Ultraviolet sensing component, ultraviolet sensing kit

Abstract

The present application provides a kind of easy to determine whether the irradiation amount of irradiation of inactivated new coronavirus is irradiated ultraviolet sensing component and ultraviolet sensing kit.The ultraviolet sensing component of the present application uses KrCl excimer lamp as light source, with the filter that substantially shields the light of wavelength 230-300 nm, irradiate light to the ultraviolet sensing component, until the irradiation amount of light of wavelength 222 nm becomes 3mJ / cm 2 After that, when measuring the optical density of the specified color of the ultraviolet sensing component before light irradiation and the ultraviolet sensing component after light irradiation using spectrophotometer Spectrolino (Gretag Macbeth Company), the optical density represents the specified value.

Description

Technical Field

[0001] This invention relates to an ultraviolet sensing component and an ultraviolet sensing kit. Background Technology

[0002] The determination of ultraviolet (UV) irradiation levels is carried out in various fields. Specific examples include the determination of UV irradiation levels on the irradiated object during the curing reaction of UV-curable resins and the determination of UV irradiation levels on the irradiated object during UV sterilization of food and other products.

[0003] In the measurement of ultraviolet radiation, for example, Patent Document 1 discloses a method using a "UV marker" (manufactured by NICHIYUGIKEN KOGYO COMPANY, LIMITED, which manufactures UV-H) and Patent Document 2 discloses a method using a "UV scale" (manufactured by FUJIFILM Corporation).

[0004] On the other hand, in recent years, COVID-19 infection has become a major social problem.

[0005] In this context, Non-Patent Literature 1 reports a passivation effect on the novel coronavirus using ultraviolet light with a wavelength of 222 nm. More specifically, Non-Patent Literature 1 reports the passivation effect of irradiation at an illuminance of 0.1 mW / cm². 2 Using 222nm ultraviolet light for 30 seconds, 99.7% of the novel coronavirus can be inactivated.

[0006] Previous technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2015-191001

[0009] Patent Document 2: International Publication No. 2017 / 158943

[0010] Non-patent literature

[0011] Non-patent literature 1: Hiroki, Kitagawa et al., “Disinfection effect of 222nm ultraviolet light on SARS-CoV-2 surface contamination”, American Journal of Infection Control, Internet (https: / / www.sciencedirect.com / science / article / pii / S0196655320308099) Summary of the Invention

[0012] The technical problem to be solved by the invention

[0013] As described in Non-Patent Document 1, since ultraviolet light with a wavelength of 222 nm is effective in passivating the novel coronavirus, infection with the novel coronavirus can be prevented, for example, by irradiating parts touched by an unspecified number of people, such as door handles or touch panels, with ultraviolet light with a wavelength of 222 nm. In this case, it is desirable to be able to easily measure whether the amount of ultraviolet light that achieves the passivation of the novel coronavirus has been irradiated at a specified location.

[0014] The inventors used conventionally known UV markers and UV scales to measure the amount of light irradiated with a wavelength of 222nm, which is insensitive to SARS-CoV-2 infection. The results showed almost no change in hue in the UV markers and UV scales, making it impossible to determine the amount of irradiation. More specifically, even when the UV markers and UV scales were measured with a cumulative irradiance of 3mJ / cm², the results were insufficient. 2 Even when exposed to ultraviolet light with a wavelength of 222nm, almost no change in hue was observed.

[0015] The objective of this invention is to provide an ultraviolet sensing component that can easily determine whether an ultraviolet light source has been irradiated with an amount of light that has insensitive the novel coronavirus, in view of the above circumstances.

[0016] The objective of this invention is to provide an ultraviolet sensing kit.

[0017] means for solving technical problems

[0018] As a result of in-depth research to solve the above-mentioned problems, the inventors discovered that the problem could be solved by the structure shown below, and thus completed the present invention.

[0019] (1) An ultraviolet sensing component

[0020] Using a KrCl excimer lamp as the light source, and with filters that substantially block light in the 230–300 nm wavelength range, the ultraviolet sensing component was irradiated until the irradiation dose of light at a wavelength of 222 nm reached 3 mJ / cm². 2Then, using a Spectrolino spectrophotometer (GretagMacbeth), the optical concentrations of yellow, magenta, and cyan in the ultraviolet sensing component before and after light irradiation were measured. When the optical concentration of cyan in the ultraviolet sensing component before light irradiation was set as C1, the optical concentration of cyan in the ultraviolet sensing component after light irradiation was set as C2, the optical concentration of yellow in the ultraviolet sensing component before light irradiation was set as Y1, the optical concentration of yellow in the ultraviolet sensing component after light irradiation was set as Y2, the optical concentration of magenta in the ultraviolet sensing component before light irradiation was set as M1, and the optical concentration of magenta in the ultraviolet sensing component after light irradiation was set as M2, any one of the differences between C1 and C2, Y1 and Y2, and M1 and M2 was greater than 0.20.

[0021] (2) An ultraviolet sensing component

[0022] Using a KrCl excimer lamp as the light source, and with filters that substantially block light in the 230–300 nm wavelength range, the ultraviolet sensing component was irradiated until the irradiation dose of light at a wavelength of 222 nm reached 3 mJ / cm². 2 At that time, the color difference ΔE between before and after light irradiation is greater than 20.0.

[0023] (3) An ultraviolet sensing component.

[0024] Using a KrCl excimer lamp as the light source, and with filters that substantially block light in the 230–300 nm wavelength range, the ultraviolet sensing component was irradiated until the irradiation dose of light at a wavelength of 222 nm reached 3 mJ / cm². 2 When the cumulative value 1 of the absorbance of the ultraviolet sensing component in the wavelength range of 450 to 700 nm before light irradiation, obtained by method 1 described later, and the cumulative value 2 of the absorbance of the ultraviolet sensing component in the wavelength range of 450 to 700 nm after light irradiation, obtained by method 2 described later, are 18.0 or more.

[0025] (4) The ultraviolet sensing component according to any one of (1) to (3) is sheet-shaped.

[0026] (5) The ultraviolet sensing component according to any one of (1) to (4) includes an ultraviolet sensing layer containing a colorant.

[0027] (6) The ultraviolet sensing component according to (5), wherein,

[0028] The content of the colorant in the ultraviolet sensing layer is 0.140 g / m² relative to the unit area of ​​the ultraviolet sensing layer. 2 the following.

[0029] (7) The ultraviolet sensing component according to (5) or (6), wherein,

[0030] The color-developing agent is selected from a group consisting of color-developing agents that develop color through oxidation and color-developing agents that develop color through the action of acid.

[0031] The ultraviolet sensing layer contains at least one photoactive agent selected from the group consisting of photooxidants and photoacid generators.

[0032] (8) The ultraviolet sensing component according to (7), wherein the colorant is a colorant that develops color through the action of acid, the ultraviolet sensing layer contains a photoacid generator, and the mass ratio of the content of the photoactive agent to the content of the colorant exceeds 1.00.

[0033] (9) The ultraviolet sensing component according to (7) or (8), wherein,

[0034] Photoactive agents include compounds represented by general formula (6) described below.

[0035] (10) The ultraviolet sensing component according to (7) or (8), wherein,

[0036] Colorants include any structure selected from the group consisting of lactone rings, lactam rings, sulfonyl lactone rings, sultine rings and their open-ring forms, and azobenzene structures.

[0037] (11) The ultraviolet sensing component according to any one of (1) to (6) has:

[0038] An ultraviolet sensing layer comprising microcapsules containing a photoactive agent, a colorant, and a solvent having heteroatoms.

[0039] (12) The ultraviolet sensing component according to (11), wherein,

[0040] The capsule wall of the microcapsule comprises one or more resins selected from the group consisting of polyurea with aliphatic rings, polyurethane urea with aliphatic rings, and polyurethane with aliphatic rings.

[0041] The peak area ratio X calculated using the peak area ratio calculation method described later is less than 30%.

[0042] (13) An ultraviolet sensing kit comprising the ultraviolet sensing component described in any one of (1) to (12).

[0043] Invention Effects

[0044] According to the present invention, an ultraviolet sensing component can be provided that can easily determine whether the irradiation amount of the insensitive COVID-19 virus has been applied.

[0045] According to the present invention, an ultraviolet sensing kit can be provided. Attached Figure Description

[0046] Figure 1 This is a schematic cross-sectional view illustrating an example of a first embodiment of the ultraviolet sensing component of the present invention. Detailed Implementation

[0047] The present invention will now be described in detail.

[0048] Furthermore, the description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0049] In this specification, the numerical range indicated by “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower and upper limits.

[0050] Furthermore, within the numerical ranges described in this specification, the upper or lower limit of a certain numerical range can be replaced with the upper or lower limit of another numerical range described in a different period. Also, within the numerical ranges described in this specification, the upper or lower limit of a certain numerical range can be replaced with the values ​​shown in the embodiments.

[0051] Furthermore, in this specification, solid components refer to components that form the composition layer formed by using the composition. When the composition contains a solvent (e.g., organic solvents and water), it refers to all components other than the solvent. Also, liquid components are considered solid components as long as they form the composition layer.

[0052] Furthermore, in this specification, ultraviolet light refers to light with a wavelength range of 10 to 400 nm.

[0053] Furthermore, in this specification, (meth)acrylic acid refers to "at least one of acrylic acid and methacrylic acid".

[0054] Furthermore, in this specification, "boiling point" refers to the boiling point under standard atmospheric pressure.

[0055] Embodiment A of the ultraviolet sensing component of the present invention is an ultraviolet sensing component in which a KrCl (krypton chloride) excimer lamp is used as the light source, and a filter that substantially blocks light with a wavelength of 230-300 nm is used to irradiate the ultraviolet sensing component until the irradiation amount of light with a wavelength of 222 nm reaches 3 mJ / cm². 2Then, using a Spectrolino spectrophotometer (GretagMacbeth), the optical concentrations of cyan, magenta, and yellow in the ultraviolet sensing component before and after light irradiation were measured. The optical concentration of cyan in the ultraviolet sensing component before light irradiation was set as C1, the optical concentration of cyan in the ultraviolet sensing component after light irradiation was set as C2, the optical concentration of yellow in the ultraviolet sensing component before light irradiation was set as Y1, the optical concentration of yellow in the ultraviolet sensing component after light irradiation was set as Y2, the optical concentration of magenta in the ultraviolet sensing component before light irradiation was set as M1, and the optical concentration of magenta in the ultraviolet sensing component after light irradiation was set as M2. Any one of the differences between C1 and C2, Y1 and Y2, and M1 and M2 was greater than 0.20.

[0056] Embodiment B of the ultraviolet sensing component of the present invention is an ultraviolet sensing component that uses a KrCl excimer lamp as a light source, and is irradiated with light through a filter that substantially blocks light with wavelengths of 230 to 300 nm until the irradiation amount of light with a wavelength of 222 nm reaches 3 mJ / cm². 2 At that time, the color difference ΔE between before and after light irradiation is greater than 20.0.

[0057] Embodiment C of the ultraviolet sensing component of the present invention is an ultraviolet sensing component that uses a KrCl excimer lamp as a light source, and is irradiated with light through a filter that substantially blocks light with a wavelength of 230 to 300 nm until the irradiation amount of light with a wavelength of 222 nm reaches 3 mJ / cm². 2 When the cumulative value 1 of the absorbance of the ultraviolet sensing component in the wavelength range of 450 to 700 nm before light irradiation, obtained by method 1 described later, and the cumulative value 2 of the absorbance of the ultraviolet sensing component in the wavelength range of 450 to 700 nm after light irradiation, obtained by method 2 described later, are 18.0 or more.

[0058] In the ultraviolet sensing components of embodiments A to C of the present invention, the cumulative irradiance is 3 mJ / cm². 2 When exposed to ultraviolet light with a wavelength of 222nm, the hue changes, making it easy to determine whether the irradiation has been applied to a level that can inactivate the coronavirus.

[0059] Furthermore, it is known that the ultraviolet sensing components of Embodiments A to C of the present invention are less likely to cause so-called haze that results in color change due to the transmission of unintended light such as fluorescent lamps.

[0060] Hereinafter, the above-described characteristics of the ultraviolet sensing components according to Embodiments A to C of the present invention will be described in detail.

[0061] First, a KrCl excimer lamp was used as the light source, and the ultraviolet sensing component was irradiated with a filter that substantially blocked light with wavelengths of 230–300 nm until the irradiation dose of light with a wavelength of 222 nm reached 3 mJ / cm². 2 From the perspective of ease of operation, the size of the ultraviolet sensing component exposed to the irradiated light is preferably 5mm to 10mm in length and 5mm to 300mm in width.

[0062] In essence, a filter that blocks light with wavelengths of 230–300 nm refers to a filter that blocks 70–100% of light in this wavelength range. In other words, such a filter has a maximum transmittance of less than 30% in the 230–300 nm wavelength range. Most filters of this type are chemical filters or filters containing dielectrics.

[0063] As an ultraviolet irradiation device that uses a KrCl excimer lamp as a light source and is equipped with a filter that substantially blocks light with wavelengths of 230–300 nm, the ultraviolet irradiation device Care222 (registered trademark) sold by USHIO INC. can be used. Care222 (registered trademark) combines a lamp that uses ultraviolet light with a wavelength of 222 nm, suitable for sterilization, as the main wavelength, and a filter that limits the wavelength range (200–230 nm) to a range harmless to humans. Therefore, when using Care222 (registered trademark) for light irradiation, light with a wavelength of 222 nm is mainly irradiated.

[0064] There are no particular restrictions on the illuminance and irradiation time. The irradiation dose can be set to 3 mJ / cm by adjusting the distance between the light source and the ultraviolet sensing component or the irradiation time. 2 .

[0065] Furthermore, a known ultraviolet measuring instrument (e.g., a handheld photometer UIT2400 (manufactured by USHIO INC.)) can be used to measure whether a specified amount of irradiation has been applied to the ultraviolet sensing component.

[0066] Next, in Embodiment A, a spectrophotometer Spectrolino (GretagMacbeth) was used to measure the optical concentrations of cyan, magenta, and yellow in the ultraviolet sensing component before and after light irradiation.

[0067] More specifically, when using the Spectrolino spectrophotometer (GretagMacbeth), the measurement conditions are set as follows.

[0068] • Concentration status: DIN

[0069] ·D65 / 2°

[0070] No filter

[0071] The ultraviolet sensing component before and after light irradiation was used as the measurement object. During the measurement, the optical density (OD) was measured using various modes of Cyan, Magenta, and Yellow. The optical density values ​​(Y values) for cyan, magenta, and yellow were measured respectively. In addition, the measurement of the optical density (OD) of the ultraviolet sensing component after light irradiation was preferably carried out within 1 hour after light irradiation.

[0072] Next, the optical concentration value of cyan in the ultraviolet sensing component before light irradiation is set as C1, the optical concentration value of cyan in the ultraviolet sensing component after light irradiation is set as C2, the optical concentration value of yellow in the ultraviolet sensing component before light irradiation is set as Y1, the optical concentration value of yellow in the ultraviolet sensing component after light irradiation is set as Y2, the optical concentration value of magenta in the ultraviolet sensing component before light irradiation is set as M1, and the optical concentration value of magenta in the ultraviolet sensing component after light irradiation is set as M2. The difference between C1 and C2, the difference between Y1 and Y2, and the difference between M1 and M2 are then calculated.

[0073] The difference between C1 and C2 is the value obtained by subtracting the smaller of C1 and C2 from the larger one. If the values ​​of C1 and C2 are the same, the difference between them is 0.

[0074] The difference between Y1 and Y2 is the value obtained by subtracting the smaller value from the larger one. If the values ​​of Y1 and Y2 are the same, the difference between them is 0.

[0075] The difference between M1 and M2 is the value obtained by subtracting the smaller of M1 and M2 from the larger one. If the values ​​of M1 and M2 are the same, the difference between them is 0.

[0076] According to the above steps, any one of the differences between C1 and C2, Y1 and Y2, and M1 and M2 is 0.20 or more, preferably 0.20 to 1.50, and more preferably 0.26 to 1.10.

[0077] From the perspective of making it easier to determine whether the irradiation dose that inactivates the coronavirus (hereinafter also referred to as "the view that the effect of the present invention is superior"), either the difference between C1 and C2 or the difference between M1 and M2 is preferably 0.20 or more.

[0078] The difference between C1 and C2 is preferably 0.20 or more, more preferably 0.20 to 1.50, and even more preferably 0.26 to 1.10.

[0079] The value of C1 is mostly between 0.00 and 0.10, with 0.00 to 0.05 being preferred.

[0080] The value of C2 is preferably 0.20 or higher, and more preferably 0.20 to 1.50.

[0081] The difference between M1 and M2 is preferably 0.20 or more, more preferably 0.20 to 1.50, and even more preferably 0.26 to 1.10.

[0082] The value of M1 is mostly between 0.00 and 0.10, with 0.00 to 0.05 being preferred.

[0083] The value of M2 is preferably 0.20 or higher, and more preferably 0.20 to 1.50.

[0084] The difference between Y1 and Y2 is preferably 0.20 or more, more preferably 0.20 to 1.50, and even more preferably 0.26 to 1.10.

[0085] The value of Y1 is mostly between 0.00 and 0.10, with 0.00 to 0.05 being preferred.

[0086] The value of Y2 is preferably 0.20 or higher, and more preferably 0.20 to 1.50.

[0087] Furthermore, in Embodiment B, the color difference ΔE between the ultraviolet sensing component before and after light irradiation is measured.

[0088] More specifically, when using the Spectrolino spectrophotometer (GretagMacbeth), the measurement conditions are set as follows.

[0089] • Irradiation type: D65

[0090] • Field of view: 2°

[0091] • Concentration standard: ANSI STATUS A

[0092] The ultraviolet sensing component before and after light irradiation were used as the measurement objects, and the luminance L*, chromaticity a*, and chromaticity b* specified by the CIE 1976 L*a*b* color system were measured using the aforementioned spectrophotometer. Furthermore, the measurement of luminance L*, chromaticity a*, and chromaticity b* of the ultraviolet sensing component after light irradiation was preferably performed within one hour of the light irradiation.

[0093] Next, the differences ΔL* between the luminance L* (hereinafter also referred to as "luminance L*1") of the ultraviolet sensing component before light irradiation and the luminance L* (hereinafter also referred to as "luminance L*2") of the ultraviolet sensing component after light irradiation, Δa* between the chromaticity a* (hereinafter also referred to as "chromaticity a*1") of the ultraviolet sensing component before light irradiation and the chromaticity a* (hereinafter also referred to as "chromaticity a*2") of the ultraviolet sensing component after light irradiation, and Δb* between the chromaticity b* (hereinafter also referred to as "chromaticity b*1") of the ultraviolet sensing component before light irradiation and the chromaticity b* (hereinafter also referred to as "chromaticity b*2") of the ultraviolet sensing component after light irradiation are calculated, and the color difference ΔE is calculated using the following formula.

[0094] ΔE={(ΔL*) 2 +(Δa*) 2 +(Δb*) 2} 1 / 2

[0095] The color difference ΔE is 20.0 or more. From the viewpoint of achieving better results in this invention, 24.0 to 130 is preferred, and 35.0 to 100 is more preferred.

[0096] Furthermore, the difference between brightness L*1 and brightness L*2 is obtained by subtracting the smaller of the two values ​​from the larger one. When brightness L*1 and brightness L*2 are the same, the difference between them is 0.

[0097] Furthermore, the difference between chroma a*1 and chroma a*2 is obtained by subtracting the smaller of the two values ​​from the larger one. When the values ​​of chroma a*1 and chroma a*2 are the same, the difference between them is 0.

[0098] Furthermore, the difference between chroma b*1 and chroma b*2 is obtained by subtracting the smaller of the two values ​​from the larger one. When the values ​​of chroma b*1 and chroma b*2 are the same, the difference between them is 0.

[0099] Furthermore, in Embodiment C, the cumulative absorbance value 1 of the ultraviolet sensing component in the wavelength range of 450–700 nm before light irradiation, obtained by Method 1, and the cumulative absorbance value 2 of the ultraviolet sensing component in the wavelength range of 450–700 nm after light irradiation, obtained by Method 2, are calculated. Additionally, the measurement of the cumulative absorbance value 2 of the ultraviolet sensing component in the wavelength range of 450–700 nm after light irradiation is preferably performed within one hour after light irradiation.

[0100] Method 1: Measure the reflectance spectrum of the ultraviolet sensing component before light irradiation to obtain a reflectance spectrum with wavelength on the horizontal axis and absorbance on the vertical axis. Then, calculate the cumulative absorbance value 1 by accumulating the absorbance of each 1 nm from wavelength 450 nm to wavelength 700 nm in the cumulative reflectance spectrum.

[0101] Method 2: After irradiating the ultraviolet sensor with light, the reflectance spectrum is measured to obtain the reflectance spectrum with wavelength on the horizontal axis and absorbance on the vertical axis. The cumulative absorbance value 2 is then calculated by accumulating the absorbance of each 1 nm from wavelength 450 nm to wavelength 700 nm in the reflectance spectrum.

[0102] The apparatus used for measuring the reflectance spectra using methods 1 and 2 described above is a UV-Vis spectrophotometer (UV-2700 / Shimadzu Corporation). The measurement range is 350–750 nm, and absorbance is measured in 1 nm increments.

[0103] Under the above-mentioned apparatus and measurement conditions, absorbance is measured by diffuse reflectance measurement to obtain a reflectance spectrum with wavelength on the horizontal axis and absorbance on the vertical axis. The cumulative absorbance value is calculated by accumulating the absorbance of each 1 nm from wavelength 450 nm to wavelength 700 nm in the reflectance spectrum.

[0104] Furthermore, when the object being measured is an ultraviolet sensing component before light irradiation, the cumulative absorbance obtained is cumulative value 1, and when the object being measured is an ultraviolet sensing component after light irradiation, the cumulative absorbance obtained is cumulative value 2.

[0105] Next, the difference between the obtained cumulative value 1 and cumulative value 2 is calculated.

[0106] The difference is 18.0 or more. From the viewpoint of achieving better results in this invention, a difference of 20.0 to 200 is preferred, and a difference of 29.0 to 150 is more preferred.

[0107] Furthermore, the difference between cumulative value 1 and cumulative value 2 is obtained by subtracting the smaller of the two values ​​from the larger one. If cumulative value 1 and cumulative value 2 are the same, the difference between them is 0.

[0108] The shape of the ultraviolet sensing component in Embodiments A to C of the present invention is not particularly limited; it can be sheet-like, or it can be block-like, such as cuboid or cylindrical. Among them, sheet-like ultraviolet sensing components, i.e., ultraviolet sensing sheets, are preferred.

[0109] Furthermore, the shape of the sheet-like ultraviolet sensing component can be various, including polygons other than quadrilaterals such as squares, rectangles, circles, ellipses, and hexagons, as well as irregular shapes. The sheet-like ultraviolet sensing component can also be elongated.

[0110] The ultraviolet sensing component can be applied to other components. When applied to other components, the ultraviolet sensing component can be bonded with adhesive layers such as adhesives and bonding agents, or it can be manufactured as part of other components. There are no particular limitations on other components, such as business cards, labels, masks, fabric products (e.g., shirts), housings (e.g., smartphone housings), and paper products (e.g., notebooks, calendars).

[0111] Hereinafter, the materials (especially chromophores and photoactive agents) that can be included in the ultraviolet sensing components of Embodiments A to C of the present invention will be described in detail. Furthermore, the ultraviolet sensing components of Embodiments A to C of the present invention will also be simply referred to as "ultraviolet sensing components" below.

[0112] (Coloring agent)

[0113] The ultraviolet sensing component preferably includes an ultraviolet sensing layer containing a colorant. The specific structure of the ultraviolet sensing component will be described in detail later.

[0114] Here, the term "color-developing agent" encompasses the concepts of coloring, color change, and color fading. Coloring includes the development of color from a substantially colorless state (colorless or pale-colored) through the action of acids, oxidation, and light irradiation. Furthermore, color change includes the transformation of color from a specific hue to other hues or colorless states (e.g., from yellow to red) through the effects of acids, oxidation, and light irradiation. "Color fading" refers to the transformation from a specific hue to a substantially colorless state (colorless or pale-colored).

[0115] There are no particular limitations on the type of color-developing agent. Examples include color-developing agents that develop color through oxidation, color-developing agents that develop color through the action of acid, and color-developing agents that develop color through the action of light. Among these, color-developing agents that develop color through oxidation or color-developing agents that develop color through the action of acid are preferred, and color-developing agents that develop color through the action of acid are more preferred.

[0116] A single colorant can be used alone, or two or more can be used in combination.

[0117] As a color-developing agent, a color-developing agent comprising any one of the following structures: lactone ring, lactam ring, sulfonyl lactone ring, sulfinyl lactone ring and their open-ring forms, and azobenzene structure.

[0118] As a color-generating agent, colorless pigments or photochromic pigments are preferred, and colorless pigments are more preferred.

[0119] As photochromic pigments, there are known compounds that develop color through isomerization under light, compounds that develop color through ring-closing reactions under light, and compounds that develop color through ring-opening reactions under light, and known photochromic pigments can be used. As a photochromic pigment, it is preferable to perform a color development and decolorization reaction reversibly by energy.

[0120] As the aforementioned colorless pigment, it is preferable to be a compound that develops color by oxidation from a substantially colorless state (hereinafter also referred to as "oxidative colorless pigment"), or a compound that develops color from a substantially colorless state through the action of acid (hereinafter also referred to as "acid colorless pigment"). Furthermore, from the viewpoint of facilitating the design of the ultraviolet sensing component in Embodiments A to C, acid colorless pigment is preferred.

[0121] Examples of colorless pigments include triarylmethane phthalides, fluorane compounds, phenanthrene compounds, indole phthalides, azidoindole phthalides, colorless gold amine compounds, rhodamine lactam compounds, triarylmethane compounds, diarylmethane compounds, triazine compounds, spiropyran compounds, thiazide compounds, and fluorene compounds.

[0122] For details regarding the above-mentioned compounds, please refer to U.S. Patent No. 3,445,234, Japanese Patent Application Publication No. 5-257,272, and International Publication No. 2009 / 008248, paragraphs 0029 to 0034.

[0123] Oxidative colorless pigments

[0124] As a method of oxidative colorless pigment, compounds having one or two hydrogen atoms that emit color by removing electrons are preferred. Examples of such oxidative colorless pigments include (a) aminotriarylmethane, (b) aminoxanthin, (c) aminothiamine, (d) amino-9,10-dihydroacridine, (e) aminophenoxazine, (f) aminophenithazine, (g) aminodihydrophenazine, (h) aminodiphenylmethane, (i) colorless indamine, (j) aminohydrocinnamic acid (blue ethane, colorless methylene), (k) hydrazine, (l) colorless indigo dye, (m) amino-2,3-dihydroanthraquinone, (n) tetrahalo-p,p'-biphenyl, (o) 2-(p-hydroxyphenyl)-4,5-diphenylimidazole, and (p) phenethylaniline. In the above (a) to (p), (a) to (i) develop color by losing 1 hydrogen atom, and (j) to (p) develop color by losing 2 hydrogen atoms.

[0125] Among these, aminoarylmethane is preferred, and aminotriarylmethane is more preferred.

[0126] As an aminotriarylmethane, the compound represented by the following formula (L) or its hydrochloric acid is preferred.

[0127] [Chemical Formula 1]

[0128]

[0129] In the formula, Ar 1 This indicates that the bond to the methane carbon atom, as explicitly stated in formula (A1), is located at the para position with R. 1 R 2 N-substituted phenyl groups. Ar 2 This indicates that the bond to the methane carbon atom, as explicitly stated in formula (A1), is located at the para position with R. 1 R 2 The phenyl group with an N-substituent, or the phenyl group having a substituent selected from the group consisting of an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms), a fluorine atom, a chlorine atom, and a bromine atom at the ortho position relative to the carbon atom of methane as specified in formula (A2). 1 and R 2 Each can be independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a 2-hydroxyethyl group, a 2-cyanoethyl group, or a benzyl group.

[0130] Ar 3 Indicates with Ar 1 and Ar 1 At least one of the groups in, or indicating a group similar to Ar 1 and Ar 2 Different groups. Ar 3 Indicates with Ar 1 and Ar 2 In the case of different groups, Ar 3 The following groups are used to represent: (B1) a phenyl group that can be substituted with a substituent selected from the group consisting of a lower alkyl group (preferably an alkyl group with 1 to 4 carbon atoms), a lower alkoxy group (preferably an alkoxy group with 1 to 4 carbon atoms), a chlorine atom, a diphenylamino group, a cyano group, a nitro group, a hydroxyl group, a fluorine atom, a bromine atom, an alkylthio group, an arylthio group, a thioester group, an alkylsulfonic acid group, an arylsulfonic acid group, a sulfonic acid group, a sulfonamide group, an alkylamide group, and an arylamide group; (B2) a naphthyl group that can be substituted with a substituent selected from the group consisting of an amino group, a di-lower alkylamino group, and an alkylamino group; (B3) a pyridyl group that can be substituted with an alkyl group; and (B4) a quinolinyl group or (B5) an indoline group that can be substituted with an alkyl group.

[0131] In the above equation (L), R 1 and R 2 Each is preferably an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

[0132] Furthermore, in the above formula (L), Ar 1 Ar 2 and Ar 3 Preferably, it means that the bond to the methane carbon atom is located at the para position relative to the bond explicitly stated in the formula, and has R. 1 R 2 N-substituted phenyl groups, wherein the same group is preferred.

[0133] Specific examples of colorless pigments with oxidative chromogenic properties include tris(4-dimethylaminophenyl)methane, tris(4-diethylaminophenyl)methane, bis(4-diethylaminophenyl)-(4-diethylamino-2-methylphenyl)methane, bis(4-diethylamino-2-methylphenyl)-(4-diethylaminophenyl)methane, bis(1-ethyl-2-methylindol-3-yl)-phenylmethane, 2-N-(3-trifluoromethylphenyl)-N-ethylamino-6-diethylamino-9-(2-methoxycarbonylphenyl)xanthine, 2-(2 2-(2-chlorophenyl)amino-6-dibutylamino-9-(2-methoxycarbonylphenyl)xanthonium, 2-dibenzylamino-6-diethylamino-9-(2-methoxycarbonylphenyl)xanthonium, benzo[a]-6-N,N-diethylamino-9,2-methoxycarbonylphenylxanthonium, 2-(2-chlorophenyl)-amino-6-dibutylamino-9-(2-methylphenylcarboxyamidophenyl)xanthonium, 3,6-dimethoxy-9-(2-methoxycarbonyl)-phenylxanthonium, benzoyl colorless methylene blue, and 3,7-bis-diethylaminophenoxazine, etc.

[0134] Acid-based colorless pigments

[0135] As a type of colorless pigment with acid chromogenic properties, compounds that emit color by donating electrons or accepting protons such as acids are preferred. Specifically, examples include compounds that have partial skeletons such as lactones (cyclic carboxylic esters), lactams (cyclic carboxylic amides), sulcolones (cyclic sulfonates), sulfinolones (cyclic sulfonamides), spiropyrans, esters, and amides, and whose partial skeletons open or cleave upon contact with acids or protons.

[0136] Furthermore, from the viewpoint of facilitating the design of the ultraviolet sensing components of Embodiments A to C, it is preferable to have a compound having a structure selected from the group consisting of lactones, lactams, sulcolones, sulfinolones, and their open-ring forms (hereinafter also referred to as "specific colorants").

[0137] A specific colorant has a defined structure that can be reversibly changed.

[0138] For example, a specific chromophore X having the following lactone structure can be a closed-ring form that substantially represents colorless and an open-ring form that represents colored. When an acid is supplied to the closed-ring form of the specific chromophore X, as shown in the following scheme, the acid (H...) + The reactions that produce open-ring forms through ring-opening and closed-ring forms through deoxygenation proceed reversibly. With a higher acid content, the equilibrium favors the ring-opening reaction. The more the equilibrium favors the ring-opening reaction, the higher the chromophore's color development, and the easier it is to determine the irradiation dose. Furthermore, as described later, when the mass ratio of photosynthetic agent to chromophore (photoreactive agent / chromophore (mass ratio)) exceeds 1.00, the amount of acid produced relative to a specific chromophore X increases, thus the equilibrium tends to shift from closed-ring to open-ring forms, resulting in further improved chromophores. Moreover, with the aforementioned mass ratio, the amount of chromophore can be relatively reduced. In this case, light absorption based on the specific chromophore X itself can be suppressed, resulting in increased light absorption based on the photosynthetic agent.

[0139] [Chemical Formula 2]

[0140]

[0141] Furthermore, while the above description focuses on compounds that open their rings through the action of acids, there are also cases where compounds close their rings through the action of acids, as described below.

[0142] A specific chromophore Y having the following sulfonyl lactone structure can be formed into an open-ring form representing blue and a closed-ring form representing yellow, as shown in the following scheme. When an acid is supplied to the open-ring form of the specific chromophore Y, as shown in the following scheme, the acid (H...) + The reactions that produce closed-loop compounds through the action of acid (A) and those that produce open-loop compounds through deoxygenation are reversible. With a higher amount of acid, the equilibrium tends to favor the reaction producing the closed-loop compound. The more the equilibrium favors the reaction producing the closed-loop compound, the higher the chromophore, and the easier it is to determine the irradiation dose.

[0143] [Chemical Formula 3]

[0144]

[0145] Furthermore, a specific chromophore Z having the following azobenzene structure can be used as an azo body representing yellow and an hydrazone representing orange to pink, as shown in the following scheme. When an acid is supplied to the azo body of the specific chromophore Z, as shown in the following scheme, the acid (H...) + The reaction that produces hydrazones and the reaction that produces azo bodies through deoxygenation proceed reversibly. When the amount of acid is high, the equilibrium is more biased towards the reaction that produces hydrazones. The more the equilibrium is biased towards the reaction that produces hydrazones, the higher the chromophore, and the easier it is to determine the radiation dose.

[0146] [Chemical Formula 4]

[0147]

[0148] Examples of specific color-developing agents mentioned above include compounds represented by formula (II) and their open-ring compounds.

[0149] [Chemical Formula 5]

[0150]

[0151] In equation (II), R b1 and R b3 Each can independently represent a hydrogen atom, an alkyl group that may have substituents, or an aryl group that may have substituents. R b2 and R b4 Each can be independently represented as an alkyl group or an aryl group that can have substituents. X b1 Indicates -NR b5 -. R b5 It represents a hydrogen atom, an alkyl group that may have substituents, or an aryl group that may have substituents.

[0152] As R b1 ~R b5 The alkyl groups mentioned above that may have substituents can be any of the following: straight-chain, branched, and cyclic, preferably straight-chain or branched.

[0153] The number of carbon atoms in the alkyl group that may have substituents is preferably 1 to 10, more preferably 1 to 5.

[0154] R b1 ~R b5 The aryl group represented above, which may have substituents, can be either monocyclic or polycyclic.

[0155] The number of carbon atoms in the aryl group that may have substituents is preferably 6 to 20.

[0156] Examples of substituents that can be present in the alkyl group and the aryl group mentioned above include halogen atoms, cyano groups, nitro groups, carboxyl groups, alkyl groups, aryl groups, and groups formed by combining them.

[0157] As R b1 ~R b4 Preferably, the alkyl group may have a substituent, and more preferably, the alkyl group may have no substituent (unsubstituted alkyl group).

[0158] Examples of specific color-developing agents include compounds represented by formula (II I) and their open-ring compounds.

[0159] [Chemical Formula 6]

[0160]

[0161] In equation (III), Ar c1 This indicates an aromatic ring that can have substituents. R c1 Represents a hydrogen atom, an alkyl group that may have substituents, or an aryl group that may have substituents. R c2 This indicates an alkyl group that may have substituents or an aryl group that may have substituents. X c1 Indicates -O- or -NR c3 -. R c3 It represents a hydrogen atom, an alkyl group that may have substituents, or an aryl group that may have substituents.

[0162] Ar c1 This indicates that an aromatic ring can have substituents.

[0163] The aromatic rings that can have substituents can be either monocyclic or polycyclic.

[0164] Examples of aromatic rings that can have substituents include aromatic hydrocarbon rings and aromatic heterocycles that can have substituents, with aromatic hydrocarbon rings that can have substituents being preferred.

[0165] Examples of substituents that can be present in the aforementioned aromatic rings that may have substituents include alkyl groups and -NR groups. N1 R N2 aryl and heteroaryl, preferably alkyl or -NR N1 R N2 R N1 and R N2 Each can be independently represented by a hydrogen atom, an alkyl group that may have substituents, or an aryl group that may have substituents.

[0166] The alkyl group can be any of the following: straight-chain, branched, and cyclic, preferably straight-chain or branched.

[0167] The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 5.

[0168] The number of ring members of the aromatic ring that may have substituents is preferably 6 to 30, more preferably 6 to 18, and even more preferably 6 to 12.

[0169] Examples of aromatic rings that may have substituents include, for instance, aromatic hydrocarbon rings that may have substituents, such as benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings; and aromatic heterocycles that may have substituents, such as indole rings, pyrrole rings, pyrazole rings, triazole rings, pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, thiophene rings, furan rings, pyran rings, thiazole rings, oxazole rings, selenophenol rings, and imidazole rings. Aromatic hydrocarbon rings that may have substituents are preferred, and benzene rings that may have substituents are more preferred.

[0170] R c1 Represents a hydrogen atom, an alkyl group that may have substituents, or an aryl group that may have substituents. R c2 This indicates an alkyl group that may have substituents or an aryl group that may have substituents.

[0171] As R c1 The alkyl groups that can have substituents and the aryl groups that can have substituents, for example, are the R groups mentioned above. b1 ~R b5 The terms represent alkyl groups that may have substituents and aryl groups that may have substituents.

[0172] As R c1 and R c2 Preferably, it is a straight-chain or branched alkyl group without substituents.

[0173] X c1 Indicates -O- or -NR c3 -. R c3 It represents a hydrogen atom, an alkyl group that may have substituents, or an aryl group that may have substituents.

[0174] As R c3 The alkyl groups that can have substituents and the aryl groups that can have substituents, for example, are the R groups mentioned above. b1 ~R b5 The terms represent alkyl groups that may have substituents and aryl groups that may have substituents.

[0175] Examples of specific color-generating agents include compounds represented by formula (IV) and their closed-ring compounds, as well as compounds represented by formula (V).

[0176] [Chemical Formula 7]

[0177]

[0178] In equation (IV), R d1 and R d2 Each can be represented independently by a halogen atom or an alkyl group that may have substituents. R d3 COO - M d + or SO3 - M d + M d + This represents a cation. nd1 and nd2 independently represent integers from 0 to 4.

[0179] In equation (V), R e1 and R e2Each can be independently represented as an alkyl group that may have substituents. R e3 COO - M e + or SO3 - M e + M e + It represents a cation. ne represents 0 or 1.

[0180] R d1 and R d2 Each can be represented independently as a halogen atom or an alkyl group that may have substituents.

[0181] Chlorine or bromine atoms are preferred as the halogen atom mentioned above.

[0182] The alkyl groups that may have substituents can be any of the following: straight-chain, branched, and cyclic.

[0183] The number of carbon atoms in the alkyl groups that can have substituents mentioned above is mostly between 1 and 10.

[0184] R d3 COO - M d + or SO3 - M d + M d + It represents a cation.

[0185] Examples of cations mentioned above include well-known cations, specifically H+. + Monovalent cations, including protons, monovalent organic cations, and monovalent inorganic cations, are preferred, especially K. + Or Na + .

[0186] nd1 and nd2 independently represent integers from 0 to 4.

[0187] nd1 and nd2 can be the same or different, but it is preferred that they represent the same integer.

[0188] The compounds represented by formula (V) will be described in detail below.

[0189] R e1 and R e2 Each can be independently represented as an alkyl group that may have substituents.

[0190] As R e1 and R e2 For example, the above R can be cited. d1 and the above R d2The alkyl group represented may have substituents.

[0191] R e3 Represents C()O - M e + or SO3 - M e + M e + It represents a cation.

[0192] M e + The meaning of M above d + The same applies, and the preferred selection method is also the same.

[0193] ne represents 0 or 1.

[0194] Examples of colorless pigments that develop color through the action of acids (acid-based colorless pigments) include 3,3-bis(2-methyl-1-octyl-3-indolyl)phthalide, 6'-(dibutylamino)-2'-bromo-3'-methylspiro[phthalide-3,9'-xanthine], 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, and 3-(4-diethylamino-2-... ethoxyphenyl)-3-(1-n-octyl-2-methylindole-3-yl)phthalide, 3-[2,2-bis(1-ethyl-2-methylindole-3-yl)vinyl]-3-(4-diethylaminophenyl)phthalide, 2-anilino-6-dibutylamino-3-methylfluorane, 6-diethylamino-3-methyl-2-(2,6-dimethylphenylamino)fluorane, 2-(2-chloroanilino)-6-dibutylaminofluorane, 3, 3-Bis(4-dimethylaminophenyl)-6-dimethylaminophthalide, 2-anilino-6-diethylamino-3-methylfluorane, 9-[ethyl(3-methylbutyl)amino]spiro[12H-benzo[a]xanthan-12,1'(3'H)isobenzofuran]-3'-one, 2'-methyl-6'-(N-p-tolyl-N-ethylamino)spiro[isobenzofuran-1(3H),9'-[9H]xanthan]-3-one, 3',6'-bis(diethylamino)-2-(4-nitrophenyl)spiro[isoindol-1,9'-xanthon]-3-one, 9-(N-ethyl-N-isopentylamino)spiro[benzo[a]xanthon-12,3'-phthalide], 2'-anilino-6'-(N-ethyl-N-isopentylamino)-3'-methylspiro[phthalide-3,9'-[9H]xanthon] and 6'-(diethylamino)-1',3'-dimethylfluorane.

[0195] From the viewpoint of achieving better results with the present invention, the colorant is preferably a compound having either an indolephthalide structure or an azidoindolephthalide structure, and more preferably a compound having an indolephthalide structure.

[0196] Compounds having an indolephthalide structure are compounds that partially possess an indolephthalide structure. Furthermore, as described above, the compounds having an indolephthalide structure (indolephthalide compounds) and compounds having an aza-indolephthalide structure (aza-indolephthalide compounds) function as chromophores. That is, the above compounds correspond to chromophores having an indolephthalide structure (especially acid chromophores) and chromophores having an aza-indolephthalide structure.

[0197] There is no particular limitation on the number of indolephthalide structures in compounds having an indolephthalide structure; there can be one or more. However, from the viewpoint of achieving better results in this invention, two or more indolephthalide structures are preferred, and more preferably two indolephthalide structures.

[0198] As a compound having an indolephthalide structure, the compound represented by general formula (A) or the compound represented by general formula (B) is preferred, and the compound represented by general formula (B) is more preferred.

[0199] [Chemical Formula 8]

[0200]

[0201] In general formula (A), R a1 and R a2 Each can be represented independently as a hydrogen atom or an alkyl group that may have substituents.

[0202] R a1 There is no particular limitation on the number of carbon atoms of the alkyl group, but from the viewpoint of better effect of the present invention, 1 to 30 is preferred, 1 to 20 is more preferred, 1 to 12 is even more preferred, and 5 to 10 is particularly preferred.

[0203] R a2 There is no particular limitation on the number of carbon atoms of the alkyl group, but from the viewpoint of better effect of the present invention, 1 to 10 is preferred, 1 to 5 is more preferred, and 1 to 3 is even more preferred.

[0204] From the viewpoint that the present invention has superior effects, R a1 and R a2 Preferably, it means that the alkyl group may have a substituent, more preferably an unsubstituted alkyl group.

[0205] R a3 It represents a hydrogen atom, an alkyl group that may have substituents, or an aryl group that may have substituents.

[0206] Ra3 There is no particular limitation on the number of carbon atoms of the alkyl group, but from the viewpoint of better effect of the present invention, 1 to 10 is preferred, and 1 to 5 is more preferred.

[0207] R a3 The aryl group can be a monocyclic structure or a polycyclic structure.

[0208] From the viewpoint of achieving better results with the present invention, as R a3 Preferably, it may be an aryl group having substituents, and more preferably an aryl group having substituents.

[0209] X a Indicates -O- or -NR a4 -

[0210] From the viewpoint of achieving superior effects of the present invention, X is... a , preferred -O-.

[0211] R a4 It represents a hydrogen atom, an alkyl group that may have substituents, or an aryl group that may have substituents.

[0212] R a4 There is no particular limitation on the number of carbon atoms of the alkyl group, but from the viewpoint of better effect of the present invention, 1 to 10 is preferred, and 1 to 5 is more preferred.

[0213] R a4 The aryl group can be a monocyclic structure or a polycyclic structure.

[0214] There is no particular limitation on the molecular weight of the compound represented by general formula (A), but it is preferably 300 or more, more preferably 500 or more. There is no particular upper limit, but it is preferably 2000 or less, more preferably 1000 or less.

[0215] [Chemical Formula 9]

[0216]

[0217] In general formula (B), R v1 ~R b4 Each can be represented independently as a hydrogen atom or an alkyl group that may have substituents.

[0218] R v1 and R b3 There is no particular limitation on the number of carbon atoms of the alkyl group, but from the viewpoint of better effect of the present invention, 1 to 30 is preferred, 1 to 20 is more preferred, 1 to 12 is even more preferred, and 5 to 10 is particularly preferred.

[0219] R b2 and R b4There is no particular limitation on the number of carbon atoms of the alkyl group, but from the viewpoint of better effect of the present invention, 1 to 10 is preferred, 1 to 5 is more preferred, and 1 to 3 is even more preferred.

[0220] From the viewpoint of achieving better results with the present invention, as R v1 ~R b4 Preferably, it may be an alkyl group with a substituent, more preferably an unsubstituted alkyl group.

[0221] X b Indicates -O- or -NR b5 -

[0222] From the viewpoint of achieving superior effects of the present invention, X is... b , preferred -O-.

[0223] R b5 It represents a hydrogen atom, an alkyl group that may have substituents, or an aryl group that may have substituents.

[0224] R b5 There is no particular limitation on the number of carbon atoms of the alkyl group, but from the viewpoint of better effect of the present invention, 1 to 10 is preferred, and 1 to 5 is more preferred.

[0225] R b5 The aryl group can be a monocyclic structure or a polycyclic structure.

[0226] There is no particular limitation on the molecular weight of the compound represented by general formula (B), but it is preferably 300 or more, more preferably 500 or more. There is no particular upper limit, but it is preferably 2000 or less, more preferably 1000 or less.

[0227] There is no particular limitation on the content of the colorant in the ultraviolet sensing layer, but from the viewpoint of achieving better results in this invention, the content of the colorant per unit area (m²) of the ultraviolet sensing layer is considered to be higher. 2 ) Preferably 0.500g / m 2 Below, 0.300 g / m is preferred. 2 The following is a further preferred value of 0.140 g / m 2 The following is particularly preferred: 0.070 g / m 2 The following is a lower limit; there is no particular limitation, but 0.020 g / m³ is preferred. 2 More preferably, 0.030 g / m 2 The above suggests that by setting the content of the colorant in the ultraviolet sensing layer to the above range, excessive absorption at 222nm based on the colorant can be suppressed. Therefore, it is possible to set the minimum colorant dose required for the color reaction, and the optical concentration difference can be 0.20 or higher.

[0228] The content of the aforementioned chromophore can be calculated by cutting an area with a large amount of ultraviolet sensing layer from the ultraviolet sensing element, immersing the ultraviolet sensing layer in methanol for 2 days, and then analyzing the solvent obtained using liquid chromatography. Furthermore, during the immersion period, methanol should not be allowed to evaporate. Additionally, if necessary, a calibration curve for the content of the chromophore to be detected can be prepared before the liquid chromatography determination.

[0229] The determination conditions for liquid chromatography are as follows.

[0230] Device: Nexera manufactured by Shimadzu Corporation

[0231] Column: Capcell pak C18 UG-120

[0232] Eluent: Water / Methanol

[0233] Oven: 40℃

[0234] Injection: 5μL

[0235] Detection: The wavelength of maximum absorption of the chromophore being detected.

[0236] Flow rate: 0.2 mL / min

[0237] (Photoactive agents)

[0238] The ultraviolet sensing layer preferably contains a photoactive agent.

[0239] There are no particular limitations on the photoactive agent, as long as it is a photoactivated compound. However, it is preferable that the photoactivated photoactive agent acts on the chromophore to produce color, and it is more preferably a compound activated by ultraviolet light. As a photoactive agent, it is preferable to have one or more of a photooxidant and a photoacid-producing agent. If the ultraviolet sensing component includes a chromophore that produces color through oxidation, it is preferable that the photoactive agent includes a photooxidant. If the ultraviolet sensing component includes a chromophore that produces color through the action of acid, it is preferable that the photoactive agent includes a photoacid-producing agent.

[0240] A single photoactive agent can be used alone, or two or more can be used in combination.

[0241] From the viewpoint of achieving better results with the present invention, the mass ratio of the content of the photoactive agent to the content of the chromophore (photoactive agent / chromophore (mass ratio)) is preferably greater than 1.00, more preferably 3.00 or more, even more preferably 8.00 or more, and particularly preferably 10.00 or more. There is no particular upper limit, but it is preferably 40.00 or less, more preferably 30.00 or less, even more preferably 25.00 or less, and particularly preferably 20.00 or less. It is conjectured that by setting the mass ratio of the content of the photoactive agent to the content of the chromophore within the above range, excessive absorption at 222 nm based on the chromophore can be suppressed, and the photoactive agent effectively absorbs at 222 nm, thereby enabling effective color development and achieving an optical concentration difference of 0.20 or more.

[0242] Methanol can be extracted in the same manner as the chromophore described above, and the mass ratio of the photoactive agent content to the chromophore content can be determined by liquid chromatography. Furthermore, the photoactive agent is detected at its maximum absorption wavelength, and the chromophore is detected at its maximum absorption wavelength, and their mass ratio is calculated.

[0243] Photooxidants

[0244] As a photooxidizing agent, it is preferably a compound that is activated by ultraviolet light to generate free radicals and / or enables the colorant to develop color by exhibiting the effect of extracting hydrogen atoms from the colorant.

[0245] Among these, the photooxidizing agent is preferably one or more of a free radical generator and an organohalogen compound. As a photoacid generator, it is also preferable to use both a free radical generator and an organohalogen compound simultaneously. When both a free radical generator and an organohalogen compound are used, from the viewpoint of achieving better color gradation in the chromatic area, the content ratio of the free radical generator to the organohalogen compound (free radical generator / organohalogen compound (mass ratio)) is preferably 0.1 to 10, more preferably 0.5 to 5.

[0246] Free radical generators

[0247] There are no particular restrictions on compounds that can generate free radicals when activated by ultraviolet light.

[0248] As a free radical generator, a hydrogen-abstraction type free radical generator is preferred. Hydrogen-abstraction type free radical generators exhibit the ability to promote the oxidation of the chromophore by abstracting hydrogen atoms from it.

[0249] Examples of free radical generators include, for instance, the azide polymer described on page 55 of the keynote speech at the Spring 1968 Research Presentation of the Photographic Society of Japan; azide compounds such as 2-azidobenzoxazole, benzoyl azide, and 2-azidobenzimidazole described in US Patent No. 3,282,693; 3'-ethyl-1-methoxy-2-anthocyanin perchlorate pyridinium thiophosphate and 1-methoxy-2-methylpyridinium p-toluenesulfonate described in US Patent No. 3,615,568; 2,4,5-triarylimidazolium dimer and other benzophenone dimers described in Japanese Patent Publication No. 62-039728; benzophenone; p-aminophenyl ketone; polynuclear quinone; thioxanthium, etc.

[0250] Preferably, it is selected from one or more of rofenamic acid dimer and benzophenone, and more preferably rofenamic acid dimer.

[0251] Examples of hexaaryl biimidazole compounds can be cited as hexaaryl biimidazole dimers. Compounds described in paragraph 0047 of International Publication No. 2016 / 017701 can be referenced as hexaaryl biimidazole compounds, and these contents are incorporated herein by reference.

[0252] Of particular, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole is preferred. As 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, for example, "B-IMD" (manufactured by KUROGANE KASEICo., Ltd.) and "B-CIM" (manufactured by Hodogaya Chemical Co., Ltd.) can be used.

[0253] As a dimer of roxene, the compound represented by the following general formula (1) is also preferred.

[0254] [Chemical Formula 10]

[0255]

[0256] In the formula, A, B and D independently represent unsubstituted carbocyclic or heteroaryl groups or substituents that do not hinder the dissociation of the dimer towards the imidazole group or the oxidation of the chromogenic agent.

[0257] B and D are each preferably unsubstituted or have 1 to 3 substituents, and A is preferably unsubstituted or has 1 to 4 substituents.

[0258] The compounds represented by general formula (1) and their preparation methods can be utilized using known discoveries such as loperamide dimers. For example, the descriptions in column 4, line 22 and column 6, line 3 of U.S. Patent No. 3,552,973 can be cited and incorporated into this specification.

[0259] Free radical generators can be used alone or in combination of two or more.

[0260] Organic halogen compounds

[0261] Organohalogen compounds can promote the oxidation of colorants.

[0262] From the viewpoint of superior color gradation in the chromatic area, compounds with three or more halogen atoms within the molecule are preferred as organohalogen compounds. As an upper limit for the number of halogen atoms, nine or fewer is preferred. Furthermore, the organohalogen compound is a compound other than robin base dimer and benzophenone.

[0263] Organic halogen compounds can be used alone or in combination of two or more.

[0264] As organohalogen compounds, examples include compounds represented by the following general formulas (2) to (7).

[0265] P 0 -CX3……(2)

[0266] In the formula, P 0 This represents a hydrogen atom, a halogen atom, an alkyl group that may have substituents, or an aryl group that may have substituents. X represents a halogen atom independently.

[0267] As P 0 The halogen atom represented by X can be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, with chlorine or bromine atom being preferred.

[0268] As P 0 The alkyl and aryl groups represented may have substituents, such as hydroxyl, halogen atom, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, acetyl, and alkoxy with 1 to 6 carbon atoms.

[0269] Examples of compounds represented by general formula (2) include chloroform, tribromomethane, carbon tetrachloride, carbon tetrabromide, p-nitrobenzotribromo, bromochloromethane, trichlorotoluene, hexabromoethane, triiodomethane, 1,1,1-tribromo-2-methyl-2-propanol, 1,1,2,2-tetrabromoethane, 2,2,2-tribromoethanol, and 1,1,1-trichloro-2-methyl-2-propanol.

[0270] [Chemical Formula 11]

[0271]

[0272] In the formula, R represents a substituent. x represents an integer from 0 to 5.

[0273] Examples of substituents represented by R include nitro, halogen atom, alkyl group with 1 to 3 carbon atoms, haloalkyl group with 1 to 3 carbon atoms, acetyl group, haloacetyl group, and alkoxy group with 1 to 3 carbon atoms.

[0274] Furthermore, when there are multiple R in the formula, R can be the same as each other or different from each other.

[0275] For x, 0 to 3 are preferred.

[0276] Examples of compounds represented by general formula (3) include o-nitro-α,α,α-tribromoacetophenone, m-nitro-α,α,α-tribromoacetophenone, p-nitro-α,α,α-tribromoacetophenone, α,α,α-tribromoacetophenone and α,α,α-tribromo-3,4-chloroacetophenone.

[0277] R 1 -SO2-X 1 ……(4)

[0278] In the formula, R 1 X represents a hydrogen atom, an alkyl group that may have substituents, or an aryl group that may have substituents. 1 This represents a halogen atom.

[0279] As R 1 The alkyl group represented is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.

[0280] As R 1 The aryl group represented is preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 14 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms.

[0281] As R 1 The alkyl and aryl groups represented may have substituents, for example, nitro, halogen atom, alkyl with 1 to 3 carbon atoms, haloalkyl with 1 to 3 carbon atoms, acetyl, haloacetyl and alkoxy with 1 to 3 carbon atoms.

[0282] As X 1 The halogen atom represented can be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom or a bromine atom.

[0283] Examples of compounds represented by general formula (4) include 2,4-dinitrobenzenesulfonyl chloride, o-nitrobenzenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, 3,3'-diphenylsulfonyl disulfonyl chloride, ethanesulfonyl chloride, p-bromobenzenesulfonyl chloride, p-nitrobenzenesulfonyl chloride, 3-p-benzenesulfonyl chloride, p-acetamidebenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, p-toluenesulfonyl chloride, methanesulfonyl chloride, and benzenesulfonyl bromide.

[0284] R 2 -SX 2 ……(5)

[0285] In the formula, R 2 This indicates an alkyl group that may have substituents or an aryl group that may have substituents. X 2 This represents a halogen atom.

[0286] As R 2 The alkyl groups and aryl groups represented can have substituents, and are related to R in general formula (4). 1 The same applies, and the preferred selection method is also the same.

[0287] As X 2 The halogen atom represented can be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom or a bromine atom.

[0288] Examples of compounds represented by general formula (5) include 2,4-dinitrobenzenesulfonyl chloride and o-nitrobenzenesulfonyl chloride.

[0289] R 3 -L 1 -CX 3 X 4 X 5 ……(6)

[0290] In the formula, R 3 This indicates an aryl group that may have substituents or a heteroaryl group that may have substituents. L 1 Indicates -SO- or SO2-. X 3 X 4 and X 5 Each can be represented independently as a hydrogen atom or a halogen atom. However, X 3 X 4 and X 5 It is not entirely composed of hydrogen atoms.

[0291] As R 3 The aryl group represented is preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 14 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms.

[0292] As R 3 The heteroaryl group represented is preferably a heteroaryl group with 4 to 20 carbon atoms, more preferably a heteroaryl group with 4 to 13 carbon atoms, and even more preferably a heteroaryl group with 4 to 9 carbon atoms.

[0293] As R 3The substituents that the aryl and heteroaryl groups represented can have include, for example, nitro, halogen atom, alkyl with 1 to 3 carbon atoms, haloalkyl with 1 to 3 carbon atoms, acetyl, haloacetyl and alkoxy with 1 to 3 carbon atoms.

[0294] As X 3 X 4 and X 5 The halogen atom represented may include, for example, fluorine, chlorine, bromine and iodine atoms, preferably chlorine, bromine or iodine atom, more preferably chlorine or bromine atom.

[0295] Examples of compounds represented by general formula (6) include hexabromodimethyl sulfoxide, pentabromodimethyl sulfoxide, hexabromodimethyl sulfone, trichloromethylphenyl sulfone, tribromomethylphenyl sulfone (BMPS), trichloro-p-chlorophenyl sulfone, tribromomethyl-p-nitrophenyl sulfone, 2-trichloromethylbenzothiazole sulfone, 4,6-dimethylpyrimidine-2-tribromomethyl sulfone, tetrabromodimethyl sulfone, 2,4-dichlorophenyl-trichloromethyl sulfone, 2-methyl-4-chlorophenyltrichloromethyl sulfone, 2,5-dimethyl-4-chlorophenyltrichloromethyl sulfone, 2,4-dichlorophenyltrimethyl sulfone, and tri-p-tolylsulfonium trifluoromethanesulfonate, preferably trichloromethylphenyl sulfone or tribromomethylphenyl sulfone (BMPS).

[0296] R 4 CX 6 X 7 X 8 ……(7)

[0297] In the formula, R 4 This indicates a heteroaryl group that can have substituents. X 6 X 7 and X 8 Each can be represented independently as a hydrogen atom or a halogen atom. However, X 6 X 7 and X 8 It is not entirely composed of hydrogen atoms.

[0298] As R 4 The heteroaryl group represented is preferably a heteroaryl group with 4 to 20 carbon atoms, more preferably a heteroaryl group with 4 to 13 carbon atoms, and even more preferably a heteroaryl group with 4 to 9 carbon atoms.

[0299] As R 4 The substituents that the heteroaryl group can have include, for example, nitro, halogen atom, alkyl group with 1 to 3 carbon atoms, haloalkyl group with 1 to 3 carbon atoms, acetyl group, haloacetyl group and alkoxy group with 1 to 3 carbon atoms.

[0300] As X 6 X 7 and X 8The halogen atom represented may include, for example, fluorine, chlorine, bromine and iodine atoms, preferably chlorine, bromine or iodine atom, more preferably chlorine or bromine atom.

[0301] Examples of compounds represented by general formula (7) include tribromoquinazine, 2-tribromomethyl-4-methylquinoline, 4-tribromomethylpyrimidine, 4-phenyl-6-tribromomethylpyrimidine, 2-trichloromethyl-6-nitrobenzothiazole, 1-phenyl-3-trichloromethylpyrazole, 2,5-ditribromomethyl-3,4-dibromothiophene, 2-trichloromethyl-3-(p-butoxystyryl)-1,3,4-oxadiazole, 2,6-ditrichloromethyl-4-(p-methoxyphenyl)-triazine, and 2-(4-methylphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine.

[0302] Among these, the compounds represented by general formula (3), general formula (6), or general formula (7) are preferred as organohalogen compounds. From the viewpoint of superior effect of the present invention, the compound represented by general formula (6) is more preferred. The reason for the superior effect of the present invention is not yet clear, but it is speculated that the compound represented by the above general formula (6) has good compatibility with a wavelength of 222 nm.

[0303] The halogen atom present in the above-mentioned compounds is preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a chlorine atom or a bromine atom.

[0304] Organic halogen compounds can be used alone or in combination of two or more.

[0305] Photo-acid generator

[0306] As a photoacid generator, a compound that generates acid through ultraviolet light cracking and enables the colorant to develop color through the action of the aforementioned acid is preferred.

[0307] Examples of photoacid generators include nonionic and ionic photoacid generators. From the viewpoint of superior performance of the present invention, nonionic photoacid generators are preferred. Examples of nonionic photoacid generators include organohalogen compounds and oxime compounds. From the viewpoint of superior performance of the present invention, organohalogen compounds are preferred, and compounds represented by the above general formula (6) are more preferred.

[0308] From the viewpoint of achieving superior color gradation in the chromatic region, compounds with three or more halogen atoms in their molecules are preferred as organohalogen compounds. As an upper limit for the number of halogen atoms, nine or fewer are preferred.

[0309] Organic halogen compounds can be used alone or in combination of two or more.

[0310] As a specific example of an organohalogen compound, the same organohalogen compound as the organohalogen compound mentioned as a photooxidant in the previous section can be cited.

[0311] Examples of ionic photoacid-generating agents include diazonium salts, iodinated salts, and sulfonium salts, with iodinated salts or sulfonium salts being preferred. Examples of ionic photoacid-generating agents include compounds described in Japanese Patent Application Publication Nos. 62-161860, 61-67034, and 62-050382, and these contents are incorporated herein by reference.

[0312] Furthermore, as a photoacid generator, there are no particular limitations as long as it is a compound that generates acid through light. It can be a photoacid generator that generates inorganic acids such as hydrogen halides (e.g., hydrochloric acid), sulfuric acid, and nitric acid, or it can be a photoacid generator that generates organic acids such as carboxylic acids and sulfonic acids. From the viewpoint of better performance of the present invention, it is preferable to be a photoacid generator that generates inorganic acids, and more preferably a photoacid generator that generates hydrogen halides.

[0313] Specific examples of photoacid-generating agents include triarylsulfonium hexafluorophosphate, triarylsulfonium arsenate, triarylsulfonium antimonate, diaryliodohexafluorophosphate, diaryliodoarsenate, diaryliodoantimonate, dialkylbenzoylmethylsulfonium tetrafluoroboronic acid, dialkylbenzoylmethylsulfonium hexafluorophosphate, dialkyl-4-hydroxyphenylsulfonium tetrafluoroboronic acid, dialkyl-4-hydroxyphenylsulfonium hexafluorophosphate, N-bromosuccinimide, tribromomethylphenyl sulfone, diphenyliodide, 2-trichloromethyl-5-(p-butoxystyryl)-1,3,4-oxadiazole, and 2,6-ditrichloromethyl-4-(p-methoxyphenyl)-triazine.

[0314] The ultraviolet sensing layer may contain components other than colorants and photoactive agents.

[0315] Other components that can be cited as examples are those described in the first embodiment described below (polymer binder, reducing agent, light stabilizer, crosslinking agent, sensitizer, ultraviolet absorber, surfactant, and colorant, etc.).

[0316] The following provides a detailed explanation of the specific methods used to describe the ultraviolet sensing component.

[0317] [First Embodiment]

[0318] The first embodiment of the ultraviolet sensing component of the present invention is an ultraviolet sensing component having an ultraviolet sensing layer, the ultraviolet sensing layer comprising microcapsules containing a photoactive agent, a chromophore, and a solvent having heteroatoms. That is, the ultraviolet sensing components of embodiments A to C of the present invention described above can be ultraviolet sensing components having an ultraviolet sensing layer, the ultraviolet sensing layer comprising microcapsules containing a photoactive agent, a chromophore, and a solvent having heteroatoms.

[0319] Solvents containing heteroatoms will be referred to as "specific solvents" below.

[0320] With the first embodiment, it is easy to control any one of the differences between C1 and C2, Y1 and Y2, and M1 and M2 to be above 0.20.

[0321] Figure 1 This is a schematic cross-sectional view of an example of the first embodiment of the ultraviolet sensing component.

[0322] The ultraviolet sensing component 10 includes a support 12 and an ultraviolet sensing layer 14. The ultraviolet sensing layer 14 contains microcapsules containing a photoactive agent, a colorant, and a specific solvent disposed on one surface of the support 12. In the ultraviolet sensing layer 14 that receives ultraviolet irradiation, a color-emitting portion (not shown) is formed that emits color at a color concentration corresponding to the amount of ultraviolet irradiation.

[0323] As mentioned above, in Figure 1 The image shows a sheet-like arrangement of the ultraviolet sensing component, but it is not limited to this arrangement.

[0324] In addition, as will be described later, the ultraviolet sensing component 10 may or may not have a support body 12, as long as it has an ultraviolet sensing layer 14.

[0325] also, Figure 1 The ultraviolet sensing component 10 shown is a two-layer structure consisting of a support 12 and an ultraviolet sensing layer 14, but it is not limited to this structure. As will be described later, it may also have other layers besides the support 12 and the ultraviolet sensing layer 14 (such as a reflective layer, a gloss layer, and a filter layer).

[0326] If the ultraviolet sensing layer included in the ultraviolet sensing component receives ultraviolet radiation when measuring the amount of ultraviolet radiation, a color-emitting section (color-emitting image) is formed in the area receiving ultraviolet radiation (the area irradiated by ultraviolet radiation) with a color-emitting concentration corresponding to the amount of ultraviolet radiation (e.g., cumulative illuminance). Color-emitting with a color-emitting concentration corresponding to the amount of ultraviolet radiation means that the color-emitting image has color gradation corresponding to the amount of ultraviolet radiation.

[0327] The aforementioned primary color-emitting mechanism of the ultraviolet (UV) sensing layer originates from the microcapsules contained within it. When the UV sensing layer receives UV irradiation, a color-emitting agent typically emits color within the microcapsules located in the UV-irradiated area. Specifically, a photoactive agent absorbs UV light and is activated to generate acids and / or free radicals, which the color-emitting agent then reacts with. The amount of acid and / or free radicals generated from the photoactive agent varies depending on the amount of UV irradiation, and consequently, the amount of color-emitting agent varies accordingly. As a result, in the UV-irradiated area of ​​the UV sensing layer, a color-emitting region is formed with varying concentrations of color depending on the amount of UV irradiation, exhibiting a color concentration corresponding to the amount of UV irradiation.

[0328] The inventors hypothesize that when the microcapsules in the ultraviolet sensing layer contain a specific solvent, the specific solvent has low absorption relative to the wavelength of 222 nm. In addition, the specific solvent has high solubility for photoactive agents and colorants, and is not likely to hinder the color reaction, thus helping to improve the sensitivity at the wavelength of 222 nm.

[0329] The minimum thickness of the ultraviolet sensing component 10 is preferably 5 μm or more, more preferably 25 μm or more. Furthermore, the maximum thickness is preferably 1 cm or less, more preferably 2 mm or less.

[0330] Hereinafter, each component of the first embodiment of the ultraviolet sensing component will be described in detail.

[0331] <<Support Body>>

[0332] The support is a component used to support the ultraviolet sensing layer.

[0333] In addition, if the ultraviolet sensing layer itself can be processed, the ultraviolet sensing component may not need a support.

[0334] Examples of materials that can be used as a support include resin sheets, paper (including synthetic paper), cloth (including woven and nonwoven fabrics), glass, wood, and metal. Resin sheets or paper are preferred as the support, more preferably resin sheets or synthetic paper, and even more preferably resin sheets.

[0335] Examples of resin sheet materials include polyethylene resins, polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, polyvinyl chloride resins, fluorinated resins, poly(meth)acrylic acid resins, polycarbonate resins, polyester resins (such as polyethylene terephthalate and polyethylene naphthalate), various nylon and other polyamide resins, polyimide resins, polyamide-imide resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyethersulfone resins, polyurethane resins, acetal resins, and cellulose resins.

[0336] Examples of synthetic paper include synthetic paper (such as YUPO) that is biaxially stretched to form multiple micropores by polypropylene or polyethylene terephthalate, synthetic paper made of synthetic fibers such as polyethylene, polypropylene, polyethylene terephthalate and polyamide, and synthetic paper in which these are layered on one or both sides of a paper.

[0337] Furthermore, as another preferred method for resin sheets, white resin sheets formed by dispersing white pigment in resin can also be cited. The same material as the resin used in the aforementioned white resin sheets can be used.

[0338] The white resin sheet is reflective of ultraviolet light. Therefore, when the support is a white resin sheet, the ultraviolet light irradiating the ultraviolet sensing element is reflected by the support, thus suppressing the scattering of ultraviolet light within the ultraviolet sensing element. As a result, the detection accuracy of the ultraviolet irradiation amount of the ultraviolet sensing element can be further improved.

[0339] As for white pigments, reference can be made to the white pigments described in paragraph 0080 of International Publication No. 2016 / 017701, and these contents are incorporated into this specification.

[0340] Regarding white resin sheets, white polyester sheets are preferred, and white polyethylene terephthalate sheets are more preferred.

[0341] Commercially available white resin sheets include YUPO (manufactured by Yupo Corporation), Lumirror (manufactured by Toray Industries, Inc.), and CRISPR (manufactured by TOYOBO CO., LTD.).

[0342] The minimum thickness of the support is preferably 5 μm or more, more preferably 25 μm or more, and even more preferably 50 μm or more. Furthermore, the maximum thickness is preferably 1 cm or less, more preferably 2 mm or less, and even more preferably 500 μm or less.

[0343] <<Ultraviolet Sensing Layer>>

[0344] The ultraviolet sensing layer contains microcapsules (hereinafter also referred to as "specific microcapsule A") containing photosynthetic agents, colorants, and specific solvents.

[0345] The following is a detailed description of the various components that can be included in the ultraviolet sensing layer.

[0346] <Specific Microcapsule A>

[0347] The ultraviolet sensing layer contains a specific microcapsule A.

[0348] The materials constituting the specific microcapsule A will be described in detail below.

[0349] A specific microcapsule A typically has a core and a capsule wall for containing the core material (the contained substance (hereinafter also referred to as the "inclusion component")) that constitutes the core.

[0350] Specific microcapsule A contains a photoactive agent, a colorant, and a specific solvent as the core material (inner components).

[0351] As a preferred method for a specific microcapsule A, the photoactive agent can be a photooxidant, and the colorant can be a colorant that develops color through oxidation.

[0352] Furthermore, as another preferred method for a specific microcapsule A, the photoactive agent can be a photoacid-generating agent, and the color-generating agent can be a color-generating agent that develops color through the action of acid.

[0353] As for the specific microcapsule A, it is preferable to prevent contact between substances inside and outside the capsule through the material isolation effect of the capsule wall at room temperature. Specifically, Japanese Patent Application Publication Nos. 59-190886 and 60-242094 can be cited, and these contents are incorporated into this specification.

[0354] (Capsule wall)

[0355] The capsule wall of the specific microcapsule A is preferably substantially composed of resin. "Substantially composed of resin" means that the resin content is 90% by mass or more, preferably 100% by mass, relative to the total mass of the capsule wall. That is, the capsule wall of the specific microcapsule is preferably composed of resin.

[0356] Examples of the aforementioned resins include polyurethane, polyurea, polyester, polycarbonate, urea-formaldehyde resin, melamine-formaldehyde resin, polystyrene, styrene-methacrylate copolymer, gelatin, polyvinylpyrrolidone, and polyvinyl alcohol. From the viewpoint of having a dense cross-linked structure that prevents leakage of inclusions and controlling the transmittance at a wavelength of 222 nm, thereby further improving the sensitivity at 222 nm, one or more resins selected from the group consisting of polyurea, polyurethane urea, and polyurethane are more preferable.

[0357] Polyurea is preferably a polymer having multiple urea bonds and is a reaction product formed from raw materials containing polyamines and polyisocyanates.

[0358] In addition, by reacting a portion of the polyisocyanate with water to form a polyamine, it is possible to synthesize polyurea using polyisocyanate without using polyamine.

[0359] Furthermore, the polyurethane urea is preferably a polymer having urethane bonds and urea bonds, and is a reaction product formed from raw materials containing polyols, polyamines and polyisocyanates.

[0360] In addition, when polyols are reacted with polyisocyanates, a portion of the polyisocyanate reacts with water to become polyamines, sometimes resulting in polyurethane urea.

[0361] Furthermore, the polyurethane is preferably a polymer having multiple urethane bonds and is a reaction product formed from raw materials comprising polyols and polyisocyanates.

[0362] Polyisocyanates preferably have aromatic or alicyclic rings.

[0363] From the viewpoint of achieving better results in this invention, the polyisocyanate preferably has an alicyclic structure. When using alicyclic polyisocyanate, the transparency of the microcapsule wall is excellent, and therefore the sensitivity at a wavelength of 222 nm is superior.

[0364] Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles, with aromatic hydrocarbon rings being preferred.

[0365] The aromatic hydrocarbon rings mentioned above may have substituents.

[0366] There is no particular limitation on the number of carbon atoms in the aromatic hydrocarbon ring, but 6 to 30 is preferred, 6 to 18 is more preferred, and 6 to 10 is even more preferred.

[0367] Examples of aromatic hydrocarbon rings include the benzene ring.

[0368] There is no particular limitation on the number of aromatic rings in polyisocyanate; it can be one or more, but one is preferred.

[0369] The aforementioned alicyclic rings may have substituents.

[0370] There is no particular limitation on the number of carbon atoms in the aforementioned alicyclic ring, but 3 to 30 is preferred, 3 to 18 is more preferred, and 6 to 10 is even more preferred.

[0371] As an alicyclic ring, cyclohexane ring can be cited as an example.

[0372] There is no particular limitation on the number of alicyclic rings in polyisocyanate; it can be one or more, preferably one to three.

[0373] Examples of aromatic polyisocyanates include aromatic diisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxy-biphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4-chloroxylene-1,3-diisocyanate, 2-methylxylene-1,3-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 4,4'-diphenylhexafluoropropane diisocyanate.

[0374] Examples of aliphatic polyisocyanates include aliphatic diisocyanates such as trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexene-1,2-diisocyanate, cyclohexene-1,3-diisocyanate, cyclohexene-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,4-bis(isocyanate methyl)cyclohexane, 1,3-bis(isocyanate methyl)cyclohexane, isophorone diisocyanate, lysine diisocyanate, hydrogenated toluene diisocyanate, and hydrogenated diphenylene diisocyanate.

[0375] Examples of polyisocyanates include polyisocyanates with three or more functions (e.g., triisocyanates with three functions and tetraisocyanates with four functions).

[0376] As a polyisocyanate with three or more functions, it is preferred to be an adduct (addition product) of an aromatic or alicyclic diisocyanate and a compound having three or more active hydrogen groups in one molecule (e.g., polyols, polyamines, or polythiols with three or more functions), i.e., a polyisocyanate with three or more functions (addition-type polyisocyanates with three or more functions) and a trimer of an aromatic or alicyclic diisocyanate (biuret type or isocyanurate type).

[0377] Examples of polyisocyanates include formalin condensates of benzene isocyanate, methacryloyloxyethyl isocyanate, and lysine triisocyanate, which have polymerizable groups.

[0378] For polyisocyanates, one can refer to the "Polyurethane Resin Handbook" (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun (1987)).

[0379] Commercially available polyisocyanates include, for example, TAKENATE (registered trademark) D-102, D-103, D-103H, D-103M2, P49-75S, D-110N, D-120N, D-140N, D-160N, D-127N, D-170N, D-170HN, D-172N, D-177N, D-204, D-165N, NP1100 (manufactured by Mitsui Chemica, Inc.), SUMIDUR N3300, Desmodur (registered trademark) L75, UL57SP, N3200, N3600, N3900, Z4470BA (manufactured by Sumika Bayer Utethane Co., Ltd.), and coronate (registered trademark) HL, HX, L, HK (Nippon Polyurethane Industry). (manufactured by Co., Ltd.), P301-75E (manufactured by ASAHI KASEI CORPORATION), DURANATE (registered trademark) TPA-100, TKA-100, TSA-100, TSS-100, TLA-100, 24A-100, TSE-100 (manufactured by ASAHI KASEI CORPORATION), and BURNOCK (registered trademark) D-750 (manufactured by DIC Corporation).

[0380] Examples of polyols include aliphatic and aromatic polyols, hydroxyl polyesters, and hydroxyl polyalkylene ethers.

[0381] Specifically, examples include the polyols listed in Japanese Patent Application Publication No. 60-049991, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, propylene glycol, 2,3-dihydroxybutane, 1,2-dihydroxybutane, 1,3-dihydroxybutane, 2,2-dimethyl-1,3-propanediol, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, dihydroxycyclohexane, diethylene glycol, and 1... Condensation products of aromatic polyols and alkyl oxides, such as 2,6-trihydroxyhexane, 2-phenylpropanediol, 1,1,1-trimethylolpropane, hexanetriol, pentaerythritol, pentaerythritol ethylene oxide adduct, glycerol ethylene oxide adduct, glycerol, 1,4-bis(2-hydroxyethoxy)benzene, resorcinol dihydroxyethyl ether, etc., terephthalic acid, isophthalic acid, α,α'-dihydroxy-p-diisopropylbenzene, 4,4'-dihydroxy-diphenylmethane, 2-(p,p'-dihydroxy-diphenylmethyl)benzyl alcohol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A.

[0382] The polyol is preferably used in an amount of 0.02 to 2 moles of hydroxyl groups relative to 1 mole of isocyanate groups.

[0383] Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2-hydroxytrimethylenediamine, diethylenetriamine, trimethylenetriamine, trimethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, and amine adducts of epoxides.

[0384] Polyisocyanates can also react with water to form polymers.

[0385] Examples of polyisocyanates, polyols, and polyamines include, for example, U.S. Patent Nos. 3,281,383, 3,773,695, 3,793,268, Japanese Patent Publication Nos. Sho 48-040347, 49-024159, 48-080191, and 48-084086, and these contents are incorporated herein by reference.

[0386] The average particle size of the microcapsules, measured in terms of volume average particle size, is preferably 0.1 to 100 μm. As a lower limit, it is more preferably 0.3 μm or more, and even more preferably 0.5 μm or more. As an upper limit, it is more preferably 10 μm or less, and even more preferably 5 μm or less. When the average particle size (volume average particle size) of the microcapsules is 0.1 μm or more, the core material inside the capsule can be protected more stably. On the other hand, when the average particle size (volume average particle size) of the microcapsules is 100 μm or less, the resolution of the colorimetric image is further improved.

[0387] In addition, the average particle size (volume average particle size) of the microcapsules can be measured, for example, by a laser analysis / scattering particle size distribution measuring device LA950 (manufactured by HORIBA, Ltd.).

[0388] Furthermore, when determining the average particle size of the microcapsules contained in the ultraviolet sensing component, the average particle size (volume average particle size) of the microcapsules can be measured using a scanning electron microscope (SEM). Specifically, the surface of the ultraviolet sensing layer is observed at 5000x magnification using an SEM, and the average particle size of all microcapsules present in the observed field of view is determined through image analysis. Alternatively, if microcapsules cannot be observed on the surface, cross-sectional sections are prepared, and measurements are performed in the same manner as described above.

[0389] In addition, the above-mentioned microcapsules refer to the concept of including specific microcapsule A and other microcapsules besides specific microcapsule A.

[0390] (Specific solvent)

[0391] A specific microcapsule A contains a specific solvent.

[0392] A specific solvent is a solvent containing heteroatoms; examples include aromatic solvents containing heteroatoms and non-aromatic solvents containing heteroatoms.

[0393] "Aromatic solvents" refer to solvents that have aromatic rings within their molecules. "Non-aromatic solvents" refer to solvents that do not have aromatic rings within their molecules.

[0394] Non-aromatic solvents with heteroatoms

[0395] As a non-aromatic solvent with heteroatoms (also known as non-aromatic solvent X), there are no particular restrictions as long as it is a non-aromatic solvent that has heteroatoms in the molecule but no aromatic ring.

[0396] As the non-aromatic solvent X, a non-aromatic solvent having an aliphatic structure is preferred.

[0397] "Having an aliphatic structure" means that the molecule contains hydrocarbon groups that do not have aromatic rings.

[0398] The aforementioned hydrocarbon group without an aromatic ring can be straight-chain, branched, or cyclic. Furthermore, in the aforementioned hydrocarbon group without an aromatic ring, the carbon atom in the hydrocarbon group can be replaced by a heteroatom or a carbonyl carbon. Moreover, the aforementioned hydrocarbon group can further have substituents, and the substituents can have heteroatoms.

[0399] As heteroatoms, examples include atoms other than carbon and hydrogen atoms, with nitrogen, oxygen, phosphorus or sulfur atoms being preferred, and oxygen atoms being more preferred.

[0400] There is no particular limitation on the number of carbon atoms in the aforementioned hydrocarbon group, but 1 to 50 is preferred, 6 to 50 is more preferred, and 8 to 30 is even more preferred.

[0401] As the non-aromatic solvent X, it is preferably one or more solvents selected from the group consisting of aliphatic carboxylic acids, fatty acid esters, ether solvents, alcohol solvents, amide solvents, and ketone solvents. From the viewpoint of promoting the color development reaction, alcohol solvents are preferred; however, from the viewpoint of suitability for encapsulation reaction and safety, aliphatic carboxylic acids, fatty acid esters, ether solvents, amide solvents, and ketone solvents are preferred.

[0402] Examples of aliphatic carboxylic acids include oleic acid, dimethyl succinate, diethyl succinate, and methyl laurate.

[0403] Examples of fatty acid esters include unsaturated and saturated fatty acid esters. Specifically, examples include natural vegetable and animal oils such as soybean oil, corn oil, cottonseed oil, rapeseed oil, olive oil, coconut oil, castor oil, and fish oil.

[0404] Furthermore, examples of fatty acid esters include aliphatic carboxylic acid esters, aliphatic sulfonates, and aliphatic phosphate esters, with aliphatic phosphate esters being preferred. Specifically, tris(2-ethylhexyl) phosphate esters are an example.

[0405] Examples of ether solvents include propylene glycol monobutyl ether.

[0406] Examples of ketone solvents include cyclohexanone.

[0407] From the viewpoint of facilitating the capsule-forming reaction, long-chain alkyl alcohols are preferred as alcohol solvents, and long-chain alkyl monools are more preferred, especially long-chain alkyl monools with 6 to 20 carbon atoms. Octanol is an example.

[0408] Examples of amide solvents include N,N-diethyldodecanoamide.

[0409] The boiling point of the non-aromatic solvent X is preferably 100°C or higher, more preferably 120°C or higher, and even more preferably 140°C or higher. There is no particular upper limit, but 500°C or lower is preferred. When the boiling point of the non-aromatic solvent X is 100°C or higher, in heating processes such as microencapsulation reactions, the solvent may not be eliminated from the specific microcapsule A and may remain.

[0410] There are no particular restrictions on the molecular weight of the non-aromatic solvent X, but it is mostly above 100, preferably above 150. There is no particular upper limit, but it is preferably below 1000, more preferably below 600, and even more preferably below 500.

[0411] Non-aromatic solvent X can be used alone or in combination with two or more.

[0412] In a specific microcapsule A, the content of the non-aromatic solvent X, relative to the total mass of the solvent, is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and even more preferably 25 to 100% by mass.

[0413] Regarding the non-aromatic solvent X, the ultraviolet sensing layer can be extracted with acetone, the obtained filtrate can be concentrated and analyzed by GC-MS (Gas Chromatography Mass Spectrometry) to determine its type, content and composition ratio.

[0414] Aromatic solvents containing heteroatoms

[0415] As an aromatic solvent with heteroatoms (also known as aromatic solvent Y), there are no particular restrictions as long as it has heteroatoms in the molecule and an aromatic ring.

[0416] The aromatic rings that Y, as an aromatic solvent, possess can be, for example, aromatic hydrocarbon rings and aromatic heterocycles, with aromatic hydrocarbon rings being preferred.

[0417] The aromatic hydrocarbon ring can be either a monocyclic ring or a condensed polycyclic ring, with a monocyclic ring being preferred.

[0418] Furthermore, the aforementioned aromatic hydrocarbon ring may have substituents. Additionally, if the aforementioned aromatic hydrocarbon ring has multiple substituents, the substituents may bond with each other to form an alicyclic ring. Furthermore, the aforementioned aromatic hydrocarbon ring may have an aliphatic structure.

[0419] There is no particular limitation on the number of carbon atoms in the aromatic hydrocarbon ring, but 6 to 30 is preferred, 6 to 18 is more preferred, and 6 to 10 is even more preferred.

[0420] Examples of monocyclic aromatic hydrocarbon rings include the benzene ring.

[0421] Examples of polycyclic aromatic hydrocarbon rings include naphthalene rings.

[0422] The aforementioned aromatic heterocycles can be either monocyclic or polycyclic.

[0423] Furthermore, the aforementioned aromatic heterocycles may have substituents.

[0424] There is no particular limitation on the number of aromatic rings in aromatic solvents; they can be one or more. In addition, when there are two or more aromatic rings, the two aromatic rings can also bond to each other through substituents that can exist on each aromatic ring to form a polycyclic structure (however, condensed polycyclic structures are not included).

[0425] Examples of aromatic solvents Y include aromatic solvents having aromatic heterocycles within the molecule, and aromatic solvents having heteroatoms and aromatic hydrocarbon rings within the molecule.

[0426] Examples of heteroatoms in aromatic solvent Y include atoms other than carbon and hydrogen atoms, with nitrogen, oxygen, sulfur, or phosphorus atoms being preferred, and oxygen or phosphorus atoms being more preferred. From the viewpoint of ensuring transmittance at a wavelength of 222 nm, promoting the colorimetric reaction, and having superior sensitivity at a wavelength of 222 nm, aromatic solvent Y preferably contains at least one group selected from the group consisting of carboxylic acid ester linkages, sulfonate ester linkages, phosphate ester linkages, carbonyl linkages, or sulfonate linkages.

[0427] Examples of aromatic solvents Y include substituted or unsubstituted benzenesulfonates such as methyl benzenesulfonate, ethyl benzenesulfonate, methyl toluenesulfonate, and ethyl toluenesulfonate; substituted or unsubstituted phthalate diesters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, and dicyclohexyl phthalate; triphenyl phosphate (TPP), tricresyl phosphate (TCP), and tris(xyl)-xylphenol phosphate (TX). Aromatic phosphates include methyl methacrylate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate (t-BDP), bis-(tert-butylphenyl)phenyl phosphate (BBDP), tri-(tert-butylphenyl) phosphate (TBDP), isopropylphenyl diphenyl phosphate (IPP), bis-(isopropylphenyl) diphenyl phosphate (BIPP), and tri-(isopropylphenyl) phosphate (TIPP).

[0428] Aromatic solvent Y can be used alone or in combination with two or more other solvents.

[0429] The boiling point, molecular weight, and content of aromatic solvent Y are the same as those of the non-aromatic solvent X mentioned above, and the preferred method is also the same.

[0430] The type, content, and composition ratio of the solvent can be analyzed using the same methods as those used for the non-aromatic solvent X described above.

[0431] The specific solvent preferably includes one or more solvents with a boiling point of 100°C or higher, and more preferably all the specific solvents included in the specific microcapsule A have a boiling point of 100°C or higher. In addition, as an upper limit for the boiling point of the specific solvent, it is preferably 500°C or lower.

[0432] All solvents contained in the specific microcapsule A preferably have a boiling point of 100°C or higher. Furthermore, as an upper limit for the boiling points of all solvents, 500°C or lower is preferred.

[0433] (Coloring agent)

[0434] The specific microcapsule A contains a color-developing agent. Examples of color-developing agents contained in the specific microcapsule A are of the same type as those contained in the ultraviolet sensing layer described above, and preferably in the same manner.

[0435] (Photoactive agents)

[0436] The specific microcapsule A contains a photosynthetic agent. Examples of photosynthetic agents contained in the specific microcapsule A are of the same type as those contained in the ultraviolet sensing layer described above, and preferably in the same manner.

[0437] (Light stabilizer)

[0438] The specific microcapsule A preferably contains a light stabilizer.

[0439] There are no particular restrictions on light stabilizers as long as they are light-stabilized materials, but they are preferred to function as so-called free radical scavenging substances that capture the free radicals of activated photoactive agents.

[0440] Light stabilizers can be used alone or in combination of two or more.

[0441] Examples of light stabilizers include 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, hydroquinone, catechol, resorcinol and polyvalent phenols such as hydroxyhydroquinone, as well as aminophenols such as o-aminophenol and p-aminophenol.

[0442] The ratio of light stabilizer to photoactive agent (light stabilizer / photoactive agent (molar ratio)) is preferably 0.0001 to 10, more preferably 0.0002 to 5.

[0443] (reducing agent)

[0444] Specific microcapsule A may contain a reducing agent.

[0445] Reducing agents have the function of deactivating photooxidizing agents.

[0446] When a specific microcapsule A contains a reducing agent, it can suppress drastic changes in the color concentration of the UV-sensing layer based on UV irradiation, and the color concentration is easily affected by the amount of UV irradiation. The reducing agent also sometimes functions as an antioxidant.

[0447] A reducing agent can be used alone or in combination with two or more.

[0448] Examples of reducing agents include cyclic phenylhydrazine compounds. Specifically, examples include 1-phenylpyrazolidine-3-one, 1-phenyl-4-methylpyrazolidine-3-one, 1-phenyl-4,4-dimethylpyrazolidine-3-one, 3-methyl-1-p-sulfophenyl-2-pyrazolino-5-one, 3-methyl-1-phenyl-2-pyrazolino-5-one, and 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidineone (manufactured by Dimezone S, DAITO CHEMICAL CO., LTD.).

[0449] As a reducing agent, reference can be made to the reducing agents described in paragraphs 0072 to 0075 of International Publication No. 2016 / 017701, and these contents are incorporated into this specification.

[0450] (UV absorber)

[0451] Specific microcapsule A may contain a UV absorber.

[0452] Examples of UV absorbers include benzotriazole compounds (UV absorbers with a benzotriazole structure), benzophenone compounds, triazine compounds, and benzodithiol compounds.

[0453] From the perspective of superior sensitivity at a wavelength of 222nm, ultraviolet absorbers are preferably less absorbent at a wavelength of 222nm. Specifically, triazine compounds, benzophenone compounds, and benzodithiols are preferred.

[0454] Furthermore, the specific microcapsule A preferably does not contain a benzotriazole compound with high absorption at a wavelength of 222 nm. If the specific microcapsule A contains a benzotriazole compound, the content of the benzotriazole compound relative to the total mass of the photosynthetic agent is preferably 1% by mass or less, more preferably 0.5% by mass or less. There is no limitation on the lower limit; for example, it can be 0.0001% by mass or more.

[0455] Furthermore, the content of the benzotriazole compound relative to the total mass of the colorant is preferably 1% by mass or less, more preferably 0.5% by mass or less. There is no limitation on the lower limit, for example, it is 0.0001% by mass or more.

[0456] Ultraviolet absorbers can be used alone or in combination of two or more.

[0457] Commercially available triazine compounds include, for example, ADEKA STAB LA-F70 (manufactured by ADEKA CORPORATION), Tinuvin 1577ED, Tinuvin 1600 (manufactured by BASF), 2,4-bis(2,4-dimethylyl)-6-(2-hydroxy-4-n-octyloxophenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine, and ethylhexyltriazinone (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0458] Commercially available benzophenone compounds include, for example, Chimassorb 81 and Chimassorb 81FL (manufactured by BASF).

[0459] Examples of benzodithiols include those described in International Publication No. 2019 / 159570.

[0460] [Other ingredients]

[0461] In addition to the above-mentioned components, specific microcapsules A may contain one or more types of paraffin, solvents other than specific solvents, and additives such as deodorizers, as needed.

[0462] <Manufacturing Method of Specific Microcapsule A>

[0463] There are no particular limitations on the manufacturing method of the specific microcapsule A. For example, well-known methods such as interfacial polymerization, internal polymerization, phase separation, external polymerization, and condensation can be cited.

[0464] As an example of a method for manufacturing a specific microcapsule A, a method comprising an emulsification step and an encapsulation step as described below can be cited. Furthermore, in the encapsulation step, it is preferable to form the resin wall (capsule wall) by interfacial polymerization.

[0465] Emulsification process: The process of preparing an emulsion by mixing a colorant, a photosynthetic agent, a specific solvent, and an emulsifier in water.

[0466] Encapsulation process: The process of encapsulating oil droplets containing colorants, photosynthetic agents, and specific solvents obtained from the emulsion process to form a resin wall (capsule wall).

[0467] The following describes the interfacial polymerization method using a specific microcapsule A with a capsule wall of polyurea or polyurethane urea as an example.

[0468] As an interfacial polymerization method, an interfacial polymerization method comprising the following steps is preferred: a step of preparing an emulsion by dispersing an oil phase containing a photoactive agent, a specific solvent, a solvent containing an aliphatic structure with a boiling point of less than 100°C (hereinafter also referred to as "encapsulation solvent"), a colorant, and a capsule wall material (e.g., polyisocyanate) in an aqueous phase containing an emulsifier (emulsification step); and a step of polymerizing the capsule wall material at the interface between the oil phase and the aqueous phase to form a capsule wall, thereby forming microcapsules containing a photoactive agent, a specific solvent, and a colorant selected from oxidants and photoacid generators (encapsulation step).

[0469] In the emulsification process described above, the encapsulation solvent is a component that can typically be added to improve the solubility of the core material in the solvent. Furthermore, the encapsulation solvent does not contain aromatic rings within its molecules. Moreover, the encapsulation solvent is removed through a drying process in the UV sensing layer formation method described later. Therefore, the microcapsules in the UV sensing component preferably do not contain the encapsulation solvent.

[0470] There are no particular limitations on the solvents used for capsule manufacturing; examples include ethyl acetate (boiling point 77°C), isopropyl acetate (boiling point 89°C), methyl ethyl ketone (boiling point 80°C), and dichloromethane (boiling point 40°C).

[0471] The solvent used for capsule making can be a single solvent or a mixture of two or more solvents.

[0472] Furthermore, there are no particular restrictions on the types of emulsifiers used in the emulsification process described above; for example, dispersants and surfactants can be cited.

[0473] As a dispersant, examples include water-soluble polymers selected from known anionic polymers, nonionic polymers, and amphoteric polymers. Specifically, examples include polyvinyl alcohol, gelatin, and cellulose derivatives, with polyvinyl alcohol being preferred.

[0474] Dispersants can be used alone or in combination of two or more.

[0475] As a surfactant, anionic or nonionic surfactants are preferred, such as alkylbenzene sulfonates (e.g., sodium dodecylbenzene sulfonate and ammonium dodecylbenzene sulfonate), alkyl sulfonates (e.g., sodium lauryl sulfate and sodium octyl succinate sulfonate), and polyalkylene glycols (e.g., nonylphenol polyoxyethylene ether).

[0476] Surfactants can be used alone or in combination of two or more.

[0477] Furthermore, other methods for manufacturing specific microcapsule A can also be referenced to the methods described in U.S. Patent Nos. 3,726,804 and 3,796,696. These contents are incorporated herein by reference.

[0478] The content of specific microcapsules A in the ultraviolet sensing layer is not particularly limited, but is preferably 50-99% by mass, more preferably 60-90% by mass, relative to the total mass of the ultraviolet sensing layer.

[0479] The content of specific microcapsules A in the ultraviolet sensing layer (solid component coating amount) is also preferably 0.1 to 30 g / m². 2 As a lower limit, 0.5 g / m³ is preferred. 2 More preferably, 1g / m 2 The above is the upper limit, preferably 25g / m³. 2 Below, 20g / m is preferred. 2 the following.

[0480] The ultraviolet sensing layer may contain other components besides the specific microcapsule A mentioned above.

[0481] Other components include, for example, polymeric binders, reducing agents, light stabilizers, crosslinking agents, sensitizers, ultraviolet absorbers, surfactants, and colorants.

[0482] Compounds used as other components can be used alone or in combination of two or more.

[0483] Examples of polymeric adhesives include polyvinyl alcohol, methylcellulose, ethylcellulose, carboxymethylcellulose, carboxypropylcellulose, gum arabic, gelatin, polyvinylpyrrolidone, casein, styrene-butadiene latex, acrylonitrile-butadiene latex, polyvinyl acetate, polyacrylate, and ethylene-vinyl acetate copolymers.

[0484] Furthermore, as a polymeric adhesive, the polymeric adhesive described in paragraph 0078 of Japanese Patent Application Publication No. 2017-167155 can be referenced, and this content is incorporated into this specification.

[0485] Polymer adhesives can be cross-linked. In other words, polymer adhesives can be cross-linked adhesives.

[0486] There are no particular limitations on the crosslinking agent; for example, ethylenedioxazole can be used. Furthermore, the crosslinking agent described in paragraph 0079 of Japanese Patent Application Publication No. 2017-167155 can also be referenced. This information is incorporated herein by reference.

[0487] As reducing agents, sensitizing agents, and surfactants, reference can be made to the descriptions on page 9 (bottom left column) to page 10 (top left column) of Japanese Patent Application Publication No. 1-207741, and in paragraphs 0038-0039 and 0048-0059 of Japanese Patent Application Publication No. 2004-233614, and these contents are incorporated into this specification.

[0488] Furthermore, as reducing agents, light stabilizers, ultraviolet absorbers, and surfactants, they can also be used in specific microcapsules A.

[0489] The colorant can be easily controlled by using it in conjunction with the aforementioned colorant.

[0490] As coloring agents, dyes or pigments can be cited. There are no particular limitations on pigments; for example, yellow pigments or inorganic particles used as white pigments can be cited as described in paragraphs 0018 to 0022 of International Publication No. 2016 / 017701.

[0491] Furthermore, the colorant may be contained within the aforementioned specific microcapsule A, or it may be contained in the ultraviolet sensing layer outside the specific microcapsule A. Additionally, when the specific microcapsule A contains a colorant, the colorant is preferably a colorant that is soluble in a solvent.

[0492] There is no particular limitation on the mass per unit area (solid component coating amount) of the ultraviolet sensing layer, but, for example, 0.1 to 30 g / m² is preferred. 2 More preferably 0.5–25 g / m 2 Further optimization of 1-10 g / m 2 .

[0493] The thickness of the ultraviolet sensing layer is preferably 0.1 to 30 μm, more preferably 0.5 to 25 μm, and even more preferably 1 to 10 μm.

[0494] <Method for forming an ultraviolet sensing layer>

[0495] There are no particular limitations on the method for forming the ultraviolet sensing layer, and well-known methods can be cited.

[0496] For example, a method can be described as coating a dispersion containing a specific microcapsule A into a support and then drying the coating as needed.

[0497] The dispersion for forming the ultraviolet sensing layer contains specific microcapsules A. Alternatively, the microcapsule dispersion obtained by the interfacial polymerization method described above can be used as the dispersion for forming the ultraviolet sensing layer.

[0498] The dispersion for forming the ultraviolet sensing layer may contain other components that can be included in the ultraviolet sensing layer described above.

[0499] There are no particular limitations on the method of using a dispersion for forming an ultraviolet sensing layer. Examples of coating machines used for coating include air knife coating machines, bar coating machines, rod coating machines, curtain coating machines, gravure coating machines, extrusion coating machines, die coating machines, sliding bead coating machines, and doctor blade coating machines.

[0500] After the ultraviolet sensing layer is formed by coating a dispersion onto a support, the coating can be dried as needed. For example, heat treatment can be used as a drying process.

[0501] Furthermore, while the method of forming an ultraviolet sensing layer on a support has been described above, it is not limited to the above method. For example, after forming an ultraviolet sensing layer on a temporary support, the temporary support can be peeled off to form an ultraviolet sensing component composed of an ultraviolet sensing layer.

[0502] As a temporary support, there are no particular restrictions as long as it is a peelable support.

[0503] <<Other Layers>>

[0504] The ultraviolet sensing component may have other layers besides the support and ultraviolet sensing layer mentioned above.

[0505] Other layers include reflective layers, gloss layers, filter layers, and sensitivity adjustment layers.

[0506] <Reflective layer>

[0507] The ultraviolet sensing component can be further equipped with a reflective layer.

[0508] When the ultraviolet sensing layer has a reflective layer, the ultraviolet rays that are irradiated onto the ultraviolet sensing component can be reflected by the ultraviolet-reflective layer. Therefore, the scattering of ultraviolet rays inside the ultraviolet sensing component can be suppressed, and the detection accuracy of ultraviolet irradiation can be further improved.

[0509] The reflectivity of the reflective layer relative to light with wavelengths of 200–380 nm is preferably 10% or more, more preferably 50% or more. Furthermore, the reflectivity can be measured, for example, by using a UV-Vis spectrophotometer (UV-2700 / manufactured by Shimadzu Corporation) for diffuse reflectance measurement.

[0510] In addition, when the support and the reflective layer are arranged adjacent to each other, an adhesive layer can be provided between the support and the reflective layer.

[0511] As for reflective layers, adhesive layers, and methods for manufacturing them, reference can be made to the reflective layers, adhesive layers, and methods for manufacturing them described in paragraphs 0082 to 0091 of International Publication No. 2016 / 017701. These contents are incorporated herein by reference.

[0512] <Gloss Layer>

[0513] The ultraviolet sensing component can be further equipped with a glossy layer.

[0514] When the ultraviolet sensing layer has a glossy layer, the visibility of both the front and back sides can be improved.

[0515] As for the glossy layer and the method for manufacturing the same, reference can be made to the glossy layer and the method for manufacturing the same described in paragraphs 0092 to 0094 of International Publication No. 2016 / 017701, and these contents are incorporated into this specification.

[0516] <Filter Layer>

[0517] The ultraviolet sensing component preferably further includes a filter layer.

[0518] A filter layer is a layer that selectively transmits light of a specific wavelength. Here, "selectively transmits light of a specific wavelength" means that light of a specific wavelength is transmitted while blocking other light. The transmittance of the transmitted wavelength is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The transmittance of the blocked wavelength is preferably 30% or less, more preferably 20% or more, and even more preferably 10% or more.

[0519] The filter layer is preferably a filter layer that blocks light with a wavelength of 300 nm or higher, and more preferably a filter layer that blocks light with a wavelength of 230 nm or higher. An ultraviolet bandpass filter or a filter containing a dielectric material is preferred.

[0520] In addition, the spectral characteristics of the filter layer and the sensitivity adjustment layer described later can be measured, for example, using a UV-Vis spectrophotometer (UV-2700 / manufactured by Shimadzu Corporation).

[0521] From the viewpoint of blocking light beyond a specific wavelength, the filter layer preferably contains an ultraviolet absorber. Known ultraviolet absorbers can be used as ultraviolet absorbers. Furthermore, from the viewpoint of blocking light with wavelengths exceeding 230 nm, an ultraviolet absorber that can be contained within a specific microcapsule A is preferred.

[0522] As for the filter layer and the method of manufacturing the same, reference can be made to the filter layer and the method of manufacturing the same described in paragraphs 0016 to 0026 of International Publication No. 2016 / 017701, and these contents are incorporated into this specification.

[0523] <Sensitivity Adjustment Layer>

[0524] When the ultraviolet sensing component has a filter layer, a sensitivity adjustment layer can be further provided on the surface of the filter layer.

[0525] As for the sensitivity adjustment layer and the manufacturing method thereof, reference can be made to the sensitivity adjustment layer and the manufacturing method thereof described in paragraphs 0095 to 0109 of International Publication No. 2016 / 017701, and these contents are incorporated into this specification.

[0526] [Second Implementation]

[0527] A second embodiment of the ultraviolet sensing component of the present invention is an ultraviolet sensing component having an ultraviolet sensing layer comprising microcapsules (hereinafter also referred to as "specific microcapsule B") containing a photoactive agent, a colorant, and a solvent. In this ultraviolet sensing component, the capsule wall of the microcapsule comprises one or more resins selected from the group consisting of polyurea having an aliphatic ring, polyurethane urea having an aliphatic ring, and polyurethane having an aliphatic ring, and the peak area ratio X calculated by the peak area ratio calculation method X is 30% or less.

[0528] Peak area ratio calculation method X: Cut two test pieces of the same size from the ultraviolet sensing component, and perform liquid chromatography analysis on the first solution obtained by immersing one of the test pieces in n-propanol for 7 days and the second solution obtained by immersing the other test piece in n-propanol for 1 hour. The peak area ratio X is calculated as the ratio of the peak area of ​​the chromogenic agent in the second solution to the peak area of ​​the chromogenic agent in the first solution.

[0529] With the second embodiment, it is easy to control any one of the differences between C1 and C2, Y1 and Y2, and M1 and M2 to be above 0.20.

[0530] The second embodiment is identical in structure to the first embodiment except that it uses a specific microcapsule B and the peak area ratio X represents a predetermined value. Therefore, descriptions other than the specific microcapsule B and the peak area ratio X are omitted.

[0531] The inventors discovered that, as a reason why the desired effect could not be obtained in conventional ultraviolet sensing components, firstly, the capsule wall material of microcapsules often contains aromatic groups. In this case, light with a wavelength of 222 nm is absorbed by the capsule wall, resulting in less light reaching the photoactive agent and thus poor sensitivity. Therefore, in this invention, sensitivity is further improved by using a prescribed resin containing an aliphatic ring with excellent transmittance at a wavelength of 222 nm.

[0532] Furthermore, the inventors discovered that in conventional ultraviolet sensing components, the contents of microcapsules are prone to leakage, resulting in poor sensitivity at a wavelength of 222 nm. It is believed that within the microcapsule, since a chromophore is present in a liquid phase called a solvent, the photosynthetic agent functions well relative to the chromophore. However, leakage of the contents causes the chromophore to precipitate from the solvent, thus impairing the photoactive agent's effect on chromophore performance and overall chromophore quality. Additionally, the reason for the tendency for contents leakage in conventional technologies is presumed to be insufficient polymerization of the resin constituting the capsule wall. Therefore, as long as the peak area ratio X (described later) is within a specified range, leakage of contents from the microcapsule can be suppressed, resulting in superior performance.

[0533] <<Peak Area Ratio X>>

[0534] The peak area ratio X is a value calculated using the following peak area ratio calculation method X. This peak area ratio X is an indicator of the ease with which the chromophore leaks from the microcapsule; the smaller the value, the less likely the chromophore is to leak from the microcapsule. More specifically, in the following method X, firstly, by immersing the UV sensing component in n-propanol for 7 days, the chromophore contained in the microcapsules of the UV sensing component dissolves into the n-propanol, obtaining a first solution containing the chromophore. This first solution serves as a reference relative to the second solution described later. Next, by immersing the UV sensing component in n-propanol for 1 hour, the chromophore contained in the microcapsules of the UV sensing component dissolves into the n-propanol, obtaining a second solution containing the chromophore. If the amount of chromophore dissolved in the second solution is greater than the amount dissolved in the first solution (in other words, a larger peak area ratio X), it means that the chromophore contained in the microcapsule dissolves in a short time, and that the chromophore is prone to leaking from the microcapsule. If the amount of chromogenic agent dissolved in the second solution is less than the amount of chromogenic agent dissolved in the first solution (in other words, the peak area ratio X is smaller), it means that the chromogenic agent contained in the microcapsule is not easy to dissolve and the chromogenic agent is not easy to leak out of the microcapsule.

[0535] Peak area ratio calculation method X: Cut two test pieces of the same size from the ultraviolet sensing component, and perform liquid chromatography analysis on the first solution obtained by immersing one of the test pieces in n-propanol for 7 days and the second solution obtained by immersing the other test piece in n-propanol for 1 hour. The peak area ratio X is calculated as the ratio of the peak area of ​​the chromogenic agent in the second solution to the peak area of ​​the chromogenic agent in the first solution.

[0536] The following is a detailed explanation of the steps involved in calculating the peak area ratio X.

[0537] First, two test pieces of the same size (circular shape with a diameter of 2 cm) are cut from the ultraviolet sensing component that will be the subject of the test.

[0538] Next, the solution obtained by immersing one of the cut test pieces in n-propanol (20 ml) at room temperature (20–25 °C) for 7 days is used as the first solution. During immersion, no stirring is performed; the sample is allowed to stand. After 7 days, the test piece is typically removed from the first solution. Furthermore, measures are taken to prevent the n-propanol from evaporating during the immersion period.

[0539] Furthermore, the solution obtained by immersing one of the cut test pieces in n-propanol (20 ml) at room temperature (20–25 °C) for 1 hour is used as the second solution. During immersion, no stirring is performed, and the solution is allowed to stand. In addition, the test piece is usually removed from the second solution after 1 hour.

[0540] Next, the obtained first and second solutions were analyzed by liquid chromatography. Furthermore, the injection volumes of the first and second solutions were the same during the liquid chromatography analysis.

[0541] The conditions for liquid chromatography determination are as follows.

[0542] Device: Nexera manufactured by Shimadzu Corporation

[0543] Column: Capcell pak C18 UG-120

[0544] Eluent: Water / Methanol

[0545] Oven: 40℃

[0546] Injection: 5μL

[0547] Detection: The wavelength of maximum absorption of the chromophore being detected.

[0548] Flow rate: 0.2 mL / min

[0549] Next, the peak area of ​​the chromogenic agent in the first solution (hereinafter also referred to as "peak area 1") is determined from the liquid chromatography results of the first solution. In addition, the peak area of ​​the chromogenic agent in the second solution (hereinafter also referred to as "peak area 2") is determined from the liquid chromatography results of the second solution. The ratio of peak area 2 to peak area 1, {(peak area 2 / peak area 1)×100}, i.e., the peak area ratio X, is then calculated.

[0550] The peak area ratio X is 30% or less, and from the viewpoint of better performance of the present invention, it is preferably 20% or less, more preferably 10% or less. There is no particular limitation on the lower limit, but 0% is preferred, and it is mostly 1% or more.

[0551] A specific microcapsule B typically has a core and a capsule wall for containing the core material (the inclusions (hereinafter also referred to as "inclusion components") that constitutes the core.

[0552] Certain microcapsules contain photoactive agents and colorants as core materials (components).

[0553] As a preferred method for a specific microcapsule B, the photoactive agent can be a photooxidant, and the colorant can be a colorant that develops color through oxidation.

[0554] Furthermore, as another preferred method for a specific microcapsule B, the photoactive agent can be a photoacid-generating agent, and the colorant can be a colorant that develops color through the action of acid.

[0555] (Capsule wall)

[0556] The capsule wall of the specific microcapsule B comprises one or more resins selected from the group consisting of polyurea having an aliphatic ring, polyurethane urea having an aliphatic ring, and polyurethane having an aliphatic ring (hereinafter, they are also collectively referred to as "specific resins").

[0557] The capsule wall of a particular microcapsule is preferably substantially composed of a particular resin. "Substantially composed of a particular resin" means that the content of the particular resin is 90% by mass or more, preferably 100% by mass, relative to the total mass of the capsule wall. That is, the capsule wall of a particular microcapsule is preferably composed of a particular resin.

[0558] The aliphatic rings in a particular resin can be either monocyclic or polycyclic. There is no particular limitation on the number of rings in a polycyclic structure; for example, 2 to 3 rings can be included.

[0559] There is no particular limitation on the number of carbon atoms contained in the aliphatic ring, but 6 to 20 is preferred, and 6 to 12 is more preferred.

[0560] As an aliphatic ring, it can be either a saturated aliphatic ring or an unsaturated aliphatic ring.

[0561] Examples of aliphatic rings include cycloalkanes (e.g., cyclohexane), adamantane, and norbornene.

[0562] From the viewpoint of achieving better results with the present invention, the capsule wall of the specific microcapsule B preferably has a structure derived from a polyisocyanate having an aliphatic ring. Specifically, the capsule wall of the specific microcapsule B preferably comprises one or more resins selected from the group consisting of polyurea having a structure derived from a polyisocyanate having an aliphatic ring, polyurethane urea having a structure derived from a polyisocyanate having an aliphatic ring, and polyurethane having a structure derived from a polyisocyanate having an aliphatic ring.

[0563] The aliphatic rings contained in polyisocyanates with aliphatic rings are explained above.

[0564] There is no particular limitation on the number of aliphatic rings contained in polyisocyanates with aliphatic rings; they can be one or more, preferably one to three.

[0565] There is no particular limitation on the number of isocyanate groups contained in polyisocyanates with aliphatic rings, preferably 2 to 10, more preferably 2 to 5, and even more preferably 2 to 3.

[0566] The capsule wall of a specific microcapsule B may further have an aromatic ring. That is, the capsule wall of a specific microcapsule B may contain one or more resins selected from the group consisting of polyurea having aliphatic and aromatic rings, polyurethane urea having aliphatic and aromatic rings, and polyurethane having aliphatic and aromatic rings.

[0567] As an aromatic ring, examples include aromatic hydrocarbon rings and aromatic heterocycles, with aromatic hydrocarbons being preferred.

[0568] The aromatic hydrocarbon rings mentioned above can be either monocyclic or condensed polycyclic.

[0569] There is no particular limitation on the number of carbon atoms in the aromatic hydrocarbon ring, but 6 to 30 is preferred, 6 to 18 is more preferred, and 6 to 10 is even more preferred.

[0570] Examples of monocyclic aromatic hydrocarbon rings include the benzene ring.

[0571] Examples of aromatic hydrocarbon rings that are condensed polycyclic aromatic hydrocarbons include, for example, the naphthalene ring.

[0572] Examples of the polyisocyanates and polyols used include those described in the first embodiment above.

[0573] As the colorant contained in the specific microcapsule B, examples can be made of the same type of colorant as the colorant contained in the ultraviolet sensing layer described above, and the preferred method is also the same.

[0574] As a photosynthetic agent contained in a specific microcapsule B, examples can be made of the same type as the photosynthetic agent contained in the ultraviolet sensing layer described above, and the preferred method is also the same.

[0575] The specific microcapsule B contains a solvent.

[0576] There are no particular restrictions on the types of solvents; aromatic solvents and non-aromatic solvents can be cited as examples.

[0577] As an aromatic solvent, the aromatic solvent Y described in the first embodiment can be cited as an example. As a non-aromatic solvent, the non-aromatic solvent X described in the first embodiment can be cited as an example.

[0578] The solvent contained in a particular microcapsule is preferably a solvent miscible with n-propanol. A miscible solvent is one that does not undergo phase separation when mixed with an equal amount of n-propanol.

[0579] In addition to the above-mentioned components, specific microcapsules B may contain one or more additives such as reducing agents, light stabilizers, paraffin wax, ultraviolet absorbers, and deodorizers, as needed. Among these, light stabilizers are preferred.

[0580] The details of the various components mentioned above (such as reducing agents and light stabilizers) are as described in the description of the first embodiment.

[0581] [Other Implementation Methods]

[0582] In the first and second embodiments described above, the use of microcapsules was described, but it is also possible to use a method without microcapsules. For example, it could be an ultraviolet sensing component comprising an ultraviolet sensing layer containing a defined adhesive resin and a colorant dispersed and / or melted in the adhesive resin. Furthermore, the ultraviolet sensing layer may also contain a photosynthetic agent. Moreover, the ultraviolet sensing layer may contain other components mentioned above (reducing agents, light stabilizers, crosslinking agents, sensitizers, ultraviolet absorbers, surfactants, and colorants, etc.).

[0583] Furthermore, it can be a molded body in which specific microcapsules are compounded into an adhesive resin.

[0584] The adhesive resin described above preferably includes either a water-soluble adhesive resin or a non-water-soluble adhesive resin.

[0585] Examples of adhesive resins include cellulose resins such as methylcellulose, ethylcellulose, carboxymethylcellulose, and carboxypropylcellulose; polyvinyl alcohol; polyvinyl butyral; gum arabic; gelatin; polyvinylpyrrolidone; casein; styrene-butadiene copolymer; acrylonitrile-butadiene copolymer; polyvinyl acetate; acrylic resin; polyvinyl chloride; and ethylene-vinyl acetate copolymer. From the viewpoint of excellent sensitivity at a wavelength of 222 nm, adhesive resins that are substantially free of aromatic groups are preferred, with cellulose resins and acrylic resins being particularly desirable.

[0586] From the viewpoint of achieving better results with the present invention, the adhesive is preferably a resin containing hydroxyl groups. Examples of resins containing hydroxyl groups include cellulose resins, polyvinyl alcohol, and polyvinyl butyral.

[0587] From the viewpoint of not developing color under no irradiation and exhibiting excellent storage stability, a low acid value is preferred for the adhesive. More preferably, it is 0–50 mg KOH / g, and even more preferably, it is 0–20 mg KOH / g.

[0588] The adhesive suppresses excessive absorption of light at a wavelength of 222 nm, and therefore preferably does not contain aromatic ring groups. "Substantially does not contain aromatic ring groups" means that the content of aromatic ring groups is preferably 0 to 1% by mass, more preferably 0 to 0.1% by mass, relative to the total mass of the adhesive.

[0589] Furthermore, as an adhesive resin, the polymeric adhesive described in paragraph 0078 of Japanese Patent Application Publication No. 2017-167155 can be referenced, and this content is incorporated into this specification.

[0590] Adhesive resins can be used alone or in combination of two or more.

[0591] Adhesive resins can be cross-linked. In other words, adhesive resins can be cross-linked adhesive resins.

[0592] There are no particular limitations on the crosslinking agent; for example, ethylenedioxazole can be used. Furthermore, the crosslinking agent described in paragraph 0079 of Japanese Patent Application Publication No. 2017-167155 can also be referenced. This information is incorporated herein by reference.

[0593] [Ultraviolet Sensing Kit]

[0594] Furthermore, the present invention also relates to an ultraviolet sensing kit comprising the aforementioned ultraviolet sensing component.

[0595] The ultraviolet sensing kit contains at least the ultraviolet sensing components described above.

[0596] There are no particular limitations on the specific structure of the ultraviolet sensing kit; for example, it can include an ultraviolet sensing component; and

[0597] Other components are selected from the group consisting of a component having a filter layer that selectively transmits light of a specific wavelength (preferably a filter that blocks light with a wavelength greater than 300 nm, more preferably a filter that blocks light with a wavelength greater than 230 nm), a light-blocking bag (ultraviolet cut-off bag), a judgment sample, a limit sample (calibration sheet), a focusing fixture such as a lens and a concave mirror, and a holding component for holding the ultraviolet sensing component.

[0598] In addition, the aforementioned holding member may have an opening for irradiating ultraviolet light onto the held ultraviolet sensing member, or the holding member may be integrated with the judgment sample.

[0599] Example

[0600] The following examples and comparative examples further illustrate the features of the present invention. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the present invention. However, the scope of the present invention should not be interpreted as limited by the specific examples shown below.

[0601] [Fabrication and Evaluation of Ultraviolet Sensing Components]

[0602] [Example 1]

[0603] The mixture 1 with the following composition was added to a 5% by mass aqueous solution of polyvinyl alcohol (202 parts by mass), and then emulsified and dispersed at 20°C to obtain an emulsion with a volume average particle size of 1 μm. Furthermore, the obtained emulsion was continuously stirred at 50°C for 4 hours. Water was then added to adjust the concentration to obtain a microcapsule solution containing a colorant with a solid content of 15.9% by mass.

[0604] <Composition of Mixture 1>

[0605] Colorant: 3,3-bis(2-methyl-1-octyl-3-indolyl)phthalide (manufactured by BASF) ... 0.7 parts by weight

[0606] Organohalogen compound: Tribromomethylphenyl sulfone (manufactured by Sumitomo Seika Chemicals Company, Limited) ... 10 parts by weight

[0607] Aromatic solvent: Trimethylbenzene phosphate (manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD.) ... 23 parts by weight

[0608] Solvent for capsule manufacturing: Ethyl acetate (manufactured by SHOWA DENKO KK) ... 50 parts by weight

[0609] Light stabilizer: 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) ... 0.03 parts by weight

[0610] Polyisocyanate: (addition of xylene diisocyanate and trimethylolpropane, product name "TAKENATED-110N", manufactured by Mitsui Chemicals, Inc., 75% by weight ethyl acetate solution)...8 parts by weight

[0611] A dispersion for forming an ultraviolet sensing layer (composition for forming an ultraviolet sensing layer) was prepared by mixing the obtained microcapsule liquid containing a color-developing agent (20 parts by mass), a 6% aqueous solution of polyvinyl alcohol (product name "DENKA SIZE EP-130", manufactured by Denka Company Limited) (5 parts by mass), 0.05 parts by mass of glyoxal (manufactured by DAITOCHEMICAL CO., LTD.) and 0.09 parts by mass of sodium dodecylbenzenesulfonate (manufactured by DKS Co.Ltd.).

[0612] The obtained ultraviolet sensing layer dispersion was coated onto a 188 μm thick white polyethylene terephthalate sheet (product name "CRISPR K1212", manufactured by TOYOBO CO., LTD.) to achieve a coating amount of 21 mL / m. 2 The UV sensor sheet, consisting of a support and a UV sensing layer, was fabricated by heating and drying at 105°C for 1 minute. The solid content of the UV sensing layer was 3 g / m². 2 Furthermore, the thickness of the ultraviolet sensing layer is approximately 3 μm.

[0613] [Examples 2-14]

[0614] Except for the changes to the types of ingredients, amounts of ingredients, concentrations of solid components, content of colorant per unit area in the ultraviolet sensing layer, and conditions for forming the capsule wall material recorded in Table 1, the ultraviolet sensing sheets of Examples 2 to 14 were produced using the same method as in Example 1.

[0615] In addition, the peak area ratio X in the tablets of Examples 5, 6 and 12 was 4%, the peak area ratio X in the tablet of Example 7 was 6%, and the peak area ratio X in tablet C3 of Comparative Example 2 was 62%. The measurement method was as described above.

[0616] [Comparative Examples 1-2]

[0617] Referring to Example 1 and Comparative Example 1 of Japanese Patent Application Publication No. 2014-164125, the ingredients and formulations were modified to those described in Table 1, and the liquid coating amount was 88 mL / m 2 The coating was applied in the same manner as in Example 1. In addition, the ultraviolet sensing sheet C1 of Comparative Example 1 and the ultraviolet sensing sheet C2 of Comparative Example 2 were prepared by the same method as in Example 1.

[0618] [Comparative Examples 3-4]

[0619] Use commercially available UV markers (S type, manufactured by NICHIYU GIKEN KOGYO COMPANY LIMITED) and UV scales (L type, manufactured by FUJIFILM Corporation).

[0620] Table 1 is shown below.

[0621] In addition, the components shown in Table 1 are as follows.

[0622] • TCP (Trimethylbenzene phosphate, manufactured by DAIHACHI CHEMICAL INDUSTRY CO.,LTD., boiling point 231~255℃, miscible with n-propanol)

[0623] • Soybean oil (manufactured by FUJIFILM Wako Pure Chemical Corporation, boiling point above 300°C, miscible with n-propanol)

[0624] • SAS-296 (Phenylene dimethyl ethane, product name "Nippon Oil Hysol SAS296", manufactured by JX NipponOil & Energy Corporation, boiling point 290~305℃, miscible with n-propanol)

[0625] •BMPS: Tribromomethylphenyl sulfone (manufactured by Sumitomo Seika Chemicals Company, Limited)

[0626] • Colorant A: 3,3-bis(2-methyl-1-octyl-3-indolyl)phthalide (manufactured by BASF)

[0627] • Colorant C: 3',6'-bis(diethylamino)-2-(4-nitrophenyl)spiro[isoindole-1,9'-xanthon]-3-one (manufactured by Hodogaya Chemical Co., Ltd.)

[0628] • LCV: Colorless crystal violet (Product name "LCV", manufactured by Yamada Chemical Co., Ltd.)

[0629] • BTHQ: 2,5-Bis(1,1,3,3-Tetramethylbutyl)hydroquinone (manufactured by Tokyo Chemical Co., Ltd.)

[0630] • D-110N (Adduct of xylene-1,3-diisocyanate and trimethylolpropane, product name "TAKENATE D-110N", manufactured by Mitsui Chemicals, Inc., 75% by mass ethyl acetate solution)

[0631] • D-120N (an adduct of hydrogenated xylene-1,3-diisocyanate and trimethylolpropane, product name "TAKENATE D-120N", manufactured by Mitsui Chemicals, Inc., 75% by mass ethyl acetate solution)

[0632] • D-140N (an adduct of isophorone diisocyanate and trimethylolpropane, product name "TAKENATED-140N", manufactured by Mitsui Chemicals, Inc., 75% by mass ethyl acetate solution)

[0633] • D-160N (an adduct of hexamethylene diisocyanate and trimethylolpropane, product name "TAKENATED-160N", manufactured by Mitsui Chemicals, Inc., 75% by mass ethyl acetate solution)

[0634] Furthermore, in Table 1, the values ​​in parentheses listed alongside the ingredient names refer to the content (parts by mass).

[0635] Furthermore, LCV corresponds to a color-developing agent that develops color through oxidation, and it turns blue upon oxidation. Color-developing agent A corresponds to a color-developing agent that develops color through the action of acid, and it turns red upon the action of acid.

[0636] Furthermore, in the embodiments in Table 1, pieces 1 to 14 correspond to Embodiment 1, and pieces 5 to 7 and 12 correspond to Embodiment 2.

[0637] In the embodiments, the ethyl acetate used as a solvent for capsule fabrication did not remain within the microcapsules after the ultraviolet sensing component was fabricated. In other words, the microcapsules in the ultraviolet sensing component of the present invention do not contain ethyl acetate.

[0638] [Optical Concentration Measurement and Evaluation]

[0639] (Optical concentration difference at a wavelength of 222nm)

[0640] Using Care222 (registered trademark), the ultraviolet sensing components fabricated in the various embodiments were irradiated with light until the irradiation dose of light with a wavelength of 222 nm reached 3 mJ / cm². 2 .

[0641] Subsequently, using a Spectrolino spectrophotometer (GretagMacbeth), the optical concentrations of yellow, magenta, and cyan in the ultraviolet (UV) sensing element before and after illumination were measured. The optical concentration of cyan before illumination was designated C1, and the optical concentration of cyan after illumination was designated C2. The optical concentration of yellow before illumination was designated Y1, and the optical concentration of yellow after illumination was designated Y2. The optical concentration of magenta before illumination was designated M1, and the optical concentration of magenta after illumination was designated M2. The differences between C1 and C2, Y1 and Y2, and M1 and M2 were measured. The maximum values ​​of these optical concentration differences are shown in the "Optical Concentration Difference Wavelength 222nm" column of Table 2.

[0642] (Evaluation of Tone Changes)

[0643] For the ultraviolet sensing components fabricated in each embodiment, the cumulative irradiance is 3 mJ / cm². 2 When the distance and time of illumination are adjusted, the ability to determine the color change of the ultraviolet sensing component is evaluated.

[0644] AA: It is very easy to make a judgment.

[0645] A: It can be easily determined.

[0646] B: Not easily determined

[0647] (Fog Assessment)

[0648] Imagine a haze under a fluorescent lamp. A handheld UV lamp, SLUV-8 (AS ONE), is used to illuminate the ultraviolet sensing component fabricated in each embodiment until the irradiation dose of light with a wavelength of 365 nm reaches 20 mJ / cm². 2 .

[0649] Subsequently, using a Spectrolino spectrophotometer (GretagMacbeth), the optical concentrations of yellow, magenta, and cyan in the ultraviolet (UV) sensing element before and after illumination were measured. The optical concentration of cyan before illumination was designated C1, and the optical concentration of cyan after illumination was designated C2. The optical concentration of yellow before illumination was designated Y1, and the optical concentration of yellow after illumination was designated Y2. The optical concentration of magenta before illumination was designated M1, and the optical concentration of magenta after illumination was designated M2. The differences between C1 and C2, Y1 and Y2, and M1 and M2 were measured. The maximum values ​​of these optical concentration differences are shown in the "Optical Concentration Difference Wavelength 365nm" column of Table 2. The smaller the differences between C1 and C2, Y1 and Y2, and M1 and M2, the better the fog can be suppressed. Furthermore, fog refers to the change in hue caused by the influence of light of different wavelengths measured with respect to the light.

[0650] Furthermore, the greater the difference between the optical concentration difference when irradiated at a wavelength of 365nm and the optical concentration difference when irradiated at a wavelength of 222nm, the easier it is to determine whether the irradiation dose that has inactivated the novel coronavirus has been applied, and the ability to suppress fog is also enhanced.

[0651] Table 1 shows the "chromogenic dose / UV sensing layer g / m" 2 The column indicates the content of the colorant per unit area (g / m²) in the ultraviolet sensing layer. 2 ).

[0652] In Table 2, the column “Color Difference ΔE” represents the color difference ΔE of the ultraviolet sensing components of each embodiment and comparative example before and after light irradiation, measured according to the method described in Embodiment B above.

[0653] In Table 2, the "Cumulative Value Difference" column represents the difference between the cumulative value 1 and the cumulative value 2 of the absorbance of the ultraviolet sensing components of each embodiment and comparative example, measured according to the method described in Embodiment C above.

[0654] In Table 2, the column “Difference between 365nm optical concentration difference and 222nm optical concentration difference” represents the difference between the optical concentration difference shown in the column “Optical concentration difference wavelength 365nm” and the optical concentration difference shown in the column “Optical concentration difference wavelength 222nm”.

[0655] [Table 1]

[0656]

[0657] [Table 2]

[0658]

[0659] As shown in Table 2, the ultraviolet sensing component of the present invention exhibits the desired effect.

[0660] A comparison of the examples and comparative examples confirms that when the ultraviolet sensing component contains a photoactive agent, and the mass ratio of the photoactive agent content to the colorant content exceeds 1.0, it can be easily determined.

[0661] Furthermore, a comparison of Examples 1, 8, 10, and 11 confirms that when the mass ratio of the content of the photoactive agent to the content of the colorant is 8.00 or more and 30.00 or less, it can be easily determined, and gray fog at a wavelength of 365 nm can be suppressed.

[0662] Furthermore, comparisons of Examples 4, 6-7, 12 and Comparative Example 2 confirmed that the ultraviolet sensing component includes microcapsules containing a photoactive agent, a colorant and a solvent. The capsule wall of the microcapsule contains one or more resins selected from the group consisting of polyurea with an aliphatic ring, polyurethane urea with an aliphatic ring and polyurethane with an aliphatic ring. When the peak area ratio X calculated by the peak area ratio calculation method X is less than 30%, it can be easily determined and the gray fog at a wavelength of 365 nm can be suppressed.

[0663] Furthermore, a comparison between the examples and comparative examples confirmed that the content of the colorant in the ultraviolet sensing layer is 0.14 g / m² relative to the unit area of ​​the ultraviolet sensing layer. 2 In the following situations, it is easy to make a judgment.

[0664] Furthermore, a comparison between the examples and comparative examples confirms that when the photoactive agent is a photoacid-generating agent and the color-generating agent is a color-generating agent that generates color through the action of acid, the effect of the present invention is even better.

[0665] <Examples 15-16>

[0666] Except for the changes to the types of ingredients, amounts of ingredients, concentrations of solid components, content of colorant per unit area in the ultraviolet sensing layer, and conditions for forming the capsule wall material recorded in Table 3, the ultraviolet sensing sheets of Examples 15 and 16 were produced by the same method as in Example 1.

[0667] <Example 17>

[0668] Polyvinyl butyral (PVB) (50 parts by weight), tetrahydrofuran (300 parts by weight), and ethanol (68.2 parts by weight) were mixed and the polymer was dissolved. Tribromomethylphenyl sulfone (manufactured by Sumitomo Seika Chemicals Company, Limited) (BMPS) (10.0 parts by weight) and 3,3-bis(2-methyl-1-octyl-3-indolyl)phthalide (manufactured by BASF) (colorant A) (5.0 parts by weight) were added to the obtained polymer solution to obtain a solution for forming the ultraviolet sensing layer. The obtained solution for forming the ultraviolet sensing layer was coated onto a 188 μm thick white polyethylene terephthalate sheet (product name "CRISPR K1212", manufactured by TOYOBO CO., LTD.) to achieve a dried film thickness of 5 μm, and then dried to produce an ultraviolet sensing sheet having a support and an ultraviolet sensing layer.

[0669] <Examples 18-21>

[0670] Except for the changes to the amount of compounding agent and the content of colorant per unit area in the ultraviolet sensing layer recorded in Table 4, the ultraviolet sensing sheets of Examples 18 to 21 were produced by the same method as in Example 17.

[0671] [Table 3]

[0672]

[0673] [Table 4]

[0674]

[0675] Furthermore, in Tables 3 and 4, the values ​​in parentheses listed alongside the ingredient names refer to the content (parts by mass).

[0676] Colorant C corresponds to colorants that develop color through the action of acid, and turns red when acted upon by acid.

[0677] The above evaluation was performed using the ultraviolet sensing sheet prepared above. The results are summarized in Table 5.

[0678] [Table 5]

[0679]

[0680] As shown in Table 5, the ultraviolet sensing component of the present invention exhibits the desired effect.

[0681] Symbol Explanation

[0682] 10-Ultraviolet sensing component, 12-Support body, 14-Ultraviolet sensing layer.

Claims

1. An ultraviolet sensing component, Using a KrCl excimer lamp as the light source, and with filters that substantially block light wavelengths from 230 nm to 300 nm, the ultraviolet sensing component was irradiated until the irradiation dose of light at a wavelength of 222 nm reached 3 mJ / cm². 2 Subsequently, using a GretagMacbeth Spectrolino spectrophotometer, the optical concentrations of yellow, magenta, and cyan in the ultraviolet (UV) sensing element before and after light irradiation were measured. When the optical concentration of cyan in the UV sensing element before irradiation was set as C1, the optical concentration of cyan in the UV sensing element after irradiation was set as C2, the optical concentration of yellow in the UV sensing element before irradiation was set as Y1, the optical concentration of yellow in the UV sensing element after irradiation was set as Y2, the optical concentration of magenta in the UV sensing element before irradiation was set as M1, and the optical concentration of magenta in the UV sensing element after irradiation was set as M2, any one of the differences between C1 and C2, Y1 and Y2, and M1 and M2 was greater than 0.

20. The ultraviolet sensing component includes an ultraviolet sensing layer containing a colorant. The content of the colorant in the ultraviolet sensing layer is 0.140 g / m² relative to the area of ​​the ultraviolet sensing layer. 2 the following, The color-developing agent is selected from the group consisting of color-developing agents that develop color by oxidation and color-developing agents that develop color by the action of acid. The ultraviolet sensing layer contains at least one photoactive agent selected from the group consisting of photooxidants and photoacid generators. The mass ratio of the photoactive agent content to the colorant content, i.e., the photoactive agent / colorant mass ratio, is 8.00 or more and 30.00 or less.

2. An ultraviolet sensing component, Using a KrCl excimer lamp as the light source, and with filters that substantially block light wavelengths from 230 nm to 300 nm, the ultraviolet sensing component was irradiated until the irradiation dose of light at a wavelength of 222 nm reached 3 mJ / cm². 2 At that time, the color difference ΔE between before and after light irradiation is greater than 20.

0. The ultraviolet sensing component includes an ultraviolet sensing layer containing a colorant. The content of the colorant in the ultraviolet sensing layer is 0.140 g / m² relative to the area of ​​the ultraviolet sensing layer. 2 the following, The color-developing agent is selected from the group consisting of color-developing agents that develop color by oxidation and color-developing agents that develop color by the action of acid. The ultraviolet sensing layer contains at least one photoactive agent selected from the group consisting of photooxidants and photoacid generators. The mass ratio of the photoactive agent content to the colorant content, i.e., the photoactive agent / colorant mass ratio, is 8.00 or more and 30.00 or less.

3. An ultraviolet sensing component, Using a KrCl excimer lamp as the light source, and with filters that substantially block light wavelengths from 230 nm to 300 nm, the ultraviolet sensing component was irradiated until the irradiation dose of light at a wavelength of 222 nm reached 3 mJ / cm². 2 When the cumulative absorbance value 1 of the ultraviolet sensing component in the wavelength range of 450nm to 700nm before light irradiation, obtained by method 1, and the cumulative absorbance value 2 of the ultraviolet sensing component in the wavelength range of 450nm to 700nm after light irradiation, obtained by method 2, are 18.0 or more, Method 1: Before light irradiation, measure the reflectance spectrum of the ultraviolet sensing component to obtain a reflectance spectrum with wavelength on the horizontal axis and absorbance on the vertical axis. Then, accumulate the absorbance of each 1 nm from wavelength 450 nm to 700 nm in the reflectance spectrum to calculate the cumulative absorbance value 1. Method 2: After irradiating the ultraviolet sensor with light, the reflectance spectrum is measured to obtain a reflectance spectrum with wavelength on the horizontal axis and absorbance on the vertical axis. Then, the absorbance of each 1 nm from wavelength 450 nm to wavelength 700 nm in the reflectance spectrum is accumulated to calculate the cumulative absorbance value 2. The ultraviolet sensing component includes an ultraviolet sensing layer containing a colorant. The content of the colorant in the ultraviolet sensing layer is 0.140 g / m² relative to the area of ​​the ultraviolet sensing layer. 2 the following, The color-developing agent is selected from the group consisting of color-developing agents that develop color through oxidation and color-developing agents that develop color through the action of acid. The ultraviolet sensing layer contains at least one photoactive agent selected from the group consisting of photooxidants and photoacid-producing agents. The mass ratio of the photoactive agent content to the colorant content, i.e., the photoactive agent / colorant mass ratio, is 8.00 or more and 30.00 or less.

4. The ultraviolet sensing component according to any one of claims 1 to 3, wherein it is sheet-shaped.

5. The ultraviolet sensing component according to claim 1, wherein, The color-developing agent is one that develops color through the action of acid. The ultraviolet sensing layer contains a photoacid-producing agent.

6. The ultraviolet sensing component according to claim 1, wherein, The photoactive agent comprises compounds represented by general formula (6). R 3 -L 1 -CX 3 X 4 X 5 (6) In general formula (6), R 3 L represents an aryl group optionally having substituents or a heteroaryl group optionally having substituents. 1 Indicates -SO- or -SO2-, X 3 X 4 and X 5 Each can be represented independently as a hydrogen atom or a halogen atom, where X 3 X 4 and X 5 Except for the case where all atoms are hydrogen atoms.

7. The ultraviolet sensing component according to claim 1, wherein, The color-developing agent comprises any structure selected from the group consisting of lactone rings, lactam rings, sulfonyl lactone rings, sulfinyl lactone rings and their open-ring forms, and azobenzene structures.

8. The ultraviolet sensing component according to any one of claims 1 to 3, comprising: An ultraviolet sensing layer comprising microcapsules containing a photoactive agent, a colorant, and a solvent having heteroatoms.

9. The ultraviolet sensing component according to claim 8, wherein, The capsule wall of the microcapsule comprises one or more resins selected from the group consisting of polyurea with aliphatic rings, polyurethane urea with aliphatic rings, and polyurethane with aliphatic rings. The peak area ratio X calculated using the following method is below 30%. Peak area ratio calculation method X: Two test pieces of the same size are cut from the ultraviolet sensing component. Liquid chromatography is performed on the first solution obtained by immersing one of the test pieces in n-propanol for 7 days and the second solution obtained by immersing the other test piece in n-propanol for 1 hour. The peak area ratio X is calculated as the ratio of the peak area of ​​the chromogenic agent in the second solution to the peak area of ​​the chromogenic agent in the first solution.

10. An ultraviolet sensing kit comprising the ultraviolet sensing component according to any one of claims 1 to 9.

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