Ultraviolet sensing member, microcapsule, method for producing microcapsule, dispersion for forming ultraviolet sensing layer, ultraviolet sensing kit

Abstract

A first object of the present application is to provide an ultraviolet ray sensing member having excellent storage stability and image storage properties. Also, a second object of the present application is to provide a microcapsule, a method for producing a microcapsule, a dispersion liquid for forming an ultraviolet ray sensing layer, and an ultraviolet ray sensing kit. The ultraviolet ray sensing member of the present application is an ultraviolet ray sensing member provided with an ultraviolet ray sensing layer including a microcapsule containing a photoactive agent, a chromogenic agent, and an aromatic solvent. The aromatic solvent includes a heteroatom-containing aromatic solvent and a heteroatom-free aromatic solvent.

Description

Technical Field

[0001] This invention relates to an ultraviolet sensing component, microcapsules, a method for manufacturing microcapsules, a dispersion for forming an ultraviolet sensing layer, and an ultraviolet sensing kit. Background Technology

[0002] Ultraviolet (UV) radiation levels are measured in various fields. Specific examples include measuring the UV radiation levels of irradiated objects during the curing reaction of UV-curable resins and during UV sterilization of food and other materials.

[0003] An ultraviolet photometer can be used to measure ultraviolet radiation levels.

[0004] Ultraviolet (UV) photometers come in various types, including those that utilize semiconductor electromotive force and those that utilize photochromism. For example, Patent Document 1 discloses a UV sensor sheet comprising a UV sensing layer containing a capsule containing a chromophore and a photooxidant as a UV photometer.

[0005] Previous technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2016 / 017701 Summary of the Invention

[0008] The technical problem to be solved by the invention

[0009] The inventors studied the ultraviolet sensing sheet described in Patent Document 1 and found that even in its unused state (i.e., before being used for ultraviolet measurement), the sheet sometimes discolors when placed in a hot environment for a long time. In other words, it has been determined that there is room for improvement in the storage stability of the ultraviolet sensing sheet.

[0010] Furthermore, the inventors have discovered that when the ultraviolet sensor described in Patent Document 1 is placed in a humid and hot environment for an extended period after being used in ultraviolet measurement, the color concentration of the chromatic area that develops color under ultraviolet irradiation (in other words, the color concentration of the chromatic image) sometimes becomes lighter. That is, it has been found that there is room for improvement, and the color concentration of the chromatic area that develops color under ultraviolet irradiation is less likely to decrease even after prolonged placement (hereinafter also referred to as "excellent image preservation").

[0011] Therefore, the objective of this invention is to provide an ultraviolet sensing component with excellent preservation stability and image preservation stability.

[0012] Furthermore, the objective of this invention is to provide a microcapsule, a method for manufacturing the microcapsule, a dispersion for forming an ultraviolet sensing layer, and an ultraviolet sensing kit.

[0013] means for solving technical problems

[0014] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the above problems could be solved by the structure shown below, thereby completing the present invention.

[0015] [1] An ultraviolet sensing component comprising an ultraviolet sensing layer including microcapsules containing a photoactive agent, a colorant, and an aromatic solvent,

[0016] The aforementioned aromatic solvents include aromatic solvents containing heteroatoms and aromatic solvents without heteroatoms.

[0017] [2] The ultraviolet sensing component according to [1], wherein the photoactive agent contains a compound represented by the general formula (6) described below.

[0018] [3] The ultraviolet sensing component according to [1] or [2], wherein the mass content ratio of the aromatic solvent containing heteroatoms to the aromatic solvent without heteroatoms is 35 / 65 to 85 / 15.

[0019] [4] The ultraviolet sensing component according to any one of [1] to [3], wherein the aromatic solvent contains one or more aromatic solvents with a boiling point of 100°C or higher.

[0020] [5] The ultraviolet sensing component according to any one of [1] to [4], wherein the aromatic solvent containing heteroatoms comprises an aromatic phosphate ester.

[0021] [6] The ultraviolet sensing component according to any one of [1] to [5], wherein the photoactive agent is a photooxidant.

[0022] The above-mentioned colorant is an oxidative colorant.

[0023] [7] The ultraviolet sensing component according to any one of [1] to [5], wherein the photoactive agent is a photoacid generator.

[0024] The aforementioned colorant is a colorant that develops color through the action of acid.

[0025] [8] The ultraviolet sensing component according to any one of [1] to [7], wherein the capsule wall of the microcapsule comprises one or more resins selected from the group consisting of polyurea, polyurethane urea and polyurethane.

[0026] [9] A microcapsule containing a photosynthetic agent, a colorant, and an aromatic solvent.

[0027] The aforementioned aromatic solvents include aromatic solvents containing heteroatoms and aromatic solvents without heteroatoms.

[0028]

[10] The microcapsule according to [9], wherein the above-mentioned photoactive agent contains a compound represented by the general formula (6) described below.

[0029]

[11] The microcapsule according to [9] or

[10] , wherein the mass ratio of the aromatic solvent containing heteroatoms to the aromatic solvent without heteroatoms is 35 / 65 to 85 / 15.

[0030]

[12] The microcapsule according to any one of [9] to

[11] , wherein the aromatic solvent contains one or more aromatic solvents with a boiling point of 100°C or higher.

[0031]

[13] The microcapsule according to any one of [9] to

[12] , wherein the aromatic solvent containing heteroatoms comprises an aromatic phosphate ester.

[0032]

[14] The microcapsules according to any one of [9] to

[13] , wherein the above-mentioned photoactive agent is a photooxidant.

[0033] The above-mentioned colorant is an oxidative colorant.

[0034]

[15] The microcapsules according to any one of [9] to

[13] , wherein the above-mentioned photoactive agent is a photoacid-producing agent.

[0035] The aforementioned colorant is a colorant that develops color through the action of acid.

[0036]

[16] The microcapsule according to any one of [9] to

[15] , wherein the capsule wall of the microcapsule comprises one or more resins selected from the group consisting of polyurea, polyurethane urea and polyurethane.

[0037]

[17] A method for manufacturing a microcapsule, which is the method for manufacturing a microcapsule as described in any one of [9] to

[16] , comprising:

[0038] The process of preparing an emulsion by mixing the above-mentioned colorant, the above-mentioned photoactive agent, the above-mentioned aromatic solvent and emulsifier in water;

[0039] The process of forming resin walls and encapsulating oil droplets containing the above-mentioned colorant, photosynthetic agent and aromatic solvent in the emulsion obtained in the above process to form the above-mentioned microcapsules.

[0040]

[18] A dispersion for forming an ultraviolet sensing layer, comprising microcapsules as described in any one of [9] to

[16] .

[0041]

[19] An ultraviolet sensing kit comprising an ultraviolet sensing component as described in any one of [1] to [8].

[0042] Invention Effects

[0043] According to the present invention, an ultraviolet sensing component with excellent preservation stability and image preservation stability can be provided.

[0044] Furthermore, according to the present invention, a microcapsule, a method for manufacturing the microcapsule, a dispersion for forming an ultraviolet sensing layer, and an ultraviolet sensing kit can be provided. Attached Figure Description

[0045] Figure 1 This is a schematic cross-sectional view illustrating an example of an embodiment of the ultraviolet sensing component of the present invention.

[0046] Figure 2 This is a schematic cross-sectional view illustrating another embodiment of the ultraviolet sensing component of the present invention.

[0047] Figure 3 This is a schematic cross-sectional view illustrating another embodiment of the ultraviolet sensing component of the present invention.

[0048] Figure 4 This is a schematic cross-sectional view illustrating another embodiment of the ultraviolet sensing component of the present invention.

[0049] Figure 5 This is a schematic cross-sectional view illustrating another embodiment of the ultraviolet sensing component of the present invention.

[0050] Figure 6 This is a schematic cross-sectional view illustrating another embodiment of the ultraviolet sensing component of the present invention. Detailed Implementation

[0051] The present invention will now be described in detail.

[0052] In addition, the necessary conditions for the following construction are sometimes described according to representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0053] 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.

[0054] Furthermore, within the numerical ranges described in this specification, the upper or lower limit of a particular numerical range can be replaced with the upper or lower limit of other numerical ranges described in different stages. Also, within the numerical ranges described in this specification, the upper or lower limit of a particular numerical range can be replaced with the values ​​shown in the embodiments.

[0055] Furthermore, in this specification, solid components refer to components that form the composition layer formed using the composition. When the composition contains a solvent (organic solvent, water, etc.), it refers to all components other than the solvent. Also, if a component forms the composition layer, liquid components are also considered solid components.

[0056] Furthermore, in this specification, ultraviolet light refers to light with a wavelength range of 10 to 400 nm.

[0057] Furthermore, in this specification, (meth)acrylic acid refers to "at least one of acrylic acid and methacrylic acid".

[0058] Furthermore, in this specification, "boiling point" refers to the boiling point under standard atmospheric pressure.

[0059] [Ultraviolet Sensing Component]

[0060] The ultraviolet sensing component of the present invention is

[0061] An ultraviolet sensing component comprising an ultraviolet sensing layer including microcapsules containing a photoactive agent, a colorant, and an aromatic solvent.

[0062] The aforementioned aromatic solvents include aromatic solvents containing heteroatoms and aromatic solvents without heteroatoms.

[0063] The ultraviolet sensing component of the present invention, having this structure, exhibits excellent storage stability and image preservation. While the details are not explicitly stated, the inventors speculate as follows.

[0064] When the ultraviolet sensing layer of the ultraviolet sensing component of the present invention is irradiated with ultraviolet light while measuring the amount of ultraviolet light, a color-emitting portion (color-emitting image) is formed in the area irradiated with ultraviolet light (the area where ultraviolet light is irradiated) with a color-emitting concentration corresponding to the amount of ultraviolet light (e.g., cumulative illuminance). The color-emitting image, represented by a color-emitting concentration corresponding to the amount of ultraviolet light, has a grayscale corresponding to the amount of ultraviolet light.

[0065] The primary color-developing mechanism of the UV-sensing layer originates from the microcapsules contained within it. When the UV-sensing layer is irradiated with UV light, the color-developing agent typically develops color within the microcapsules located in the irradiated area. Specifically, for example, when the photoactive agent is a compound that absorbs UV light and is activated to produce acids and / or free radicals, the color-developing agent develops color by reacting with these acids and / or free radicals. In this case, the amount of acids and / or free radicals produced by the photoactive agent varies depending on the amount of UV light irradiated, and the amount of color-developing agent also varies depending on the amount of acids and / or free radicals produced. As a result, in the UV-irradiated area of ​​the UV-sensing layer, the color concentration varies according to the amount of UV light irradiated, forming a color-developing region that develops color at a concentration corresponding to the amount of UV light irradiated.

[0066] As a feature of the ultraviolet sensing component of the present invention, the following point can be cited: the microcapsules in the ultraviolet sensing layer contain a photoactive agent, a colorant, and an aromatic solvent, and the aforementioned aromatic solvents include aromatic solvents containing heteroatoms and aromatic solvents without heteroatoms.

[0067] Aromatic solvents containing heteroatoms have relatively high polarity due to the presence of heteroatoms, while aromatic solvents without heteroatoms have relatively low polarity due to the absence of heteroatoms.

[0068] In this study, the inventors discovered that when the microcapsules in the ultraviolet sensing layer contain only aromatic solvents with heteroatoms as the aromatic solvent, even unused components tend to develop color (poor storage stability) when exposed to heat for extended periods. The reason for this is presumably that the chromophore within the microcapsules becomes overly stable due to the presence of relatively highly polar heteroatoms in the aromatic solvent (for example, when the chromophore is a colorless pigment, it readily generates a colorless reducing agent (chromophore)). On the other hand, it was found that when the microcapsules in the ultraviolet sensing layer contain only aromatic solvents without heteroatoms as the aromatic solvent, the color concentration of the chromophore portion that develops color after ultraviolet measurement is lightened when the component is exposed to ultraviolet light for extended periods in a humid and hot environment. The reason for this is presumably that the chromophore (chromophore) generated by the chromophore reaction of the chromophore within the microcapsules in the component after ultraviolet measurement is difficult to stabilize using an aromatic solvent without relatively low-polarity heteroatoms.

[0069] Based on the results of in-depth research on the above findings, the inventors have discovered that when the microcapsules in the ultraviolet sensing layer contain aromatic solvents with heteroatoms and aromatic solvents without heteroatoms as aromatic solvents, the preservation stability of the ultraviolet sensing component in its unused state and the image preservation stability of the ultraviolet sensing component after ultraviolet measurement can be achieved at an excellent level.

[0070] In addition, in the following, the superior preservation stability, superior image preservation and / or superior sensitivity of the ultraviolet sensing component are sometimes referred to as "superior effects of the present invention".

[0071] Hereinafter, embodiments of the ultraviolet sensing component of the present invention will be described in detail with reference to the accompanying drawings.

[0072] [First Embodiment]

[0073] Figure 1 This is a schematic cross-sectional view of one embodiment of the ultraviolet sensing component.

[0074] The ultraviolet sensing component 10 includes a support 12 and an ultraviolet sensing layer 14 disposed on one surface of the support 12 and comprising microcapsules containing a photoactive agent, a colorant, and an aromatic solvent. In the ultraviolet sensing layer 14 exposed to ultraviolet light, a color-emitting portion (not shown) that emits color at a color concentration corresponding to the amount of ultraviolet light can be formed.

[0075] Figure 1 (and the following section shows) Figures 2-6 The diagram shows an ultraviolet sensing component in the form of a sheet, but it is not limited to this method. The shape of the ultraviolet sensing component can be various shapes, such as cuboids, cylinders, or block shapes. Among these, a sheet-shaped ultraviolet sensing component is preferred.

[0076] 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.

[0077] As will be described later, the ultraviolet sensing component 10 may have an ultraviolet sensing layer 14 or may not have a support 12.

[0078] 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 configuration. As will be described later, it may include other layers besides the support 12 and the ultraviolet sensing layer 14 (e.g., a reflective layer, a glossy layer, a filter layer, etc.).

[0079] The lower limit of the thickness of the ultraviolet sensing component 10 is preferably 5 μm or more, more preferably 25 μm or more. Furthermore, the upper limit is preferably 1 cm or less, more preferably 2 mm or less, and even more preferably 250 μm or less.

[0080] The following is a detailed description of each component of the ultraviolet sensing component.

[0081] <<Support Body>>

[0082] The support is a component used to support the ultraviolet sensing layer. Alternatively, if the ultraviolet sensing layer itself can be processed, the ultraviolet sensing component may not need a support.

[0083] Examples of supports include resin sheets, paper (including synthetic paper), cloth (including woven and nonwoven fabrics), glass, wood, and metal. Resin sheets or paper are preferred as supports, more preferably resin sheets or synthetic paper, and even more preferably resin sheets.

[0084] 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, polyarylphthalide resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyethersulfone resins, polyurethane resins, acetal resins, and cellulose resins.

[0085] Examples of synthetic paper include synthetic paper with numerous micropores (such as Uber) formed by biaxially stretched polypropylene or polyethylene terephthalate, synthetic paper made from synthetic fibers such as polyethylene, polypropylene, polyethylene terephthalate and polyamide, and synthetic paper in which these are laminated on one or both sides of a paper.

[0086] Furthermore, as another preferred method for resin sheets, white resin sheets formed by dispersing white pigment in resin can be cited. The same material as the resin used in the aforementioned white resin sheets can be cited.

[0087] 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 inside the ultraviolet sensing element. As a result, the detection accuracy of the ultraviolet light quantity by the ultraviolet sensing element can be further improved.

[0088] For white pigments, refer to paragraph 0080 of International Publication No. 2016 / 017701. This information is incorporated into this specification.

[0089] The white resin sheet is preferably, for example, a white polyester sheet, and more preferably a white polyethylene terephthalate sheet.

[0090] Commercially available white resin sheets include Yupo (manufactured by YUPO CORPORATION), Lumirror (manufactured by TORAY INDUSTRIES, INC.), and Crisper (manufactured by Toyobo Co., Ltd.).

[0091] The lower limit of the 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 upper limit is preferably 1 cm or less, more preferably 2 mm or less, and even more preferably 250 μm or less.

[0092] <<Ultraviolet Sensing Layer>>

[0093] The ultraviolet sensing layer includes microcapsules containing a photoactive agent, a colorant, an aromatic solvent containing heteroatoms as an aromatic solvent, and an aromatic solvent without heteroatoms (hereinafter also referred to as "specific microcapsules").

[0094] The following is a detailed description of the various components that can be included in the ultraviolet sensing layer.

[0095] <Specific Microcapsules>

[0096] The ultraviolet sensing layer contains specific microcapsules.

[0097] The materials that constitute a specific microcapsule will be described in detail below.

[0098] Certain microcapsules typically have a core and a capsule wall for containing the core material that constitutes the core (the contained component, also known as the encapsulated component).

[0099] Certain microcapsules contain photoactive agents, colorants, and aromatic solvents as core materials (components).

[0100] As specific microcapsules, at room temperature, the material barrier of the capsule wall prevents contact between the substances inside and outside the capsule. Specifically, examples include Japanese Patent Application Publication No. 59-190886 and Japanese Patent Application Publication No. 60-242094, the contents of which are incorporated in this specification.

[0101] (Capsule wall)

[0102] The capsule walls of the preferred microcapsules are 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 walls of the preferred microcapsules are preferably composed of resin.

[0103] Examples of the aforementioned resins include polyurethane, polyurea, polyester, polycarbonate, urea-formaldehyde resin, melamine-formaldehyde resin, polystyrene, styrene-methacrylate copolymer, gelatin, and polyvinylpyrrolidone (polyvinyl alcohol). From the viewpoint that a dense, cross-linked structure that prevents leakage of the inner contents can further improve the effectiveness of the present invention, it is preferable to select one or more resins selected from the group consisting of polyurea, polyurethane urea, and polyurethane.

[0104] Furthermore, polyurea refers to a polymer having multiple urea bonds, and is preferably a reaction product formed from raw materials containing polyamines and polyisocyanates. Additionally, by utilizing the phenomenon that a portion of polyisocyanate reacts with water to form a polyamine, it is also possible to synthesize polyurea using polyisocyanate without using polyamines.

[0105] Furthermore, polyurethane urea refers to a polymer having urethane bonds and urea bonds, and is preferably a reaction product formed from raw materials containing polyols, polyamines, and polyisocyanates. Additionally, when polyols react with polyisocyanates, a portion of the polyisocyanate reacts with water to form a polyamine, sometimes resulting in the formation of polyurethane urea.

[0106] Furthermore, polyurethane refers to a polymer having multiple urethane bonds, preferably a reaction product formed from raw materials comprising polyols and polyisocyanates.

[0107] Examples of polyisocyanates include, for example, 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-4,4'-biphenyl-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, and cyclohexyl-1,2-diisocyanate. - Diisocyanates and diisocyanates such as xylenehexyl-1,4-diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, and dicyclohexylmethane diisocyanate; triisocyanates such as 4,4',4'-biphenylmethane triisocyanate and toluene-2,4,6-triisocyanate; tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate; isocyanate prepolymers such as adducts of hexamethylene diisocyanate and trimethylolpropane, adducts of 2,4-toluene diisocyanate and trimethylolpropane, adducts of benzylylene diisocyanate and trimethylolpropane, and adducts of toluene diisocyanate and glycerol; etc.

[0108] Furthermore, commercially available polyisocyanates include 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 Chemicals, Inc.), SUMIDUR N3300, Desmodule (registered trademark) L75, UL57SP, N3200, N3600, N3900, Z4470BA (manufactured by Sumika Bayer), and CORONATE (registered trademark) HL, HX, L, HK (Nippon Polyurethane Industry). Co., Ltd., P301-75E (Asahi Kasei Corporation), Durnate (registered trademark) TPA-100, TKA-100, TSA-100, TSS-100, TLA-100, 24A-100, TSE-100 (Asahi Kasei Corporation), and Barnock (registered trademark) D-750 (DIC Corporation).

[0109] Examples of polyols include aliphatic and aromatic polyols, hydroxyl polyesters, and hydroxyl polyalkylene ethers.

[0110] Specifically, examples include 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-butanediol, 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... 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 and other aromatic polyols condensed with olefinic oxygen, terephthalic acid, isophthalic acid, α,α'-dihydroxy-p-diisopropylbenzene, 4,4'-dihydroxy-diphenylmethane, 2-(p,p'-dihydroxydiphenylmethyl)benzyl alcohol, ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A, etc.

[0111] The polyol is preferably used in an amount of 0.02 to 2 moles of hydroxyl groups relative to 1 mole of isocyanate groups.

[0112] Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2-hydroxytrimethylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, and amine adducts of epoxides.

[0113] Polyisocyanates can also react with water to form polymers.

[0114] Polyisocyanates, polyols, and polyamines are described in the specifications of U.S. Patent Nos. 3,281,383, 3,773,695, and 3,793,268, as well as in Japanese Patent Publication Nos. 48-040347, 49-024159, 48-080191, and 48-084086, the contents of which are also incorporated herein by reference.

[0115] The average particle size of the microcapsules is preferably 0.1 to 100 μm. The lower limit is more preferably 0.3 μm or more, and even more preferably 0.5 μm or more. The upper limit 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 within the capsule can be more stably protected. 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.

[0116] In addition, the average particle size (volume average particle size) of the microcapsules can be determined, for example, using a laser analysis / scattering particle size distribution measuring device LA950 (manufactured by HORIBA, Ltd.).

[0117] 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 scanning electron microscopy (SEM). Specifically, the surface of the ultraviolet sensing layer is observed at 5000x magnification using SEM, and the average particle size of all microcapsules present in the field of view is determined through image analysis. Alternatively, if microcapsules cannot be observed on the surface, cross-sectional sections are prepared and measured using the same method as described above.

[0118] In addition, the term "microcapsule" refers to both specific microcapsules and concepts other than specific microcapsules.

[0119] (Coloring agent)

[0120] Certain microcapsules contain color-developing agents.

[0121] Here, "color-developing agent" refers to a compound that develops color from a substantially colorless state (colorless or light-colored state). As described later, a compound that develops color by reacting with an acid and / or free radical generated by a photoactive agent is preferred as a color-developing agent.

[0122] As a color-developing agent, it is preferred to use a compound that develops color through oxidation or through the action of an acid, and colorless pigments are preferred.

[0123] As the aforementioned colorless pigment, the preferred options are compounds that develop color by oxidation from a substantially colorless state (hereinafter also referred to as "oxidative color-developing colorless pigments"), or compounds that develop color from a substantially colorless state through the action of acid (hereinafter also referred to as "acid-developing colorless pigments").

[0124] Examples of colorless pigments include triarylmethane phthalides, fluorane compounds, phenothiazine compounds, indole phthalides, azaindole phthalides, colorless auramine compounds, rhodamine lactam compounds, triarylmethane compounds, diarylmethane compounds, triazene compounds, spiropyran compounds, thiazine compounds, and fluorene compounds.

[0125] For a detailed description of the above compounds, please refer to paragraphs

[0029] to

[0034] of U.S. Patent No. 3,445,234, Japanese Patent Application Publication No. 5-257,272 and International Publication No. 2009 / 8248.

[0126] A single colorant can be used alone, or two or more can be used in combination.

[0127] Oxidative colorless pigments

[0128] 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) aminothioxanthine, (d) amino-9,10-dihydroacridine, (e) aminophenoxazine, (f) aminophenothiazine, (g) aminodihydrophenazine, (h) aminodiphenylmethane, (i) leuco indamine, (j) aminohydrocinnamic acid (cyanoethane, leucomethyl), (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 (a) to (p) above, (a) to (i) develop color by losing 1 hydrogen atom, and (j) to (p) develop color by losing 2 hydrogen atoms.

[0129] Preferably, it is aminoarylmethane, and more preferably, it is aminotriarylmethane.

[0130] The preferred form of aminotriarylmethane is a compound represented by the following formula (L) or its acid salt.

[0131] [Chemical Formula 1]

[0132]

[0133] In the formula, Ar 1 This indicates that, relative to the position explicitly stated in formula (A1) where the carbon atom of methane is bonded to the para position, the R-type atom has... 1 R 2 N-substituted phenyl groups. Ar 2 This indicates that the para position of the bond in the methane carbon atom explicitly stated in formula (A1) has R. 1 R 2 The phenyl group with an N-substituent, or the phenyl group having a substituent selected from the group consisting of alkyl (preferably an alkyl group having 1 to 4 carbon atoms), alkoxy (preferably an alkoxy group having 1 to 4 carbon atoms), fluorine atom, chlorine atom and bromine atom at the ortho position relative to the carbon atom of methane 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.

[0134] Ar 3 Indicates with Ar 1 and Ar 2 At least one identical group in, or indicating a group similar to Ar 1 and Ar 2 Different groups. Ar 3 Indicates with Ar 1 and Ar 2 When different groups are used, Ar 3 The phenyl group can be substituted by a substituent selected from the group consisting of (B1) lower alkyl (preferably alkyl with 1 to 4 carbon atoms), lower alkoxy (preferably alkoxy with 1 to 4 carbon atoms), chlorine atom, diphenylamino, cyano, nitro, hydroxyl, fluorine atom, bromine atom, alkylthio, arylthio, thioester, alkylsulfonic acid, arylsulfonic acid, sulfonic acid, sulfonamide, alkylamide and arylamide, (B2) naphthyl group can be substituted by a substituent selected from the group consisting of amino, di-lower alkylamino and alkylamino, (B3) pyridyl group can be substituted by an alkyl group, (B4) quinolinyl group or (B5) indoline group can be substituted by an alkyl group.

[0135] In the above equation (L), R 1 and R 2Preferably, it is an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

[0136] Furthermore, in the above formula (L), Ar is preferred. 1 Ar 2 and Ar 3 All of these indicate that the bond positions of the methane carbon atoms explicitly shown in formula (A1) have R. 1 R 2 N-substituted phenyl groups, wherein the same group is preferred.

[0137] 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)xanthone, 2-(2- Xanthine, 2-dibenzylamino-6-dibutylamino-9-(2-methoxycarbonylphenyl)xanthine, benzo[a]-6-N,N-diethylamino-9,2-methoxycarbonylphenyl)xanthine, 2-(2-chlorophenyl)-amino-6-dibutylamino-9-(2-methylphenylcarboxyamide phenyl)xanthine, 3,6-dimethoxy-9-(2-methoxycarbonyl)-phenylxanthine, benzoyl colorless methylene blue, and 3,7-bis(diethylaminophenoxazine), etc.

[0138] Acid-based colorless pigments

[0139] As a type of acid-chromogenic colorless pigment, compounds that emit color by donating electrons or accepting protons from acids are preferred. Specifically, examples include compounds having partial skeletons such as lactones, lactams, sulopentalides, spiropyrans, esters, and amides, and whose partial skeletons open or cleave upon contact with acids or protons.

[0140] 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-azaphthalolide, and 3-(4-diethylamino-2-... 3-(1-n-octyl-2-methylindol-3-yl)phthalolide, 3-[2,2-bis(1-ethyl-2-methylindol-3-yl)vinyl]-3-(4-diethylaminophenyl)phthalolide, 2-anilino-6-dibutylamino-3-methylfluorane, 6-diethylamino-3-methyl-2-(2,6-dimethylanilino)fluorane, 2-(2-chloroanilino)-6-dibutylaminofluorane, 3 3-Bis(4-dimethylaminophenyl)-6-dimethylaminophthalolactone, 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'-xanthine]-3-one, 9-(N-ethyl-N-isopentylamino)spiro[benzo[a]xanthine-12,3'-phthalide], 2'-aniline-6'-(N-ethyl-N-isopentylamino)-3'-methylspirocyclic[phthalide-3,9'-[9H]xanthine] and 6'-(diethylamino)-1',3'-dimethylfluorane.

[0141] (Photoactive agents)

[0142] The microcapsules contain a photoactive agent. There are no particular limitations on the photoactive agent, as long as it is a photoactivated compound; however, compounds that cause the chromophore to develop color in a photoactivated state are preferred. The photoactive agent is preferably a compound activated by ultraviolet light, and more preferably one or more of a photooxidant and a photoacid-producing agent.

[0143] In specific microcapsules, from the viewpoint of superior sensitivity, the content ratio of photosynthetic agent to chromophore (photoactive agent / chromophore (mass ratio)) is preferably 0.1 to 30, more preferably 0.3 to 20. From the viewpoint of superior effect of the present invention, when the photosynthetic agent is a photooxidant, the content ratio of photosynthetic agent to chromophore is more preferably 0.4 to 3, and when the photosynthetic agent is a photoacid-generating agent, the content ratio of photosynthetic agent to chromophore is further preferably 3 to 20. The content ratio of photosynthetic agent to chromophore can be analyzed by extracting the ultraviolet sensing layer with methanol and using a methanol / water mixture as the eluent for liquid chromatography analysis.

[0144] Photooxidants

[0145] Preferred photooxidants are compounds that can be activated by ultraviolet light to generate free radicals and / or that can cause the chromophore to develop color by exhibiting the effect of abstracting hydrogen atoms from the chromophore.

[0146] The photooxidizing agent is preferably one or more of a free radical generator and an organohalogen compound. Furthermore, the photoacid generator is preferably prepared by using both a free radical generator and an organohalogen compound. When using both a free radical generator and an organohalogen compound, the 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, from the viewpoint of achieving better grayness in the colored portion.

[0147] Free radical generators

[0148] There are no particular limitations on compounds that can be activated by ultraviolet light to generate free radicals as free radical generators.

[0149] As a free radical generator, a hydrogen abstraction type free radical generator is preferred. Hydrogen abstraction type free radical generators have the function of abstracting hydrogen atoms from the chromophore, thus promoting the oxidation of the chromophore.

[0150] Examples of free radical generators include, for instance, the azide polymers described on page 55 of the summary of the research presentation at the Photographic Society of Japan in the spring of 1968; azide compounds such as 2-azidobenzoxazole, benzoyl azide, and 2-azidobenzimidazole as described in US Patent No. 3,282,693; 3'-ethyl-1-methoxy-2-pyridine thiocyanate and 1-methoxy-2-methylpyridine p-toluenesulfonate as described in US Patent No. 3,615,568; rotenoid dimers such as 2,4,5-triarylimidazolium dimer as described in Japanese Patent Publication No. 62-039728; benzophenone; p-aminophenyl ketone; polynuclear quinone; thioxanthone; etc.

[0151] The preferred ingredients are selected from one or more of robinin dimer and benzophenone, with robinin dimer being particularly preferred.

[0152] Examples of hexaaryl biimidazole compounds that are lobeline dimers include, for instance, hexaaryl biimidazole compounds. Compounds described in paragraph 0047 of International Publication No. 2016 / 017701 may be considered as hexaaryl biimidazole compounds. These contents are incorporated herein by reference.

[0153] Preferably, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole is used. For example, "B-CIM" manufactured by Hodogaya Chemical Co., Ltd. can be used.

[0154] As a dimer of roxene, the compound represented by the following general formula (1) is also preferred.

[0155] General formula (1)

[0156] [Chemical Formula 2]

[0157]

[0158] In general formula (1), A, B and D independently represent unsubstituted or substituented carbocyclic or heteroaryl groups that are dissociated into imidazole groups or substituents that do not hinder the oxidation of the colorant.

[0159] B and D are each preferably unsubstituted or have 1 to 3 substituents, and A is preferably unsubstituted or has 1 to 4 substituents.

[0160] For the compounds represented by general formula (1) and their methods of preparation, known knowledge such as that of lobeline dimers can be used. For example, reference can be made to the description in column 4, line 22 and column 6, line 3 of the specification of U.S. Patent No. 3,552,973, the contents of which are incorporated herein by reference.

[0161] Free radical generators can be used alone or in combination of two or more.

[0162] ...organohalogen compounds

[0163] Organohalogen compounds can promote the oxidation of colorants.

[0164] From the viewpoint of superior grayness in the chromatic part, compounds with three or more halogen atoms in the molecule are preferred as organohalogen compounds. The upper limit for the number of halogen atoms is preferably nine or less. Furthermore, the organohalogen compound is a compound other than robin base dimer and benzophenone.

[0165] Organic halogen compounds can be used alone or in combination of two or more.

[0166] Examples of organohalogen compounds include those represented by the following general formulas (2) to (7).

[0167] P 0 -CX3……(2)

[0168] 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.

[0169] 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.

[0170] As P 0 The alkyl and aryl groups 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.

[0171] Examples of compounds represented by general formula (2) include chloroform, tribromomethane, carbon tetrachloride, carbon tetrabromide, p-nitrobenzotribromo, bromochloromethane, trichlorotoluene, hexabromoethane, iodoform, 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.

[0172] General formula (3)

[0173] [Chemical Formula 3]

[0174]

[0175] In the formula, R represents a substituent. x represents an integer from 0 to 5.

[0176] 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.

[0177] Furthermore, when there are multiple R in the formula, R can be the same as each other or different from each other.

[0178] For x, 0 to 3 are preferred.

[0179] 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-dichloroacetophenone.

[0180] R 1 -SO2-X 1 ...General formula (4)

[0181] In the formula, R 1 This indicates an alkyl group that may have substituents or an aryl group that may have substituents. X 1 This represents a halogen atom.

[0182] As R 1 The alkyl group indicated 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.

[0183] As R 1 The aryl group 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.

[0184] As R 1 The alkyl and aryl groups may have substituents, such as 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.

[0185] 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, more preferably a chlorine atom or a bromine atom.

[0186] Examples of compounds represented by general formula (4) include 2,4-dinitrobenzenesulfonyl chloride, o-nitrobenzenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, 3,3'-dibenzenesulfonyl disulfonyl chloride, ethanesulfonyl chloride, p-bromobenzenesulfonyl chloride, p-nitrobenzenesulfonyl chloride, p-3-benzenesulfonyl chloride, p-acetamidobenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, p-toluenesulfonyl chloride, methanesulfonyl chloride, and benzenesulfonyl bromide.

[0187] R 2 -SX 2 ...General formula (5)

[0188] 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.

[0189] As R 2 The alkyl group and aryl group that can have substituents are represented by R of general formula (4). 1 The same applies to both, and the preferred selection method is also the same.

[0190] As X 2The 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, more preferably a chlorine atom or a bromine atom.

[0191] Examples of compounds represented by general formula (5) include 2,4-dinitrophenylsulfonyl chloride and o-nitrobenzenesulfinyl chloride.

[0192] R 3 -L 1 -CX 3 X 4 X 5 ……(6)

[0193] In the formula, R 3 L represents an aryl group that may have substituents or a heteroaryl group that may have 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.

[0194] As R 3 The aryl group 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.

[0195] 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.

[0196] As R 3 The aryl and heteroaryl groups may have substituents, such as 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.

[0197] As X 3 X 4 and X 5 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, more preferably a chlorine atom or a bromine atom.

[0198] Examples of compounds represented by general formula (6) include hexabromodimethyl sulfoxide, pentabromodimethyl sulfoxide, hexabromodimethyl sulfone, trichloromethylphenyl sulfone, tribromomethylphenyl sulfone, 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-tolylthionium trifluoromethanesulfonate, among which trichloromethylphenyl sulfone or tribromomethylphenyl sulfone is preferred.

[0199] R 4 CX 6 X 7 X 8 ……(7)

[0200] 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 either a hydrogen atom or a halogen atom. Where X... 6 X 7 and X 8 Except for the case where all atoms are hydrogen atoms.

[0201] 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.

[0202] As R 4 The heteroaryl group can have substituents, such as nitro, halogen atom, alkyl group with 1 to 3 carbon atoms, haloalkyl group with 1 to 3 carbon atoms, acetyl group, haloacetyl group, alkoxy group with 1 to 3 carbon atoms, etc.

[0203] As X 6 X 7 and X 8 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, more preferably a chlorine atom or a bromine atom.

[0204] 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.

[0205] From the viewpoint of achieving better results from the present invention, compounds represented by general formula (3), general formula (6) or general formula (7) are preferred, and compounds represented by general formula (6) are more preferred. The halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom, and more preferably a chlorine atom or a bromine atom.

[0206] Photo-acid generator

[0207] The preferred photoacid generator is a compound that is cleaved by ultraviolet light to produce acid and can cause the colorant to develop color through the action of the aforementioned acid.

[0208] 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, among which organohalogen compounds are preferred, and compounds represented by the above general formula (6) are more preferred.

[0209] From the viewpoint of superior grayness in the chromatic part, compounds with three or more halogen atoms in the molecule are preferred as organohalogen compounds. The upper limit for the number of halogen atoms is preferably nine or less.

[0210] Organic halogen compounds can be used alone or in combination of two or more.

[0211] As a specific example of an organohalogen compound, the same compound as the organohalogen compound mentioned as a photooxidant in the previous section can be cited.

[0212] Examples of ionic photoacid generators include diazonium salts, iodinated salts, and sulfonium salts, with iodinated salts or sulfonium salts being preferred. Examples of ionic photoacid color-generating agents include Japanese Patent Application Publications Nos. 62-161860, 61-067034, and 62-050382, the contents of which are incorporated herein by reference.

[0213] Furthermore, as a photoacid-generating agent, any compound that generates acid through light is acceptable and is not particularly limited. It can be a photoacid-generating agent that generates inorganic acids such as hydrogen halides (e.g., hydrochloric acid), sulfuric acid, and nitric acid, or it can be a photoacid-generating agent that generates organic acids such as carboxylic acids and sulfonic acids. From the viewpoint of achieving better results with the present invention, a photoacid-generating agent that generates inorganic acids is preferred, and a photoacid-generating agent that generates hydrogen halides is more preferred.

[0214] Specific examples of photoacid-generating agents include triarylsulfonium hexafluorophosphate, triarylsulfonium arsenate and triarylsulfonium antimonate, diaryliodohexafluorophosphate, diaryliodomonium arsenate and diaryliodoammonium antimonate, dialkylbenzoylsulfonium tetrafluoroborate and dialkylbenzoylsulfonium hexafluorophosphate, dialkyl-4-hydroxyphenyl sulfone tetrafluoroborate and dialkyl-4-hydroxyphenyl sulfone hexafluorophosphate, N-bromosuccinimide, tribromomethylphenyl sulfone, diphenyl iodide, 2-trichloromethyl-5-(p-butoxystyryl)-1,3,4-oxadiazole and 2,6-ditrichloromethyl-4-(p-methoxyphenyl)-triazine, etc.

[0215] (Aromatic solvents)

[0216] Some microcapsules contain aromatic solvents.

[0217] Furthermore, each of the specific microcapsules contains both aromatic solvents containing heteroatoms and aromatic solvents without heteroatoms as aromatic solvents.

[0218] Aromatic solvents are solvents whose molecules contain aromatic rings. These aromatic rings can be monocyclic or fused polycyclic.

[0219] Aromatic rings included in aromatic solvents include aromatic hydrocarbon rings and aromatic heterocycles. From the viewpoint of better performance of the present invention, aromatic hydrocarbon rings are preferred.

[0220] The aromatic hydrocarbon ring described above can be either a monocyclic ring or a fused polycyclic ring, but from the viewpoint of achieving better results in this invention, a monocyclic ring is preferred.

[0221] Furthermore, the aforementioned aromatic hydrocarbon ring may have substituents. Additionally, when the aforementioned aromatic hydrocarbon ring has multiple substituents, the substituents can combine with each other to form an alicyclic ring. In other words, the aforementioned aromatic hydrocarbon ring may contain an alicyclic structure.

[0222] The number of carbon atoms in the aromatic hydrocarbon ring is not particularly limited, but is preferably 6 to 30, more preferably 6 to 18, and even more preferably 6 to 10.

[0223] Examples of monocyclic aromatic hydrocarbon rings include the benzene ring.

[0224] Examples of fused polycyclic aromatic hydrocarbon rings include naphthalene rings.

[0225] The aforementioned aromatic heterocycles can be either monocyclic or fused polycyclic.

[0226] Furthermore, the aforementioned aromatic heterocycle may have substituents. Additionally, when the aforementioned aromatic heterocycle has multiple substituents, the substituents can combine with each other to form an alicyclic ring. In other words, the aforementioned aromatic heterocycle may contain an alicyclic structure.

[0227] Examples of heteroatoms contained in the aforementioned aromatic heterocycles include nitrogen, oxygen, and sulfur atoms. The number of rings in the aromatic heterocycle is not particularly limited, but is preferably 5 to 18.

[0228] Examples of aromatic heterocycles mentioned above include pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, triazine rings, thiophene rings, thiazole rings, imidazole rings, and thiazolidinium rings.

[0229] There is no particular limitation on the number of aromatic rings in aromatic solvents; they can be one or more. Furthermore, in the case of two or more aromatic rings, these two aromatic rings can be bonded together by any substituents present on each aromatic ring to form a polycyclic structure (excluding fused polycyclic structures).

[0230] As mentioned above, each of the specific microcapsules contains both heteroatom-containing aromatic solvents and heteroatom-free aromatic solvents as aromatic solvents.

[0231] In aromatic solvents containing heteroatoms, there are no particular restrictions on the position of the heteroatoms. Examples of aromatic solvents containing heteroatoms include aromatic solvents containing aromatic heterocycles within the molecule and aromatic solvents containing both heteroatoms and aromatic hydrocarbon rings within the molecule.

[0232] As heteroatoms in aromatic solvents containing heteroatoms, atoms other than carbon and hydrogen atoms can be cited as examples. Nitrogen atoms, oxygen atoms, sulfur atoms, or phosphorus atoms are preferred, and phosphorus atoms are more preferred from the viewpoint of better performance of the present invention.

[0233] Examples of heteroatom-containing aromatic solvents include substituted or unsubstituted benzenesulfonates such as compounds represented by general formula (1A) described below, substituted or unsubstituted phthalate diesters such as compounds represented by general formula (1B) described below, and aromatic phosphates such as compounds represented by general formula (1C) described below. Among these, aromatic phosphates are preferred from the viewpoint of superior effects of the present invention.

[0234] As an aromatic solvent that does not contain heteroatoms, it corresponds to an aromatic solvent that does not contain atoms other than carbon and hydrogen atoms.

[0235] From the viewpoint of achieving better results with respect to aromatic solvents that do not contain heteroatoms, aromatic solvents that do not contain polycyclic aromatic hydrocarbon rings are preferred, aromatic solvents that contain one or two monocyclic aromatic hydrocarbon rings are more preferred, and aromatic solvents that contain one or two benzene rings are even more preferred.

[0236] Examples of aromatic solvents that do not contain heteroatoms include compounds represented by general formula (1D) and general formula (1E) described below.

[0237] In a specific microcapsule, a heteroatom-containing aromatic solvent may be contained in one or more forms. Furthermore, in a specific microcapsule, a heteroatom-free aromatic solvent may be contained in one or more forms.

[0238] From the viewpoint of achieving better results with the present invention, the mass ratio of heteroatom-containing aromatic solvent to heteroatom-free aromatic solvent in a specific microcapsule (heteroatom-containing aromatic solvent / heteroatom-free aromatic solvent) is preferably 35 / 65 to 85 / 15.

[0239] From the viewpoint that the excellent solubility of the colorant results in a more superior effect of the present invention, in a specific microcapsule, the mass ratio of aromatic solvent to colorant (aromatic solvent / colorant) is preferably 1 to 100, more preferably 5 to 50, and even more preferably 5 to 25.

[0240] The mass ratio of heteroatom-containing aromatic solvents to heteroatom-free aromatic solvents in specific microcapsules can be determined by GCMS (gas chromatography-mass spectrometry). Specifically, the UV-sensing layer of the UV-sensing component can be extracted with acetone, and the resulting extract (filtered if necessary) can be concentrated and analyzed by GCMS to determine the various types and mass ratios of heteroatom-containing and heteroatom-free aromatic solvents. Furthermore, the mass ratio of chromogenic agents to aromatic solvents in specific microcapsules can be determined by liquid chromatography. Specifically, the UV-sensing layer of the UV-sensing component can be extracted with methanol, and the resulting extract can be analyzed by liquid chromatography using methanol / water as the eluent.

[0241] As a heteroatom-containing aromatic solvent, compounds represented by the following general formulas (1A) to (1C) are preferred, for example; and as a heteroatom-free aromatic solvent, compounds represented by the following general formulas (1D) to (1E) are preferred.

[0242] [Chemical Formula 4]

[0243]

[0244] In general formula (1A), L11 Indicates oxysulfonyl group (*) 1 -SO2-O-* 2 ) or sulfonyloxy (* 1 -O-SO2-* 2 ).in addition,* 1 Indicates the bonding position with the phenyl group explicitly stated in general formula (1A), * 2 Indicates with R 12 The bonding positions.

[0245] R 11 This indicates a non-aromatic substituent.

[0246] As a result of R 11 There are no particular restrictions on the non-aromatic substituents represented, but monovalent aliphatic hydrocarbon groups are preferred.

[0247] As a result of R 11 The monovalent aliphatic hydrocarbon group can be any one of an L-valent saturated aliphatic hydrocarbon group and a monovalent unsaturated aliphatic hydrocarbon group. Furthermore, it can be any one of a straight-chain, branched, or cyclic form.

[0248] The number of carbon atoms in the monovalent aliphatic hydrocarbon group is not particularly limited, for example, it is 1 to 20, preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 6, particularly preferably 1 to 4, and most preferably 1 to 3.

[0249] Examples of monovalent aliphatic hydrocarbon groups include alkyl, alkenyl, and alkynyl groups, with alkyl being preferred.

[0250] In addition, the aforementioned monovalent aliphatic hydrocarbon groups may also have substituents.

[0251] n 11 Represents integers from 0 to 5. 11 It is preferred to represent integers between 0 and 2.

[0252] Additionally, when n 11 When representing integers greater than 2, there exist multiple R values. 11 They can be the same as each other or different from each other.

[0253] R 12 This indicates a monovalent aliphatic hydrocarbon group. As R... 12 The monovalent aliphatic hydrocarbon group represented can be exemplified by the R group mentioned above. 11 The aliphatic hydrocarbon group represented by the same monovalent aliphatic hydrocarbon group.

[0254] Compounds represented by general formula (1B) include, specifically, methyl benzenesulfonate, ethyl benzenesulfonate, methyl toluenesulfonate, and ethyl toluenesulfonate.

[0255] [Chemical Formula 5]

[0256]

[0257] In general formula (1B), R 21 Indicates a non-aromatic substituent. R 21 The non-aromatic substituents represented are the same as R in general formula (1A). 11 The non-aromatic substituents referred to have the same meaning, and the preferred methods are also the same.

[0258] n 21 Represents integers from 0 to 4. 21 It is preferred to represent integers between 0 and 2.

[0259] Additionally, when n 21 When representing integers greater than 2, there exist multiple R values. 21 They can be the same as each other or different from each other.

[0260] R 22 and R 23 Each of these groups independently represents a monovalent aliphatic hydrocarbon group. As R 22 and R 23 The monovalent aliphatic hydrocarbon group represented can be exemplified by the R group mentioned above. 11 The aliphatic hydrocarbon group represented by the same monovalent aliphatic hydrocarbon group.

[0261] Compounds represented by general formula (1B) include, specifically, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, and dicyclohexyl phthalate.

[0262] [Chemical Formula 6]

[0263]

[0264] In the above general formula (1C), R 31 ~R 33 Each can independently represent an alkyl group or an aryl group that can have substituents. Wherein, R 31 ~R 33 At least one of them represents an aryl group that can have substituents.

[0265] As R 31 ~R 33 The alkyl group can be any of the following: straight-chain, branched, or cyclic. Furthermore, the alkyl group has, for example, 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6.

[0266] As R 31 ~R 33 The aryl group shown is preferably an aryl group with 6 to 20 carbon atoms, more preferably a phenyl or naphthyl group, and even more preferably a phenyl group.

[0267] R 31 ~R 33 The alkyl and aryl groups represented may have non-aromatic substituents. Examples of substituents include those corresponding to R in general formula (1A). 11 Substituents that are the same as the non-aromatic substituents are preferred in the same manner.

[0268] Compounds represented by the general formula (1D) include, specifically, triphenyl phosphate (TPP), tricresyl phosphate (TCP), tridimethyl phosphate (TXP), cresol diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate (t-BDP), bis(tert-butylphenyl) phenyl phosphate (BBDP), tri(tert-butylphenyl) phosphate (TBDP), isopropylbenzene diphenyl phosphate (IPP), bis(isopropylphenyl) diphenyl phosphate (BIPP), and tri(isopropylphenyl) phosphate (TIPP).

[0269] [Chemical Formula 7]

[0270]

[0271] In general formula (1D), L 41 It represents a single bond or a divalent aliphatic hydrocarbon group.

[0272] As L 41 The divalent aliphatic hydrocarbon group can be any one of a divalent saturated aliphatic hydrocarbon group and a divalent unsaturated aliphatic hydrocarbon group. Furthermore, it can be any one of a straight-chain, branched, or cyclic form.

[0273] The number of carbon atoms in the aforementioned divalent aliphatic hydrocarbon group is not particularly limited, for example, it is 1 to 20, preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 6, particularly preferably 1 to 4, and most preferably 1 or 2.

[0274] Examples of divalent aliphatic hydrocarbon groups include alkylene, alkenylene, and ynylene groups, with alkylene being preferred. Furthermore, in these divalent aliphatic hydrocarbon groups, the carbon atom can be substituted by a divalent group represented by >C=CH2.

[0275] R 41 and R 42 Each can be used to represent a non-aromatic substituent that does not contain heteroatoms.

[0276] As R 41 and R 42 There are no particular restrictions on the non-aromatic substituents that do not contain heteroatoms, but they are preferably monovalent aliphatic hydrocarbon groups.

[0277] As R41 and R 42 The monovalent aliphatic hydrocarbon group can be any one of a monovalent saturated aliphatic hydrocarbon group and a monovalent unsaturated aliphatic hydrocarbon group. Furthermore, it can be any one of a straight-chain, branched, or cyclic form.

[0278] The number of carbon atoms in the aforementioned monovalent aliphatic hydrocarbon group is not particularly limited, and for example, it is 1 to 20. An example of a preferred embodiment of the number of carbon atoms in the aforementioned monovalent aliphatic hydrocarbon group is 1 to 15, more preferably 1 to 10, even more preferably 1 to 6, particularly preferably 1 to 4, and most preferably 1 to 3.

[0279] Examples of monovalent aliphatic hydrocarbon groups include alkyl, alkenyl, and alkynyl groups, with alkyl being preferred.

[0280] n 41 and n 42 Each of the integers from 0 to 5 can be represented independently. 41 and n 42 Preferably, n represents an integer between 0 and 2. 41 and n 42 One of them represents 1 or 2, and the other represents 0 or 1.

[0281] Additionally, when n 41 and n 42 When representing integers greater than 2, there exist multiple R values. 41 Each other and multiple R 42 They can be the same as each other or different from each other.

[0282] Compounds represented by general formula (1A) include, specifically, phenyl dimethyl ethane, isopropyl biphenyl (e.g., 4-isopropyl biphenyl), diisopropyl biphenyl (e.g., 4,4'-isopropyl biphenyl), α-methylstyrene dimer, 1,2-dimethyl-4-(1-phenylethyl)benzene, 1,3-dimethyl-4-(1-phenylethyl)benzene, 1,4-dimethyl-2-(1-phenylethyl)benzene, and 1-(ethylphenyl)-1-phenylethane, etc.

[0283] [Chemical Formula 8]

[0284]

[0285] In general formula (1E), L 51 Indicates a single key.

[0286] R 51 Represents a non-aromatic substituent that does not contain heteroatoms. R 51 The non-aromatic substituents without heteroatoms represented by R in general formula (1D) 41 The meanings of non-aromatic substituents that do not contain heteroatoms are the same, and the preferred methods are also the same.

[0287] n 51 Represents integers from 0 to 5. 51 It is preferred to represent integers between 0 and 2.

[0288] Additionally, when n 51 When representing integers greater than 2, there exist multiple R values. 51 They can be the same as each other or different from each other.

[0289] R 52 This indicates a monovalent aliphatic hydrocarbon group. As R... 52 The monovalent aliphatic hydrocarbon group represented can be exemplified by R in the above general formula (1A). 12 The aliphatic hydrocarbon group represented by the same monovalent aliphatic hydrocarbon group. Wherein, as R... 52 The number of carbon atoms in the monovalent aliphatic hydrocarbon group is preferably 5 to 20. Furthermore, as a group composed of R... 52 The monovalent aliphatic hydrocarbon group represented is preferably straight-chain or branched.

[0290] Examples of compounds represented by the general formula (1E) include straight-chain or branched alkylbenzenes with 5 to 20 carbon atoms.

[0291] There are no particular limitations on the molecular weight of aromatic solvents, but most are 100 or higher. Preferably, they are 150 or higher. There is no particular upper limit, but preferably they are 1000 or lower, more preferably 600 or lower, and even more preferably 500 or lower.

[0292] The aromatic solvent preferably includes one or more aromatic solvents with a boiling point of 100°C or higher. From the viewpoint of further improving the effect of the present invention, it is more preferable that all aromatic solvents contained in a particular microcapsule have a boiling point of 100°C or higher. With a boiling point of 100°C or higher, when the microcapsule is subjected to heating processes such as reactions, the aromatic solvent will not be removed from the capsule and will easily remain.

[0293] From the viewpoint of achieving better results with the present invention, the boiling point of the aromatic solvent is more preferably 120°C or higher, more preferably 150°C or higher, and especially preferably 200°C or higher. Furthermore, there is no particular limitation on the upper limit of the boiling point; for example, it may be 400°C or lower.

[0294] (Other ingredients)

[0295] In addition to the above-mentioned components, certain microcapsules may also contain, as needed, one or more solvents other than aromatic solvents, reducing agents, light stabilizers, paraffin wax, ultraviolet absorbers, and odor suppressants. Preferably, they contain solvents other than aromatic solvents and light stabilizers.

[0296] Solvents other than aromatic solvents

[0297] Certain microcapsules may contain solvents other than aromatic solvents.

[0298] In a specific microcapsule, the content of the aromatic solvent relative to the total mass of the solvent is preferably 50-100% by mass, more preferably 75-100% by mass, even more preferably 85-100% by mass, and particularly preferably 90-100% by mass.

[0299] Light stabilizers

[0300] There are no particular limitations on light stabilizers as long as they are light-stabilized materials, but it is preferable that they are free radical scavenging substances that act as photoactive agents that capture and activate free radicals.

[0301] One type of light stabilizer can be used alone, or two or more types can be used.

[0302] Examples of light stabilizers include polyvalent phenols such as 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, hydroquinone, catechol, resorcinol, and hydroxyhydroquinone, as well as aminophenols such as o-aminophenol and p-aminophenol.

[0303] The ratio of light stabilizer to photoactive agent (light stabilizer / photoactive agent (molar ratio)) is preferably 0.0001 to 100, more preferably 0.0005 to 10.

[0304] ·reducing agent

[0305] Reducing agents have the function of deactivating photooxidizing agents.

[0306] When specific microcapsules contain reducing agents, they can suppress rapid changes in the color concentration of the UV-sensing layer caused by UV irradiation, thus easily adjusting the color concentration according to the amount of UV irradiation. The reducing agent also acts as an antioxidant.

[0307] A reducing agent can be used alone or in combination with two or more.

[0308] Examples of reducing agents include cyclic phenylhydrazine compounds. Specifically, examples include 1-phenyl-3-pyrazolone, 1-phenyl-4-methyl-3-pyrazolone, 1-phenyl-4,4-dimethylpyrazolone-3-one, 3-methyl-1-p-sulfophenyl-2-pyrazolone-5-one, 3-methyl-1-phenyl-2-pyrazolone-5-one, and 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolone (Dimezon S, manufactured by Daito Chemical Co., Ltd.).

[0309] As a reducing agent, the reducing agents described in paragraphs 0072 to 0075 of International Publication No. 2016 / 017701 may be considered. These contents are incorporated into this specification.

[0310] (Manufacturing method of specific microcapsules)

[0311] There are no particular limitations on the manufacturing methods of specific microcapsules. For example, well-known methods such as interfacial polymerization, internal polymerization, phase separation, external polymerization, and agglomeration can be cited.

[0312] As a specific method for manufacturing microcapsules, one example includes an emulsification step and an encapsulation step as shown below. Furthermore, in the encapsulation step, it is preferable to form the resin wall (capsule wall) by interfacial polymerization.

[0313] Emulsification process: The process of preparing an emulsion by mixing colorant, photosynthetic agent, aromatic solvent and emulsifier in water.

[0314] Encapsulation process: This process involves encapsulating oil droplets containing colorants, photoactive agents, and aromatic solvents in the emulsion obtained in the above process to form a resin wall (capsule wall).

[0315] The following describes the interfacial polymerization method using a specific microcapsule manufacturing method with a capsule wall of polyurea or polyurethane urea as an example.

[0316] As an interfacial polymerization method, an interfacial polymerization method comprising the following steps is preferred: (emulsification step), a step of preparing an emulsion by dispersing an oil phase containing a photoactive agent selected from photooxidants and photoacid generators, an aromatic solvent, a solvent containing an aliphatic structure with a boiling point below 100°C, a colorant, and a capsule wall material (e.g., polyisocyanate) in an aqueous phase containing an emulsifier; (encapsulation step), 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 selected from oxidants and photoacid generators, an aromatic solvent, and a colorant.

[0317] In the emulsification process described above, solvents containing aliphatic structures with boiling points below 100°C are typically added to improve the solubility of the core material in the solvent. Furthermore, solvents containing aliphatic structures do not contain aromatic rings within their molecules.

[0318] There are no particular limitations on solvents containing aliphatic structures; examples include ethyl acetate, isopropyl acetate, methyl ethyl ketone, and dichloromethane.

[0319] Solvents containing aliphatic structures can be used alone or in combination of two or more.

[0320] Furthermore, there are no particular restrictions on the types of emulsifiers used in the above emulsification process; for example, dispersants and surfactants can be cited.

[0321] As a dispersant, protective colloids of water-soluble polymers selected from known anionic polymers, nonionic polymers, and amphoteric polymers can be cited, specifically polyvinyl alcohol, gelatin, and cellulose derivatives, with polyvinyl alcohol being preferred.

[0322] The preferred surfactants are anionic or nonionic surfactants, such as alkylbenzene sulfonates (e.g., sodium dodecylbenzene sulfonate and ammonium dodecylbenzene sulfonate), alkyl sulfonates (e.g., sodium lauryl sulfate and sodium dodecylbenzene sulfonate), sodium dioctyl sulfosuccinate, and polyalkylene glycols (e.g., polyoxyethylene nonylphenyl ether).

[0323] Furthermore, as other methods for manufacturing specific microcapsules, the methods described in U.S. Patent Nos. 3,726,804 and 3,796,696 may also be considered. These contents are incorporated herein by reference.

[0324] The content of specific microcapsules in the ultraviolet sensing layer is not particularly limited, but is preferably 50 to 99% by mass, more preferably 70 to 90% by mass, relative to the total mass of the ultraviolet sensing layer.

[0325] The ultraviolet sensing layer may contain other components besides the specific microcapsules mentioned above.

[0326] Other components include, for example, polymeric adhesives, reducing agents, crosslinking agents, sensitizers, ultraviolet absorbers, and surfactants.

[0327] Examples of polymeric adhesives include polyvinyl alcohol, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, rubber arabic, gelatin, polyvinylpyrrolidone, casein, styrene-butadiene latex, acrylonitrile-butadiene latex, polyvinyl acetate, polyacrylate, and ethylene-vinyl acetate copolymers.

[0328] Furthermore, as a polymeric adhesive, reference can be made to the polymeric adhesive described in paragraph 0078 of Japanese Patent Application Publication No. 2017-167155. This information is incorporated into this specification.

[0329] Polymer adhesives can be cross-linked. In other words, polymer adhesives can be cross-linked adhesives.

[0330] 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 may also be considered. These contents are incorporated into this specification.

[0331] As reducing agents, sensitizing agents, surfactants, etc., the descriptions on page 9 (bottom left column) to page 10 (top left column) of Japanese Patent Application Publication No. 1-207741, and paragraphs 0038-0039 and 0048-0059 of Japanese Patent Application Publication No. 2004-233614 are applicable and are incorporated into this specification.

[0332] Furthermore, as reducing agents, light stabilizers, ultraviolet absorbers, and surfactants, they can also be contained in specific microcapsules.

[0333] There is no particular limitation on the mass per unit area (solid component coating amount) of the ultraviolet sensing layer, but it is preferably, for example, 3 to 30 g / m². 2 More preferably 5-25 g / m 2 More preferably 5-20 g / m 2 .

[0334] The thickness of the ultraviolet sensing layer is preferably 0.1 to 30 μm, and more preferably 1 to 25 μm.

[0335] <Method for forming the ultraviolet sensing layer>

[0336] There are no particular limitations on the method for forming the ultraviolet sensing layer, and well-known methods can be cited.

[0337] For example, a method can be described by coating a dispersion containing specific microcapsules for forming an ultraviolet sensing layer onto a support, and then drying the coating as needed.

[0338] Preferably, the dispersion for forming the ultraviolet sensing layer contains at least specific microcapsules. Alternatively, the microcapsule dispersion obtained by the above-described interfacial polymerization method can be used as the dispersion for forming the ultraviolet sensing layer.

[0339] The dispersion for forming the ultraviolet sensing layer may include other components that may be included in the ultraviolet sensing layer.

[0340] There are no particular limitations on the method of coating the dispersion for forming the ultraviolet sensing layer. For example, the coating machine used for coating can be an air knife coating machine, a bar coating machine, a curtain coating machine, a gravure coating machine, an extrusion coating machine, a die coating machine, a sliding bead coating machine, and a doctor blade coating machine.

[0341] After the dispersion for forming the ultraviolet sensing layer is applied to the support, the coating can be dried as needed. One example of a drying process is heat treatment.

[0342] 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.

[0343] There are no particular restrictions on temporary supports as long as they are peelable supports.

[0344] <<Other Layers>>

[0345] The ultraviolet sensing component may have other layers besides the support and ultraviolet sensing layer described above. Examples of other layers include a reflective layer, a gloss layer, a sensitivity adjustment layer, and a filter layer.

[0346] <Reflective Layer>

[0347] The ultraviolet sensing component can also have a reflective layer.

[0348] When the ultraviolet sensing component has a reflective layer, the ultraviolet rays that hit the ultraviolet sensing component can be reflected by the ultraviolet-reflective layer, thus suppressing the scattering of ultraviolet rays inside the ultraviolet sensing component and further improving the detection accuracy of ultraviolet rays.

[0349] The reflectivity of the reflective layer to light with wavelengths of 300–380 nm is preferably 10% or more, more preferably 50% or more. Furthermore, the reflectivity can be measured, for example, using a UV-Vis spectrophotometer (UV-2700 / Shimadzu Corporation) for diffuse reflectance measurement.

[0350] 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.

[0351] For methods of manufacturing reflective layers, adhesive layers, and the like, refer to paragraphs 0082 to 0091 of International Publication No. 2016 / 017701. These contents are incorporated herein by reference.

[0352] <Glossy Layer>

[0353] The ultraviolet sensing component may also have a glossy layer.

[0354] When the ultraviolet sensing component has a glossy layer, the visibility of both the front and back sides can be improved.

[0355] 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. These contents are incorporated herein by reference.

[0356] <Filter Layer>

[0357] The ultraviolet sensing component can also have a filter layer.

[0358] A filter layer is a layer that selectively transmits light of a specific wavelength. Here, "selectively transmits light of a specific wavelength" means transmitting light of a specific wavelength 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 less, and even more preferably 10% or less.

[0359] For the filter layer and the method of manufacturing thereof, please refer to paragraphs 0016 to 0026 of International Publication No. 2016 / 017701. These contents are incorporated into this specification.

[0360] <Sensitivity Adjustment Layer>

[0361] When the ultraviolet sensing component has a filter layer, a sensitivity adjustment layer can also be provided on the surface of the filter layer. When the ultraviolet sensing component has a sensitivity adjustment layer, the amount of ultraviolet irradiation that helps with color development can be adjusted, enabling color development that corresponds to the amount of ultraviolet radiation.

[0362] Sensitivity adjustment layers can be layers that affect the amount of ultraviolet radiation that contributes to color development. Examples include layers containing resin and pigment particles, as well as films used for surface protection films and laminated films.

[0363] As for the sensitivity adjustment layer and its manufacturing method, reference can be made to the sensitivity adjustment layer and its manufacturing method described in paragraphs 0095 to 0109 of International Publication No. 2016 / 017701. These contents are incorporated into this specification.

[0364] [Other Implementation Methods]

[0365] The following shows another example of another embodiment of the ultraviolet sensing component. Furthermore, the layers described in the first embodiment can be applied to the support, ultraviolet sensing layer, reflective layer, adhesive layer, sensitivity adjustment layer, and filter layer constituting the other embodiments shown below.

[0366] <Second Implementation>

[0367] Figure 2 This is a schematic cross-sectional view illustrating another embodiment of the ultraviolet sensing component.

[0368] The ultraviolet sensing component 20 includes a support 12, an ultraviolet sensing layer 14 disposed on one surface of the support 12 and comprising microcapsules containing a photoactive agent, a colorant, and an aromatic solvent, and a filter layer 22 disposed on the surface of the ultraviolet sensing layer 14. Furthermore, a reflective layer 24 is provided on the surface of the support 12 opposite to the ultraviolet sensing layer 14. The reflective layer 24 can be formed directly on the surface of the support 12, or it can be disposed via an adhesive layer (not shown) or the like.

[0369] <Third Implementation>

[0370] Figure 3 This is a schematic cross-sectional view illustrating another embodiment of the ultraviolet sensing component.

[0371] The ultraviolet sensing component 30 includes a support 12, an ultraviolet sensing layer 14 disposed on one surface of the support 12 and comprising microcapsules containing a photoactive agent, a colorant, and an aromatic solvent, and a filter layer 22 disposed on the surface of the ultraviolet sensing layer 14. Furthermore, a reflective layer 24 is provided on the surface of the support 12 opposite to the ultraviolet sensing layer 14, and a glossy layer 26 is provided on the surface of the reflective layer 24. The reflective layer 24 can be formed directly on the surface of the support 12, or it can be disposed via an adhesive layer (not shown) or the like.

[0372] <Fourth Implementation>

[0373] Figure 4 This is a schematic cross-sectional view illustrating another embodiment of the ultraviolet sensing component.

[0374] The ultraviolet sensing component 40 includes a support 12, a reflective layer 24 disposed on one surface of the support 12, an ultraviolet sensing layer 14 disposed on the surface of the reflective layer 24 and containing microcapsules containing a photoactive agent, a colorant, and an aromatic solvent, and a filter layer 22 disposed on the surface of the ultraviolet sensing layer 14. The reflective layer 24 can be formed directly on the surface of the support 12, or it can be disposed via an adhesive layer (not shown) or the like.

[0375] <Fifth Implementation>

[0376] Figure 5 This is a schematic cross-sectional view illustrating another embodiment of the ultraviolet sensing component.

[0377] The ultraviolet sensing component 50 includes a support 12, a reflective layer 24 disposed on one surface of the support 12, an ultraviolet sensing layer 14 disposed on the surface of the reflective layer 24 and comprising microcapsules containing a photoactive agent, a colorant, and an aromatic solvent, and a filter layer 22 disposed on the surface of the ultraviolet sensing layer 14. Furthermore, the surface of the support 12 opposite to the reflective layer 24 has a glossy layer 26. The reflective layer 24 can be formed directly on the surface of the support 12, or it can be disposed via an adhesive layer (not shown) or the like.

[0378] <Sixth Implementation>

[0379] Figure 6 This is a schematic cross-sectional view illustrating another embodiment of the ultraviolet sensing component.

[0380] The ultraviolet sensing component 60 includes a support 12, an ultraviolet sensing layer 14 disposed on one surface of the support 12 and containing microcapsules containing photoactive agents, colorants and aromatic solvents, and a filter layer 22 disposed on the surface of the ultraviolet sensing layer 14.

[0381] <Other Implementation Methods>

[0382] In embodiments 2 to 6, an ultraviolet sensing component having a filter layer 22 is shown, but the filter layer 22 may not be provided.

[0383] In embodiments 2 to 6, a sensitivity adjustment layer (not shown) may be disposed adjacent to the filter layer 22.

[0384] Characteristics and applications of μ-ultraviolet sensing components

[0385] The ultraviolet sensing component of this invention emits color according to the amount of ultraviolet light, allowing for visual confirmation of color concentration differences in the emitting area. Furthermore, when designed as a thin sheet, it can measure the amount of ultraviolet light over a large area.

[0386] In the ultraviolet sensing component, the slope of the straight line plotted on a graph with the logarithm of the cumulative illuminance of light at a wavelength of 365 nm illuminating the ultraviolet sensing component on the horizontal axis and the color intensity of the ultraviolet sensing layer on the vertical axis can be appropriately adjusted according to the required application. For example, a gentle slope (in other words, when the grayscale is gradual) can be used for a wide energy range, while a steep slope (in other words, when the grayscale is steep) can read subtle energy differences.

[0387] In addition, in this specification, "cumulative illuminance" refers to the cumulative illuminance measured at a wavelength of 365 nm, such as the value measured using a 365 nm UV photometer.

[0388] Furthermore, "color intensity" is determined by reflectance intensity D = -log10 The value defined by ρ (ρ is reflectance) can be measured, for example, using a reflectance density meter (X-Rite 310, manufactured by X-Rite Corporation).

[0389] Furthermore, the method for measuring the color concentration difference of the chromophore can be the following.

[0390] The image of the component after irradiating the ultraviolet sensing component with a predetermined ultraviolet light to induce color development is read using a scanner (e.g., GT-F740 / GT-X830, manufactured by Epson) or a smartphone. The concentration of the colored portion of the image is then analyzed using a UV light distribution analysis system (FUD-7010J, manufactured by Fujifilm Corporation). Additionally, correction and calibration processes can be performed as needed.

[0391] Ultraviolet (UV) sensing components can be used, for example, to measure the amount of UV radiation received from a UV irradiation device when manufacturing components using roll-to-roll UV curing of UV-cured resin. Furthermore, for example, to determine the degree of tanning caused by UV radiation on people and objects, the amount of UV radiation during the day can be measured daily.

[0392] [Dispersion for forming ultraviolet sensing layer and its manufacturing method]

[0393] Furthermore, the present invention also relates to a dispersion for forming an ultraviolet sensing layer capable of forming the ultraviolet sensing layer of the aforementioned ultraviolet sensing component, and a method for manufacturing the same.

[0394] The ultraviolet sensing layer forming dispersion of the present invention is an ultraviolet sensing layer forming dispersion comprising microcapsules containing a photosynthetic agent, a colorant, and an aromatic solvent, wherein the aromatic solvent includes aromatic solvents containing heteroatoms and aromatic solvents without heteroatoms. That is, the ultraviolet sensing layer forming dispersion of the present invention corresponds to a dispersion containing the aforementioned specific microcapsules.

[0395] The composition of the dispersion for forming the ultraviolet sensing layer of the present invention will be described in detail below.

[0396] The dispersion for forming the ultraviolet sensing layer of the present invention contains specific microcapsules. These specific microcapsules are the same as those contained in the ultraviolet sensing component, and preferably in the same manner.

[0397] In the dispersion for forming the ultraviolet sensing layer, the content of specific microcapsules, relative to the total solids content in the composition, is preferably 50 to 99% by mass, more preferably 70 to 90% by mass.

[0398] The dispersion for forming the ultraviolet sensing layer of the present invention may contain other components besides specific microcapsules that may be included in the ultraviolet sensing layer. Examples of other components include, for instance, polymeric adhesives, crosslinking agents (crosslinking agents for forming crosslinked polymeric adhesives (e.g., dioxazole), reducing agents, sensitizers, surfactants, etc.). Specific examples of other components are described above.

[0399] When the dispersion for forming the ultraviolet sensing layer contains a polymeric binder, the content of the polymeric binder relative to the total solids content in the composition is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass.

[0400] When the dispersion for forming the ultraviolet sensing layer contains a surfactant, the surfactant content, relative to the total solids content in the composition, is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.2 to 1% by mass.

[0401] There are no particular limitations on the manufacturing method of the dispersion for forming the ultraviolet sensing layer. For example, a method including the manufacturing method of the specific microcapsules described above can be cited. That is, a manufacturing method including the emulsification step and the encapsulation step described above can be cited. In addition, the dispersion for forming the ultraviolet sensing layer is preferably a composition in which any component for forming the ultraviolet sensing layer is further added to the microcapsule dispersion obtained by the manufacturing method including the emulsification step and the encapsulation step described above.

[0402] [Ultraviolet Sensing Kit]

[0403] Furthermore, the present invention also relates to an ultraviolet sensing kit comprising the aforementioned ultraviolet sensing component.

[0404] The ultraviolet sensing kit includes at least the ultraviolet sensing component described above.

[0405] There are no particular limitations on the specific structure of the ultraviolet sensing kit. Examples include a component that includes an ultraviolet sensing element, a component with a filter layer that selectively transmits light of a specific wavelength (preferably a filter that blocks light with a wavelength of 300 nm or more, more preferably a filter that blocks light with a wavelength of 230 nm or more), a light-blocking bag (ultraviolet cut-off bag), a judgment sample, a limit sample (calibration table), a focusing fixture such as a lens and a concave mirror, and other elements selected from the group consisting of a holding component for holding the ultraviolet sensing element.

[0406] In addition, the aforementioned holding member may have an opening for irradiating ultraviolet light onto the held ultraviolet sensing member, and the holding member and the judgment sample may be integrated.

[0407] Furthermore, specific microcapsules can be kneaded into a resin to form a molded body. Examples of resins that can be used as support sheets include resins.

[0408] Example

[0409] The present invention will now be described in further detail based on embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below. Furthermore, unless otherwise specified, "parts" and "%" are used as mass units.

[0410] [Fabrication of the ultraviolet sensing component]

[0411] [Example 1]

[0412] The following mixture 1 was added to 202 parts by mass of a 5% aqueous solution of polyvinyl alcohol, and then emulsified and dispersed at 20°C to obtain an emulsion with a volume average particle size of 1 μm. The resulting emulsion was then continuously stirred at 50°C for 8 hours. Afterwards, it was returned to room temperature and filtered to obtain an aqueous capsule dispersion.

[0413] <Composition of Mixture 1>

[0414] Colorant: 2.5 parts colorless crystal violet (trade name "LCV", manufactured by YAMADA CHEMICAL CO., LTD.)

[0415] Organohalogen compound: 1.25 parts of tribromomethylphenyl sulfone (BMPS, manufactured by SUMITOMO SEIKA CHEMICALS CO., LTD.)

[0416] Aromatic solvent 1: Trimethylbenzene phosphate (manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD.) 23 parts

[0417] Aromatic solvent 2: 7 parts of phenyl dimethyl ethane (trade name "Nisseki Hisol SAS296", manufactured by JX Nippon Oil & Energy Corporation).

[0418] Non-aromatic solvent: 50 parts of ethyl acetate (made by SHOWA DENKO KK)

[0419] Light stabilizer: 3 parts of 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone (BTHQ, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0420] Capsule wall material: 31 parts of polyisocyanate (trade name "TAKENATE D-110N", manufactured by Mitsui Chemicals, Inc., an adduct of xylene-1,3-diisocyanate and trimethylolpropane, 75% by mass ethyl acetate solution).

[0421] Mix 20 parts of the obtained capsule dispersion, 5 parts of a 6% by mass aqueous solution of polyvinyl alcohol (trade name "Denkasize EP-130", manufactured by Denka Company Limited), 0.04 parts of glyoxal (manufactured by Daito Chemical Co., Ltd.), and 0.09 parts of a 50% by mass aqueous solution of sodium dodecylbenzenesulfonate (manufactured by DKS Co., Ltd.) to prepare a dispersion for forming an ultraviolet sensing layer (coating solution for forming an ultraviolet sensing layer).

[0422] The obtained ultraviolet sensing layer forming coating liquid was coated with a solid component amount of 20 g / m. 2 A sheet-like ultraviolet sensing component, comprising a support and an ultraviolet sensing layer, was fabricated by coating a 75 μm thick white polyethylene terephthalate sheet (trade name "Crisper K1212", manufactured by Toyobo Co., Ltd.) with a coating method and drying it at 105 °C for 1 minute. The ultraviolet sensing layer was approximately 20 μm thick.

[0423] [Example 2]

[0424] Except that the mixture 1 is changed to the mixture 2 with the following composition, the ultraviolet sensing component is manufactured in the same way as in Example 1.

[0425] <Composition of Mixture 2>

[0426] Colorant A: 2.5 parts of 3,3-bis(2-methyl-1-octyl-3-indolyl)phthalide (manufactured by BASF).

[0427] Organohalogen compound: Tribromomethylphenyl sulfone (BMPS, SUMITOMO SEIKA CHEMICALS CO., LTD.) 1.25 parts

[0428] Aromatic solvent 1: Trimethylbenzene phosphate (manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD.) 23 parts

[0429] Aromatic solvent 2: 7 parts of phenyl dimethyl ethane (trade name "Nisseki Hisol SAS296", manufactured by JX Nippon Oil & Energy Corporation).

[0430] Non-aromatic solvent: 50 parts of ethyl acetate (made by SHOWA DENKO KK)

[0431] Light stabilizer: 3 parts of 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone (BTHQ, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0432] Polyisocyanate: (trade name "TAKENATE D-110N", Mitsui Chemicals, Inc. 31 parts)

[0433] [Examples 3-10]

[0434] Except for changing the ingredients and formulations as described in Table 1, the ultraviolet sensing components of Examples 3 to 10 were manufactured using the same method as in Example 1.

[0435] [Example 11]

[0436] Except for changing the ingredients and formulation as described in Table 1, the ultraviolet sensing component of Example 11 was manufactured in the same manner as in Example 2.

[0437] [Comparative Examples 1 and 2]

[0438] Except for changing the ingredients and formulations as described in Table 1, the ultraviolet sensing components of Comparative Examples 1 and 2 were manufactured using the same method as in Example 1.

[0439] Table 1 is shown below.

[0440] In addition, the components shown in Table 1 are as follows.

[0441] Trimethylbenzene phosphate (manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD.)

[0442] • Phenylenedimethyl ethane (trade name "Nisseki Hisol SAS296", manufactured by JX Nippon Oil & Energy Corporation)

[0443] • Isopropyl biphenyl (manufactured by KUREHA CORPORATION)

[0444] • α-Methylstyrene dimer (manufactured by Mitsui Chemicals, Inc.)

[0445] • Dicyclohexyl phthalate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[0446] ·BMPS: Tribromomethylphenyl sulfone (manufactured by SUMITOMO SEIKA CHEMICALS CO., LTD.)

[0447] • B-IMD: Profen dimer (2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, trade name "B-IMD", manufactured by KUROGANE KASEI Co., Ltd.)

[0448] • LCV: Colorless crystal violet (trade name "LCV", manufactured by YAMADA CHEMICAL CO., LTD.)

[0449] • Colorant A: 3,3-bis(2-methyl-1-octyl-3-indolyl)phthalide (manufactured by BASF)

[0450] • BTHQ: 2,5-Bis(1,1,3,3-Tetramethylbutyl)hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0451] Furthermore, in the "Photoactive Agents" column of Table 1, the values ​​in parentheses listed together with the ingredient names indicate the proportions (parts by mass).

[0452] Furthermore, the color-developing agents used in Examples 1, 3-10 and Comparative Examples 1, 2 correspond to color-developing agents that develop color through oxidation. The color-developing agents used in Examples 1, 3-10 and Comparative Examples 1, 2 are blue upon oxidation. On the other hand, the color-developing agents used in Examples 2 and 11 correspond to color-developing agents that develop color through the action of acid. The color-developing agents used in Examples 2 and 11 are red under the action of acid.

[0453] Furthermore, the column "mass content ratio of aromatic solvent 1 to aromatic solvent 2" in Table 1 indicates "aromatic solvent 1 / aromatic solvent 2".

[0454] [Table 1]

[0455]

[0456] [Measurement and Evaluation]

[0457] The image retention, retention stability, and sensitivity of the ultraviolet sensing components fabricated in each embodiment and comparative example were measured and evaluated using the following methods.

[0458] In addition, the color intensity of the ultraviolet sensing component was measured using a reflectance concentration meter (X-Rite 310, manufactured by X-Rite Corporation). As described above, the colorant used in Examples 1, 3-10 and Comparative Examples 1, 2 turned blue upon oxidation, while the colorant used in Examples 2 and 11 turned red upon contact with acid. When measuring the color intensity of the ultraviolet sensing component, the OD-M values ​​were used in Examples 2 and 11, and the OD-C values ​​were used in Examples 1, 3-10 and Comparative Examples 1, 2.

[0459] [Image preservation]

[0460] The ultraviolet sensing layer of the ultraviolet sensing component fabricated in each embodiment and comparative example was subjected to a cumulative illuminance of 10 mJ / cm² using a high-pressure mercury lamp. 2 The ultraviolet light was irradiated in this manner. Then, a reflectance density meter was used to measure the concentration (DA1) of the chromophore formed on the ultraviolet sensing layer.

[0461] Next, the ultraviolet sensing component irradiated with ultraviolet light was stored for one day at a temperature of 40°C and a humidity of 90% RH. After storage, the concentration (DA2) of the chromophore formed on the ultraviolet sensing layer was measured using a reflectance concentration meter.

[0462] Then, based on the concentration maintenance rate calculated by the following equation (1), an evaluation was conducted according to the following evaluation criteria. The results are shown in Table 1.

[0463] Equation (1): Concentration maintenance rate (%) = Concentration DA2 / Concentration DA1 × 100

[0464] (Evaluation Criteria)

[0465] "A": Concentration maintenance rate (%) is above 95%.

[0466] "B": Concentration maintenance rate (%) is above 90% and less than 95%.

[0467] "C": Concentration maintenance rate (%) less than 90%

[0468] (Maintain stability)

[0469] Using a reflectance concentration meter, the initial concentration (DA3) of the ultraviolet sensing layer of the ultraviolet sensing component (unused) fabricated in each embodiment and comparative example was determined.

[0470] Next, the concentration (DA4) of the ultraviolet sensing element (unused) produced in each embodiment and comparative example was measured using a reflectance concentration meter after being kept at a temperature of 140°C for 600 seconds.

[0471] Then, based on the value obtained by subtracting concentration DA3 from concentration DA4 (concentration change ΔD), the evaluation was carried out according to the following evaluation criteria. The results are shown in Table 1. Furthermore, a smaller ΔD value indicates that the color will not develop during long-term storage, indicating good storage stability.

[0472] <Evaluation Criteria>

[0473] “A”: ΔD is below 0.2

[0474] "B": ΔD is greater than 0.2 and less than 0.4.

[0475] “C”: ΔD exceeds 0.4

[0476] [Sensitivity]

[0477] The ultraviolet sensing layer of the ultraviolet sensing component fabricated in each embodiment and comparative example was subjected to a cumulative illuminance of 10 mJ / cm² using a high-pressure mercury lamp. 2 The ultraviolet light was irradiated in this manner. Then, using a reflectance concentrator, the concentration (DA5) of the chromophore formed on the ultraviolet sensing layer was measured, and sensitivity was evaluated based on the following criteria. A higher DA5 concentration indicates higher sensitivity. The results are shown in Table 1.

[0478] <Evaluation Criteria>

[0479] "A": 0.4 or more

[0480] "B": Less than 0.4

[0481] As can be seen from the results in Table 1, the ultraviolet sensing component of the present invention exhibits excellent preservation stability and image preservation performance. Furthermore, the ultraviolet sensing component of the present invention also demonstrates excellent sensitivity.

[0482] Furthermore, based on a comparison of Example L and Example 2, it was confirmed that when the colorant is a colorant that develops color through oxidation, the image preservation is superior.

[0483] Based on the comparison of Examples 1, 3 to 6, it was confirmed that when the mass content ratio of heteroatom-containing aromatic solvent (aromatic solvent 1) to heteroatom-free aromatic solvent (aromatic solvent 2) in the microcapsules (heteroatom-containing aromatic solvent / heteroatom-free aromatic solvent) is 35 / 65 to 85 / 15, the preservation stability, image preservation and sensitivity are better.

[0484] Symbol Explanation

[0485] 10, 20, 30, 40, 50, 60 - Ultraviolet sensing component, 12 - Support body, 14 - Ultraviolet sensing layer, 22 - Filter layer, 24 - Reflective layer, 26 - Gloss layer.

Claims

1. An ultraviolet sensing component comprising an ultraviolet sensing layer including microcapsules containing a photosynthetic agent, a colorant, and an aromatic solvent. The aromatic solvents include aromatic solvents containing heteroatoms and aromatic solvents without heteroatoms. The heteroatom-containing aromatic solvent is selected from compounds represented by general formulas (1A) to (1C), and the heteroatom-free aromatic solvent is selected from compounds represented by general formulas (1D) to (1E). In general formula (1A), L 11 This indicates that the oxysulfonyl group is * 1 -SO2-O-* 2 Or sulfonyloxy, i.e. * 1 -O-SO2-* 2 , * 1 Indicates the bonding position with the phenyl group explicitly stated in general formula (1A), * 2 Indicates with R 12 The bonding position, R 11 Indicates a non-aromatic substituent. n 11 Represents integers from 0 to 5, where, When n 11 When representing integers greater than 2, there exist multiple R values. 11 They are the same or different from each other. R 12 This indicates a monovalent aliphatic hydrocarbon group. In general formula (1B), R 21 Indicates a non-aromatic substituent. n 21 Represents integers from 0 to 4, where when n 21 When representing integers greater than 2, there exist multiple R values. 21 They are the same or different from each other. R 22 and R 23 Each can be independently represented by a monovalent aliphatic hydrocarbon group. In the above general formula (1C), R 31 ~R 33 Each independently represents an alkyl group optionally having substituents or an aryl group optionally having substituents, wherein R 31 ~R 33 At least one of them represents an aryl group having substituents. In general formula (1D), L 41 Indicates a single bond or a divalent aliphatic hydrocarbon group. R 41 and R 42 Each can be used independently to represent a non-aromatic substituent that does not contain a heteroatom. n 41 and n 42 Each of the integers from 0 to 5 can be represented independently, where when n 41 and n 42 When representing integers greater than 2, there exist multiple R values. 41 Each other and multiple R 42 They are the same or different from each other. In general formula (1E), L 51 Indicates a single key. R 51 This indicates a non-aromatic substituent that does not contain heteroatoms. n 51 Represents integers from 0 to 5, where when n 51 When representing integers greater than 2, there exist multiple R values. 51 They are the same or different from each other. R 52 It represents a monovalent aliphatic hydrocarbon group.

2. The ultraviolet sensing component according to claim 1, wherein, The photoactive agent contains a compound represented by the following general formula (6). R 3 -L 1 -CX 3 X 4 X 5 (6) In the formula, 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.

3. The ultraviolet sensing component according to claim 1 or 2, wherein, The mass ratio of the aromatic solvent containing heteroatoms to the aromatic solvent without heteroatoms is 35 / 65 to 85 / 15.

4. The ultraviolet sensing component according to claim 1 or 2, wherein, The aromatic solvent contains one or more aromatic solvents with a boiling point of 100°C or higher.

5. The ultraviolet sensing component according to claim 1 or 2, wherein, The heteroatom-containing aromatic solvent comprises aromatic phosphate esters.

6. The ultraviolet sensing component according to claim 1 or 2, wherein, The photoactive agent is a photooxidant, and the colorant is an oxidative colorant.

7. The ultraviolet sensing component according to claim 1 or 2, wherein, The photoactive agent is a photoacid-generating agent, and the color-developing agent is a color-developing agent that develops color through the action of acid.

8. The ultraviolet sensing component according to claim 1 or 2, wherein, The capsule wall of the microcapsule contains one or more resins selected from the group consisting of polyurea, polyurethane urea, and polyurethane.

9. A microcapsule containing a photosynthetic agent, a colorant, and an aromatic solvent. The aromatic solvents include aromatic solvents containing heteroatoms and aromatic solvents without heteroatoms. The heteroatom-containing aromatic solvent is selected from compounds represented by general formulas (1A) to (1C), and the heteroatom-free aromatic solvent is selected from compounds represented by general formulas (1D) to (1E). In general formula (1A), L 11 This indicates that the oxysulfonyl group is * 1 -SO2-O-* 2 Or sulfonyloxy, i.e. * 1 -O-SO2-* 2 , * 1 Indicates the bonding position with the phenyl group explicitly stated in general formula (1A), * 2 Indicates with R 12 The bonding position, R 11 Indicates a non-aromatic substituent. n 11 Represents integers from 0 to 5, where, When n 11 When representing integers greater than 2, there exist multiple R values. 11 They are the same or different from each other. R 12 This indicates a monovalent aliphatic hydrocarbon group. In general formula (1B), R 21 Indicates a non-aromatic substituent. n 21 Represents integers from 0 to 4, where when n 21 When representing integers greater than 2, there exist multiple R values. 21 They are the same or different from each other. R 22 and R 23 Each can be independently represented by a monovalent aliphatic hydrocarbon group. In the above general formula (1C), R 31 ~R 33 Each independently represents an alkyl group optionally having substituents or an aryl group optionally having substituents, wherein R 31 ~R 33 At least one of them represents an aryl group having substituents. In general formula (1D), L 41 Indicates a single bond or a divalent aliphatic hydrocarbon group. R 41 and R 42 Each can be used independently to represent a non-aromatic substituent that does not contain a heteroatom. n 41 and n 42 Each of the integers from 0 to 5 can be represented independently, where when n 41 and n 42 When representing integers greater than 2, there exist multiple R values. 41 Each other and multiple R 42 They are the same or different from each other. In general formula (1E), L 51 Indicates a single key. R 51 This indicates a non-aromatic substituent that does not contain heteroatoms. n 51 Represents integers from 0 to 5, where when n 51 When representing integers greater than 2, there exist multiple R values. 51 They are the same or different from each other. R 52 It represents a monovalent aliphatic hydrocarbon group.

10. The microcapsule according to claim 9, wherein, The photoactive agent contains a compound represented by the following general formula (6). R 3 -L 1 -CX 3 X 4 X 5 (6) In the formula, 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.

11. The microcapsule according to claim 9 or 10, wherein, The mass ratio of the aromatic solvent containing heteroatoms to the aromatic solvent without heteroatoms is 35 / 65 to 85 / 15.

12. The microcapsule according to claim 9 or 10, wherein, The aromatic solvent contains one or more aromatic solvents with a boiling point of 100°C or higher.

13. The microcapsule according to claim 9 or 10, wherein, The heteroatom-containing aromatic solvent comprises aromatic phosphate esters.

14. The microcapsule according to claim 9 or 10, wherein, The photoactive agent is a photooxidant, and the colorant is an oxidative colorant.

15. The microcapsule according to claim 9 or 10, wherein, The photoactive agent is a photoacid-generating agent, and the color-developing agent is a color-developing agent that develops color through the action of acid.

16. The microcapsule according to claim 9 or 10, wherein, The capsule wall of the microcapsule contains one or more resins selected from the group consisting of polyurea, polyurethane urea, and polyurethane.

17. A method for manufacturing microcapsules, comprising the method for manufacturing microcapsules according to any one of claims 9 to 16, including: The process of preparing an emulsion by mixing the colorant, the photoactive agent, the aromatic solvent and the emulsifier in water; The process involves forming resin walls and encapsulating oil droplets containing the colorant, the photoactive agent, and the aromatic solvent in the emulsion obtained in the process to form the microcapsules.

18. A dispersion for forming an ultraviolet sensing layer, comprising the microcapsules according to any one of claims 9 to 16.

19. An ultraviolet sensing kit comprising an ultraviolet sensing component according to any one of claims 1 to 8.

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