WO2023085370A1 - 画像記録物及び画像記録方法 - Google Patents
画像記録物及び画像記録方法 Download PDFInfo
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F19/00—Advertising or display means not otherwise provided for
- G09F19/12—Advertising or display means not otherwise provided for using special optical effects
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F19/00—Advertising or display means not otherwise provided for
- G09F19/12—Advertising or display means not otherwise provided for using special optical effects
- G09F19/14—Advertising or display means not otherwise provided for using special optical effects displaying different signs depending upon the view-point of the observer
Definitions
- the present disclosure relates to an image recorded matter and an image recording method.
- International Publication No. 2018/043678 has a cholesteric liquid crystal layer having wavelength-selective reflectivity, and the cholesteric liquid crystal layer has a striped pattern of bright and dark portions observed with a scanning electron microscope in cross section. and the striped pattern has a wavy structure, and the average value of the peak-to-peak distances of the wavy structure is 0.5 ⁇ m to 50 ⁇ m.
- the present disclosure includes the following aspects. ⁇ 1> comprising a substrate and an image recorded on the substrate;
- the image includes a cholesteric liquid crystal layer,
- the cholesteric liquid crystal layer has a striped pattern of bright and dark areas observed with a scanning electron microscope (hereinafter sometimes abbreviated as "SEM") in a cross section along the thickness direction of the image, At least two regions in which the absolute value of the difference in the orientation angle is 5° or more when the angle between the continuous line, which is the light or dark portion, and the main surface of the substrate is the orientation angle,
- SEM scanning electron microscope
- ⁇ 2> The recorded image according to ⁇ 1>, wherein the orientation angle is -5° to 5° in at least part of the cholesteric liquid crystal layer.
- ⁇ 3> The image recorded matter according to ⁇ 1> or ⁇ 2>, wherein at least one of the two regions has a width of 1 mm to 40 mm in the in-plane direction of the substrate.
- ⁇ 4> The image is The image recorded matter according to any one of ⁇ 1> to ⁇ 3>, including a region having a film thickness difference of 0.5 ⁇ m or more within a width of 40 mm in the in-plane direction of the substrate.
- the image is The image recorded matter according to any one of ⁇ 1> to ⁇ 4>, including a region having a film thickness difference of 1 ⁇ m to 30 ⁇ m within a width of 10 mm in the in-plane direction of the substrate.
- ⁇ 6> The image recorded matter according to any one of ⁇ 1> to ⁇ 6>, wherein the image has a selective reflection wavelength of 460 nm or more.
- ⁇ 7> Any one of ⁇ 1> to ⁇ 5>, wherein another image not containing a cholesteric liquid crystal layer is further arranged between the substrate and the image or on the image on the substrate.
- image recordings of ⁇ 8> A step of applying an ink containing a polymerizable liquid crystal compound, a chiral compound, and a solvent onto a substrate by an inkjet recording method; A step of irradiating the ink applied on the base material with an active energy ray to record an image, which is a cured film of the ink; including In the step of applying the ink, an image recording method in which the ink is applied under the condition that the film thickness difference within a width of 40 mm in the in-plane direction of the substrate is 0.5 ⁇ m or more in the image to be recorded.
- the solvent contains a solvent having a boiling point of 100°C or higher and lower than 300°C.
- ⁇ 10> further comprising heating the substrate to 45° C. or higher;
- ⁇ 11> After the step of applying the ink and before the step of irradiating the active energy ray, further comprising heating the ink applied on the substrate, In the step of heating the ink, any one of ⁇ 8> to ⁇ 10>, wherein the content of the solvent in the ink after heating is 50% by mass or less with respect to the content of the solvent at the time of applying the ink.
- an image recorded matter and an image recording method that provide a stereoscopic effect are provided.
- FIG. 1 is a schematic diagram showing a striped pattern of bright portions and dark portions observed by SEM of a cross section of an image recording material, and is a diagram for explaining the orientation angle.
- FIG. 2 is a diagram for explaining a method of confirming a change in orientation angle.
- FIG. 3A is a schematic top view of an image recorded matter with varying film thicknesses.
- FIG. 3B is a schematic top view of an image recorded matter with varying film thicknesses.
- FIG. 4A is an example of image data in which the print rate is continuously changed, centering on a portion with a high print rate.
- FIG. 4B is an example of image data in which solid images with different print rates are arranged adjacently.
- FIG. 4C is an example of image data in which the print rate is continuously changed, centering on a portion with a low print rate.
- the numerical range indicated using “to” means a range including the numerical values before and after “to” as the minimum and maximum values, respectively.
- the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise.
- the upper limit or lower limit described in a certain numerical range may be replaced with the values shown in the examples.
- the amount of each component in the composition refers to the total amount of the multiple substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified.
- step is used not only for independent steps, but also for cases where the intended purpose of the step is achieved, even if it cannot be clearly distinguished from other steps. include.
- the image recorded matter of the present disclosure includes a substrate and an image recorded on the substrate, the image includes a cholesteric liquid crystal layer, and the cholesteric liquid crystal layer is scanned in a cross section along the thickness direction of the image.
- the absolute difference in the orientation angle when the orientation angle is the angle between the continuous line, which is the bright or dark area, and the main surface of the substrate, which has a striped pattern of bright and dark areas observed with a type electron microscope.
- At least two regions having a value of 5° or more are included, and each of the two regions has a width length of 1 mm or more in the in-plane direction of the substrate.
- the striped pattern observed in the SEM of the image cross section there are two regions where the absolute value of the difference in the orientation angle is 5 ° or more, and the width of each region is 1 mm or more.
- parts of the image appear to be shadowed.
- the presence of shadows makes it possible to visually recognize a macroscopically flat image as if it were three-dimensional.
- a remarkable stereoscopic effect can be obtained.
- the background color is white and observed, there is a portion where glossiness becomes noticeable depending on the angle, and a stereoscopic effect can be obtained by locally shining.
- the background color is other than white and black, the same stereoscopic effect can be obtained.
- the striped pattern observed by SEM of the image cross section has a wavy structure, and the average value of the peak-to-peak distance of the wavy structure is 0.5 ⁇ m to 50 ⁇ m. Therefore, it exhibits high brightness even when viewed from a direction away from the specular reflection of the illumination light, and does not focus on the stereoscopic effect.
- An image record of the present disclosure includes a substrate.
- the base material is not particularly limited, and any base material can be selected.
- the substrate may be an ink-absorbing substrate, a low-ink-absorbing substrate, or a non-ink-absorbing substrate.
- Substrates include, for example, paper, leather, cloth, and resin. Above all, from the viewpoint of color development, the substrate is preferably an ink-non-absorbing substrate, and more preferably a resin substrate.
- the resin constituting the resin base material examples include cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, acrylic resin, chlorinated polyolefin resin, polyethersulfone resin, and polyethylene terephthalate. (PET), polyethylene naphthalate, nylon, polyethylene, polystyrene, polypropylene, polycycloolefin resin, polyimide resin, polycarbonate resin, and polyvinyl acetal.
- the resin base material may be a base material containing only one of these resins, or may be a base material in which two or more of these resins are mixed. Moreover, other layers such as an easy-adhesion layer, an antistatic layer, and an antifouling layer may be formed on these resins, and the surface of the base material may be subjected to hydrophilic treatment.
- the thickness of the base material is not particularly limited, and is, for example, 1 ⁇ m to 10 mm.
- An image record of the present disclosure includes an image recorded on a substrate.
- the image includes a cholesteric liquid crystal layer, and the cholesteric liquid crystal layer has a striped pattern of bright and dark portions observed by SEM in a cross section along the thickness direction of the image, and a continuous line that is a bright or dark portion.
- the main surface of the substrate is the orientation angle, the absolute value of the difference in orientation angle is 5 ° or more.
- the width length in the direction is 1 mm or more.
- a cholesteric liquid crystal layer is a layer containing at least a cholesteric liquid crystal phase.
- a cholesteric liquid crystal phase means a phase in which liquid crystal molecules are helically arranged. In the case of the cholesteric liquid crystal layer, a striped pattern of bright and dark portions is observed by SEM.
- a striped pattern of bright and dark areas observed by SEM can be confirmed by, for example, the following method.
- the image is cut through the thickness of the image to obtain cross-sectional samples.
- a cross-sectional SEM image is observed using a scanning electron microscope (accelerating voltage: 2 kV, observation magnification: 5000 and 10000 times). It can be confirmed that there is a dark and light striped pattern due to the change in the refractive index of the cholesteric liquid crystal phase.
- black portions are referred to as dark portions
- white portions are referred to as bright portions.
- one cycle of bright and dark areas corresponds to the 180-degree twist of the liquid crystal. Therefore, the two cycles of the bright portion and the dark portion correspond to 360 degrees of twist of the liquid crystal. That is, the width of two cycles of the bright portion and the dark portion corresponds to the length of the helical pitch in the cholesteric liquid crystal layer.
- the normal direction of the continuous line which is the bright portion or the dark portion, means the direction of the helical axis in the cholesteric liquid crystal layer.
- the orientation angle is the angle between the continuous line, which is the bright portion or the dark portion, and the main surface of the substrate.
- the main surface of the substrate refers to the surface with the widest area among the surfaces of the substrate.
- FIG. 1 is a schematic diagram showing a striped pattern of bright and dark portions observed by SEM of a cross section of an image recorded product in which an image 2 is recorded on a substrate 1, and is used for explaining the orientation angle. It is a diagram. For example, as shown in FIG. 1, a straight line 21 is drawn along the continuous line of the dark area. As the orientation angle, the angle ⁇ 1 between the main surface 11 of the substrate and the straight line 21 is measured.
- the orientation angle is positive when the straight line is upward-sloping (that is, has a positive slope in the XY coordinates), and is represented as a plus when the straight line is downward-sloping (that is, it has a negative slope in the XY coordinates). ), it shall be expressed as a minus. Therefore, in FIG. 1, the angle ⁇ 1 is represented by a plus.
- FIG. 2 is a diagram for explaining a method of confirming a change in orientation angle.
- first virtual line 32 (first virtual lines 321 to 324 in FIG. 2) is drawn at an arbitrary position on the image record 30 .
- second virtual line 33 (second virtual lines 331 to 339 in FIG. 2) orthogonal to the first virtual line is drawn.
- the first virtual lines 321-324 are parallel to each other and the second virtual lines 331-339 are parallel to each other.
- the number of first virtual lines and second virtual lines is not particularly limited.
- the directions of the first virtual line and the second virtual line are not particularly limited as long as they are orthogonal to each other.
- the directions of the first virtual line and the second virtual line are the direction parallel to the direction in which the film thickness changes. is preferably perpendicular to the direction in which .
- the direction in which the film thickness is changing can be confirmed by visually observing the image recorded matter having the film thickness difference.
- the film thickness is changing includes a mode in which the film thickness increases and a mode in which the film thickness decreases in an arbitrary direction. Further, the film thickness may vary over the entire image recorded matter, or may vary only in part of the image recorded matter.
- the orientation angle at the intersection of the first virtual line and the second virtual line is measured. , measured according to the method for measuring the orientation angle described above.
- the intersection points t1, t2, and t3 shown in FIG. 2 are the intersection points of the first virtual line 321 and the second virtual lines 331, 332, and 333 in the cross section obtained by cutting along the first virtual line 321. be.
- the orientation angle at the intersection of the first virtual line and the second virtual line is measured according to the orientation angle measurement method described above.
- the intersection points s1, s2, and s3 shown in FIG. 2 are the intersection points of the second virtual line 338 and the first virtual lines 321, 322, and 323 in the cross section obtained by cutting along the second virtual line 338. be.
- the change direction of the orientation angle can be determined.
- the length in the direction in which the orientation angle is changing is defined as the width length of two regions whose absolute value of the orientation angle difference is 5° or more.
- the change in the orientation angle in the cross section obtained by cutting along the first virtual line, the change in the orientation angle can be confirmed, and in the cross section obtained by cutting along the second virtual line, the orientation is confirmed. and a mode in which a change in angle can be confirmed.
- a method for identifying two regions in which the absolute value of the orientation angle difference is 5° or more in the above two modes will be described using an image recorded matter having a film thickness difference.
- the image recorded matter shown in FIG. 3A is an example of an image recorded matter obtained by performing image recording using the image data shown in FIG. 4A, which will be described later.
- an arrow 41 indicates the direction in which the film thickness is changing.
- the film thickness gradually increases in the direction of arrow 41 from the left side of the image recorded product, the film thickness is the thickest in the central portion of the image recorded product, and the film thickness increases in the direction of arrow 41 from the central portion. The film thickness is gradually thinned.
- a virtual parallel line 42 (421 to 424) parallel to the direction of the arrow 41 and a virtual orthogonal line 43 (431 to 424) perpendicular to the direction of the arrow 41 439) and draw. Measure the orientation angle at each intersection.
- the orientation angle shall be measured by observing the cross section from the left side of the paper surface of FIG. 3A.
- the orientation angle at each intersection is 0°.
- the orientation angle at the intersection of the virtual parallel line 421 and the virtual orthogonal line 431 is -15°
- the orientation angle at the intersection of the virtual parallel line 421 and the virtual orthogonal line 432 is -8°
- the orientation angle at the intersection of the virtual parallel line 421 and the virtual orthogonal line 432 is -8°
- the orientation angle at the intersection of the virtual parallel line 421 and the virtual orthogonal line 433 is -5°
- the orientation angle at the intersection of the virtual parallel line 421 and the virtual orthogonal line 434 is -2.5°
- the orientation angle at the intersection of the virtual parallel line 421 and the virtual orthogonal line 435 is 0°
- the orientation angle at the intersection of the virtual parallel line 436 is the orientation angle at the intersection of the virtual parallel line
- the orientation angle at the intersection of the virtual parallel line 422 and the virtual orthogonal line 431 is also ⁇ 15°.
- the orientation angle at the intersection point is also ⁇ 15°
- the orientation angle at the intersection point between the imaginary parallel line 424 and the imaginary orthogonal line 431 is also ⁇ 15°. That is, the orientation angle is substantially constant in the cross section obtained by cutting along the virtual orthogonal line 431 .
- the orientation angles are substantially constant in respective cross sections obtained by cutting along imaginary orthogonal lines 432, 433, 434, 435, 436, 437, 438, and 439.
- FIG. In the specific description of the orientation angle above, the “virtual parallel line 421” can be read as the virtual parallel line 422, the virtual parallel line 423, or the virtual parallel line 424.
- the orientation angle in the section obtained by cutting along the imaginary orthogonal line, which is the section having the largest absolute value of the orientation angle is adopted. Also, in this case, it can be seen that the orientation angle changes in the direction of arrow 41 .
- the length in the direction in which the orientation angle is changing is defined as the width length of two regions whose absolute value of the orientation angle difference is 5° or more.
- the orientation angle in the region from the virtual orthogonal line 431 to the virtual orthogonal line 434 is -15° to -2.5°
- the orientation angle in the region from the virtual orthogonal line 436 to the virtual orthogonal line 439 is 2.5°. 5° to 15°.
- both of the above distances are 1 mm or more, at least two regions in which the absolute value of the orientation angle difference is 5° or more are included, and both of the two regions are the width in the in-plane direction of the base material.
- the length is 1 mm or more. If the distance from the virtual orthogonal line 431 to the virtual orthogonal line 434 and the distance from the virtual orthogonal line 436 to the virtual orthogonal line 439 are 1 mm or more, the area from the virtual orthogonal line 431 to the virtual orthogonal line 434 and the virtual orthogonal line The area from line 436 to imaginary orthogonal line 439 corresponds to the above two areas.
- the upper limit of the absolute value of the orientation angle difference is not particularly limited, it is, for example, 25°. Also, the upper limit of the width of the two regions whose absolute value of the orientation angle difference is 5° or more is not particularly limited, but is, for example, 40 mm.
- the image recorded matter shown in FIG. 3B is an example of an image recorded matter obtained by performing image recording using the image data shown in FIG. 4B, which will be described later.
- the image data shown in FIG. 4B When the image data shown in FIG. 4B is used, there is a tendency that the ink film is smoothly formed at the boundary portions where the coverage ratios are different. Therefore, the image has a portion where the film thickness changes continuously.
- an arrow 51 indicates the direction in which the film thickness is changing.
- the film thickness is almost The film thickness is constant, and the film thickness gradually decreases in the direction of the arrow 51 in the region sandwiched between virtual orthogonal lines 533 and 537 which will be described later.
- a virtual parallel line 52 (521 to 524) and a virtual orthogonal line 53 (531 to 539) are drawn. Measure the orientation angle at each intersection.
- the orientation angle shall be measured by observing the cross section from the lower side of the paper surface of FIG. 3B.
- the orientation angle at each intersection is 0°.
- the orientation angle at the intersection of the virtual parallel line 521 and the virtual orthogonal line 531 is 0°
- the orientation angle at the intersection of the virtual parallel line 521 and the virtual orthogonal line 532 is 0°
- the orientation angle at the intersection of the virtual parallel line 521 and the virtual orthogonal line 533 is 0°
- the orientation angle at the intersection of the virtual parallel line 521 and the virtual orthogonal line 534 is -7°
- the orientation angle at the intersection of the imaginary parallel line 521 and the imaginary orthogonal line 535 is -10°
- the orientation angle at the intersection of the imaginary parallel line 521 and the imaginary orthogonal line 536 is -7°
- the orientation angle at the intersection of the virtual parallel line 521 and the virtual orthogonal line 537 is 0°
- the orientation angle at the intersection of the virtual parallel line 521 and the virtual orthogonal line 538 is 0°
- the orientation angle at each intersection of the virtual parallel line 522 and the virtual orthogonal lines 531, 532, 533, 534, 535, 536, 537, 538, 539 are respectively 0°, 0°, 0°, ⁇ 7°, ⁇ 10°, ⁇ 7°, 0°, 0°, 0°.
- the orientation angle in the cross section obtained by cutting along the virtual parallel line 521 and the orientation angle in the cross section obtained by cutting along the virtual parallel lines 522, 523, and 534 are substantially constant on the same virtual orthogonal line. be.
- the “virtual parallel line 521” can be read as the virtual parallel line 522, the virtual parallel line 523, or the virtual parallel line 524.
- the orientation angle in the section obtained by cutting along the imaginary parallel line which is the section having the largest absolute value of the orientation angle
- the orientation angle changes in the direction of arrow 51 .
- the length in the direction in which the orientation angle is changing is defined as the width length of two regions whose absolute value of the orientation angle difference is 5° or more.
- the orientation angle in the region from the virtual orthogonal line 531 to the virtual orthogonal line 533 is 0°
- the orientation in the region from the virtual orthogonal line 534 to the virtual orthogonal line 536 is 0°.
- the angle is -10° to -7°.
- both of the above distances are 1 mm or more, at least two regions in which the absolute value of the orientation angle difference is 5° or more are included, and both of the two regions are the width in the in-plane direction of the base material. It is an image record that satisfies that the length is 1 mm or more. If the distance from the virtual orthogonal line 531 to the virtual orthogonal line 533 and the distance from the virtual orthogonal line 534 to the virtual orthogonal line 536 are 1 mm or more, the area from the virtual orthogonal line 531 to the virtual orthogonal line 533 and the virtual orthogonal line The area from line 534 to imaginary orthogonal line 536 corresponds to the above two areas.
- the orientation angle in the region from the virtual orthogonal line 537 to the virtual orthogonal line 539 is 0°. to an imaginary orthogonal line 539 and an area from an imaginary orthogonal line 534 to an imaginary orthogonal line 536 may be regarded as the above two areas.
- the image recorded matter of the present disclosure includes at least two regions in which the absolute value of the orientation angle difference is 5° or more, and the width length of the two regions is 1 mm or more. , the above two regions need only exist. That is, it may be determined whether or not the above two areas exist in a part of the image recorded matter. In the case of the image recorded matter 50 shown in FIG. 3B, focusing on the change in the orientation angle, it is confirmed whether or not the above two areas exist only in the area from the virtual orthogonal line 531 to the virtual orthogonal line 536. can be done.
- the cholesteric liquid crystal layer includes at least two regions in which the absolute value of the orientation angle difference is 5° or more, and both of the two regions have a width in the in-plane direction of the substrate.
- the length is 1 mm or more.
- the image record of the present disclosure may include other areas than the at least two areas.
- the distance between the two regions where the absolute value of the orientation angle difference is 5° or more is small, from the viewpoint of enhancing the stereoscopic effect.
- regions with the shortest distance between the two regions are also referred to as region 1 and region 2, respectively.
- the distance between the regions 1 and 2 is preferably 5 mm or less, more preferably 1 mm or less, and even more preferably 0.5 mm or less.
- the absolute value of the orientation angles of the regions 1 and 2 is preferably 0° to 25°, more preferably 0° to 15°. Further, an embodiment in which the orientation angle of one of the regions 1 and 2 is ⁇ 25° to ⁇ 2.5° and the orientation angle of the other of the regions 1 and 2 is 2.5° to 25°; More preferably, the absolute value of the orientation angle of one of the regions 1 and 2 is 3° or less, and the absolute value of the orientation angle of the other is 8° or more.
- the orientation angle is preferably -5° to 5°, more preferably -1° to 1°, in at least part of the cholesteric liquid crystal layer. That is, the cholesteric liquid crystal layer preferably includes a region with an orientation angle of -5° to 5°. If the cholesteric liquid crystal layer contains a region of horizontal alignment (that is, the alignment angle is 0°) or a region close to horizontal alignment, and there is a region of high alignment angle in the adjacent region, the stereoscopic effect is obtained. is more pronounced.
- both of the two regions where the absolute value of the orientation angle difference is 5° or more have a width length of 1 mm or more in the in-plane direction of the base material, and from the viewpoint of further exhibiting the stereoscopic effect, the two regions are At least one of the regions preferably has a width of 1 mm to 40 mm in the in-plane direction of the substrate. Further, from the viewpoint of further exerting the stereoscopic effect, it is more preferable that at least one of the two regions has a width of 1 mm to 5 mm in the in-plane direction of the substrate. In particular, in at least one of the regions 1 and 2, the width in the in-plane direction of the substrate is preferably 1 mm to 40 mm, more preferably 1 mm to 5 mm.
- the image preferably includes an area having a film thickness difference of 0.5 ⁇ m or more within a width of 40 mm in the in-plane direction of the substrate. More preferably, the film thickness difference is 1 ⁇ m or more.
- the upper limit of the film thickness difference is not particularly limited, and is, for example, 30 ⁇ m. More preferably, the image includes a region having a film thickness difference of 1 ⁇ m to 30 ⁇ m within a width of 10 mm in the in-plane direction of the substrate. More preferably, the film thickness difference is 1 ⁇ m to 10 ⁇ m.
- the film thickness difference is the value obtained by subtracting the thickness of the thinnest portion of the image (i.e., minimum thickness) from the thickness of the thickest portion of the image (i.e., maximum thickness).
- the film thickness of the image is measured by the following method.
- the image record is cut along the thickness direction of the image to obtain a cross section of the image.
- a section of the image is observed using a scanning electron microscope (accelerating voltage: 2 kV, observation magnification: 5000 times and 10000 times) to measure the film thickness of the image.
- the image has a selective reflection wavelength of 460 nm or more from the viewpoint of exhibiting a stereoscopic effect.
- the selective reflection wavelength is calculated by measuring spectral reflectance with a fluorescence spectrodensitometer.
- the selective reflection wavelength is calculated using a fluorescence spectrodensitometer (product name “FD-7”, manufactured by Konica Minolta).
- FD-7 fluorescence spectrodensitometer
- a black sheet of opacity measurement paper standard: JIS K 5600, manufactured by TP Giken
- the color is measured by setting the image so that it is the outermost layer.
- another image not including a cholesteric liquid crystal layer is arranged between the substrate and the image or on the image on the substrate.
- the other image may or may not contain colorant.
- an image containing no colorant is placed between the substrate and the image or above the image on the substrate, while retaining the stereoscopic effect obtained with the present disclosure including the cholesteric liquid crystal layer, A special design property can be imparted by the difference in texture such as glossiness and the combination with the background color.
- the substrate preferably has a light transmittance of 30% or more at a wavelength of 600 nm. The image can also be visually recognized from the substrate side.
- the image recording method of the present disclosure includes a step of applying an ink containing a polymerizable liquid crystal compound, a chiral compound, and a solvent onto a substrate by an inkjet recording method (hereinafter also referred to as an “ink applying step”); A step of irradiating the ink applied on the material with an active energy ray to record an image as a cured film of the ink (hereinafter also referred to as an “active energy ray irradiation step”) is included. Then, in the ink applying step, the ink is applied under the condition that the film thickness difference within the width of 40 mm in the in-plane direction of the base material is 0.5 ⁇ m or more in the image to be recorded.
- an ink containing a polymerizable liquid crystal compound, a chiral compound, and a solvent is applied onto the substrate by an inkjet recording method.
- Only one type of ink may be applied in the ink applying step, or two or more types may be applied.
- the types and contents of the polymerizable liquid crystal compound, chiral compound, and solvent contained in each ink may be the same or different.
- a polymerizable liquid crystal compound is a liquid crystal compound having a polymerizable group.
- the liquid crystal compound may be a rod-like liquid crystal compound or a discotic liquid crystal compound, but is preferably a rod-like liquid crystal compound.
- rod-shaped liquid crystal compounds examples include rod-shaped nematic liquid crystal compounds.
- Rod-like nematic liquid crystal compounds include 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, phenyl Dioxane compounds, tolan compounds or alkenylcyclohexylbenzonitrile compounds are preferably used.
- the rod-shaped liquid crystal compound not only a low-molecular-weight liquid crystal compound but also a high-molecular-weight liquid crystal compound can be used.
- a polymerizable liquid crystal compound is obtained by introducing a polymerizable group into a liquid crystal compound.
- Polymerizable groups include, for example, polymerizable unsaturated groups, epoxy groups and aziridinyl groups. 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, it is more preferable that the polymerizable liquid crystal compound has two polymerizable groups in the molecule.
- polymerizable liquid crystal compound examples include the following compounds (1) to (17).
- the polymerizable liquid crystal compound is not limited to the following examples.
- each X 1 independently represents an integer of 2 to 5.
- examples of polymerizable liquid crystal compounds other than those exemplified above include cyclic organopolysiloxane compounds as disclosed in JP-A-57-165480.
- the ink may contain only one type of polymerizable liquid crystal compound, or may contain two or more types.
- the ink preferably contains two or more different polymerizable liquid crystal compounds. Color reproducibility can be further improved by using two or more kinds of polymerizable liquid crystal compounds.
- 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 more preferably 15% by mass to 45% by mass with respect to the total amount of the ink. It is particularly preferred to have
- a chiral compound is also called an optically active compound.
- a chiral compound has a function of inducing a helical structure of a polymerizable liquid crystal compound. The twist direction or pitch of the induced helical structure differs depending on the type and content of the chiral compound.
- the chiral compound is not particularly limited. described) can be used, and include, for example, isosorbide derivatives and isomannide derivatives.
- a chiral compound generally contains an asymmetric carbon atom, but it may be a compound that does not contain an asymmetric carbon atom as long as it has chirality.
- Examples of chiral compounds include axially chiral compounds having a binaphthyl structure, helical chiral compounds having a helicene structure, and planar chiral compounds having a cyclophane structure.
- the chiral compound may have 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 produced by the polymerization reaction of the chiral compound and the polymerizable liquid crystal compound. It is formed.
- the polymerizable group is preferably the same kind of group as the polymerizable group possessed by the polymerizable liquid crystal compound.
- the polymerizable group of the chiral compound is preferably a polymerizable unsaturated group, an epoxy group or an aziridinyl group, more preferably a polymerizable unsaturated group, and particularly preferably an ethylenically unsaturated group.
- the chiral compound itself may be a liquid crystal compound.
- chiral compounds include the following compounds.
- the chiral compound that can be used in the ink composition is not limited to the following examples.
- "Me" in a compound means a methyl group.
- each X independently represents an integer of 2 to 5.
- the content of the chiral compound is preferably 1 part by mass to 15 parts by mass, more preferably 1.5 parts by mass to 5 parts by mass, with respect to 100 parts by mass of the polymerizable liquid crystalline compound in the ink composition. is more preferable.
- solvent The type of solvent is not particularly limited and can be appropriately selected depending on the purpose.
- solvents examples include ketone solvents, alkyl halide solvents, amide solvents, sulfoxide solvents, heterocyclic compounds, hydrocarbon solvents, ester solvents, and ether solvents.
- the solvent preferably contains a solvent with a boiling point of 100°C or more and less than 300°C.
- a solvent having a boiling point of 100° C. or more and less than 300° C. is contained, the ink jettability is improved.
- a boiling point means a boiling point under 1 atmosphere (101325 Pa).
- the boiling point is measured with a boiling point meter, for example, using a boiling point measuring instrument manufactured by Titan Technologies (product name "DosaTherm 300").
- ethylene glycol (boiling point: 198°C), propylene glycol (boiling point: 188°C), 1,2-butanediol (boiling point: 194°C), 2,3-butanediol (boiling point: 183°C), 2-methyl-1, 3-propanediol (boiling point: 124°C), 2-methyl-2,4-pentanediol (boiling point: 198°C), 1,2,6-hexanetriol (boiling point: 178°C), 1,2,3-butane triol (boiling point: 175°C), 1,2,4-butanetriol (boiling point: 170°C), diethylene glycol (boiling point: 244°C), dipropylene glycol (boiling point: 231°C), 1,3-propanediol (boiling point: 214°C), 1,3-butanediol
- the content of the solvent is preferably 20% by mass to 90% by mass, preferably 40% by mass to 80% by mass, and more preferably 50% by mass to 80% by mass with respect to the total amount of the ink. preferable.
- the ink preferably further contains a polymerization initiator.
- the polymerization initiator is preferably a photopolymerization initiator, and more preferably a radical polymerization initiator having a function of generating radicals upon irradiation with ultraviolet rays.
- polymerization initiators examples 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. agents.
- the polymerization initiator is preferably an acylphosphine oxide photopolymerization initiator, specifically, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide or bis(2,4,6-trimethylbenzoyl)phenyl Phosphine oxides are preferred.
- the content of the polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 12 parts by mass, with respect to 100 parts by mass of the polymerizable liquid crystal compound. preferable.
- the ink may contain additives as necessary within a range that does not impair the effects of the present disclosure.
- Additives include, for example, surfactants, cross-linking agents, and non-polymerizable polymers for improving ink ejection properties.
- the polymerizable liquid crystal compound is horizontally aligned on the air interface side when the ink is cured, and the helical axis direction is controlled to be more uniform.
- the surfactant is preferably a compound capable of functioning as an alignment control agent for stably or rapidly forming a cholesteric structure of planar alignment.
- Examples of surfactants include silicone-based surfactants and fluorine-based surfactants, with fluorine-based surfactants being preferred.
- the content of the surfactant is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.01 parts by mass to 5 parts by mass, and 0.01 parts by mass with respect to 100 parts by mass of the content of the polymerizable liquid crystal compound. parts to 1 part by mass is more preferable.
- the viscosity of the ink is preferably 7 mPa ⁇ s or more, more preferably 8 mPa ⁇ s or more, and even more preferably 10 mPa ⁇ s or more.
- the upper limit of the viscosity of the ink is, for example, 30 mPa ⁇ s from the viewpoint of the ejection property of the ink.
- the viscosity of the ink is measured at 25°C using a viscometer, for example, using a viscometer (product name "RE-85L", manufactured by Toki Sangyo Co., Ltd.).
- the surface tension of the ink is preferably 20 mN/m to 40 mN/m, more preferably 23 mN/m to 35 mN/m.
- the surface tension of the ink is measured at 25°C using a surface tension meter, for example, using a surface tension meter (product name "DY-700", manufactured by Kyowa Interface Science Co., Ltd.).
- Inkjet recording method As the inkjet recording method, a generally known method can be used. method), an acoustic ink jet method in which an electric signal is converted into an acoustic beam to irradiate the ink composition and eject the ink composition using radiation pressure, and an acoustic ink jet method in which the ink composition is heated to form bubbles and the pressure generated is A thermal ink jet method to be used can be mentioned.
- image recording methods by an inkjet recording apparatus include a shuttle scan method (also referred to as a "serial head method”) in which an image is recorded using a short serial head, and a recording element corresponding to the entire width of the recording medium.
- a single-pass method also referred to as a "line head method” in which image recording is performed using a line head in which are arranged.
- the shuttle scan method image recording is performed while scanning the serial head in the width direction of the recording medium.
- the single-pass method an image can be printed on the entire surface of the printing medium by scanning the printing medium in a direction perpendicular to the array direction of the printing elements.
- the single pass method does not require a transport system such as a carriage for scanning the serial head. Further, in the single-pass method, complicated scanning control of the movement of the carriage and the print medium is not required, and only the print medium is moved, so that the printing speed can be increased compared to the shuttle scan method.
- the shuttle scan method By applying ink to the same position multiple times, the film thickness of the image can be increased. Further, when the shuttle scan method is used, coalescence of the ink droplets is suppressed, so the stereoscopic effect is enhanced.
- the ink is applied under the condition that the film thickness difference within the width of 40 mm in the in-plane direction of the substrate is 0.5 ⁇ m or more in the image to be recorded.
- the film thickness of the image to be recorded can be controlled by, for example, the amount of ejected liquid droplets, the printing rate, and the like. Therefore, as a method of making the film thickness difference of a recorded image 0.5 ⁇ m or more, there is a method of changing the amount of ejected droplets, the printing ratio, etc., depending on the position of the ink applied on the base material.
- a) A method in which the amount of liquid droplets ejected is reduced in portions where the film thickness is to be thinned, and the amount of ejected liquid droplets is increased in portions where the film thickness is to be thickened.
- b) A method in which the print rate is lowered in the portion where the film thickness is to be thinned and the print rate is increased in the portion where the film thickness is to be thickened.
- c) Any combination of a) and b).
- FIG. 4A to 4C show specific examples of image data with varying printing ratios.
- FIG. 4A is an example of image data in which the print rate is continuously changed, centering on a portion with a high print rate.
- FIG. 4B is an example of image data in which solid images with different print rates are arranged adjacently.
- FIG. 4C is an example of image data in which the print rate is continuously changed, centering on a portion with a low print rate.
- An image recorded matter 40 shown in FIG. 3A is an example of an image recorded material obtained when the image data shown in FIG. 4A is used.
- An image recorded matter 50 shown in FIG. 3B is an example of an image recorded matter obtained when the image data shown in FIG. 4B is used.
- an image recorded matter 50 shown in FIG. 3B is an example of an image recorded matter obtained when the image data shown in FIG. 4B is used.
- an image recorded matter is obtained in which the film thickness is the thinnest at the central portion and the film thickness gradually increases from the central portion toward the two opposite sides.
- the ink under the condition that the film thickness difference within the width of 40 mm in the in-plane direction of the base material is 0.5 ⁇ m or more. .
- the film thickness difference of an image to be recorded there is no particular upper limit for the film thickness difference of an image to be recorded, and it is, for example, 30 ⁇ m.
- ⁇ Active energy ray irradiation step the ink applied on the substrate is irradiated with an active energy ray to record an image, which is a cured film of the ink.
- examples of active energy rays include ultraviolet rays, visible rays, and electron beams.
- the active energy rays are preferably ultraviolet rays (hereinafter also referred to as “UV”).
- the peak wavelength of ultraviolet rays is preferably 100 nm to 405 nm, more preferably 200 nm to 395 nm.
- the amount of ultraviolet light exposure is preferably 20 mJ/cm 2 to 5 J/cm 2 , more preferably 100 mJ/cm 2 to 1,500 mJ/cm 2 .
- the irradiation conditions and basic irradiation method the irradiation conditions and irradiation method disclosed in JP-A-60-132767 can be applied.
- the irradiation method includes a method in which light sources are provided on both sides of the head unit including the ink ejection device, and the head unit and the light source are scanned by a so-called shuttle method, or a method in which a separate light source is used without driving. preferable. Among them, it is preferable to uniformly irradiate the entire image recording surface with ultraviolet rays.
- Mercury lamps, gas lasers, and solid-state lasers are mainly used as light sources for ultraviolet irradiation, and mercury lamps, metal halide lamps, and ultraviolet fluorescent lamps are widely known.
- UV-LEDs light-emitting diodes
- UV-LDs laser diodes
- 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.
- the image recording method of the present disclosure preferably further includes a step of heating the substrate (hereinafter referred to as "substrate heating step”). After the substrate heating step, the ink is preferably applied onto the heated substrate in the ink application step.
- the means for heating the substrate is not particularly limited, and examples thereof include heat drums, hot air, infrared lamps, ovens, heat plates, and hot plates.
- the heating temperature of the substrate is preferably 40°C or higher, more preferably 40°C to 100°C, even more preferably 45°C to 80°C.
- the image recording method of the present disclosure further includes a step of heating the ink applied onto the substrate after the ink application step and before the active energy ray irradiation step (hereinafter referred to as "ink heating step”). is preferably included.
- the content of the solvent in the ink after heating is preferably 50% by mass or less, more preferably 10% by mass or less, relative to the solvent content at the time the ink is applied. .
- the solvent content in the ink is preferably 50% by mass or less before the active energy ray irradiation step.
- the liquid crystal compound contained in the ink is rapidly oriented. A region having a larger absolute value of the orientation angle can be formed in the cross section along the thickness direction of the image, and the stereoscopic effect of the image recorded matter can be further exhibited.
- the lower limit of the solvent content in the ink after heating relative to the solvent content at the time the ink is applied is not particularly limited, and is, for example, 0% by mass.
- the image recording method of the present disclosure after recording an image containing the cholesteric liquid crystal layer by applying the ink onto the substrate, another image not containing the cholesteric liquid crystal layer may be recorded.
- the other image may be a specific pattern, characters, or the like, or may be a solid image.
- the substrate is a transparent substrate and the image recorded matter is observed from the side opposite to the image recording surface of the substrate, the stereoscopic effect is remarkable.
- the ink may be applied to record the image containing the cholesteric liquid crystal layer.
- the ink may be applied to record the image containing the cholesteric liquid crystal layer.
- Other images that do not include a cholesteric liquid crystal layer include, for example, color images and clear images.
- a color image is recorded by applying ink containing a coloring material, for example.
- a clear image is recorded, for example, by applying ink that does not contain a coloring material.
- the ink for recording other images is preferably an active energy ray-curable ink, and it is preferable to irradiate the active energy ray after applying the ink.
- the method of applying the ink is not particularly limited, it is preferable to apply the ink using an inkjet recording method.
- Image recordings can also be used by attaching them to walls, glass, plastic panels, building materials, displays, car decorations, lights, molded products, etc.
- Ink preparation (Ink Rm1) Ink Rm1 was prepared by mixing the components shown below.
- the viscosity (25° C.) of ink Rm1 was 11 mPa ⁇ s.
- ⁇ Diethylene glycol diethyl ether ... 62.38 parts by mass
- ⁇ Mixture A1 of polymerizable liquid crystal compound ... 34 parts by mass
- Polymerization initiator bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (product name "Omnirad 819”) ...
- the ink Rm1 forms an ink film with a selective reflection wavelength of 640 nm.
- the selective reflection wavelength of the ink film was calculated by the following method. On a PET substrate heated to 50° C., the ink was applied under the conditions of a halftone dot rate of 100% and dried at 80° C. for 5 minutes. Next, an ink film was obtained by curing with a metal halide lamp (product name: "CSOT-40, manufactured by GS Yuasa). The selective reflection wavelength was measured by using a fluorescence spectrodensitometer (product name: "FD-7", Konica (manufactured by Minolta Co., Ltd.) to measure the spectral reflectance. At the time of measurement, black paper for measuring the opacity rate (standard: JIS K 5600, manufactured by TP Giken) was placed under the substrate, and the color was measured by setting the ink film to be the outermost layer.
- a fluorescence spectrodensitometer product name: "FD-7"
- Konica manufactured by Minolta Co., Ltd.
- FIG. 4A is a schematic diagram, and in Example 1, the scale was changed as appropriate.
- a PET sheet product name “Viewful UV TP-188”, manufactured by Kimoto Co., Ltd.
- the substrate was placed on a hot plate prepared by bonding a rubber heater to a metal plate, and heated to a temperature of 70°C.
- Ink Rm1 was ejected onto the substrate heated to 70° C. using an inkjet printer (product name “UJF3042HG”, manufactured by Mimaki Engineering Co., Ltd.).
- the image resolution was set to 600 dpi ⁇ 720 dpi, the number of passes was set to 32, and the image was recorded according to the created image data.
- the substrate was further heated at 80° C. for 5 minutes, and UVA (ultraviolet A (wave) was exposed so that the cumulative exposure amount was 500 mJ/cm 2 , and an image recorded matter was obtained.
- the maximum film thickness was 2.5 ⁇ m and the minimum film thickness was 1.7 ⁇ m, and the film thickness varied continuously from the high-density portion to the low-density portion of the image data. rice field.
- Example 2 An image record was obtained in the same manner as in Example 1, except that the amount of change in printing rate in the image data was changed.
- the maximum film thickness was 2.5 ⁇ m and the minimum film thickness was 1.4 ⁇ m, and the film thickness varied continuously from the high-density portion to the low-density portion of the image data. rice field.
- Example 3 An image record was obtained in the same manner as in Example 1, except that the amount of change in printing rate in the image data was changed.
- the maximum film thickness was 2.5 ⁇ m and the minimum film thickness was 1.1 ⁇ m, and the film thickness varied continuously from the high-density portion to the low-density portion of the image data. rice field.
- Example 4 An image recorded matter was obtained in the same manner as in Example 3, except that the width of the image in the image data was changed to 20 mm.
- Example 5 An image record was obtained in the same manner as in Example 3, except that the width of the image in the image data was changed to 40 mm.
- Example 8> A solid image B with a width and length of 10 mm and a solid image C with a width and length of 10 mm, which has a printing rate lower than that of the solid image B, are arranged adjacent to each other to prepare image data shown in FIG. 4B.
- An image record was obtained in the same manner as in Example 1, except that the image data was changed.
- the maximum film thickness was 2.5 ⁇ m
- the minimum film thickness was 2.0 ⁇ m.
- Example 9 An image record was obtained in the same manner as in Example 8, except that the printing rate of image C in the image data was changed.
- the maximum film thickness was 2.5 ⁇ m
- the minimum film thickness was 1.75 ⁇ m.
- Example 10 An image record was obtained in the same manner as in Example 8, except that the printing rate of image C in the image data was changed.
- the maximum film thickness was 2.5 ⁇ m
- the minimum film thickness was 1.1 ⁇ m.
- Ink preparation (Ink Gm1) Ink Gm1 was prepared by thoroughly mixing the components shown below.
- the viscosity (25° C.) of ink Gm1 was 11 mPa ⁇ s.
- ⁇ Diethylene glycol diethyl ether ... 62.28 parts by mass
- ⁇ Mixture A1 of polymerizable liquid crystal compound ... 34 parts by mass
- Polymerization initiator bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (product name "Omnirad 819”) ... 1.8 parts by mass Chiral compound A: 1.9 parts by mass Fluorosurfactant (product name “Ftergent 208G”, manufactured by Neos): 0.02 parts by mass
- the ink Gm1 forms an ink film with a selective reflection wavelength of 550 nm.
- Ink preparation (Ink Bm1) Ink Bm1 was prepared by thoroughly mixing the components shown below.
- the viscosity (25° C.) of the ink Bm1 was 11 mPa ⁇ s.
- ⁇ Diethylene glycol diethyl ether ... 62.08 parts by mass
- ⁇ Mixture A1 of polymerizable liquid crystal compound ... 34 parts by mass
- Polymerization initiator bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (product name "Omnirad 819”) ... 1.7 parts by mass
- Chiral compound A 2.2 parts by mass Fluorosurfactant (product name “Ftergent 208G”, manufactured by Neos): 0.02 parts by mass
- the ink Bm1 was an ink forming an ink film with a selective reflection wavelength of 440 nm.
- Example 13> The print settings were changed so that the amount of ink applied was doubled, and the image data of the solid image C was used to print once. After that, the image recording surface was subjected to hydrophilic treatment using a corona surface modification evaluation device (product name "TEC-4AX", manufactured by Kasuga Denki Co., Ltd.), and the image data of image C was used again to print again.
- An image recorded matter was obtained in the same manner as in Example 8, except for the above. In the obtained image recorded matter, the maximum film thickness was 10.0 ⁇ m and the minimum film thickness was 2.0 ⁇ m.
- Example 14> The print settings were changed so that the amount of ink applied was doubled, and the image data of the solid image C was used to print once. After that, the image recording surface is subjected to hydrophilic treatment using a corona surface modification evaluation device (product name “TEC-4AX”, manufactured by Kasuga Denki Co., Ltd.), and the image data of image C is superimposed and printed. bottom. Further, an image recorded matter was obtained in the same manner as in Example 8, except that the image recording surface was subjected to the same hydrophilization treatment as described above, and the image data of image C was used for printing. . The obtained image recorded matter had a maximum film thickness of 18.0 ⁇ m and a minimum film thickness of 8.0 ⁇ m.
- Image data was prepared by arranging a solid image B with a width and length of 10 mm and a solid image D with a width and length of 10 mm adjacent to each other.
- Solid image B has a printing rate of ink Rm1 of 100%
- solid image C has a printing rate of ink Rm1 of 40% and a printing rate of ink Bm1 of 60%.
- the substrate temperature was set to 70° C.
- ink Rm1 and ink Bm1 were ejected from each head, and image recording was performed according to the prepared image data.
- the film thickness of the resulting image record was 3.0 ⁇ m.
- Image data shown in FIG. 4B was prepared by arranging a solid image E with a width and length of 10 mm and a solid image F with a width and length of 10 mm adjacent to each other.
- Solid image E has a printing rate of ink Rm1 of 100% and ink Bm1 of 50%.
- Solid image F has a printing rate of ink Rm1 of 50% and ink Bm1 of 50%.
- the substrate temperature was set to 70° C., ink Rm1 and ink Bm1 were ejected from each head, and image recording was performed according to the prepared image data.
- the film thickness of the solid image E was 4.5 ⁇ m
- the film thickness of the solid image F was 3.0 ⁇ m.
- Image data shown in FIG. 4B was prepared by arranging a solid image G with a width and length of 10 mm and a solid image H with a width and length of 10 mm adjacent to each other.
- Solid image G has a printing rate of ink Rm1 of 100%, ink Bm1 of 25%, and ink Gm1 of 25%.
- Solid image H has a printing rate of ink Rm1 of 50%, ink Bm1 of The print rate was set to 25%, and the print rate of ink Gm1 was set to 25%.
- the temperature of the base material was set to 70° C., ink Rm1, ink Bm1, and ink Gm1 were ejected from each head, and image recording was performed according to the created image data.
- the film thickness of the solid image G was 4.5 ⁇ m
- the film thickness of the solid image H was 3.0 ⁇ m.
- Image data shown in FIG. 4B was prepared by arranging a solid image I with a width and length of 10 mm and a solid image J with a width and length of 10 mm adjacent to each other.
- Solid image I has a printing rate of 100% for ink Rm1 and 100% for ink Gm1
- solid image J has a printing rate of 50% for ink Rm1 and 50% for ink Gm1.
- the temperature of the base material was set to 70° C.
- the ink Rm1 and the ink Gm1 were ejected from each head, and image recording was performed according to the prepared image data.
- the film thickness of the solid image I was 6.0 ⁇ m
- the film thickness of the solid image J was 3.0 ⁇ m.
- Ink preparation (Ink Rm2) Ink Rm2 was prepared by mixing 1 part by mass of FLORSTAB UV12 (manufactured by Kromachem) instead of 1 part by mass of diethylene glycol diethyl ether in ink Rm1.
- the viscosity (25° C.) of ink Rm2 was 11 mPa ⁇ s.
- the maximum film thickness was 3.0 ⁇ m and the minimum film thickness was 1.3 ⁇ m, and the film thickness varied continuously from the high-density portion to the low-density portion of the image data. rice field.
- the ink Rm2 was an ink forming an ink film with a selective reflection wavelength of 640 nm.
- Ink preparation (Ink Rm3) Ink Rm3 was prepared in the same manner as Ink Rm1, except that chiral compound A was 1.4 parts by mass, FLORSTAB UV12 (manufactured by Kromachem) was 1 part by mass, and diethylene glycol diethyl ether was 61.58 parts by mass. prepared. The viscosity (25° C.) of ink Rm3 was 11 mPa ⁇ s. An image recorded matter was obtained in the same manner as in Example 19 using ink Rm3. When the reflectance in the visible light region of the ink film formed with the ink Rm3 was measured, the ink Rm3 was an ink forming an ink film with a selective reflection wavelength of 700 nm.
- Example 21 An image record was obtained in the same manner as in Example 1, except that the amount of change in printing rate in the image data was changed.
- the maximum film thickness was 7.0 ⁇ m and the minimum film thickness was 3.0 ⁇ m, and the film thickness varied continuously from the high-density portion to the low-density portion of the image data. rice field.
- ⁇ Comparative Example 3> An image record was obtained in the same manner as in Example 8, except that the printing rate of image C in the image data was changed.
- ⁇ Comparative Example 4> After the ink was applied to the entire surface of the substrate so that the film thickness was 2.5 ⁇ m, the substrate was dried at 95° C. for 60 seconds. After the temperature was lowered from 95°C to 25°C at a rate of -7°C/s, exposure was performed at 25°C to obtain an image record.
- regions with the shortest distance between the two regions were defined as region 1 and region 2, respectively.
- the orientation angles of the regions 1 and 2 and the width lengths of the regions 1 and 2 are shown in Tables 1 and 2.
- Tables 1 and 2 in Comparative Examples 1 to 4, the absolute value of the orientation angle difference was 5° or more and the width length was 1 mm or more. and "-" in the column related to region 2.
- the orientation angles of Area 1 and Area 2 were measured in the same manner as for the image recorded matter 40 shown in FIG. 3A.
- Example 1 to 7 and Examples 19 to 21 the orientation angle was measured by focusing on the region (full width region) corresponding to the virtual orthogonal line 431 to the virtual orthogonal line 439 shown in FIG. 3A. .
- the orientation angles of Area 1 and Area 2 were measured in the same manner as for the image recorded matter 50 shown in FIG. 3B.
- the orientation angles were measured by focusing on the region corresponding to the virtual orthogonal line 531 to the virtual orthogonal line 536 shown in FIG. 3B.
- Example 15 the direction orthogonal to the 20 mm width of the image recorded matter (the sum of the 10 mm width of the solid image B and the 10 mm width of the solid image D) is assumed to be the virtual orthogonal lines 431 to 439 shown in FIG. was measured.
- the image record was placed horizontally on the black portion of the paper for measuring the concealment rate, and the image record was observed from the normal direction and the direction at 60° from the normal direction. Specifically, by changing the observation direction, it was confirmed whether or not the color development changed and looked like a shadow, and the degree of the shadow was determined. If the coloring property changes and it looks like a shadow, it can be said that there is a stereoscopic effect.
- B A shadow can be visually recognized, and the width of the shadow is large.
- C A shadow can be visually recognized.
- D A shadow is slightly visible.
- E No stereoscopic effect.
- Examples 1-21 include a substrate and an image recorded on the substrate, the image including a cholesteric liquid crystal layer, the cholesteric liquid crystal layer comprising: In the cross section along the thickness direction of the image, it has a striped pattern of bright and dark parts observed with a scanning electron microscope, and the angle between the continuous line that is the bright or dark part and the main surface of the substrate is oriented. When expressed as an angle, it includes at least two regions in which the absolute value of the difference in orientation angle is 5° or more, and each of the two regions has a width of 1 mm or more in the in-plane direction of the base material, A stereoscopic effect was obtained for the recorded image.
- Example 101 After an image was recorded on the substrate in the same manner as in Example 10, a 100% solid black image was recorded using an inkjet printer (product name: "Acuity LED 1600II", manufactured by FUJIFILM Corporation).
- Example 102 After an image was recorded on the substrate in the same manner as in Example 10, a white 100% solid image was recorded using an inkjet printer (product name: "Acuity LED 1600II", manufactured by FUJIFILM Corporation).
- Example 103 After an image was recorded on the substrate in the same manner as in Example 10, the image was laminated to a transparent vinyl chloride sheet.
- Example 104 After an image was recorded on the substrate in the same manner as in Example 10, the image and glass were bonded together.
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Abstract
Description
<1>
基材と、基材上に記録された画像と、を含み、
画像は、コレステリック液晶層を含み、
コレステリック液晶層は、画像の厚み方向に沿った断面において、走査型電子顕微鏡(以下、「SEM」と略記することがある。)にて観測される明部と暗部との縞模様を有し、
明部又は暗部である連続線と基材の主面との角度を配向角度としたとき、配向角度の差の絶対値が5°以上である2つの領域を、を少なくとも含み、
2つの領域はいずれも、基材の面内方向における幅長が1mm以上である、画像記録物。
<2>
配向角度は、コレステリック液晶層の少なくとも一部において、-5°~5°である、<1>に記載の画像記録物。
<3>
2つの領域のうち少なくとも一方の領域は、基材の面内方向における幅長が1mm~40mmである、<1>又は<2>に記載の画像記録物。
<4>
画像は、
基材の面内方向における幅長40mmの範囲内の膜厚差が0.5μm以上である領域を含む、<1>~<3>のいずれか1つに記載の画像記録物。
<5>
画像は、
基材の面内方向における幅長10mmの範囲内の膜厚差が1μm~30μmである領域を含む、<1>~<4>のいずれか1つに記載の画像記録物。
<6>
画像は、選択反射波長が460nm以上である、<1>~<6>のいずれか1つに記載の画像記録物。
<7>
基材と画像との間、又は、基材上の画像の上に、さらに、コレステリック液晶層を含まない他の画像が配置されている、<1>~<5>のいずれか1つに記載の画像記録物。
<8>
基材上に、重合性液晶化合物、キラル化合物、及び溶剤を含むインクを、インクジェット記録方式にて付与する工程と、
基材上に付与されたインクに活性エネルギー線を照射して、インクの硬化膜である画像を記録する工程と、
を含み、
インクを付与する工程では、記録される画像の、基材の面内方向における幅長40mmの範囲内の膜厚差が0.5μm以上となる条件で、インクを付与する、画像記録方法。
<9>
溶剤は、沸点が100℃以上300℃未満の溶剤を含む、<8>に記載の画像記録方法。
<10>
基材を45℃以上に加熱する工程をさらに含み、
インクを付与する工程では、加熱された基材上にインクを付与する、<8>又は<9>に記載の画像記録方法。
<11>
インクを付与する工程の後であって、活性エネルギー線を照射する工程の前に、基材上に付与されたインクを加熱する工程をさらに含み、
インクを加熱する工程では、加熱後のインク中の溶剤の含有量を、インクを付与した時点の溶剤の含有量に対して50質量%以下とする、<8>~<10>のいずれか1つに記載の画像記録方法。
本明細書において「~」を用いて示された数値範囲は、「~」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を意味する。
本明細書に段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書において、組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合には、特に断らない限り、組成物中に存在する複数の物質の合計量を意味する。
また、本明細書において、2以上の好ましい態様の組み合わせは、より好ましい態様である。
さらに、本明細書において、「工程」という語は、独立した工程だけでなく、他の工程と明確に区別できない場合であっても、その工程の所期の目的が達成されれば、本用語に含まれる。
本開示の画像記録物は、基材と、基材上に記録された画像と、を含み、画像は、コレステリック液晶層を含み、コレステリック液晶層は、画像の厚み方向に沿った断面において、走査型電子顕微鏡にて観測される明部と暗部との縞模様を有し、明部又は暗部である連続線と基材の主面との角度を配向角度としたとき、配向角度の差の絶対値が5°以上である2つの領域を、を少なくとも含み、2つの領域はいずれも、基材の面内方向における幅長が1mm以上である。
特に、透明基材の上に記録された画像を、背景色を黒にして観察した場合に、顕著な立体視効果が得られる。背景色を白にして観察した場合には、角度によって光沢感が顕著となる部分が生じ、局所的に光って見えることにより立体視効果が得られる。また、背景色が白、黒以外の場合であっても、同様に立体視効果を得ることができる。
本開示の画像記録物は、基材を含む。
本開示の画像記録物は、基材上に記録された画像を含む。画像は、コレステリック液晶層を含み、コレステリック液晶層は、画像の厚み方向に沿った断面において、SEMにて観測される明部と暗部との縞模様を有し、明部又は暗部である連続線と基材の主面との角度を配向角度としたとき、配向角度の差の絶対値が5°以上である2つの領域を、を少なくとも含み、2つの領域はいずれも、基材の面内方向における幅長が1mm以上である。
画像を、画像の厚さ方向に向かって切断し、断面サンプルを得る。走査型電子顕微鏡(加速電圧:2kV、観察倍率:5000倍及び10000倍)を用いて、断面のSEM画像を観察する。コレステリック液晶相の屈折率の変化に由来する濃淡の縞模様があることを確認することができる。
本開示では、濃淡の縞模様において、黒い部分を暗部、白い部分を明部という。
図1は、基材1上に画像2が記録された画像記録物の断面のSEMにて観測される明部と暗部との縞模様を示した模式図であり、配向角度を説明するための図である。例えば、図1に示すように、暗部の連続線に沿った直線21を引く。配向角度として、基材の主面11と直線21との角度θ1を測定する。
なお、配向角度は、直線が右肩上がりである(すなわち、XY座標で正の傾きである)場合にはプラスで表し、直線が右肩下がりである(すなわち、XY座標で負の傾きである)場合にはマイナスで表すものとする。したがって、図1において、角度θ1は、プラスで表される。
図2は、配向角度の変化を確認する方法を説明するための図である。
図2に示す交点t1、t2、t3は、第1の仮想線321に沿って切断して得られる断面において、第1の仮想線321と第2の仮想線331、332、333との交点である。
同様に、第2の仮想線に沿って切断して得られる断面において、第1の仮想線と第2の仮想線との交点における配向角度を、上記配向角度の測定方法に従って測定する。
図2に示す交点s1、s2、s3は、第2の仮想線338に沿って切断して得られる断面において、第2の仮想線338と第1の仮想線321、322、323との交点である。
仮想直交線432に沿って切断して得られる断面において、仮想平行線421と仮想直交線432との交点における配向角度が-8°、
仮想直交線433に沿って切断して得られる断面において、仮想平行線421と仮想直交線433との交点における配向角度が-5°、
仮想直交線434に沿って切断して得られる断面において、仮想平行線421と仮想直交線434との交点における配向角度が-2.5°、
仮想直交線435に沿って切断して得られる断面において、仮想平行線421と仮想直交線435との交点における配向角度が0°、
仮想直交線436に沿って切断して得られる断面において、仮想平行線421と仮想直交線436との交点における配向角度が2.5°、
仮想直交線437に沿って切断して得られる断面において、仮想平行線421と仮想直交線437との交点における配向角度が5°、
仮想直交線438に沿って切断して得られる断面において、仮想平行線421と仮想直交線438との交点における配向角度が8°、
仮想直交線439に沿って切断して得られる断面において、仮想平行線421と仮想直交線439との交点における配向角度が15°である。
また、この場合、矢印41の方向に向かって配向角度が変化していることが分かる。配向角度が変化している方向における長さを、本開示における、配向角度の差の絶対値が5°以上である2つの領域の幅長とする。
これにより、例えば、仮想直交線431から仮想直交線434までの距離と、仮想直交線436から仮想直交線439までの距離と、がいずれも1mm以上であるか否かを判定する。
上記距離がいずれも1mm以上である場合には、配向角度の差の絶対値が5°以上である2つの領域を、を少なくとも含み、2つの領域はいずれも、基材の面内方向における幅長が1mm以上であることを満たす、画像記録物である。
仮想直交線431から仮想直交線434までの距離と、仮想直交線436から仮想直交線439までの距離とが1mm以上であれば、仮想直交線431から仮想直交線434までの領域と、仮想直交線436から仮想直交線439までの領域が、上記2つの領域に該当する。
図4Bに示す画像データを用いた場合には、印字率が異なる境界部分において、インク膜がなだらかに形成される傾向にある。そのため、画像の中に、膜厚が連続的に変化する部分が存在する。
図3Bにおいて、矢印51は、膜厚が変化している方向を示す。図3Bに示す画像記録物50では、後述する仮想直交線531と仮想直交線533とに挟まれる領域と、後述する仮想直交線537と仮想直交線539とに挟まれる領域は、膜厚がほぼ一定であり、後述する仮想直交線533と仮想直交線537とに挟まれる領域は、矢印51の方向に向かって、膜厚が徐々に薄くなっている。
仮想平行線521と仮想直交線532との交点における配向角度が0°、
仮想平行線521と仮想直交線533との交点における配向角度が0°、
仮想平行線521と仮想直交線534との交点における配向角度が-7°、
仮想平行線521と仮想直交線535との交点における配向角度が-10°、
仮想平行線521と仮想直交線536との交点における配向角度が-7°、
仮想平行線521と仮想直交線537との交点における配向角度が0°、
仮想平行線521と仮想直交線538との交点における配向角度が0°、
仮想平行線521と仮想直交線539との交点における配向角度が0°である。
また、この場合、矢印51の方向に向かって配向角度が変化していることが分かる。配向角度が変化している方向における長さを、本開示における、配向角度の差の絶対値が5°以上である2つの領域の幅長とする。
これにより、例えば、仮想直交線531から仮想直交線533までの距離と、仮想直交線534から仮想直交線536までの距離と、がいずれも1mm以上であるか否かを判定する。
上記距離がいずれも1mm以上である場合には、配向角度の差の絶対値が5°以上である2つの領域を、を少なくとも含み、2つの領域はいずれも、基材の面内方向における幅長が1mm以上であることを満たす、画像記録物である。
仮想直交線531から仮想直交線533までの距離と、仮想直交線534から仮想直交線536までの距離とが1mm以上であれば、仮想直交線531から仮想直交線533までの領域と、仮想直交線534から仮想直交線536までの領域が、上記2つの領域に該当する。
なお、上記例では、仮想直交線537から仮想直交線539までの領域における配向角度は0°であり、仮想直交線537から仮想直交線539までの距離が1mm以上であれば、仮想直交線537から仮想直交線539までの領域と、仮想直交線534から仮想直交線536までの領域を、上記2つの領域とみなしてもよい。
特に、領域1及び領域2の少なくとも一方の領域において、基材の面内方向における幅長が1mm~40mmであることが好ましく、1mm~5mmであることがより好ましい。
選択反射波長は、蛍光分光濃度計で分光反射率を測定することにより算出される。例えば、選択反射波長は、蛍光分光濃度計(製品名「FD-7」、コニカミノルタ製社製)を用いて算出される。なお、測定時は、基材の下に、隠ぺい率測定紙(規格:JIS K 5600、TP技研製)の黒紙を置き、画像が最表層になるようにセットして測色する。
本開示の画像記録方法は、基材上に、重合性液晶化合物、キラル化合物、及び溶剤を含むインクを、インクジェット記録方式にて付与する工程(以下、「インク付与工程」ともいう)と、基材上に付与されたインクに活性エネルギー線を照射して、インクの硬化膜である画像を記録する工程(以下、「活性エネルギー線照射工程」ともいう)を含む。そして、インク付与工程では、記録される画像の、基材の面内方向における幅長40mmの範囲内の膜厚差が0.5μm以上となる条件で、インクを付与する。
インク付与工程では、基材上に、重合性液晶化合物、キラル化合物、及び溶剤を含むインクを、インクジェット記録方式にて付与する。
本開示において、重合性液晶化合物とは、重合性基を有する液晶化合物のことである。
液晶化合物は、棒状液晶化合物であっても、円盤状液晶化合物であってもよいが、棒状液晶化合物であることが好ましい。
キラル化合物は光学活性化合物ともいう。キラル化合物は、重合性液晶化合物の螺旋構造を誘起する機能を有する。キラル化合物の種類及び含有量によって、誘起する螺旋構造のねじれ方向又はピッチが異なる。
溶剤の種類は特に限定されず、目的に応じて適宜選択することができる。
沸点が100℃以上300℃未満の溶剤としては、例えば、
エチレングリコール(沸点:198℃)、プロピレングリコール(沸点:188℃)、1,2-ブタンジオール(沸点:194℃)、2,3-ブタンジオール(沸点:183℃)、2-メチル-1,3-プロパンジオール(沸点:124℃)、2-メチル-2,4-ペンタンジオール(沸点:198℃)、1,2,6-ヘキサントリオール(沸点:178℃)、1,2,3-ブタントリオール(沸点:175℃)、1,2,4-ブタントリオール(沸点:170℃)、ジエチレングリコール(沸点:244℃)、ジプロピレングリコール(沸点:231℃)、1,3-プロパンジオール(沸点:214℃)、1,3-ブタンジオール(沸点:208℃)、1,4-ブタンジオール(沸点:230℃)、1,2-ペンタンジオール(沸点:206℃)、2,4-ペンタンジオール(沸点:201℃)、2-メチル-1,3-ブタンジオール(沸点:203℃)、3-メチル-1,3-ブタンジオール(沸点:203℃)、1,5-ペンタンジオール(沸点:242℃)、2,2-ジメチル-1,3-プロパンジオール(沸点:208℃)、1,2-ヘキサンジオール(沸点:223℃)、1,6-ヘキサンジオール(沸点:250℃)、2,5-ヘキサンジオール(沸点:217℃)、2-エチル-1,3-ヘキサンジオール(沸点:243℃)、トリエチレングリコール(沸点:287℃)、トリプロピレングリコール(沸点:273℃)、グリセリン(沸点:290℃)等の多価アルコール;
エチレングリコールモノメチルエーテル(沸点:124℃)、エチレングリコールモノエチルエーテル(沸点:135℃)、エチレングリコール-n-プロピルエーテル(沸点:150℃)、エチレングリコールモノブチルエーテル(沸点:171℃)、プロピレングリコールモノメチルエーテル(沸点:120℃)、プロピレングリコールモノエチルエーテル(沸点:133℃)、プロピレングリコール-n-ブチルエーテル(沸点:171℃)、プロピレングリコール-t-ブチルエーテル(沸点:153℃)、テトラエチレングリコールモノメチルエーテル(沸点:159℃)、ジエチレングリコールメチルエーテル(沸点:194℃)、ジエチレングリコールジエチルエーテル(沸点:162℃)、ジエチレングリコール-n-ブチルエーテル(沸点:230℃)、ジプロピレングリコールモノメチルエーテル(沸点:188℃)、ジエチレングリコールモノエチルエーテル(沸点:202℃)、ジエチレングリコールモノブチルエーテル(沸点:230℃)、トリエチレングリコールメチルエーテル(沸点:249℃)、ジプロピレングリコール-n-プロピルエーテル(沸点:213℃)、トリプロピレングリコールメチルエーテル(沸点:243℃)、トリエチレングリコールエチルエーテル(沸点:256℃)、ジエチレングリコール-n-ヘキシルエーテル(沸点:259℃)、トリプロピレングリコール-n-プロピルエーテル(沸点:261℃)、3-メトキシブタノール(沸点:161℃)等の多価アルコールアルキルエーテル;
エチレングリコールフェニルエーテル(沸点:237℃)、プロピレングリコールフェニルエーテル(沸点:243℃)、エチレングリコールモノベンジルエーテル(沸点:256℃)等の多価アルコールアリールエーテル;
ε-カプロラクタム(沸点:137℃)、N-メチルホルムアミド(沸点:199℃)、N,N-ジメチルホルムアミド(沸点:153℃)、N-メチル-2-ピロリドン(沸点:204℃)、2-ピロリドン(沸点:245℃)、1,3-ジメチルイミダゾリジノン(沸点:220℃)、N-メチルピロリジノン(沸点:202℃)等の含窒素化合物;
プロピレングリコールモノメチルエーテルアセテート(沸点:146℃)、酢酸3-メトキシブチル(沸点:172℃)等のエステル化合物;
ダイアセトンアルコール(沸点:169℃)、γ-ブチロラクトン(沸点:204℃)等のケトン化合物が挙げられる。
インクは、さらに重合開始剤を含有することが好ましい。重合開始剤は、光重合開始剤であることが好ましく、紫外線の照射によってラジカルを生成する機能を有するラジカル重合開始剤であることがより好ましい。
インクは、必要に応じ、本開示の効果を損なわない範囲で添加剤を含有することができる。
インクの粘度は、7mPa・s以上であることが好ましく、8mPa・s以上であることがより好ましく、10mPa・s以上であることがさらに好ましい。インクの粘度の上限値は、インクの吐出性の観点から、例えば、30mPa・sである。
インクジェット記録方式は、通常公知の方式を用いることができ、例えば、静電誘引力を利用してインク組成物を吐出させる電荷制御方式、ピエゾ素子の振動圧力を利用するドロップオンデマンド方式(圧力パルス方式)、電気信号を音響ビームに変えインク組成物に照射して放射圧を利用してインク組成物を吐出させる音響インクジェット方式、及びインク組成物を加熱して気泡を形成し、生じた圧力を利用するサーマルインクジェット方式が挙げられる。
インク付与工程では、記録される画像の、基材の面内方向における幅長40mmの範囲内の膜厚差が0.5μm以上となる条件で、インクを付与する。
記録される画像の膜厚は、例えば、吐出液滴量、印字率等によって制御することができる。したがって、記録される画像の膜厚差を0.5μm以上とする方法としては、基材上におけるインクの付与位置によって、吐出液滴量、印字率等を変化させる方法が挙げられる。
a) 膜厚を薄くする部分は、吐出液滴量を少なくし、膜厚を厚くする部分は、吐出液滴量を多くする方法。
b) 膜厚を薄くする部分は、印字率を低くし、膜厚を厚くする部分は、印字率を高くする方法。
c) a)及びb)を任意に組み合わせる方法。
図4Bに示す画像データを用いた場合には、中心部分に、膜厚が連続的に変化する部分が存在する。図3Bに示す画像記録物50は、図4Bに示す画像データを用いた場合に得られる画像記録物の一例である。
図4Cに示す画像データを用いた場合には、中心部分において最も膜厚が薄く、中心部分から、向かい合う2辺に向かって膜厚が徐々に厚くなっている画像記録物が得られる。
活性エネルギー線照射工程では、基材上に付与されたインクに活性エネルギー線を照射して、インクの硬化膜である画像を記録する。
本開示の画像記録方法は、さらに、基材を加熱する工程(以下、「基材加熱工程」という)を含むことが好ましい。基材加熱工程の後に、インク付与工程において、加熱された基材上にインクを付与することが好ましい。
本開示の画像記録方法は、さらに、インク付与工程の後であって、活性エネルギー線照射工程の前に、基材上に付与されたインクを加熱する工程(以下、「インク加熱工程」という)を含むことが好ましい。
本開示の画像記録方法では、基材上に上記インクを付与してコレステリック液晶層を含む画像を記録した後に、コレステリック液晶層を含まない他の画像を記録してもよい。他の画像は、特定の絵柄、文字等であってもよく、ソリッド画像であってもよい。この態様によれば、基材上に、コレステリック液晶層を含む画像と、コレステリック液晶層を含まない他の画像とが、この順に配置された画像記録物が得られる。特に、基材が透明基材であって、基材の画像記録面とは反対側から画像記録物を観察した場合に、立体視効果が顕著である。
[インクの調製]
(インクRm1)
下記に示す成分を混合し、インクRm1を調製した。インクRm1の粘度(25℃)は、11mPa・sであった。
・ジエチレングリコールジエチルエーテル …62.38質量部
・重合性液晶化合物の混合物A1 …34質量部
・重合開始剤:ビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキシド(製品名「Omnirad 819」) …2質量部
・キラル化合物A …1.6質量部
・フッ素系界面活性剤(製品名「フタージェント208G」、ネオス社製) …0.02質量部
なお、重合性液晶化合物の混合物は、以下の割合で混合させたものである。
重合性液晶化合物の混合物A1:化合物(10)50質量%、化合物(11)50質量%
化合物(10)~(11)は棒状液晶化合物である。化合物(10)、化合物(11)、及びキラル化合物Aの構造は以下のとおりである。
50℃に加熱されたPET基材上に、網点率100%の条件でインクを付与し、さらに80℃で5分間乾燥させた。次いで、メタルハライドランプ(製品名「CSOT-40、GSユアサ製)で硬化させることによってインク膜を得た。選択反射波長は、このインク膜を蛍光分光濃度計(製品名「FD-7」、コニカミノルタ製社製)で分光反射率を測定することにより算出した。なお、測定時は基材の下に、隠ぺい率測定紙(規格:JIS K 5600、TP技研製)の黒紙を置き、インク膜が最表層になるようにセットして測色した。
幅10mm、長さ5mmにおいて、印字率が高い部分を中心として、印字率を連続的に変化させた、図4Aに示すような画像データを作製した。図4Aは模式図であり、実施例1では、縮尺を適宜変更した。
基材としてPETシート(製品名「ビューフルUV TP-188」、きもと社製)を用いた。基材は、ラバーヒーターを金属版に貼り合わせて作成したホットプレートの上に設置され、基材の温度が70℃になるように加熱した。70℃に加熱された基材上に、インクジェットプリンタ(製品名「UJF3042HG」、ミマキエンジニアリング社製)を用いて、インクRm1を吐出した。具体的には、画像解像度を600dpi×720dpiとし、パス数を32とし、作製した画像データに従い、画像記録を行った。
画像記録終了後、さらに基材を80℃で5分加熱した後に、紫外線照射装置(製品名「CSOT-40」、GSユアサ社製)に搭載されているメタルハライドランプを用いて、UVA(紫外線A波)の積算露光量が500mJ/cm2となるように露光し、画像記録物を得た。
得られた画像記録物において、膜厚の最大値は2.5μm、膜厚の最小値は1.7μmであり、画像データの濃度の濃い部分から薄い部分にかけて膜厚は連続的に変化していた。
画像データにおける印字率の変化量を変更したこと以外は、実施例1と同様の方法で、画像記録物を得た。
得られた画像記録物において、膜厚の最大値は2.5μm、膜厚の最小値は1.4μmであり、画像データの濃度の濃い部分から薄い部分にかけて膜厚は連続的に変化していた。
画像データにおける印字率の変化量を変更したこと以外は、実施例1と同様の方法で、画像記録物を得た。
得られた画像記録物において、膜厚の最大値は2.5μm、膜厚の最小値は1.1μmであり、画像データの濃度の濃い部分から薄い部分にかけて膜厚は連続的に変化していた。
画像データにおける画像の幅を20mmに変更したこと以外は、実施例3と同様の方法で、画像記録物を得た
画像データにおける画像の幅を40mmに変更したこと以外は、実施例3と同様の方法で、画像記録物を得た。
画像データにおける画像の幅を6mmに変更したこと以外は、実施例3と同様の方法で、画像記録物を得た。
<実施例7>
実施例3において、インクの付与量を変更した以外は実施例3と同様の方法で、画像記録物を得た。
幅10mm、長さ5mmのベタ画像データを作製した。画像データを変更したこと以外は、実施例1と同様の方法で、画像記録物を得た。
<比較例2>
画像データにおける画像の幅を80mmに変更したこと以外は、実施例3と同様の方法で、画像記録物を得た。
幅及び長さが10mmのベタ画像Bと、ベタ画像Bより印字率の低い、幅及び長さが10mmのベタ画像Cとを隣接して配置した、図4Bに示す画像データを作製した。画像データを変更したこと以外は、実施例1と同様の方法で、画像記録物を得た。
得られた画像記録物において、膜厚の最大値は2.5μm、膜厚の最小値は2.0μmであった。
画像データにおける画像Cの印字率を変更したこと以外は、実施例8と同様の方法で、画像記録物を得た。
得られた画像記録物において、膜厚の最大値は2.5μm、膜厚の最小値は1.75μmであった。
画像データにおける画像Cの印字率を変更したこと以外は、実施例8と同様の方法で、画像記録物を得た。
得られた画像記録物において、膜厚の最大値は2.5μm、膜厚の最小値は1.1μmであった。
[インクの調製]
(インクGm1)
下記に示す成分を完全に混合し、インクGm1を調製した。インクGm1の粘度(25℃)は、11mPa・sであった。
・ジエチレングリコールジエチルエーテル …62.28質量部
・重合性液晶化合物の混合物A1 …34質量部
・重合開始剤:ビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキシド(製品名「Omnirad 819」) …1.8質量部
・キラル化合物A …1.9質量部
・フッ素系界面活性剤(製品名「フタージェント208G」、ネオス社製) …0.02質量部
インクの種類をインクGm1に変更したこと以外は、実施例10と同様の方法で、画像記録物を得た。
[インクの調製]
(インクBm1)
下記に示す成分を完全に混合し、インクBm1を調製した。インクBm1の粘度(25℃)は、11mPa・sであった。
・ジエチレングリコールジエチルエーテル …62.08質量部
・重合性液晶化合物の混合物A1 …34質量部
・重合開始剤:ビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキシド(製品名「Omnirad 819」) …1.7質量部
・キラル化合物A …2.2質量部
・フッ素系界面活性剤(製品名「フタージェント208G」、ネオス社製) …0.02質量部
インクの種類をインクBm1に変更したこと以外は、実施例10と同様の方法で、画像記録物を得た。
インクの付与量が2倍となるよう印刷設定を変更し、ベタ画像Cの画像データを用いて、1回印字した。その後、画像記録面にコロナ表面改質評価装置(製品名「TEC-4AX」、春日電機株式会社製)を用いて親水化処理を行い、再度画像Cの画像データを用いて重ねて印字したこと以外は、実施例8と同様の方法で、画像記録物を得た。
得られた画像記録物において、膜厚の最大値は10.0μm、膜厚の最小値は2.0μmであった。
インクの付与量が2倍となるよう印刷設定を変更し、ベタ画像Cの画像データを用いて、1回印字した。その後、画像記録面に対して、コロナ表面改質評価装置(製品名「TEC-4AX」、春日電機株式会社製)を用いて親水化処理を行い、画像Cの画像データを用いて重ねて印字した。さらに、画像記録面に対して、上記と同様の親水化処理を行い、画像Cの画像データを用いて重ねて印字したこと以外は、実施例8と同様の方法で、画像記録物を得た。
得られた画像記録物において、膜厚の最大値は18.0μm、膜厚の最小値は8.0μmであった。
幅及び長さが10mmのベタ画像Bと、幅及び長さが10mmのベタ画像Dとを隣接して配置した、画像データを作製した。
ベタ画像Bは、インクRm1の印字率を100%とし、ベタ画像Cは、インクRm1の印字率を40%、インクBm1の印字率を60%とした。
基材の温度を70℃とし、インクRm1及びインクBm1を各ヘッドから吐出し、作製した画像データに従い、画像記録を行った。
得られた画像記録物において、膜厚は3.0μmであった。
幅及び長さが10mmのベタ画像Eと、幅及び長さが10mmのベタ画像Fとを隣接し
て配置した、図4Bに示す画像データを作製した。
ベタ画像Eは、インクRm1の印字率を100%、インクBm1の印字率を50%とし、ベタ画像Fは、インクRm1の印字率を50%、インクBm1の印字率を50%とした。
基材の温度を70℃とし、インクRm1及びインクBm1を各ヘッドから吐出し、作製した画像データに従い、画像記録を行った。
得られた画像記録物において、ベタ画像Eの膜厚は4.5μm、ベタ画像Fの膜厚は3.0μmであった。
幅及び長さが10mmのベタ画像Gと、幅及び長さが10mmのベタ画像Hとを隣接して配置した、図4Bに示す画像データを作製した。
ベタ画像Gは、インクRm1の印字率を100%、インクBm1の印字率を25%、インクGm1の印字率を25%とし、ベタ画像Hは、インクRm1の印字率を50%、インクBm1の印字率を25%、インクGm1の印字率を25%とした。
基材の温度を70℃とし、インクRm1、インクBm1、及びインクGm1を各ヘッドから吐出し、作製した画像データに従い、画像記録を行った。
得られた画像記録物において、ベタ画像Gの膜厚は4.5μm、ベタ画像Hの膜厚は3.0μmであった。
幅及び長さが10mmのベタ画像Iと、幅及び長さが10mmのベタ画像Jとを隣接して配置した、図4Bに示す画像データを作製した。
ベタ画像Iは、インクRm1の印字率を100%、インクGm1の印字率を100%とし、ベタ画像Jは、インクRm1の印字率を50%、インクGm1の印字率を50%とした。
基材の温度を70℃とし、インクRm1及びインクGm1を各ヘッドから吐出し、作製した画像データに従い、画像記録を行った。
得られた画像記録物において、ベタ画像Iの膜厚は6.0μm、ベタ画像Jの膜厚は3.0μmであった。
[インクの調製]
(インクRm2)
インクRm1において、ジエチレングリコールジエチルエーテル1質量部の代わりに、FLORSTAB UV12(Kromachem社製)1質量部を混合し、インクRm2を調製した。インクRm2の粘度(25℃)は、11mPa・sであった。インクRm2を用いて、実施例3と同様の画像データ、印字条件を用いて、インクの付与量のみ装置上で調整した。
得られた画像記録物において、膜厚の最大値は3.0μm、膜厚の最小値は1.3μmであり、画像データの濃度の濃い部分から薄い部分にかけて膜厚は連続的に変化していた。
インクRm2で形成されるインク膜の可視光領域における反射率を測定したところ、インクRm2は、選択反射波長が640nmのインク膜を形成するインクであった。
[インクの調製]
(インクRm3)
キラル化合物Aを1.4質量部とし、FLORSTAB UV12(Kromachem社製)を1質量部とし、ジエチレングリコールジエチルエーテルを61.58質量部としたこと以外は、インクRm1と同様の方法で、インクRm3を調製した。インクRm3の粘度(25℃)は、11mPa・sであった。インクRm3を用いて、実施例19と同様の方法で、画像記録物を得た。
インクRm3で形成されるインク膜の可視光領域における反射率を測定したところ、インクRm3は、選択反射波長が700nmのインク膜を形成するインクであった。
画像データにおける印字率の変化量を変更したこと以外は、実施例1と同様の方法で、画像記録物を得た。
得られた画像記録物において、膜厚の最大値は7.0μm、膜厚の最小値は3.0μmであり、画像データの濃度の濃い部分から薄い部分にかけて膜厚は連続的に変化していた。
画像データにおける画像Cの印字率を変更したこと以外は実施例8と同様にして画像記録物を得た。
<比較例4>
膜厚が2.5μmとなるように、基材全面にインクを付与した後、95℃で60秒乾燥させた。95℃から25℃まで、-7℃/sの速度で降温した後、25℃で露光し、画像記録物を得た。
実施例及び比較例で得られた画像記録物を、厚み方向に沿って切断して断面サンプルを作製した。走査型電子顕微鏡(加速電圧:2kV、観察倍率:5000倍及び10000倍)を用いて、断面のSEM画像を観察し、明部と暗部との縞模様の有無を確認した。その結果、実施例1~実施例21及び比較例1~4において、縞模様が確認された。
また、画像記録物の断面を解析し、配向角度の差の絶対値が5°以上であって、幅長が1mm以上である2つの領域を特定した。また、配向角度の差の絶対値が5°以上である2つの領域の組み合わせの中で、2つの領域間の距離が最も小さい領域をそれぞれ、領域1、領域2とした。領域1及び領域2の配向角度、並びに、領域1及び領域2の幅長を、表1及び表2に記載した。表1及び表2中、比較例1~比較例4では、配向角度の差の絶対値が5°以上であり、かつ、幅長が1mm以上である2つの領域が存在しなかったため、領域1及び領域2に関する欄に「-」を記載した。
実施例1~実施例7、実施例19~実施例21では、上記図3Aに示す画像記録物40と同様の方法で、領域1及び領域2の配向角度を測定した。なお、実施例1~実施例7、実施例19~実施例21では、図3Aに示す仮想直交線431から仮想直交線439に相当する領域(全幅領域)に着目して、配向角度を測定した。
実施例8~実施例14、及び、実施例16~実施例18では、図3Bに示す画像記録物50と同様の方法で、領域1及び領域2の配向角度を測定した。なお、実施例8~実施例18では、図3Bに示す仮想直交線531から仮想直交線536に相当する領域に着目して、配向角度を測定した。
実施例15では、画像記録物の幅20mm(ベタ画像Bの幅10mmとベタ画像Dの幅10mmを合わせた長さ)に直交する方向を図3Aに示す仮想直交線431から439とし、配向角度を測定した。
画像記録物を隠ぺい率測定用の紙の黒色部分の上に水平に置き、法線方向と、法線方向から60°の方向と、から画像記録物を観察した。具体的には、観察方向を変化させることによって、発色性が変化して影のように見えるか否かを確認し、影の度合いを判定した。発色性が変化して影のように見える場合は、立体視効果があるといえる。
A:影が濃く、影の幅が大きい。
B:影が視認でき、影の幅が大きい。
C:影が視認できる。
D:影がわずかに視認できる。
E:立体視効果がない。
基材上に、実施例10と同様の方法で画像を記録した後、インクジェットプリンタ(製品名「Acuity LED 1600II」、富士フイルム株式会社製)を用いて、黒色の100%ベタ画像を記録した。
基材上に、実施例10と同様の方法で画像を記録した後、インクジェットプリンタ(製品名「Acuity LED 1600II」、富士フイルム株式会社製)を用いて、白色の100%ベタ画像を記録した。
基材上に、実施例10と同様の方法で画像を記録した後、画像と透明の塩化ビニル製のシートとを貼り合わせた。
基材上に、実施例10と同様の方法で画像を記録した後、画像とガラスとを貼り合わせた。
と、から観察したところ、両面で立体視効果が確認できた。
Claims (11)
- 基材と、前記基材上に記録された画像と、を含み、
前記画像は、コレステリック液晶層を含み、
前記コレステリック液晶層は、前記画像の厚み方向に沿った断面において、走査型電子顕微鏡にて観測される明部と暗部との縞模様を有し、
前記明部又は前記暗部である連続線と前記基材の主面との角度を配向角度としたとき、前記配向角度の差の絶対値が5°以上である2つの領域を、を少なくとも含み、
前記2つの領域はいずれも、前記基材の面内方向における幅長が1mm以上である、画像記録物。 - 前記配向角度は、前記コレステリック液晶層の少なくとも一部において、-5°~5°である、請求項1に記載の画像記録物。
- 前記2つの領域のうち少なくとも一方の領域は、前記基材の面内方向における幅長が1mm~40mmである、請求項1又は請求項2に記載の画像記録物。
- 前記画像は、
前記基材の面内方向における幅長40mmの範囲内の膜厚差が0.5μm以上である領域を含む、請求項1又は請求項2に記載の画像記録物。 - 前記画像は、
前記基材の面内方向における幅長10mmの範囲内の膜厚差が1μm~30μmである領域を含む、請求項1又は請求項2に記載の画像記録物。 - 前記画像は、選択反射波長が460nm以上である、請求項1又は請求項2に記載の画像記録物。
- 前記基材と前記画像との間、又は、前記基材上の前記画像の上に、さらに、コレステリック液晶層を含まない他の画像が配置されている、請求項1又は請求項2に記載の画像記録物。
- 基材上に、重合性液晶化合物、キラル化合物、及び溶剤を含むインクを、インクジェット記録方式にて付与する工程と、
前記基材上に付与されたインクに活性エネルギー線を照射して、前記インクの硬化膜である画像を記録する工程と、
を含み、
前記インクを付与する工程では、前記記録される画像の、前記基材の面内方向における幅長40mmの範囲内の膜厚差が0.5μm以上となる条件で、前記インクを付与する、画像記録方法。 - 前記溶剤は、沸点が100℃以上300℃未満の溶剤を含む、請求項8に記載の画像記録方法。
- 前記基材を45℃以上に加熱する工程をさらに含み、
前記インクを付与する工程では、加熱された基材上に前記インクを付与する、請求項8又は請求項9に記載の画像記録方法。 - 前記インクを付与する工程の後であって、前記活性エネルギー線を照射する工程の前に、前記基材上に付与されたインクを加熱する工程をさらに含み、
前記インクを加熱する工程では、加熱後のインク中の溶剤の含有量を、前記インクを付与した時点の溶剤の含有量に対して50質量%以下とする、請求項8又は請求項9に記載の画像記録方法。
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