. Examples of the substrate include paper, leather, cloth, and resin. Among them, from the viewpoint of color development, the substrate is preferably an ink-non-absorbing substrate, and more preferably a resin substrate.

[0073] As the resin constituting the resin substrate, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, nitrocellulose, acrylic resin, chlorinated polyolefin resin, polyether sulfone resin, polyethylene terephthalate (PET), polyethylene naphthalate, nylon, polyethylene, polystyrene, polypropylene, polycycloolefin resin, polyvinyl chloride, polyamide, polyimide, polycarbonate, polyether sulfone, polyether ether ketone, polyvinyl acetal and polyurethane can be cited. The resin substrate can be a substrate containing only one of these resins, or a substrate formed by mixing these resins with more than two kinds. In addition, other layers such as an easy-adhesion layer, an antistatic layer, and an antifouling layer can be formed on these resins, and hydrophilization treatment can also be implemented on the surface of the substrate. In addition, the substrate can include an adhesive layer or a protective layer, and coatings such as an ink receiving layer and an easy-adhesion layer can also be provided.

[0074] Among them, the substrate preferably comprises polyethylene terephthalate (PET).

[0075] The substrate may contain various additives such as a UV (ultraviolet) absorber, matting agent fine particles, a plasticizer, a degradation inhibitor, and a release agent.

[0076] The substrate may be transparent or colored. In addition, when the image recorded object is visually recognized from the side opposite to the image recording surface, the substrate preferably has a visible light transmittance of 60% or more. The transmittance is more preferably 80% or more, and further preferably 90% or more. The substrate may be translucent or have a matte finish on one side.

[0077] Furthermore, the substrate preferably has low birefringence in the visible light region. For example, the phase difference of the substrate at a wavelength of 550 nm is preferably 50 nm or less, more preferably 20 nm or less.

[0078] In the image recorded material of the present invention, if the alignment regulating force of the substrate on the liquid crystal is strong, the diffuse reflectivity decreases. Therefore, it is preferable to use a substrate which has not been subjected to surface treatment such as corona treatment or rubbing treatment.

[0079] The thickness of the substrate is not particularly limited, and is, for example, 1 μm to 10 mm. From the viewpoint of thinning and handling properties, the thickness of the substrate is preferably 10 μm to 200 μm, and more preferably 20 μm to 200 μm.

[0080] The above-mentioned thickness refers to an average thickness, which is a value obtained by measuring the thickness at 5 arbitrary points of the substrate and arithmetically averaging the thicknesses.

[0081] <Inkjet imaging>

[0082] The image recorded matter of the present invention comprises an inkjet image disposed on a substrate.

[0083] The image recorded material of the present invention may have an inkjet image directly provided on a substrate, or may have another layer provided between the substrate and the inkjet image.

[0084] Examples of the other layers include an ink receiving layer, an adhesive layer, a base layer or an overcoat layer made of a transparent ink, and a printed layer made of a color ink. Details of the other layers will be described later.

[0085] In the present invention, an inkjet image refers to an image recorded using an inkjet recording method. Whether it is an inkjet image can be determined by observing the surface of the image (ink film) using an optical microscope. If it is an inkjet image, points unique to the inkjet recording method can be confirmed.

[0086] Compared with images formed by a coating method, inkjet images have higher diffuse reflectivity and higher color rendering properties, and can provide a three-dimensional effect.

[0087] In the present invention, the inkjet image includes a cholesteric liquid crystal layer having a striped pattern of light and dark portions observed by SEM in a cross section along the thickness direction of the image, and the lines indicating the light or dark portions are wavy lines.

[0088] At this time, a part of the region may include a bright portion or a dark portion that is not a wavy line, and a stripe pattern may not be formed in a part.

[0089] The cholesteric liquid crystal layer refers to a layer containing at least a cholesteric liquid crystal phase. The cholesteric liquid crystal phase refers to a phase in which liquid crystal molecules are arranged in a spiral shape. In the case of a cholesteric liquid crystal layer, a stripe pattern of bright and dark parts can be observed using a SEM.

[0090] The stripe pattern of the bright portion and the dark portion observed by SEM can be confirmed by, for example, the following method.

[0091] The image was cut along the thickness direction of the image to obtain a cross-sectional sample. When the SEM image of the cross section was observed using a scanning electron microscope (accelerating voltage: 2 kV, observation magnification: 5000 times and 10000 times), the presence of a deep and shallow stripe pattern could be confirmed.

[0092] In the present invention, in the light-dark stripe pattern, a portion having a high color density and observed as black is referred to as a dark portion, and a portion having a low color density and observed as white is referred to as a bright portion.

[0093] In the cross-sectional SEM image, one cycle of bright and dark portions corresponds to 180 degrees of twisting of the liquid crystal. Therefore, two cycles of bright and dark portions correspond to 360 degrees of twisting of the liquid crystal. That is, the width of two cycles of bright and dark portions corresponds to the length of the helical pitch in the cholesteric liquid crystal layer.

[0094] Furthermore, the normal direction of a line indicating a bright portion or a dark portion refers to the direction of the helical axis in the cholesteric liquid crystal layer.

[0095] In the present invention, a line indicating a bright part or a dark part is a wavy line. A wavy line is a line that is different from a straight line and is undulating.

[0096] The waves constituting the wavy line may be periodic or non-periodic. The wavy line may be a line having a shape with periodic amplitude in the gravity direction and the anti-gravity direction with respect to the horizontal direction.

[0097] For example, by keeping the wettability of the substrate and the ink within an appropriate range and suppressing the wetting and diffusion of the ink, a wavy line can be formed. Furthermore, the shape of the wavy line (period length, amplitude, etc.) can be controlled by the amount of the surfactant and horizontal alignment agent contained in the ink and the drying speed after the ink is applied. The drying speed can be controlled by the boiling point of the solvent contained in the ink, the content of the solvent, the heating temperature of the substrate during image recording, the amount of ink applied, the printing speed, etc.

[0098] Figure 1 The figure is a schematic diagram showing a stripe pattern of bright areas 14 and dark areas 16 observed by SEM in a cross section of an image recorded material 100 in which an inkjet image 12 is arranged on a substrate 10 .

[0099] like Figure 1 As shown, the image recorded material 100 includes a substrate 10 and an inkjet image 12 disposed on the substrate 10 .

[0100] like Figure 1 As shown, in the cross section of the image recorded material 100 , the line 14 indicating the bright portion and the line 16 indicating the dark portion are both wavy lines.

[0101] In the lines (wavy lines) representing bright or dark areas, the wave period length L1 is preferably 5 μm to 125 μm, more preferably 5 μm to 80 μm, and further preferably 10 μm to 80 μm. If the wave period length L1 is within the above range, the diffuse reflectance is high, the color rendering is excellent, and a more three-dimensional image can be obtained.

[0102] For example, when the lines representing the bright or dark parts are formed roughly horizontally and flatly relative to the surface of the substrate or the ink film, and the proportion of wavy lines is small, the ratio of the reflectivity of the diffuse reflection component to the reflectivity of the total reflection component based on the ink film is 15% or less. In this case, high brightness is displayed at a specific observation angle, but bright colors cannot be felt at other angles. On the other hand, if the lines representing the bright or dark parts are wavy lines, the diffuse reflection component becomes more than 50%, and bright colors can be felt at various observation angles. In particular, when the diffuse reflection component is more than 80%, visual recognition is high regardless of the observation angle, and it is preferably used as a decoration.

[0103] The wave cycle length L1 refers to the length of one cycle of the wave. One cycle refers to the distance between adjacent convex parts in the wavy line.

[0104] The wave period length L1 is measured by the following method.

[0105] First, draw an imaginary straight line representing a bright or dark part. The imaginary straight line representing a bright or dark part is obtained by approximating a wavy line to a straight line. The number of wave cycles included in the imaginary straight line of the wavy line within a width of 500 μm is calculated.

[0106] The maximum value L2 of the amplitude of the line (wavy line) representing the bright or dark part in the direction perpendicular to the imaginary straight line representing the bright or dark part is preferably 20nm to 3000nm, more preferably 50nm to 1000nm, further preferably 100nm to 1000nm, and particularly preferably 100nm to 500nm. If the maximum value L2 of the amplitude is within the above range, the diffuse reflectance is high, the color rendering is excellent, and a more three-dimensional image can be obtained.

[0107] The maximum amplitude value L2 is the sum of the distance from the virtual straight line to the maximum displacement in one direction and the distance from the virtual straight line to the minimum displacement in the other direction, with the virtual straight line as the center.

[0108] The maximum value L2 of the amplitude is measured by the following method.

[0109] First, an imaginary straight line of the wavy line is drawn. The direction perpendicular to the imaginary straight line of the wavy line is defined as the amplitude direction. The distance between the convex part and the concave part in the wavy line is measured along the amplitude direction.

[0110] The line representing the bright part or the dark part may be a continuous line or may include a discontinuous part. If the line representing the bright part or the dark part is continuous, the haze of the image is low and the transparency is excellent. If it includes a discontinuous part, the haze becomes high and a white turbidity is generated in the image.

[0111] In a width of 500 μm in a direction parallel to the virtual straight line of the wavy line, the number of discontinuous portions is preferably 20 or less, more preferably 10 or less, and particularly preferably 0.

[0112] In the image recorded material of the present invention, the cholesteric liquid crystal layer preferably includes a region having an alignment angle of 5° or more, where the angle between an imaginary straight line representing a bright or dark portion (wavy line) and the main surface of the substrate is defined as the alignment angle.

[0113] The main surface of the substrate refers to the surface having the largest area among the surfaces of the substrate.

[0114] refer to Figure 2 , the method for measuring the orientation angle is explained.

[0115] Figure 2 The figure is a schematic diagram showing a stripe pattern of bright areas 24 and dark areas 26 observed by SEM in a cross section of an image recorded material 200 in which an inkjet image 22 is arranged on a substrate 20 , and is a diagram for explaining an orientation angle.

[0116] like Figure 2 As shown, the image recorded material 200 includes a substrate 20 and an inkjet image 22 disposed on the substrate 20 .

[0117] For example, Figure 2 As shown in FIG. 1 , a virtual straight line 24A representing the bright portion line 24 is drawn. As the orientation angle, an angle θ1 between the main surface 21 of the substrate and the virtual straight line 24A is measured.

[0118] In addition, Figure 2 In the figure, the imaginary straight line 24A rises to the right (i.e., it has a positive slope in the XY coordinates). In the case where the imaginary straight line rises to the right (i.e., it has a positive slope in the XY coordinates), and in the case where the imaginary straight line descends to the right (i.e., it has a negative slope in the XY coordinates), the orientation angle is expressed as positive.

[0119] In the region with an orientation angle of 5° or more, the reflectivity and reflection wavelength are different from those in the region with an orientation angle of 0° under the same light source and observation angle. Therefore, it looks like shadows, highlights, etc. in the image, and a three-dimensional effect can be obtained. In addition, in two regions with an orientation angle of 5° or more, when one orientation angle has a positive slope and the other orientation angle has a negative slope and is placed adjacent to each other, the effect of alternating shadows and highlights when the observation angle is changed can be obtained, and a three-dimensional effect can be obtained.

[0120] The presence or absence of orientation angle difference can also be detected by color measurement using a multi-angle colorimeter. Although the image is recorded using the same ink, the color difference ΔEab is large in the part where the color appears to change and the part where the light and dark changes significantly. For example, when comparing the color measurement values ​​at 45° using a multi-angle colorimeter such as CM-M6 (manufactured by Konica Minolta, Inc.), when the color difference is greater than 25, the color difference can be clearly detected even when visually observed. In particular, in an image having an orientation angle of 5° or more, an area with an orientation angle of 0°, or an area with an orientation angle of 5° or more and an opposite slope has the characteristic that the color difference becomes larger when the light receiving angle is 25° or 45°.

[0121] The slope of the imaginary straight line (i.e., positive or negative) is determined by the type of the chiral compound. The positive and negative slopes are opposite depending on whether the helical twisting force (HTP) induced by the chiral compound contained in the ink is rightward or leftward.

[0122] That is, in the same image, the tilt direction is determined by whether the helical twisting force of the chiral compound contained in the ink is right-handed or left-handed. At an observation angle where the reflection of light becomes stronger in a chiral compound having a right-handed helical twisting force, the reflection of light in an image recorded using a chiral compound having a left-handed helical twisting force becomes darker, and the opposite phenomenon may also occur.

[0123] The orientation angle is preferably 5° to 45°, more preferably 10° to 30°, and most preferably 10° to 20°.

[0124] When the orientation angle is within an appropriate range, the brightness when viewing the entire image recording surface is maintained within a preferred range, and high design properties can be obtained.

[0125] The image recorded material of the present invention has an image with excellent color development and a three-dimensional effect, and therefore can be preferably used as a decorative plate.

[0126] The image recorded article of the present invention may further have a transparent or opaque substrate on the inkjet image. It may be used in conjunction with a laminated film, or in conjunction with a laminated film containing a UV cut-off agent. An adhesive layer may be provided between the inkjet image and the transparent or opaque substrate. Furthermore, it may be combined with a color image, a primer layer, or an overcoat layer, or may be transferred to other substrates after printing. Furthermore, it may be laminated to glass, or transferred after printing, or used in conjunction with a polarizing plate.

[0127] The image recorded article of the present invention preferably has a base layer disposed between the substrate and the inkjet image.

[0128] Examples of the base layer include a layer for improving the color development of an inkjet image and a functional layer such as an adhesive layer.

[0129] The base layer preferably contains at least one binder. In addition to the binder, the base layer may contain, for example, a crosslinking agent, a matting agent, a surfactant, and the like.

[0130] Examples of the binder include polyester resins, polyurethane resins, polyester-based polyurethanes, acrylic resins, polyolefins, and polyvinyl alcohol.

[0131] The functional layer such as the easy-adhesion layer preferably contains at least one kind of particles. As particles, particles such as silicon dioxide, calcium carbonate, magnesium oxide, magnesium carbonate, and tin oxide are preferred. Among them, particles of tin oxide or silicon dioxide are preferred from the viewpoint of small reduction in adhesion under a hot and humid environment.

[0132] The average particle size of the particles is preferably 10 nm to 700 nm, more preferably 20 nm to 300 nm, and further preferably 20 nm to 100 nm. By using particles having an average particle size in the above range, good adhesion can be obtained. The shape of the particles is not particularly limited and can be any of spherical, irregular, and needle-shaped.

[0133] Examples of a method for forming the base layer on the substrate include a method of laminating a polymer sheet having high adhesiveness to the substrate and a method of applying and drying a base layer forming composition.

[0134] The coating method is not particularly limited, and for example, a known method such as a gravure coater or a bar coater can be used.

[0135] The thickness of the base layer is not particularly limited, but if it is 0.01 μm to 8 μm, the surface shape can be maintained more satisfactorily.

[0136] Furthermore, the base layer preferably has transparency.

[0137] The base layer preferably contains at least one binder resin selected from polyester resins, polyurethane resins and acrylic resins, and at least one crosslinking agent selected from oxazoline compounds and carbodiimide compounds. Furthermore, the base layer may contain other components as necessary.

[0138] Examples of the polyester resin include polyhydroxybutyrate (PHB), polycaprolactone (PCL), polycaprolactone butylene succinate, polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene succinate carbonate, polyethylene terephthalate succinate, polybutylene adipate terephthalate, polytetramethylene adipate terephthalate, polybutylene adipate terephthalate, polyethylene succinate (PES), polyglycolic acid (PGA), polylactic acid (PLA), carbonate copolymers of aliphatic polyesters, copolymers of aliphatic polyesters and polyamides, and the like.

[0139] The polyester resin may be a commercially available product.

[0140] Examples of commercially available products include FINE-TECH ES650 and ES2200 (manufactured by DIC Corporation), Vylonal MD1245, MD1400 and MD1480 (manufactured by TOYOBO CO., LTD.), PESR ESIN A-110, A-124GP, A-520 and A-640 (manufactured by TAKAMATSU OIL & FAT CO., LTD.), and Plascoat Z561, Z730, Z687 and Z592 (manufactured by GOOCHEMICAL CO., LTD.).

[0141] Polyurethane resin is a general term for polymers having urethane bonds in the main chain, and is generally obtained by the reaction of polyisocyanate and polyol.

[0142] Examples of polyisocyanates include TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate), NDI (naphthalene diisocyanate), TODI (dimethylbiphenyl diisocyanate),

[0143] ), HDI (hexamethylene diisocyanate) and IPDI (isophorone diisocyanate).

[0144] Examples of the polyol include ethylene glycol, propylene glycol, glycerin, and hexanetriol.

[0145] Furthermore, the polyurethane resin may be a polymer obtained by subjecting a urethane polymer obtained by a reaction between polyisocyanate and polyol to a chain extension treatment to increase the molecular weight.

[0146] Polyisocyanate, polyol and chain extension treatment are described in, for example, "Polyurethane Handbook" (edited by Keiji Iwata, published by NIKKAN KOGYO SHIMBUN, LTD. in 1987).

[0147] The polyurethane resin may be a commercially available product.

[0148] Examples of commercially available products include SUPERFLEX 470, 210, 150HS, ELASTRON H-3 (manufactured by DKS Co. Ltd.), HYDRAN AP-20, AP-40F, WLS-210 (manufactured by DIC Corporation), TAKELAC W-6061, and OLESTER UD-350 (manufactured by Mitsui Chemicals, Inc.).

[0149] Among them, the binder resin is preferably a polyurethane resin.

[0150] The acrylic resin is a resin having a structural unit derived from a (meth)acrylic compound.

[0151] The acrylic resin may be a commercially available product.

[0152] Examples of commercially available products include JURYMERET-410 (manufactured by TOAGOSEI CO., LTD.) and EM-48D (manufactured by Daicel Corporation).

[0153] The binder resin may be a resin other than polyester resin, polyurethane resin and acrylic resin. Examples of other resins include polystyrene, polyolefin and polyamide.

[0154] The binder resin contained in the base layer preferably contains at least one of a polyester resin, a polyurethane resin and an acrylic resin. The mass ratio of the polyester resin, the polyurethane resin and the acrylic resin (polyester resin: polyurethane resin: acrylic resin) is preferably 0.1 to 0.9: 0.1 to 0.9: 0 to 0.3, more preferably 0.3 to 0.7: 0.3 to 0.7: 0 to 0.2, and particularly preferably 0.4 to 0.6: 0.4 to 0.6: 0.

[0155] The content of the binder resin is preferably 67% to 97% by mass, more preferably 77% to 97% by mass, and particularly preferably 87% to 97% by mass relative to the total solid content in the base layer. When there are two or more resins, the above content refers to the total content of the resins.

[0156] The base layer preferably contains at least one crosslinking agent selected from the group consisting of oxazoline compounds and carbodiimide compounds. The crosslinking agent may be one type or two or more types.

[0157] The oxazoline compound is a compound having an oxazoline group.

[0158] As oxazoline compound, can enumerate by making the polymer with oxazoline group for example the polymerizable monomer with oxazoline group and other polymerizable monomers by known method (such as solution polymerization, emulsion polymerization etc.) copolymerization and polymer obtained as required.As the polymerizable monomer with oxazoline group, for example can enumerate 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline and 2-isopropenyl-5-methyl-2-oxazoline.

[0159] The oxazoline compound may be a commercially available product.

[0160] Examples of commercially available products include EPOCROS K-2020E, EPOCROS K-2010E, EPOCROS K-2020E, EPOCROS K-2030E, EPOCROS WS-300, EPOCROS WS-500, and EPOCROS WS-700 (manufactured by NIPPONSHOKUBAI CO., LTD.).

[0161] The carbodiimide compound is a compound having a functional group represented by -N=C=N-. Polycarbodiimide is usually synthesized by a condensation reaction of an organic diisocyanate. The organic diisocyanate is not particularly limited and may be an aromatic diisocyanate or an aliphatic diisocyanate, but from the viewpoint of reactivity, an aliphatic diisocyanate is preferred. As a raw material for synthesizing polycarbodiimide, an organic isocyanate, an organic diisocyanate, an organic triisocyanate, etc. are used. As the organic isocyanate, an aromatic isocyanate and an aliphatic isocyanate can be mentioned.

[0162] Examples of the organic diisocyanate include 4,4′-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and 1,3-phenylene diisocyanate.

[0163] Examples of the organic monoisocyanate include isophorone isocyanate, phenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate.

[0164] Furthermore, the carbodiimide compound may be a commercially available product.

[0165] As a commercially available item, CARBODILITE V-02-L2 (made by Nisshinbo Co., Ltd.) is mentioned, for example.

[0166] The content of the crosslinking agent is preferably 3% to 30% by mass, more preferably 3% to 15% by mass, relative to the content of the binder resin. If the content of the crosslinking agent is within the above range, the adhesion to the substrate is further improved. If the content of the crosslinking agent is 3% or more by mass relative to the content of the binder resin, the penetration of the ink into the base layer becomes good, and it is easy to improve the ink adhesion after image recording. If the content of the crosslinking agent is 30% or less by mass relative to the content of the binder resin, the crosslinking reaction of the base layer will not be excessive, and the hardness of the base layer will not become too high, so it is easy to improve the ink adhesion after the heat treatment.

[0167] The base layer may contain, in addition to the binder resin and the crosslinking agent, a surfactant, a lubricant, a defoaming agent, an antifoaming agent, a dye, a fluorescent brightener, a preservative, a water-proofing agent, particles, distilled water, and the like as necessary.

[0168] The particles can be organic particles or inorganic particles.

[0169] Examples of the organic particles include particles of polystyrene, polymethyl methacrylate (PMMA), silicone resin, benzoguanamine resin, and the like.

[0170] Examples of the inorganic particles include particles of silicon dioxide, calcium carbonate, magnesium oxide, magnesium carbonate, and the like.

[0171] The particles may be commercially available.

[0172] Examples of commercially available products include crosslinked PMMA particles MR-2G (manufactured by Soken Chemical & Engineering Co., Ltd.), silica particles SEAHOSTAR KE-W10 (manufactured by Nippon Shokub AI Co., Ltd.), QUARTRON PL-3, manufactured by Fuso Chemical Co., Ltd., and OX-50 (manufactured by Nippon Aerosil Co., Ltd.).

[0173] Among them, silica is preferred because it can suppress a decrease in adhesiveness when exposed to a hot and humid environment.

[0174] The number of particles may be one or two or more.

[0175] The average particle size of the particles is preferably 10 nm to 700 nm, more preferably 20 nm to 300 nm, and further preferably 20 nm to 100 nm. By using particles having an average particle size in the above range, good adhesion can be obtained. The shape of the particles is not particularly limited and can be any of spherical, irregular, and needle-shaped.

[0176] The thickness of the base layer is, for example, preferably 0.01 μm to 10 μm, more preferably 0.01 to 5 μm, and particularly preferably 0.05 to 1 μm.

[0177] The image recorded article of the present invention may further include an overcoat layer on the inkjet image. By providing a transparent layer having a refractive index slightly different from that of the inkjet image as the overcoat layer, it is possible to reduce graininess and scattering and impart color vividness.

[0178] Examples of methods for forming an overcoat layer include a method of laminating a film having an adhesive layer such as OCA to an inkjet image, a method of applying an overcoat layer-forming composition and drying it, and a method of curing an overcoat layer-forming composition composed of a curable monomer to form a film.

[0179] [Decorative molding]

[0180] When the image recorded article of the present invention is a decorative plate, it is suitable for producing a decorative molded body.

[0181] The decorated molded article of the present invention is preferably a decorated molded article comprising a molded article of the image recorded article of the present invention.

[0182] Specifically, the image recorded material of the present invention can be molded into a three-dimensional shape to produce a decorative molded body. A molding die such as a mold can be used for the molding process. The decorative molded body can be applied to an object having a desired three-dimensional shape to obtain a decorative article.

[0183] The surface of the image recorded material of the present invention may be planar or may have a concavo-convex structure. However, in order to obtain better color rendering and three-dimensional effect, it is preferred that the planar portion occupies a predetermined area or more.

[0184] [Method for producing image recorded material]

[0185] The method for producing an image recorded article of the present invention preferably includes: a step of preparing an ink (ink preparation step), the ink containing a solvent having a boiling point of 100° C. or higher and lower than 300° C., a liquid crystal compound, a chiral agent, a polymerization initiator, and a surfactant; a step of heating a substrate to 45° C. or higher (substrate heating step); a step of imparting the ink to the heated substrate by an inkjet recording method (ink imparting step); a step of heating the imparted ink (ink heating step); and a step of irradiating the imparted ink with active energy rays (active energy ray irradiation step).

[0186] Hereinafter, each step in the method for producing an image recorded material of the present invention will be described in detail.

[0187] (Ink preparation process)

[0188] The method for producing an image recorded material of the present invention includes a step of preparing an ink containing a solvent having a boiling point of 100° C. or higher and lower than 300° C., a polymerizable liquid crystal compound, a chiral compound, a polymerization initiator, and a surfactant.

[0189] <Polymerizable liquid crystal compound>

[0190] In the present invention, the polymerizable liquid crystal compound is a liquid crystal compound having a polymerizable group.

[0191] The liquid crystal compound may be a rod-like liquid crystal compound or a disc-like liquid crystal compound, and is preferably a rod-like liquid crystal compound.

[0192] Examples of the rod-like liquid crystal compound include

[0193] Rod-like nematic liquid crystal compounds. As rod-like nematic liquid crystal compounds, preferably used are azomethine compounds, azoxy compounds, cyanobiphenyl compounds, cyanophenyl ester compounds, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexane compounds, cyano-substituted phenylpyrimidine compounds, alkoxy-substituted phenylpyrimidine compounds, phenyldioxane compounds, diphenylacetylene compounds or alkenylcyclohexylbenzonitrile compounds. As rod-like liquid crystal compounds, not only low molecular weight liquid crystal compounds but also high molecular weight liquid crystal compounds can be used.

[0194] The polymerizable liquid crystal compound is obtained by introducing a polymerizable group into a liquid crystal compound. As the polymerizable group, for example, a polymerizable unsaturated group, an epoxy group and an aziridine group can be cited. Among them, the polymerizable group is preferably a polymerizable unsaturated group, and particularly preferably an ethylenically unsaturated group. The number of polymerizable groups possessed by the polymerizable liquid crystal compound is preferably 1 to 6, more preferably 1 to 3. From the viewpoint of the durability of the obtained image, the polymerizable liquid crystal compound further preferably has 2 polymerizable groups in the molecule.

[0195] Examples of polymerizable liquid crystal compounds include compounds described in Makromol. Chem., Vol. 190, p. 2255 (1989), Advanced Materials, Vol. 5, p. 107 (1993), U.S. Pat. No. 4,683,327, U.S. Pat. No. 5,622,648, U.S. Pat. No. 5,770,107, International Publication No. 95 / 22586, International Publication No. 95 / 24455, International Publication No. 97 / 00600, International Publication No. 98 / 23580, International Publication No. 98 / 52905, Japanese Patent Application Publication No. 1-272551, Japanese Patent Application Publication No. 6-16616, Japanese Patent Application Publication No. 7-110469, Japanese Patent Application Publication No. 11-80081, and Japanese Patent Application Publication No. 2001-328973. Furthermore, the content described in International Publication No. 2017 / 169696 and International Publication No. 2019 / 181247 may also be used.

[0196] Specific examples of the polymerizable liquid crystal compound include the following compounds (1) to (17). The polymerizable liquid crystal compound is not limited to the following examples.

[0197] [Chemical formula 1]

[0198]

[0199] [Chemical formula 2]

[0200]

[0201] [Chemical formula 3]

[0202]

[0203] In compound (12), X 1 Each independently represents an integer of 2 to 5.

[0204] [Chemical formula 4]

[0205]

[0206] [Chemical formula 5]

[0207]

[0208] Examples of polymerizable liquid crystal compounds other than those exemplified above include cyclic organopolysiloxane compounds disclosed in Japanese Patent Application Laid-Open No. 57-165480.

[0209] The ink may contain only one type of polymerizable liquid crystal compound, or may contain two or more types.

[0210] The ink preferably contains two or more different polymerizable liquid crystal compounds, and more preferably contains three or more different polymerizable liquid crystal compounds. By using two or more polymerizable liquid crystal compounds, the stability of the ink can be further improved.

[0211] The content of the polymerizable liquid crystal compound is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 60% by mass, and particularly preferably 15% by mass to 45% by mass, based on the total amount of the ink.

[0212] In the present invention, when two or more inks (for example, the first ink, the second ink, the third ink, etc.) are prepared, from the viewpoint of improving color reproducibility, the type of polymerizable liquid crystal compound and the content of the polymerizable liquid crystal compound of the first ink and the second ink may be the same or different. Furthermore, when the third ink is used together with the first ink and the second ink, the type of polymerizable liquid crystal compound and the content of the polymerizable liquid crystal compound of the first ink, the second ink and the third ink may be the same or different. Depending on the type of the polymerizable liquid crystal compound, the pitch of the spiral structure when the polymerizable liquid crystal compound becomes a cholesteric liquid crystal is different, and the wavelength of the light selectively reflected is different. By changing the type of the polymerizable liquid crystal compound, ink films of different hues can be obtained. Furthermore, by changing the content of the polymerizable liquid crystal compound and changing the mixing ratio with the chiral compound, ink films of different hues can be obtained.

[0213] (Chiral Compounds)

[0214] Chiral compounds are also called optically active compounds. Chiral compounds have the function of inducing a helical structure of a polymerizable liquid crystal compound. Depending on the type and content of the chiral compound, the torsion direction or pitch of the induced helical structure is different.

[0215] There are no particular limitations on the chiral compound, and known compounds can be used (for example, described in Handbook of Liquid Crystal Devices, Chapter 3, Item 4-3, Chiral Reagents for TN and STN, page 199, compiled by the 142nd Committee of the Japan Society for the Promotion of Science, 1989), for example, isosorbide derivatives and isomannide derivatives.

[0216] Chiral compounds generally contain an asymmetric carbon atom, but may be compounds without an asymmetric carbon atom as long as they contain chirality. Examples of chiral compounds include axial chiral compounds having a binaphthyl structure, helical chiral compounds having a helicene structure, and planar chiral compounds having a cycloaromatic structure.

[0217] The chiral compound may also have a polymerizable group. In the case where the chiral compound has a polymerizable group, a polymer having a structural unit derived from the polymerizable liquid crystal compound and a structural unit derived from the chiral compound is formed by the polymerization reaction of the chiral compound and the polymerizable liquid crystal compound. In the case where the chiral compound has a polymerizable group, the polymerizable group is preferably a group of the same type as the polymerizable group possessed by the polymerizable liquid crystal compound. Therefore, the polymerizable group of the chiral compound is preferably a polymerizable unsaturated group, an epoxy group or an aziridine group, further preferably a polymerizable unsaturated group, and particularly preferably an ethylenically unsaturated group. Furthermore, the chiral compound itself may be a liquid crystal compound.

[0218] In the ink, the content of the chiral compound is preferably 0.5% to 30% by mass relative to the total mass of the liquid crystal compound. The content of the chiral compound is preferably less because there is a tendency not to affect the liquid crystal properties. Therefore, as the chiral compound, a compound with a strong twisting force is preferred so that even a small amount can achieve the desired twisted orientation of the helical pitch.

[0219] Examples of chiral compounds showing such strong twisting force include Japanese Patent Application Laid-Open Nos. 2002-302487, 2002-80478, 2002-80851, 2002-179668, 2002-179670, 2002-338575, 2002-180051, and 2002-62-62. Chiral agents described in JP-A-81354, International Publication No. 2002 / 006195, JP-A-2011-241215, JP-A-2003-287623, JP-A-2002-302487, JP-A-2002-80478, JP-A-2002-80851, and JP-A-2014-034581, and LC-756 manufactured by BASF.

[0220] Specific examples of chiral compounds include the following compounds. The chiral compounds that can be used in inks are not limited to the following examples. "Me" in the compound means a methyl group.

[0221] [Chemical formula 6]

[0222]

[0223] [Chemical formula 7]

[0224]

[0225] [Chemical formula 8]

[0226]

[0227] [Chemical formula 9]

[0228]

[0229] In the above compounds, X each independently represents an integer of 2-5.

[0230] In the ink, the content of the chiral compound is preferably 1 to 15 parts by mass, and more preferably 3 to 9 parts by mass, relative to 100 parts by mass of the content of the polymerizable liquid crystal compound.

[0231] In the present invention, when two or more inks (e.g., a first ink, a second ink, a third ink, etc.) are prepared, the first ink and the second ink preferably have different contents of chiral compounds. Furthermore, when a third ink is further used, the contents of chiral compounds in the first ink, the second ink, and the third ink are preferably different from each other. Depending on the content of the chiral compound, the pitch of the spiral structure when the polymerizable liquid crystal compound becomes a cholesteric liquid crystal is different, and the wavelength of the selectively reflected light is different. By changing the content of the chiral compound, ink films of different hues can be obtained. When the content of the chiral compound is increased, the reflection wavelength tends to shift to the short wavelength side, and when the content of the chiral compound is reduced, the reflection wavelength tends to shift to the long wavelength side.

[0232] <Solvents having a boiling point of 100°C or higher and lower than 300°C>

[0233] The solvent may be appropriately selected according to the purpose as long as the boiling point is 100° C. or higher and lower than 300° C. The boiling point is measured under 1 atmospheric pressure.

[0234] When the boiling point of the solvent is 100° C. or higher, discharge stability is improved. Furthermore, depending on the drying speed during image recording, lines indicating bright or dark areas can be made wavy lines, and images showing vivid colors can be recorded.

[0235] When the boiling point of the solvent is lower than 300° C., landing interference during image recording can be suppressed, and a high-definition image can be recorded. In addition, since the line indicating a bright part or a dark part can be a wavy line, this is preferable.

[0236] Examples of the solvent include ketone solvents, alkyl halide solvents, amide solvents, sulfoxide solvents, heterocyclic compounds, hydrocarbon solvents, ester solvents, and ether solvents (eg, diethylene glycol diethyl ether).

[0237] Furthermore, the solvent may be an alcohol-based solvent or a pyrrolidone-based solvent.

[0238] Examples of the ether solvent include glycol ether and glycol ether ester.

[0239] Examples of the glycol ether include ethylene glycol monomethyl ether, diethylene glycol diethyl ether, triethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monobutyl ether, and triethylene glycol monomethyl ether.

[0240] Examples of the ketone solvent include methyl ethyl ketone and cyclohexanone.

[0241] Examples of the ester include 3-methoxybutyl acetate and γ-butyrolactone.

[0242] Examples of the pyrrolidone-based solvent include N-methyl-2-pyrrolidone and the like.

[0243] Among them, the ether solvent is preferably diethylene glycol diethyl ether, ethylene glycol monomethyl ether or 3-methoxybutyl acetate.

[0244] The boiling point of the solvent is more preferably 100°C to 250°C, further preferably 100°C to 220°C, and particularly preferably 120°C to 190°C.

[0245] The content of the solvent having a boiling point of 100° C. or higher and lower than 300° C. is preferably 20% to 90% by mass, preferably 40% to 80% by mass, and more preferably 50% to 80% by mass relative to the total amount of the ink. These may be used alone or in combination of two or more.

[0246] <Polymerization initiator>

[0247] The polymerization initiator is preferably a photopolymerization initiator, and more preferably a radical polymerization initiator having a function of generating radicals by irradiation with ultraviolet rays.

[0248] Examples of the photopolymerization initiator include α-carbonyl compounds (described in U.S. Patent No. 2,367,661 and U.S. Patent No. 2,367,670), acyloin ethers (described in U.S. Patent No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (described in U.S. Patent No. 2,722,512), polynuclear quinone compounds (described in U.S. Patent No. 3,046,127 and U.S. Patent No. 2,951,758), a combination of a triaryl imidazole dimer and p-aminophenyl ketone (described in U.S. Patent No. 3,549,367), acridine and phenazine compounds (described in Japanese Patent Application Laid-Open No. 60-105667 and U.S. Patent No. 4,239,850), and oxadiazole compounds (described in U.S. Patent No. 4,212,970).

[0249] Examples of the polymerization initiator include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, intramolecular hydrogen abstraction-type photopolymerization initiators, oxime ester-based photopolymerization initiators, and cationic photopolymerization initiators. Among them, the polymerization initiator is preferably an acylphosphine oxide-based photopolymerization initiator, specifically, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide or bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0250] In addition, the ink preferably contains two or more photopolymerization initiators with different absorption wavelengths. If the ink contains two or more photopolymerization initiators with different absorption wavelengths, when curing is performed using a light source having bright lines at multiple wavelengths, the amount of free radicals generated per unit exposure amount can be increased by mixing and using photopolymerization initiators suitable for the light source. As a result, the curing sensitivity is improved, and the abrasion resistance and adhesion of the image are improved.

[0251] The content of the polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 12 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0252] Furthermore, the content of the polymerization initiator is preferably 1.3% by mass or more, and more preferably 1.5% by mass or more, relative to the total amount of the ink. The upper limit of the content of the polymerization initiator is, for example, 7% by mass.

[0253] <Orientation control agent (orientation agent)>

[0254] The ink may contain an alignment control agent. By containing the alignment control agent in the ink, a cholesteric liquid crystal layer can be formed stably or quickly.

[0255] As the alignment control agent, for example, there can be mentioned fluorine-containing (meth)acrylate polymers, compounds represented by general formulas (X1) to (X3) described in WO2011 / 162291, compounds described in paragraphs

[0007] to

[0029] of JP-A-2012-211306, compounds described in paragraphs

[0020] to

[0031] of JP-A-2013-47204, compounds described in paragraphs

[0165] to

[0170] of WO2016 / 009648, and general formulas (Cy201) to (Cy211) described in paragraphs

[0077] to

[0081] of WO2016 / 092844 and Japanese Patent No. 4592225. These compounds can reduce the tilt angle of the molecules of the liquid crystal compound in the air interface of the layer or make the tilt angle of the molecules of the liquid crystal compound substantially horizontally oriented. In addition, in this specification, "horizontal orientation" means that the film surface is parallel to the long axis of the liquid crystal molecules, but it is not required to be strictly parallel. In this specification, it means an orientation with a tilt angle of less than 20° with the horizontal plane.

[0256] The alignment control agent may be used alone or in combination of two or more.

[0257] The content of the alignment control agent is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and further preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0258] <Surfactant>

[0259] When a surfactant is contained in the ink, the following effect can sometimes be obtained: when the ink is solidified, the polymerizable liquid crystal compound is horizontally oriented on the air interface side, and the direction of the helical axis is controlled to be more uniform. The surfactant is preferably a compound that can function as an orientation control agent that stably or rapidly forms a planar oriented cholesteric structure. Examples of the surfactant include silicone surfactants and fluorine surfactants, preferably fluorine surfactants.

[0260] The fluorine-based surfactant may be a commercially available product, and examples thereof include the Ftergent series manufactured by NEOS (eg, Ftergent 208G, etc.).

[0261] The content of the surfactant is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the ink.

[0262] <Additives>

[0263] The ink may contain additives as necessary within a range that does not impair the effects of the present invention.

[0264] Examples of the additives include crosslinking agents, non-polymerizable polymers, antioxidants, ultraviolet absorbers, sensitizers, stabilizers, plasticizers, chain transfer agents, polymerization inhibitors, defoamers, leveling agents, thickeners, flame retardants, dispersants, and colorants such as dyes and pigments.

[0265] <Physical Properties>

[0266] The viscosity of the ink is preferably 5 mPa·s or more, and more preferably 8 mPa·s or more. From the viewpoint of ink ejection properties, the upper limit of the viscosity of the ink is, for example, 30 mPa·s.

[0267] The viscosity of the ink is measured at 25° C. using a viscometer, for example, a viscometer (product name “RE-85L”, manufactured by Toki Sangyo Co., Ltd.).

[0268] The surface tension of the ink is preferably 20 mN / m to 40 mN / m, more preferably 23 mN / m to 35 mN / m, further preferably 26 mN / m to 30 mN / m, and most preferably 26 mN / m to 29 mN / m.

[0269] The surface tension of the ink is measured at 25° C. using a surface tensiometer, for example, a surface tensiometer (product name “DY-700”, manufactured by Kyowa Interface Science Co., Ltd.).

[0270] The ink prepared in the ink preparation step may be only one type or two or more types. From the viewpoint of being able to reproduce a variety of colors, two or more types of ink are preferred.

[0271] When two or more types of inks are prepared, the types and contents of the components contained in the two or more types of inks may be partially different from each other or may be partially the same.

[0272] In the ink preparation step, it is preferred to prepare at least two inks containing the same polymerizable liquid crystal compound and chiral compound in order to facilitate mixing of the inks. In this case, it is preferred that the chiral compound contents of the at least two inks differ from each other.

[0273] If the absolute value of the difference between the maximum reflection wavelength of the ink film formed by the first ink and the maximum reflection wavelength of the ink film formed by the second ink is 80 nm or more, the hue difference is large, and a variety of colors can be reproduced. The absolute value of the above difference is more preferably 100 nm or more, and further preferably 130 nm or more. The upper limit of the absolute value of the above difference is, for example, 400 nm.

[0274] Hereinafter, the polymerizable liquid crystal compound contained in the first ink is referred to as the first polymerizable liquid crystal compound, and the polymerizable liquid crystal compound contained in the second ink is referred to as the second polymerizable liquid crystal compound. The same applies to other components contained in the ink.

[0275] When the first polymerizable liquid crystal compound is the same as the second polymerizable liquid crystal compound, and the first chiral compound is the same as the second chiral compound, by adjusting the content of the polymerizable liquid crystal compound or the chiral compound, the absolute value of the difference between the maximum reflection wavelength of the ink film formed by the first ink and the maximum reflection wavelength of the ink film formed by the second ink can be made greater than 80 nm.

[0276] Specifically, from the viewpoint of reproducing a variety of colors, the maximum reflection wavelength of the ink film formed by the first ink is preferably 380 nm to 490 nm, and the maximum reflection wavelength of the ink film formed by the second ink is preferably 600 nm to 800 nm. Furthermore, the maximum reflection wavelength of the ink film formed by the first ink is more preferably 390 nm to 450 nm, and the maximum reflection wavelength of the ink film formed by the second ink is more preferably 600 nm to 750 nm.

[0277] The maximum reflection wavelength of the ink film is measured by the following method.

[0278] The ink was applied to a transparent polyethylene terephthalate substrate and heated at 80°C for 5 minutes. Then, a metal halide lamp (product name "CSOT-40", manufactured by GS Yuasa Corporation) was used to expose once at 120W and a conveying speed of 10m / min to form an ink film. A fluorescence spectrophotometer (product name "FD-7", manufactured by Konica Minolta, Inc.) was used to place a concealment rate measurement paper (standard: JIS K 5600-4-1: 1999, (ISO / FDIS 6504-3: 1998), manufactured by TP Technology Co., Ltd.) on the side of the substrate opposite to the image recording surface, and visible light was incident from the image recording surface side of the substrate to measure the reflectivity in the visible light region.

[0279] Furthermore, when two or more inks are prepared, when the two or more inks are respectively formed into ink films, the color difference between the two ink films is preferably 25 or more, and more preferably 30 or more. The upper limit of the color difference is not particularly limited.

[0280] When three types of inks are prepared, two of the three types of inks only need to satisfy the above-mentioned color difference conditions.

[0281] If the color difference is 25 or more, a variety of colors can be reproduced.

[0282] The color difference of the ink film was measured by the following method.

[0283] The ink was applied to a transparent polyethylene terephthalate substrate and heated at 80°C for 5 minutes. Then, a metal halide lamp (product name "CSOT-40", manufactured by GS Yuasa Corporation) was used to expose once at 120W and a conveying speed of 10m / min to form an ink film. A fluorescence spectrophotometer (product name "FD-7", manufactured by Konica Minolta, Inc.) was used to place a concealment rate measurement paper (standard: JIS K 5600-4-1: 1999, (ISO / FDIS 6504-3: 1998), manufactured by TP Technology Co., Ltd.) below the side of the substrate opposite to the image recording surface, and L was measured from the image recording surface at a viewing angle of 2°. * 、a * 、b * . The L of the first ink film * L of the second ink film * The difference is set as ΔL * , the first ink film a * a with the second ink film * The difference is set to Δa * , b of the first ink film * b with the second ink film * The difference is set as Δb * . Color difference ΔE * ab is calculated by the following formula.

[0284] ΔE * ab={(ΔL * ) 2 +(Δa * ) 2 +(Δb * ) 2} 1 / 2

[0285] From the viewpoint of reproducing more colors, it is preferable to further prepare a third ink in the ink preparation step. The absolute value of the difference between the maximum reflection wavelength of the ink film formed by the first ink and the maximum reflection wavelength of the ink film formed by the second ink and the maximum reflection wavelength of the ink film formed by the third ink is preferably 40 nm or more. In other words, the absolute value of the difference between the maximum reflection wavelength of the ink film formed by the first ink and the maximum reflection wavelength of the ink film formed by the third ink and the absolute value of the difference between the maximum reflection wavelength of the ink film formed by the second ink and the maximum reflection wavelength of the ink film formed by the third ink are preferably both 40 nm or more.

[0286] The third polymerizable liquid crystal compound contained in the third ink may be the same as or different from the first polymerizable liquid crystal compound and the second polymerizable liquid crystal compound. The third chiral compound contained in the third ink may be the same as or different from the first chiral compound and the second chiral compound. The third organic solvent contained in the third ink may be the same as or different from the first organic solvent and the second organic solvent.

[0287] The term "compounds are identical" means that two compounds have the same structure.

[0288] If the absolute value of the difference between the maximum reflection wavelength of the ink film formed by the first ink and the maximum reflection wavelength of the ink film formed by the second ink and the maximum reflection wavelength of the ink film formed by the third ink is 40 nm or more, more colors can be reproduced. The absolute value of the difference is more preferably 40 nm or more, and further preferably 70 nm or more. The upper limit of the absolute value of the difference is, for example, 150 nm.

[0289] For example, when the first polymerizable liquid crystal compound, the second polymerizable liquid crystal compound, and the third polymerizable liquid crystal compound are the same, and the first chiral compound, the second chiral compound, and the third chiral compound are the same, by adjusting the content of the polymerizable liquid crystal compound or the chiral compound, the absolute value of the difference between the maximum reflection wavelength of the ink film formed by the first ink and the maximum reflection wavelength of the ink film formed by the second ink and the maximum reflection wavelength of the ink film formed by the third ink can be made greater than 40 nm.

[0290] Specifically, from the viewpoint of reproducing a wider variety of colors, the maximum reflection wavelength of the ink film formed by the first ink is preferably 380 nm to 490 nm, the maximum reflection wavelength of the ink film formed by the second ink is preferably 600 nm to 800 nm, and the maximum reflection wavelength of the ink film formed by the third ink is preferably 500 nm to 590 nm. Furthermore, the maximum reflection wavelength of the ink film formed by the first ink is more preferably 390 nm to 470 nm, the maximum reflection wavelength of the ink film formed by the second ink is more preferably 600 nm to 700 nm, and the maximum reflection wavelength of the ink film formed by the third ink is more preferably 500 nm to 570 nm.

[0291] (Substrate heating process)

[0292] The method for producing an image record of the present invention includes a step of heating a substrate to 45° C. or higher. By preheating the substrate, ink can be applied to the heated substrate. By applying the ink to the heated substrate, the solvent contained in the ink can be evaporated more quickly. As a result, the line representing the bright or dark part resulting from the orientation of the liquid crystal formed locally when the ink is applied can be set as a wavy line and fixed in a state inclined relative to the substrate. The desired diffuse reflectivity and chromaticity can be obtained, and a part with light and dark and stereoscopic vision can be formed in the image.

[0293] The details of the substrate are as described above.

[0294] The surface energy of the substrate is preferably higher than the surface tension of the ink. If the surface energy of the substrate is higher than the surface tension of the ink, the wettability of the ink is improved, and the landing interference of the ink during image recording is suppressed, so that a continuous film is easily formed and the color development is improved.

[0295] The surface tension of the ink (25°C) is preferably 26mN / m to 29mN / m, and the surface energy of the substrate is preferably 40mN / m to 58mN / m. The surface energy of the substrate is more preferably 40mN / m to 53mN / m, and most preferably 43mN / m to 53mN / m. If the surface energy of the substrate is within the above range, the wettability of the ink to the substrate and the angle of the ink film end relative to the substrate are within an appropriate range. As a result, the lines representing the bright or dark parts are likely to become wavy lines and are easily inclined, which can give shadows to the obtained image.

[0296] In the substrate heating step, the method for heating the substrate is not particularly limited, and examples thereof include a heating drum, warm air, an infrared lamp, an oven, a heating plate, and a hot plate. The heating temperature of the substrate is 45° C. or higher, preferably 50° C. to 100° C., and more preferably 55° C. to 80° C. The heating time is preferably 0.5 minutes or longer, and although there is no upper limit, it is preferably in the range of 60 minutes or less.

[0297] (Ink applying process)

[0298] The method for producing an image recorded article of the present invention includes a step of applying ink to a heated substrate using an inkjet recording method.

[0299] In the present invention, by applying the ink to the heated substrate, the liquid crystal structure can be quickly fixed, and an image with a more three-dimensional effect can be obtained.

[0300] When two or more inks are prepared in the ink preparation step, it is preferred that a mixed region in which the two or more inks are mixed is formed on at least a portion of the substrate using the two or more inks.

[0301] The mixed area in which two kinds of inks are mixed may be formed in at least a portion of the substrate, or may be formed on the entire surface of the substrate. Furthermore, as long as the mixed area is formed in a portion of the substrate, the mixed area may not be formed in other portions of the substrate.

[0302] In the present invention, the mixed region refers to a region on a substrate where at least two types of inks are mixed. Specific examples of forming the mixed region include the following two methods.

[0303] When at least two inks are ejected continuously, the at least two inks are mixed by causing the ink ejected later to land on the ink landing area formed by the ink ejected earlier. When at least two inks are ejected simultaneously, the at least two inks are mixed by causing the ink landing areas formed by the at least two inks to land in a manner that at least a portion of the ink landing areas overlap with each other. In addition, the "mixed area" in the present invention does not include an area where the ink landing areas partially overlap with each other as the inks spread on the substrate after ejecting at least two inks in a manner that the ink landing areas do not overlap with each other.

[0304] The formation of the mixed region can be confirmed by the following method.

[0305] By measuring the reflection wavelength of the mixed area using a fluorescence spectrophotometer (product name "FD-7"), it can be confirmed that the reflection wavelength is different from that of the non-mixed area. In addition, since the color rendering of the mixed area is different from that of the non-mixed area, it can be easily confirmed by visual observation.

[0306] In the ink applying step, the ink film (also referred to as “ink layer”) formed by applying the ink on the substrate may be a single layer or a laminated layer.

[0307] For example, as a method of recording an image on a substrate, there is a method of stacking ink layers, but by forming the ink layer as a single layer, the number of steps can be reduced. In addition, the ink can be designed by considering only the interaction between the substrate and the ink (for example, wettability), and there is no need to consider the interaction between the ink layer and the ink compared to the case of stacking ink layers. Compared to the case of stacking ink layers, when a structure is formed by applying multiple inks in a single layer, it is possible to obtain an image with fewer discontinuous parts of the stripe pattern in the cholesteric liquid crystal layer and high color rendering, transparency and reflection anisotropy.

[0308] The inkjet recording method can use generally known methods, for example, a charge control method that utilizes electrostatic induction force to eject the ink composition, a drop-on-demand inkjet method (pressure pulse method) that utilizes the vibration pressure of a piezoelectric element, an acoustic inkjet method that converts an electrical signal into a sound beam and irradiates the ink composition to eject the ink composition using radiation pressure, and a thermal inkjet method that heats the ink composition to form bubbles and utilizes the generated pressure.

[0309] Generally speaking, image recording methods based on inkjet recording devices include a shuttle scanning method (also called a "serial head method") for recording images using a short serial head and a single pass method (also called a "line head method") for recording images using a line head in which recording elements are arranged in the entire area corresponding to the width direction of the substrate. In the shuttle scanning method, image recording is performed while the serial head is scanned along the width direction of the substrate. In contrast, in the single pass method, the image can be recorded on the entire surface of the substrate by scanning the substrate in a direction orthogonal to the arrangement direction of the recording elements. Therefore, in the single pass method, unlike the shuttle scanning method, a transport system such as a carriage for scanning the serial head is not required. In addition, in the single pass method, there is no need for movement of the carriage and complex scanning control of the substrate, and only the substrate moves, so the recording speed can be increased compared to the shuttle scanning method.

[0310] The method of applying the ink is not particularly limited, but a multi-pass method is preferred. Since the amount of ink applied at one time is limited, the formation of the liquid crystal structure due to heating is promoted, and the stripe pattern tends to be wavy and inclined.

[0311] In the ink application step, the application amount of ink per unit area is preferably set to 0.1 g / m 2 ~20g / m 2 The range of is preferably 1 g / m 2 ~20g / m 2 The range of is preferably 1 g / m 2 ~18g / m 2 The range of is preferably 3 g / m 2 ~25g / m 2 The most preferred range is 3 g / m 2 ~20g / m 2 range to be given.

[0312] In particular, since at least two types of ink are mixed in the mixed area, the amount of ink applied is increased compared to areas other than the mixed area. In the mixed area, by setting the total applied amount to 3.0 g / m 2 ~20g / m 2The ink droplets are not easy to spread, and high-definition images can be obtained.

[0313] Furthermore, in the ink application step, in the mixed region, the total application amount per unit area of ​​the polymerizable liquid crystal compound contained in at least two inks is preferably set to 1 g / m 2 ~10g / m 2 The range of is preferably 1 g / m 2 ~8g / m 2 The range of is preferably 1 g / m 2 ~7.5g / m 2 The most preferred range is 1 g / m 2 ~7g / m 2 range to be given.

[0314] If the total amount of the above is set to 1g / m 2 ~10g / m 2 If the range is given, the polymerizable liquid crystal compound is more uniformly oriented, and an image with high color rendering properties can be obtained.

[0315] The maximum film thickness formed by one application is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less. When the film thickness is 10 μm or less, poor alignment and defects of liquid crystal molecules are less likely to occur, and brighter colors can be obtained.

[0316] The ink application amount is calculated using the following method.

[0317] At the desired dot rate (the ratio of the portion of the recorded image to the total area calculated as a percentage), 1m 2 The image is recorded on an area of ​​. The mass of the substrate before and after the image is recorded is measured, and the amount of ink applied is calculated based on the mass difference. The amount of ink applied can be arbitrarily changed by setting the dot rate and adjusting the ink ejection amount of the device.

[0318] The amount of the polymerizable liquid crystal compound provided in the ink is calculated from the amount of the ink provided and the content of the polymerizable liquid crystal compound in the ink.

[0319] In the ink application step, the ink ejected from the inkjet head is preferably applied in a manner that the ejection amount of the ink is 1 pL (picoliter) to 30 pL, more preferably 2 pL to 10 pL. The ejection amount refers to the volume of ink ejected from one nozzle at a time by the inkjet recording method.

[0320] In the ink application step, the ink is applied at a resolution of preferably 100 dpi (dot per inch) x 100 dpi to 2400 dpi x 2400 dpi, more preferably 200 dpi x 200 dpi to 1200 dpi x 1200 dpi. "Dpi" means dots per 25.4 mm.

[0321] Furthermore, in the ink application step, the ink is applied so that the thickness of the ink film becomes 1 μm to 20 μm in one image recording, more preferably 1 μm to 15 μm, and even more preferably 1 μm to 8 μm. If the ink film is applied so that the thickness becomes 1 μm to 20 μm, the applied ink is easy to dry, the polymerizable liquid crystal compound forms a wavy structure or an inclined structure of the reflective surface more uniformly, and an image with high color rendering properties can be obtained.

[0322] The method for producing an image recorded material of the present invention includes the step of irradiating ink with active energy rays.

[0323] In the active energy ray irradiation step, examples of the active energy ray include ultraviolet rays, visible rays, and electron beams, and among them, ultraviolet rays (hereinafter also referred to as "UV") are preferred.

[0324] The peak wavelength of ultraviolet rays is preferably 200 nm to 405 nm, more preferably 220 nm to 390 nm, and further preferably 220 nm to 380 nm.

[0325] The exposure dose of ultraviolet light is preferably 20 mJ / cm 2 ~5J / cm 2 , more preferably 100 mJ / cm 2 ~1,500mJ / cm 2 The irradiation conditions and basic irradiation methods can be applied to the irradiation conditions and irradiation methods disclosed in Japanese Patent Publication No. 60-132767. Specifically, the irradiation method is preferably a method of providing light sources on both sides of a head unit of an ink ejection device, scanning the head unit and the light source in a so-called reciprocating manner, or a method of performing the irradiation by using other light sources that are not driven.

[0326] As the light source for ultraviolet irradiation, mercury lamps, gas lasers and solid lasers are mainly used, and the most well-known ones are mercury lamps, metal halide lamps and ultraviolet fluorescent lamps. In addition, UV-LED (light emitting diode) and UV-LD (laser diode) are small, have a long life, high efficiency and low cost, and are expected to be used as the light source for ultraviolet irradiation. Among them, the light source for ultraviolet irradiation is preferably a metal halide lamp, a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp or a UV-LED.

[0327] When irradiating active energy rays using a mercury lamp, the content of the polymerization initiator is preferably 3 to 15 parts by mass, more preferably 5 to 15 parts by mass, and even more preferably 6 to 11 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0328] In addition, a cooling step may be provided in the middle of the active energy ray irradiation step or before the active energy ray irradiation step.

[0329] The cooling method is not particularly limited, and examples thereof include a method of leaving the substrate still in an atmosphere at a predetermined temperature and a method of providing a portion without a heater on the conveyance path.

[0330] The cooling rate is not particularly limited, but is preferably set so as to appropriately form the wavy structures of the bright and dark parts of the cholesteric liquid crystal layer.

[0331] Specifically, the maximum value of the cooling rate is preferably 1° C. per second or more, more preferably 2° C. per second or more, and even more preferably 3° C. per second or more. The upper limit of the cooling rate is not particularly limited, but is often 10° C. per second or less.

[0332] In the method for producing an image recorded material of the present invention, if the cholesteric liquid crystal layer is exposed to wind, the surface of the formed cholesteric liquid crystal layer may become uneven. Considering this point, the wind speed in the environment to which the cholesteric liquid crystal layer is exposed is preferably 1 m / s or less.

[0333] In addition, the active energy ray irradiation step may be performed simultaneously with the cooling treatment or the substrate heating treatment.

[0334] Example

[0335] Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples unless departing from the gist of the present invention.

[0336] <Example 1>

[0337] [Preparation of ink]

[0338] (Ink Rm1)

[0339] The components shown below were heated and completely dissolved and mixed to prepare ink Rm1. The viscosity (25°C) of ink Rm1 was 10 mPa·s, and the surface tension (25°C) was 28 mN / m.

[0340] ·Diethylene glycol diethyl ether (boiling point 162°C) …… 65.57 parts by mass

[0341] ·Mixture of polymerizable liquid crystal compounds: 30 parts by mass

[0342] Polymerization initiator: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omni rad 819, manufactured by IGM Resins BV") ... 3.0 parts by mass

[0343] ·Chiral compound A……1.4 parts by mass

[0344] Fluorine-based surfactant (product name: "Ftergent 208G", manufactured by NEOS COMPANY) ... 0.03 parts by mass

[0345] The mixture of polymerizable liquid crystal compounds contains 50% by mass of compound (10) and 50% by mass of compound (11). Compounds (10) and (11) are rod-shaped liquid crystal compounds. The structures of compound (10), compound (11) and chiral compound A are as follows.

[0346] (Compound (10), Compound (11))

[0347] [Chemical formula 10]

[0348]

[0349] (Chiral Compound A)

[0350] [Chemical formula 11]

[0351]

[0352] [Image color hue (maximum reflection wavelength)]

[0353] As a substrate, a coated PET film (product name "Viewful UV TP-100N", manufactured by KIMOTO CO., LTD.) was used. On the substrate, ink Rm1 was applied in a wet film thickness of 6 μm using a wire bar. Thereafter, it was heated at 80°C for 5 minutes. Using a metal halide lamp (product name "CSOT-40", manufactured by GS Yuasa Corporation), an image (ink film) was formed by exposing once at 120 W and a conveying speed of 10 m / min. Using a fluorescence spectrophotometer (product name "FD-7", manufactured by Ko nica Minolta, Inc.), a concealment rate measurement paper (standard: JIS K 5600-4-1: 1999, (ISO / FDIS 6504-3: 1998), manufactured by TP Technology Co., Ltd.) was placed on the side of the substrate opposite to the image recording surface, and color measurement was performed from the image recording surface of the substrate to measure the reflectivity at 380 nm to 730 nm. The maximum reflection wavelength of the ink film formed by the ink Rm1 is 630 nm.

[0354] [Creation of Image Record 1]

[0355] As the substrate, a coated PET film (product name "Viewful UV TP-100N", manufactured by KIMOTO CO., LTD.) was used. The substrate was heated by a hot plate installed on a stage, and the temperature of the substrate was maintained at 50°C.

[0356] An inkjet recording device (product name "UJF3042HG", multi-pass method, manufactured by MIMAKI ENGI NEERING CO., LTD.) was used to set the resolution to 720 dpi × 600 dpi, and the ink Rm1 was ejected by 32 passes to record a 20 mm square solid image with a dot rate of 100%. After that, it was heated at 75°C for 5 minutes. Using a metal halide lamp (product name "CSOT-40", manufactured by GS Yuasa Corporation), it was exposed at 120 W and a conveying speed of 10 m / min to obtain an image recorded material 1. The thickness of the image (ink film) was 6 μm.

[0357] [Production of Image Record 2]

[0358] Image recorded material 2 was obtained by the same method as that of image recorded material 1 except that the image to be recorded was changed as follows.

[0359] Image data of 10 mm squares with a dot rate continuously changing from 100% to 45% was prepared. Using the above image data, an image of two 10 mm square images arranged line-symmetrically with the 100% dot rate portion at the center was recorded (10 mm × 20 mm, the dot rate at the center was 100%, and the dot rate continuously changed to 45% in the left-right direction).

[0360] [Analysis of Image Record 1]

[0361] The image recorded material 1 was cut along the thickness direction by an ultra-thin slicer to prepare a cut surface for cross-sectional observation. When the cut surface was observed by SEM (product name "SU8030", manufactured by Hitachi High-Technologies Corporation), a stripe pattern of bright and dark parts was confirmed. The line indicating the bright or dark part was a wavy line.

[0362] The period length, maximum amplitude, and number of discontinuous parts in the wave line were measured.

[0363] The determination method is as follows.

[0364] -Cycle Length-

[0365] The cross-sectional observation image was observed in a range of 500 μm in width in a direction parallel to the main surface of the substrate, and an imaginary straight line indicating a bright portion or a dark portion was drawn to obtain an average of one cycle.

[0366] -Maximum value of amplitude-

[0367] An imaginary straight line representing a bright or dark part was drawn, and the direction perpendicular to the imaginary straight line of the wavy line was defined as the amplitude direction. The distance between the convex part and the concave part in the wavy line was measured along the amplitude direction relative to the center in the amplitude direction.

[0368] -Number of discontinuous parts-

[0369] The number of discontinuous portions existing within a width of 500 μm in a direction parallel to the main surface of the substrate in the cross-sectional observation image was measured.

[0370] In Example 1, the period length is 31 μm, the maximum amplitude is 400 nm, and there are 15 discontinuous portions in a width of 500 μm of the wavy line in a direction parallel to the virtual straight line.

[0371] [Analysis of Image Record 2]

[0372] The image recorded material 2 was cut along the thickness direction by an ultramicrotome to prepare a cut surface for cross-sectional observation. The cutting position and direction were set to be perpendicular to the dot rate change direction at two positions 5 mm apart from the center of the image recorded material 2.

[0373] When the two cut surfaces were observed using SEM (product name "SU8030", manufactured by Hitachi High-Technologies Corporation), stripe patterns of bright and dark parts were confirmed. The lines representing the bright or dark parts are wavy lines. In addition, since the wavy lines are inclined relative to the main surface of the substrate, the orientation angle was measured. The measurement method is as follows.

[0374] -Orientation angle-

[0375] An imaginary straight line representing a bright portion or a dark portion was drawn, and the angle between the main surface of the substrate and the imaginary straight line was measured.

[0376] In Example 1, in one of the two cross sections, the line indicating the bright part or the dark part has a positive slope, and in the other cross section, the line indicating the bright part or the dark part has a negative slope. The orientation angles are all 8° to 15°.

[0377] <Example 2>

[0378] Image recorded materials 1 and 2 were obtained in the same manner as in Example 1 except that the inkjet recording apparatus used in Example 1 was changed to an inkjet recording apparatus (product name "DMP-2831", manufactured by FUJIFILM Corporation) and the ejection was performed by a single-pass method.

[0379] <Example 3>

[0380] Image recorded materials 1 and 2 were obtained in the same manner as in Example 1 except that the temperature of the substrate was changed to 60° C. and the ejection amount of the ink was adjusted so that the thickness of the image in the image recorded material 1 would be 4 μm.

[0381] <Comparative Example 1>

[0382] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that the substrate was changed to a polyester film (product name "TAIKO POLYESTER FILM FE2001", single-sided corona discharge treated type, manufactured by FUTAMURA CHEMICAL CO., LTD.) and ink Rm1 was ejected onto the corona treated surface.

[0383] When the cross sections of the image recorded materials 1 and 2 were observed using a SEM, striped patterns of light and dark areas were observed, but the lines indicating the light and dark areas were horizontal to the substrate, and no wavy structure or inclined structure was observed.

[0384] <Comparative Example 2>

[0385] Image recorded materials 1 and 2 were obtained in the same manner as in Example 1 except that the substrate was changed to a polyester film (product name "TAIKO POLYESTER FILM FE2001", single-sided corona discharge treated type, manufactured by FUTAMURA CHEMICAL CO., LTD.), the surface not subjected to corona treatment was rubbed, and ink Rm1 was ejected on the rubbed surface.

[0386] When the cross sections of the image recorded materials 1 and 2 were observed using a SEM, striped patterns of light and dark areas were observed, but the lines indicating the light and dark areas were horizontal to the substrate, and no wavy structure or inclined structure was observed.

[0387] <Example 4>

[0388] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that the substrate was changed to a PET film (product name: "Viewfull 200TA", manufactured by KIMOTO CO., LTD.).

[0389] <Example 5>

[0390] The substrate was changed to a PET film (product name "MF-100", manufactured by FUJIFILM Corporation). An inkjet recording device (product name "UJF3042HG", manufactured by MIMAKI ENGINEERING CO., LTD.) was used, and the resolution was set to 720 dpi × 600 dpi, and a transparent ink (product name "LH-100CL", manufactured by MIMAKI ENGINEERING CO., LTD.) was ejected to record a 20 mm square solid image with a dot rate of 100% in a high density mode. In addition, after corona treatment was performed using a corona surface modification evaluation device (product name "TEC-4AX", manufactured by KASUGA DENKI KOGYO CO., LTD.), image records 1 and 2 were obtained in the same manner as in Example 3.

[0391] The base layer formed of the transparent ink has irregular irregularities on the surface. Therefore, irregular irregularities are also observed on the surface of the image recorded material 1.

[0392] <Example 6>

[0393] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that the substrate was changed to a self-adhesive film (product name: "GELPOLYCLEAR 125UV-IJII", manufactured by PANAC CO., LTD.).

[0394] <Example 7>

[0395] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that the substrate was changed to a PET film (product name: "Nij-TP", manufactured by NITIE, Inc.).

[0396] <Example 8>

[0397] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that the substrate was changed to a flexible transparent conductive film (product name: "STACLEAR", manufactured by NAGAOKA INDU STRY CO., LTD.).

[0398] <Example 9>

[0399] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that the temperature of the substrate was changed to 40°C.

[0400] <Example 10>

[0401] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that the temperature of the substrate was changed to 70°C.

[0402] <Example 11>

[0403] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that the number of passes during printing was changed to 4.

[0404] <Example 12>

[0405] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that the number of passes during printing was changed to 16.

[0406] <Example 13>

[0407] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that a UV-LED lamp attached to the inkjet recording apparatus was used instead of the metal halide lamp.

[0408] <Example 14>

[0409] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that a low-pressure mercury lamp was used instead of a metal halide lamp and curing was performed over time until the stickiness on the surface disappeared.

[0410] <Example 15>

[0411] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that methoxybutyl acetate was used instead of diethylene glycol diethyl ether in ink Rm1.

[0412] <Example 16>

[0413] [Preparation of ink]

[0414] (Ink Rm2)

[0415] The following components were completely dissolved and mixed to prepare ink Rm2. The viscosity (25° C.) of ink Rm2 was 10 mPa·s, and the surface tension (25° C.) was 29.5 mN / m.

[0416] ·Diethylene glycol diethyl ether……65.598 parts by mass

[0417] ·Mixture of polymerizable liquid crystal compounds: 30 parts by mass

[0418] Polymerization initiator: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omni rad 819, manufactured by IGM Resins BV") ... 3.0 parts by mass

[0419] ·Chiral compound A……1.4 parts by mass

[0420] Fluorine-based surfactant (product name: "Ftergent 208G", manufactured by NEOS COMPANY) ... 0.002 parts by mass

[0421] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that ink Rm2 was used instead of ink Rm1.

[0422] <Example 17>

[0423] [Preparation of ink]

[0424] (Ink Rm3)

[0425] The following components were completely dissolved and mixed to prepare ink Rm3. The viscosity (25° C.) of ink Rm3 was 10 mPa·s, and the surface tension (25° C.) was 28.7 mN / m. Diethylene glycol diethyl ether: 65.59 parts by mass

[0426] ·Mixture of polymerizable liquid crystal compounds: 30 parts by mass

[0427] Polymerization initiator: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omni rad 819, manufactured by IGM Resins BV") ... 3.0 parts by mass

[0428] ·Chiral compound A……1.4 parts by mass

[0429] Fluorine-based surfactant (product name: "Ftergent 208G", manufactured by NEOS COMPANY) ... 0.01 parts by mass

[0430] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that ink Rm3 was used instead of ink Rm1.

[0431] <Example 18>

[0432] [Preparation of ink]

[0433] (Ink Rm4)

[0434] The following components were completely dissolved and mixed to prepare ink Rm4. The viscosity (25° C.) of ink Rm4 was 10 mPa·s, and the surface tension (25° C.) was 26.6 mN / m. Diethylene glycol diethyl ether: 65.5 parts by mass

[0435] ·Mixture of polymerizable liquid crystal compounds: 30 parts by mass

[0436] Polymerization initiator: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omni rad 819, manufactured by IGM Resins BV") ... 3.0 parts by mass

[0437] ·Chiral compound A……1.4 parts by mass

[0438] Fluorine-based surfactant (product name: "Ftergent 208G", manufactured by NEOS COMPANY) ... 0.1 parts by mass

[0439] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that ink Rm4 was used instead of ink Rm1.

[0440] <Example 19>

[0441] [Preparation of ink]

[0442] (Ink Rm5)

[0443] The following components were completely dissolved and mixed to prepare ink Rm5. The viscosity (25° C.) of ink composition Rm5 was 10 mPa·s, and the surface tension (25° C.) was 25.2 mN / m.

[0444] ·Diethylene glycol diethyl ether……65.35 parts by mass

[0445] ·Mixture of polymerizable liquid crystal compounds: 30 parts by mass

[0446] Polymerization initiator: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omni rad 819, manufactured by IGM Resins BV") ... 3.0 parts by mass

[0447] ·Chiral compound A……1.4 parts by mass

[0448] Fluorine-based surfactant (product name: "Ftergent 208G", manufactured by NEOS COMPANY) ... 0.25 parts by mass

[0449] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that ink Rm5 was used instead of ink Rm1.

[0450] <Example 20>

[0451] (Ink Rm1)

[0452] In the same manner as in Example 1, ink Rm1 was prepared.

[0453] (Ink Bm1)

[0454] The following components were completely dissolved and mixed to prepare ink Bm1. The viscosity (25° C.) of ink Bm1 was 10 mPa·s, and the surface tension (25° C.) was 28 mN / m.

[0455] ·Diethylene glycol diethyl ether……64.97 parts by mass

[0456] ·Mixture of polymerizable liquid crystal compounds: 30 parts by mass

[0457] Polymerization initiator: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omni rad 819, manufactured by IGM Resins BV") ... 3 parts by mass

[0458] ·Chiral compound A...2 parts by mass

[0459] Fluorine-based surfactant (product name: "Ftergent 208G", manufactured by NEOS COMPANY) ... 0.03 parts by mass

[0460] As a substrate, a coated PET film (product name "Viewful UV TP-100N", manufactured by KIMOTO CO., LTD.) was used. On the substrate, the ink Bm1 was applied in a wet film thickness of 6 μm using a wire bar. Thereafter, it was heated at 80°C for 5 minutes. Using a metal halide lamp (product name "CSOT-40", manufactured by GS Yuasa Corporation), an image (ink film) was formed by exposing once at 120 W and a conveying speed of 10 m / min. Using a fluorescence spectrophotometer (product name "FD-7", manufactured by Ko nica Minolta, Inc.), a concealment rate measurement paper (standard: JIS K 5600-4-1: 1999, (ISO / FDIS 6504-3: 1998), manufactured by TP Technology Co., Ltd.) was placed on the opposite side of the substrate from the image recording surface, and the reflectivity was measured from the image recording surface of the substrate in the range of 380 nm to 730 nm. The maximum reflection wavelength of the ink film formed by the ink Bm1 is 440 nm.

[0461] The color difference between the ink film formed by the ink Rm1 and the ink film formed by the ink Bm1 is 37.

[0462] [Production of Image Record 3]

[0463] Image data of 20 mm square was prepared so that the density of ink Bm1 was 70% and the density of ink Rm1 was 70% in halftone ratio.

[0464] As the substrate, a coated PET film (product name "Viewful UV TP-100N", manufactured by KIMOTO CO., LTD.) was used. The substrate was heated by a hot plate installed on a stage, and the temperature of the substrate was maintained at 60°C.

[0465] An inkjet recording device (product name "UJF3042HG", multi-pass method, manufactured by MIMAKI ENGI NEERING CO., LTD.) was used to record an image by ejecting ink Bm1 and ink Rm1 by 32 passes at a resolution of 720 dpi×600 dpi. Thereafter, the image was heated at 75°C for 5 minutes. A metal halide lamp (product name "CSOT-40", manufactured by GS Yuasa Corporation) was used to expose the image at 120 W and a conveying speed of 10 m / min to obtain an image recorded material 3. The thickness of the image (ink film) was 6 μm.

[0466] [Production of Image Record 4]

[0467] Image recorded material 4 was obtained by the same method as image recorded material 3 except that the image to be recorded was changed as follows.

[0468] For ink Rm1, the dot rate at the center was set to 100%, and it continuously changed from the center to the left and right to 45%. For ink Bm1, 20 mm square image data with a dot rate of 40% was prepared. An image (20 mm×20 mm) was recorded using the above image data.

[0469] <Example 21>

[0470] (Ink Rm1)

[0471] In the same manner as in Example 1, ink Rm1 was prepared.

[0472] (Ink Gm1)

[0473] The following components were completely dissolved and mixed to prepare ink Gm1. The viscosity (25° C.) of ink Gm1 was 10 mPa·s, and the surface tension (25° C.) was 28 mN / m.

[0474] ·Diethylene glycol diethyl ether……65.22 parts by mass

[0475] ·Mixture of polymerizable liquid crystal compounds: 30 parts by mass

[0476] Polymerization initiator: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omni rad 819, manufactured by IGM Resins BV") ... 3.0 parts by mass

[0477] ·Chiral compound A……1.75 parts by mass

[0478] Fluorine-based surfactant (product name: "Ftergent 208G", manufactured by NEOS COMPANY) ... 0.03 parts by mass

[0479] [Image color hue (maximum reflection wavelength)]

[0480] As a substrate, a coated PET film (product name "Viewful UV TP-100N", manufactured by KIMOTO CO., LTD.) was used. On the substrate, the ink Gm1 was applied in a wet film thickness of 6 μm using a wire bar. Thereafter, it was heated at 80°C for 5 minutes. Using a metal halide lamp (product name "CSOT-40", manufactured by GS Yuasa Corporation), an image (ink film) was formed by exposing once at 120 W and a conveying speed of 10 m / min. Using a fluorescence spectrophotometer (product name "FD-7", manufactured by Ko nica Minolta, Inc.), a concealment rate measurement paper (standard: JIS K 5600-4-1: 1999, (ISO / FDIS 6504-3: 1998), manufactured by TP Technology Co., Ltd.) was placed on the side of the substrate opposite to the image recording surface, and color measurement was performed from the image recording surface of the substrate to measure the reflectivity at 380 nm to 730 nm. The maximum reflection wavelength of the ink film formed by the ink Gm1 is 540 nm.

[0481] The color difference between the ink film formed by the ink Rm1 and the ink film formed by the ink Gm1 is 36.

[0482] [Production of Image Records 3 and 4]

[0483] Image recorded materials 3 and 4 were obtained in the same manner as in Example 20 except that ink Gm1 was used instead of ink Bm1.

[0484] In Examples 2 to 19, the image recorded matter 1 and the image recorded matter 2 were analyzed in the same manner as the image recorded matter 1 and the image recorded matter 2 in Example 1.

[0485] In Examples 20 and 21, image records 3 and 4 were analyzed in the same manner as image records 1 and 2 in Example 1.

[0486] In Examples 1 to 19, the color development was evaluated using image recorded material 1, and the three-dimensional effect was evaluated using image recorded material 2. In Examples 20 and 21, the color development was evaluated using image recorded material 3, and the three-dimensional effect was evaluated using image recorded material 4. The evaluation method is as follows.

[0487] <Color rendering>

[0488] The integrating sphere unit attached to the spectrophotometer (product name "V-770", manufactured by JASCO Corporation) was installed, and the image recording surface of the image recorded material 1 or the image recorded material 3 was directed toward the light source to measure the reflectivity of the total reflection component. In addition, the regular reflection component removal unit was installed to measure the reflectivity of the diffuse reflection component.

[0489] The color rendering was evaluated based on the ratio of the reflectance of the diffuse reflection component (maximum reflectance within the range of 400nm to 800nm ​​- minimum reflectance) to the reflectance of the total reflection component (maximum reflectance within the range of 400nm to 800nm ​​- minimum reflectance). The evaluation criteria are as follows. In A, a bright color without unevenness is presented.

[0490] A: The ratio is more than 60%.

[0491] B: The ratio is less than 60%.

[0492] <Three-dimensional effect>

[0493] A light source was placed above the image recording surface of the image recorded material 2 or 4. The thickness direction of the image recorded surface was set as the normal direction, and the image recorded surface was visually observed from a direction of 45° relative to the normal direction. The three-dimensional effect was evaluated based on the difference in brightness between the right and left halves of the image recorded surface and the magnitude of the color change in the entire image recorded material. If the brightness and color changes are large, the three-dimensional effect is excellent.

[0494] A: The difference in brightness and color changes are very large and clear.

[0495] B: Large difference in brightness and color changes.

[0496] C: Small difference in brightness and color changes.

[0497] D: Unable to confirm the change of brightness and color.

[0498] The evaluation results are shown in Tables 1 to 4.

[0499] [Table 1]

[0500]

[0501] [Table 2]

[0502]

[0503] [Table 3]

[0504]

[0505] [Table 4]

[0506]

[0507] As shown in Tables 1 to 4, in Examples 1 to 21, it can be known that: since it includes a substrate and an inkjet image arranged on the substrate, the inkjet image includes a cholesteric liquid crystal layer, and the cholesteric liquid crystal layer has a striped pattern of light and dark portions observed using a SEM in a cross-section along the thickness direction of the inkjet image, and at least a portion of the line representing the light or dark portion is a wavy line, so that an image with excellent color rendering and a three-dimensional effect can be obtained.

[0508] On the other hand, in Comparative Examples 1 and 2, in the cross section along the thickness direction of the image, no wavy line structure or inclined structure was confirmed in the stripe pattern of the bright and dark parts observed by SEM, and an image with high design was not obtained.

[0509] <Example 22>

[0510] [Preparation of ink]

[0511] (Ink Rm6)

[0512] The components shown below were completely dissolved and mixed to prepare ink Rm6. The viscosity (25°C) of ink Rm6 was 11 mPa·s, and the surface tension (25°C) was 28.5 mN / m.

[0513] ·Butoxy... 63.07 parts by mass

[0514] ·Mixture of polymerizable liquid crystal compounds……34 parts by mass

[0515] Polymerization initiator: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omni rad 819, manufactured by IGM Resins BV") ... 1.5 parts by mass

[0516] ·Chiral compound A……1.4 parts by mass

[0517] Fluorine-based surfactant (product name: "Ftergent 208G", manufactured by NEOS COMPANY) ... 0.03 parts by mass

[0518] Image recorded materials 1 and 2 were obtained in the same manner as in Example 3 except that ink Rm6 was used instead of ink Rm1.

[0519] <Example 23>

[0520] (Ink Rm7)

[0521] The following components were completely dissolved and mixed to prepare ink Rm7. The viscosity (25° C.) of ink Rm7 was 10.2 mPa·s, and the surface tension (25° C.) was 27.5 mN / m.

[0522] ·Diethylene glycol diethyl ether……65.67 parts by mass

[0523] ·Mixture of polymerizable liquid crystal compounds: 30 parts by mass

[0524] Polymerization initiator: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omni rad 819, manufactured by IGM Resins BV") ... 3 parts by mass

[0525] ·Chiral compound A……1.3 parts by mass

[0526] Fluorine-based surfactant (product name: "Ftergent 208G", manufactured by NEOS COMPANY) ... 0.03 parts by mass

[0527] [Creation of Image Record 1]

[0528] As the substrate, a coated PET film (product name "Viewful UV TP-100N", manufactured by KIMOTO CO., LTD.) was used. The substrate was heated by a hot plate installed on a stage, and the temperature of the substrate was maintained at 60°C.

[0529] An inkjet recording device (product name "UJF3042HG", multi-pass method, manufactured by MIMAKI ENGI NEERING CO., LTD.) was used, and the resolution was set to 720 dpi × 600 dpi. Ink Rm7 was ejected by 32 passes to record a 20 mm square solid image with a dot rate of 100%. After that, it was heated at 70°C for 5 minutes. A low-pressure mercury lamp was used to give a cumulative exposure of 1000 mJ / cm 2 The exposure was performed in a manner of , thereby obtaining an image recorded material 1. The thickness of the image (ink film) was 4 μm.

[0530] [Production of Image Record 2]

[0531] Image recorded material 2 was obtained by the same method as that of image recorded material 1 except that the image to be recorded was changed as follows.

[0532] Image data of 10 mm squares with a dot rate continuously changing from 100% to 45% was prepared. Using the above image data, an image of two 10 mm square images arranged line-symmetrically with the 100% dot rate portion at the center was recorded (10 mm × 20 mm, the dot rate at the center was 100%, and the dot rate continuously changed to 45% in the left-right direction).

[0533] The reflection spectrum of the image recorded material 1 was measured using a fluorescence spectrophotometer FD-7 (manufactured by Konica Minolta, Inc.), and the maximum wavelength at which the reflectance value became 0.01 or less was found to be 600 nm. The wavelength at which the reflectance value became maximum was 680 nm.

[0534] <Example 24>

[0535] (Ink Rm8)

[0536] The components shown below were completely dissolved and mixed to prepare ink Rm7. The viscosity (25° C.) of ink Rm7 was 10.5 mPa·s, and the surface tension (25° C.) was 27.6 mN / m.

[0537] ·Diethylene glycol diethyl ether……65.67 parts by mass

[0538] ·Mixture of polymerizable liquid crystal compounds: 30 parts by mass

[0539] Polymerization initiator: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omni rad 819, manufactured by IGM Resins BV") ... 2 parts by mass

[0540] Polymerization initiator: 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone (product name: “Omnirad 2959, manufactured by IGM Resins BV”) 1 part by mass

[0541] ·Chiral compound A……1.3 parts by mass

[0542] Fluorine-based surfactant (product name: "Ftergent 208G", manufactured by NEOS COMPANY) ... 0.03 parts by mass

[0543] Image recorded materials 1 and 2 were prepared in the same manner as in Example 23 except that ink Rm8 was used instead of ink Rm7. The reflection spectrum of image recorded material 1 was measured using a fluorescence spectrophotometer FD-7 (manufactured by Konica Minolta, Inc.), and the maximum wavelength at which the reflectance value became 0.01 or less was found to be 600 nm. The wavelength at which the reflectance value became the maximum was 680 nm.

[0544] <Example 25>

[0545] (Ink Rm9)

[0546] The components shown below were completely dissolved and mixed to prepare ink Rm9. The viscosity (25° C.) of ink Rm9 was 10.3 mPa·s, and the surface tension (25° C.) was 27.6 mN / m.

[0547] ·Diethylene glycol diethyl ether……67.17 parts by mass

[0548] ·Mixture of polymerizable liquid crystal compounds: 30 parts by mass

[0549] Polymerization initiator: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omni rad 819, manufactured by IGM Resins BV") ... 1.5 parts by mass

[0550] ·Chiral compound A……1.3 parts by mass

[0551] Fluorine-based surfactant (product name: "Ftergent 208G", manufactured by NEOS COMPANY) ... 0.03 parts by mass

[0552] Image records 1 and 2 were obtained in the same manner as in Example 23 except that ink Rm8 was used instead of ink Rm6. The reflection spectrum of image record 1 was measured using a fluorescence spectrophotometer FD-7 (manufactured by Konica Minolta, Inc.), and the maximum wavelength at which the reflectance became 0.01 or less was found to be 450 nm. The wavelength at which the reflectance became the maximum was 680 nm.

[0553] When the image recorded materials 1 of Examples 23 to 25 were compared visually, the image recorded materials 1 of Examples 23 and 24 showed a vivid red color, but the red hue of the image recorded material 1 of Example 25 was slightly reduced.

[0554] <Example 26>

[0555] A PET film was produced by the same method as the PET film described in paragraphs

[0142] to

[0145] and

[0154] to

[0158] of Japanese Patent Application Laid-Open No. 2011-184488.

[0556] Polyurethane resin (non-yellowing isocyanate type) (product name "SUPERFLEX 210", manufactured by D KS Co. Ltd., solid content: 33% by mass) 16.8 g

[0557] · Cross-linking agent (product name "EPOCROS WS-700", oxazoline-containing polymer, manufactured by NIPPON S HOKUBAICO., LTD., solid content: 25 mass %) 4.2 g

[0558] 2.0 g of 1 mass % ammonia water

[0559] · Colloidal silicon dioxide (product name "QUARTRON PL-3", manufactured by FUSOCHEMICAL CO., LTD., solid content: 20 mass %) 0.42 g

[0560] ·Pure water 76.6g

[0561] The above components were mixed to obtain an easy-adhesion agent composition.

[0562] The obtained easy-adhesive composition was applied by a bar coater (#6) so that the thickness after drying was 350 nm. Then, the PET film was placed in a hot air dryer (140° C.) to dry the easy-adhesive composition for about 5 minutes, thereby forming an easy-adhesive layer (0.3 μm to 0.5 μm).

[0563] An image was recorded on the highly adhesive layer in the same manner as in Example 3, thereby obtaining image recorded materials 1 and 2.

[0564] <Example 27>

[0565] The components shown below were mixed to prepare a primer composition. A solid image was formed on the corona-treated surface of the corona-treated polycarbonate using an inkjet recording device (product name "DMP-2850", manufactured by Fujifilm Corporation). An image was recorded on the solid image in the same manner as in Example 3 to obtain image records 1 and 2.

[0566] · Distilled water……97 parts

[0567] Polyvinyl alcohol (degree of polymerization 1000) ... 3 parts by mass

[0568] The evaluation results are shown in Tables 5 and 6.

[0569] [Table 5]

[0570]

[0571] [Table 6]

[0572]

[0573] <Example 28>

[0574] Image recorded materials 1 and 2 were obtained by recording images in the same manner as in Example 3 except that the curing light source was changed to an LED light source having a peak wavelength of 385 nm.

[0575] The evaluation results of color rendering and three-dimensional effect are the same as those in Example 3.

[0576] <Example 29>

[0577] A commercially available double-sided adhesive sheet OCA50 (adhesive layer having a refractive index of 1.477) was bonded to the image recorded material 1 (image recording layer having an average refractive index of 1.6) produced in Example 3.

[0578] The evaluation results of color rendering and three-dimensional effect are the same as those in Example 3.

[0579] The image recorded material obtained in Example 29 was visually observed to have less graininess and improved image quality compared to the image recorded material 1 produced in Example 3.

[0580] <Example 30>

[0581] On the image recorded material 1 (average refractive index of the image recording layer 1.6) prepared in Example 3, a solid image was recorded using ink (product name "LH-100CL", manufactured by Mimaki Engineering Co., Ltd.) and image data with a dot ratio of 100%. The average refractive index of the solid image layer was 1.55.

[0582] The evaluation results of color rendering and three-dimensional effect are the same as those in Example 3.

[0583] When the image recorded material obtained in Example 30 was visually observed, the graininess was further reduced and the image quality was further improved compared with the image recorded material obtained in Example 29.

[0584] <Example 31>

[0585] A laminate film (product name: "Graphical Long-term UV Fluorine Laminate Gloss GSL-6148", manufactured by LINTEC SIGN SYSTEM, INC.) was bonded to the image recorded material 1 produced in Example 3.

[0586] The appearance and color of the obtained image recorded material were visually observed to show no change from those of the image recorded material 1 produced in Example 3, and thus there was no practical problem.

[0587] <Example 32>

[0588] A laminate film (product name: 3M (registered trademark) Scotchcal (registered trademark) laminate film IJ4116N outdoor long-term glossy surface, manufactured by 3M Company) was bonded to the image recorded material 1 produced in Example 3.

[0589] The appearance and color of the obtained image recorded material were visually observed to confirm that there was no change from the image recorded material 1 produced in Example 3, and there was no problem in practical use.

[0590] <Example 33>

[0591] (Manufacturing of laminated glass)

[0592] -Laminated Glass A-

[0593] The image recorded material prepared in Example 3 was placed on a glass plate with a length of 50 mm, a width of 50 mm, and a thickness of 2 mm at the center of the glass plate so that the surface opposite to the image recording surface was in contact with the glass plate. An interlayer film for laminated glass (product name "S-LEC film", PVB film, manufactured by SEKISUI CHEMICAL CO., LTD., length of 50 mm, width of 50 mm, thickness of 0.38 mm) was placed on the image recording surface of the image recorded material sample A. Furthermore, a glass plate with a length of 50 mm, a width of 50 mm, and a thickness of 2 mm was placed on the interlayer film for laminated glass.

[0594] After being kept at 110° C. and 10 kPa (0.1 atmosphere) for 1 hour, the glass was heated at 130° C. and 1.3 MPa (13 atmosphere) for 20 minutes in an autoclave (manufactured by Kurihara Seisakusho Co., Ltd.) to remove bubbles, thereby obtaining laminated glass A.

[0595] -Laminated glass-

[0596] In the production of laminated glass B, an intermediate film for laminated glass (product name "S-LEC film", PVB film, manufactured by SEKISUI CHEMICAL CO., LTD., 50 mm in length, 50 mm in width, 0.38 mm in thickness) was also arranged on the back of the printed surface. Laminated glass B was obtained by the same method as that of laminated glass A.

[0597] In both of the laminated glasses A and B, no change in the appearance of the image was confirmed.

[0598] In addition, regarding the invention of Japanese Patent Application No. 2022-099947 filed on June 21, 2022 and Japanese Patent Application No. 2023-034111 filed on March 6, 2023, the entirety of the invention is incorporated into this specification by reference. Furthermore, all documents, patent applications, and technical standards described in this specification are incorporated into this specification by reference to the same extent as if each document, patent application, and technical standard were specifically and separately described as being incorporated by reference.

Claims

1. An image recorded material comprising a substrate and an inkjet image disposed on the substrate, The inkjet image comprises a cholesteric liquid crystal layer, The cholesteric liquid crystal layer has a stripe pattern of light and dark portions observed with a scanning electron microscope in a cross section along the thickness direction of the inkjet image, At least a portion of the line indicating the bright portion or the dark portion is a wavy line.

2. The image record according to claim 1, wherein: The period length of the wave of the line representing the bright portion or the dark portion is 5 μm to 125 μm.

3. The image recorded material according to claim 1 or 2, wherein: The maximum value of the amplitude of the line representing the bright portion or the dark portion in a direction perpendicular to an imaginary straight line representing the line representing the bright portion or the dark portion is 100 nm to 1000 nm.

4. The image recorded material according to claim 1 or 2, wherein: When the angle between a virtual straight line representing the bright portion or the dark portion and the main surface of the substrate is defined as an orientation angle, The cholesteric liquid crystal layer includes a region where the alignment angle is greater than or equal to 5°.

5. The image recorded material according to claim 1 or 2, wherein: The image recorded object is a decorative plate.

6. The image recorded material according to claim 1 or 2, wherein: A base layer is disposed between the substrate and the inkjet image.

7. A method for producing an image record, comprising: A step of preparing ink, wherein the ink contains a solvent having a boiling point of 100° C. or higher and lower than 300° C., a polymerizable liquid crystal compound, a chiral compound, a polymerization initiator, and a surfactant; The process of heating the substrate to above 45°C; The step of applying the ink to the heated substrate by inkjet recording; A step of heating the applied ink; and A step of irradiating the applied ink with active energy rays.

8. The method for producing an image recorded material according to claim 7, wherein: In the step of preparing the ink, two or more inks are prepared. In the step of applying the ink, a mixed region in which two or more inks are mixed is formed in at least a portion of the substrate by applying the ink. When the two or more inks are formed into ink films, the color difference between the two ink films is 25 or more.

9. The method for producing an image recorded material according to claim 7 or 8, wherein: In the process of applying the ink, the ink is applied using a multi-pass method.

10. The method for producing an image recorded material according to claim 7 or 8, wherein: irradiating the active energy ray using a mercury lamp, The content of the polymerization initiator is 6 parts by mass to 15 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound.

11. A decorative molded product comprising the molded product of the image recorded material according to claim 5.

Images