Photochromic composition and applicator containing the same

Abstract

To provide a water-discoloring composition which develops a color by contact with water, has a high color density in color development, does not form a deposit even in a room temperature environment, has a low viscosity, and is practically easy to handle, and to provide an applicator housing the same.SOLUTION: The water-discoloring composition contains at least an electron-donating color-developing organic compound, an electron-accepting compound, and a specific amide compound and / or a specific imidazolidinone compound, and the applicator contains the composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a water-colorable composition that changes color upon contact with water, and an applicator containing the same. [Background technology]

[0002] Water-discoloring materials that change color when wetted with water have been widely known. For example, Patent Document 1 discloses a technology for a water-discoloring composition that changes color when it comes into contact with water, which comprises an electron-donating color-forming organic compound, an electron-accepting compound, and a color-adjusting agent, and uses polyethylene glycol and tripropylene glycol as the color-adjusting agents.

[0003] However, in the water-discoloring composition of Patent Document 1, the solubility of polyethylene glycol and tripropylene glycol in the electron-donating color-forming organic compound and the electron-accepting compound is insufficient, and the amount of addition is limited, so the color density upon color development is insufficient. Furthermore, although the amounts of the electron-donating color-forming organic compound and the electron-accepting compound can be increased by mixing them under heating in order to increase the color density during color development, a drop in the temperature of the composition can result in the formation of precipitates. As a result, under normal use conditions (particularly at room temperature), the amounts are not sufficient to obtain a sufficient color density, and the color density during color development is insufficient. Furthermore, due to its high viscosity, it is difficult to handle in practice and its applicability is insufficient. For example, when an applicator or the like has a storage section that stores the composition inside and is applied by being discharged from an application section attached to the front end, the composition is not discharged stably and, further, precipitates may form at the discharge section, which limits the method and form of use. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2021 / 176574 Brochure Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention solves the problems of the past and provides a water-discoloring composition that changes color upon contact with water, has a high color density when colored, does not produce precipitates even in a room temperature environment, and has low viscosity, making it easy to handle in practical use, as well as an applicator containing the same. [Means for solving the problem]

[0006] [1] A water-discoloring composition comprising at least an electron-donating color-forming organic compound, an electron-accepting compound, and an amide compound represented by general formula (1) and / or an imidazolidinone compound represented by general formula (2). [ka] [In formula (1), R1 and R2 each independently represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R3 represents an alkoxyalkyl group, an alkyl group, an alkenyl group, or a hydrogen atom.] [ka] [In formula (2), R4 and R5 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms.]

[0007] [2] The water-discoloring composition according to [1], wherein in the general formula (1), R1 and R2 are both organic groups having 1 to 30 carbon atoms.

[0008] [3] The water-discoloring composition according to [1] or [2], wherein in the general formula (1), R1 and R2 are both methyl groups.

[0009] [4] An applicator containing the water-discoloring composition according to any one of [1] to [3]. [Effects of the Invention]

[0010] According to the present invention, there are provided a water-discoloring composition that develops color upon contact with water, has a high color density when developed, does not produce precipitates even in a room temperature environment, and has a low viscosity, making it easy to handle in practical use, and an applicator containing the same. DETAILED DESCRIPTION OF THE INVENTION

[0011] Specific embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.

[0012] In this specification, "moisture" refers to "water" or "liquid containing water," and does not refer to "humidity," which is moisture in the air, or "humidity," which represents its proportion.

[0013] The water-discoloring composition of the present invention is characterized by containing at least an electron-donating color-forming organic compound, an electron-accepting compound, and an amide compound represented by general formula (1) and / or an imidazolidinone compound represented by general formula (2).

[0014] <Electron-donating color-forming organic compound> The electron-donating organic color-forming compound is a component that determines color, and is a compound that donates electrons to the electron-accepting compound that functions as a color developer, thereby developing color.

[0015] Specific examples of the electron-donating color-forming organic compound include phthalide compounds, fluoran compounds, styrinoquinoline compounds, diazarhodamine lactone compounds, pyridine compounds, quinazoline compounds, and bisquinazoline compounds. Examples of the phthalide compound include a diphenylmethane phthalide compound, a phenylindolyl phthalide compound, an indolyl phthalide compound, a diphenylmethane azaphthalide compound, a phenylindolyl azaphthalide compound, and derivatives thereof. Among these, the phenylindolyl azaphthalide compound and derivatives thereof are preferred. Examples of the fluoran compound include aminofluoran compounds, alkoxyfluoran compounds, and derivatives thereof.

[0016] Examples of compounds that can be used as the electron-donating color-forming organic compound are shown below. 3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide, 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(2-n-hexyloxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-[2-ethoxy-4-(N-ethylanilino)phenyl]-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(2-acetamido-4-diethylaminophenyl)-3-(1-propyl-2-methylindol-3-yl)-4-azaphthalide, 3,6-bis(diphenylamino)fluoran, 3,6-bis(N-phenyl-Np-tolylamino)fluoran, 3,6-dimethoxyfluoran, 3,6-di-n-butoxyfluorane, 2-methyl-6-(N-ethyl-Np-tolylamino)fluoran, 3-chloro-6-cyclohexylaminofluoran, 2-methyl-6-cyclohexylaminofluoran, 2-chloroamino-6-di-n-butylaminofluoran, 2-(2-chloroanilino)-6-di-n-butylaminofluoran, 2-(3-trifluoromethylanilino)-6-diethylaminofluoran, 2-(3-trifluoromethylanilino)-6-di-n-pentylaminofluoran, 2-dibenzylamino-6-diethylaminofluoran, 2-N-methylanilino-6-(N-ethyl-Np-tolylamino)fluoran, 1,3-dimethyl-6-diethylaminofluoran, 2-chloro-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methoxy-6-diethylaminofluoran, 2-anilino-3-methyl-6-di-n-butylaminofluoran, 2-anilino-3-methoxy-6-di-n-butylaminofluoran, 2-xylidino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-(N-ethyl-Np-tolylamino)fluoran, 6-diethylamino-1,2-benzofluoran, 6-(N-ethyl-N-isobutylamino)-1,2-benzofluoran, 6-(N-ethyl-N-isopentylamino)-1,2-benzofluoran, 2-(3-methoxy-4-dodecoxystyryl)quinoline, 2-diethylamino-8-diethylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 2-di-n-butylamino-8-di-n-butylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 2-di-n-butylamino-8-diethylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 2-di-n-butylamino-8-(N-ethyl-N-isoamylamino)-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 2-di-n-butylamino-8-di-n-pentylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 4,5,6,7-tetrachloro-3-(4-dimethylamino-2-methoxyphenyl)-3-(1-n-butyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-tetrachloro-3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-tetrachloro-3-(4-diethylamino-2-ethoxyphenyl)-3-(1-n-pentyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-tetrachloro-3-(4-diethylamino-2-methylphenyl)-3-(1-ethyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone, 3',6'-bis[phenyl(2-methylphenyl)amino]spiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one, 3',6'-bis[phenyl(3-methylphenyl)amino]spiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one, 3',6'-bis[phenyl(3-ethylphenyl)amino]spiro[isobenzofuran-1(3H),9'-[9H]xanthen]-3-one, 2,6-bis(2′-ethyloxyphenyl)-4-(4′-dimethylaminophenyl)pyridine, 2,6-bis(2′,4′-diethyloxyphenyl)-4-(4′-dimethylaminophenyl)pyridine, 2,6-bis(2,4-diethyloxyphenyl)-4-[4-bis(4-methyloxyphenyl)aminophenyl]pyridine, 2-(4′-dimethylaminophenyl)-4-methoxyquinazoline, 4,4'-Ethylenedioxy-bis[2-(4-diethylaminophenyl)quinazoline]

[0017] In addition, fluorans may be compounds having a substituent on the phenyl group forming the xanthene ring, or may be compounds that have a substituent on the phenyl group forming the xanthene ring and also have a substituent on the phenyl group forming the lactone ring (for example, an alkyl group such as a methyl group, or a halogen atom such as a chlorine atom), and that exhibit a blue or black color.

[0018] The content of the electron-donating organic color former is preferably 0.1% by mass or more and 25% by mass or less, and more preferably 0.5% by mass or more and 15% by mass or less, based on the total amount of the water-discoloring composition.

[0019] <Electron-accepting compounds> The electron-accepting compound is a compound that accepts electrons from the electron-donating organic color former and functions as a developer for the electron-donating organic color former. As the electron-accepting compound, a conventionally known compound can be used, and examples thereof include compounds selected from a group of compounds having an active proton, a group of pseudo-acidic compounds (a group of compounds that are not acids but act as an acid in the water-chromic composition to cause the electron-donating color-forming organic compound to develop color), and a group of compounds having an electron vacancy.

[0020] Examples of compounds having an active proton include compounds having a phenolic hydroxy group and derivatives thereof, carboxylic acids and derivatives thereof, acidic phosphate esters and derivatives thereof, azole compounds and derivatives thereof, 1,2,3-triazole and derivatives thereof, cyclic carbosulfimides, halohydrins having 2 to 5 carbon atoms, sulfonic acids and derivatives thereof, and inorganic acids. Preferred examples of the carboxylic acids and derivatives thereof include aromatic carboxylic acids and derivatives thereof, and aliphatic carboxylic acids having 2 to 5 carbon atoms and derivatives thereof. Examples of the pseudo-acidic compounds include metal salts of compounds having a phenolic hydroxy group, metal salts of carboxylic acids, metal salts of acidic phosphate esters, metal salts of sulfonic acids, aromatic carboxylic acid anhydrides, aliphatic carboxylic acid anhydrides, mixed anhydrides of aromatic carboxylic acids and sulfonic acids, cycloolefin dicarboxylic acid anhydrides, urea and its derivatives, thiourea and its derivatives, guanidine and its derivatives, and halogenated alcohols. Compounds having electron vacancies include borates, borate esters, and inorganic salts.

[0021] Examples of compounds that can be used as the electron-accepting compound are shown below. Phenol, o-cresol, 4-np-nonylphenol, 4-n-octylphenol, 4-n-dodecylphenol, 4-n-stearylphenol, 4-chlorophenol, 4-bromophenol, 2-phenylphenol, n-butyl 4-hydroxybenzoate, n-octyl 4-hydroxybenzoate, resorcinol, 4-tert-butylcatechol, 2,4-dihydroxy-4′-tert-butylbenzophenone, dodecyl gallate, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)n-butane, 1,1-bis(4-hydroxyphenyl)n-pentane, 1,1-bis(4-hydroxyphenyl)n-hexane, 1,1-bis(4-hydroxyphenyl)n-heptane, 1,1-bis(4-hydroxyphenyl)n-octane, 1,1-bis(4-hydroxyphenyl)n-nonane, 1,1-bis(4-hydroxyphenyl)n-decane, 1,1-bis(4-hydroxyphenyl)n-dodecane, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 1,1-bis(4-hydroxyphenyl)n-methylpropane 1,1-bis(4-hydroxyphenyl)-3-methylbutane, 1,1-bis(4-hydroxyphenyl)-3-methylpentane, 1,1-bis(4-hydroxyphenyl)-2,3-dimethylpentane, 1,1-bis(4-hydroxyphenyl)-2-ethylbutane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)-3,7-dimethyloctane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1-phenyl-1,1-bi bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)n-butane, 2,2-bis(4-hydroxyphenyl)n-pentane, 2,2-bis(4-hydroxyphenyl)n-hexane, 2,2-bis(4-hydroxyphenyl)n-heptane, 2,2-bis(4-hydroxyphenyl)n-octane, 2,2-bis(4-hydroxyphenyl)n-nonane, 2,2-bis(4-hydroxyphenyl)n-decane, 2,2-bis(4-hydroxyphenyl)n-dodecane, 2,2-Bis(4-hydroxyphenyl)ethyl propionate, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl)-4-methylhexane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)butane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, bis(2-hydroxyphenyl)methane, 4,4′-dihydroxydiphenyl sulfone, 4-isopropoxy-4′-hydroxydiphenyl sulfone, bis(4-hydroxyphenyl)sulfide, 1,1,1-tris(4-hydroxyphenyl)ethane, 4,4′-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl )phenyl}ethylidene]bisphenol, 4,4'-[4-(4-hydroxyphenyl)-sec-butylidene]bis(2-methylphenol), N-(2-fluorophenyl)-N'-phenylurea, N-(2-chlorophenyl)-N'-phenylurea, N-(2-methoxyphenyl)-N'-phenylurea, N-[3-[[(4-tert-butylphenyl)sulfonyl]oxy]phenyl]-N'-phenylurea, N-[3-[[(4-methylphenyl)sulfonyl]oxy]phenyl]-N'-phenylurea, N-[3-[[(4-methyloxyphenyl)sulfonyl]oxy]phenyl]-N'-phenylurea, N-[3-[[(4-chlorophenyl)sulfonyl]oxy]phenyl]-N'-phenylurea, 4-methyl-N-[[[3-[[(4-methylphenyl)sulfonyl]oxy]phenyl]amino]carbonyl]benzenesulfonamide,

[0022] The content of the electron-accepting compound is preferably from 0.01% by mass to 30% by mass, and more preferably from 1% by mass to 25% by mass, based on the total amount of the water-discoloring composition.

[0023] <Amide compounds and imidazolidinone compounds>

[0024] The water-discoloring composition of the present invention is characterized by containing at least one of an amide compound represented by general formula (1) and an imidazolidinone compound represented by general formula (2).

[0025] [ka]

[0026] In general formula (1), R1 and R2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R3 is an alkoxyalkyl group, an alkyl group, an alkenyl group, or a hydrogen atom.

[0027] [ka]

[0028] In the general formula (2), R4 and R5 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms.

[0029] The amide compound represented by general formula (1) (hereinafter sometimes simply referred to as "amide compound") and the imidazolidinone compound represented by general formula (2) (hereinafter sometimes simply referred to as "imidazolidinone compound") are used as a reaction medium (so-called color adjuster) that causes an electron-donating reaction between an electron-donating organic color former and an electron-accepting compound, and as a solvent that dissolves the electron-donating organic color former and the electron-accepting compound.

[0030] Since the amide compound of general formula (1) or the imidazolidinone compound of general formula (2) has an amide structure, the electron-donating color-forming organic compound and the electron-accepting compound exhibit high solubility in the amide compound or the imidazolidinone compound. Therefore, even in a room temperature environment, the electron-donating color-forming organic compound and the electron-accepting compound in the water-coloring composition do not precipitate. Furthermore, the amide compound of general formula (1) or the imidazolidinone compound of general formula (2) inhibits the transfer of electrons between the electron-donating color-forming organic compound and the electron-accepting compound, preventing the color reaction and resulting in a non-coloring state. When the water-coloring composition is stored in an applicator, glass bottle, or the like, it will not naturally color due to external factors such as humidity, and the non-coloring state will be well maintained.

[0031] Furthermore, since the amide compound of general formula (1) or the imidazolidinone compound of general formula (2) has an amide structure, the amide compound or the imidazolidinone compound exhibits high solubility in water. Therefore, upon contact with moisture, the amide compound or imidazolidinone compound migrates to the moisture, and electrons are donated and accepted between the electron-donating color-forming organic compound and the electron-accepting compound, resulting in a color reaction that produces a good color-developing effect. Furthermore, since the water-discoloring composition has low viscosity, it has excellent moisture-transfer properties to the amide compound of general formula (1) or the imidazolidinone compound of general formula (2), making it easy for the composition to immediately develop color upon contact with moisture.

[0032] R1 and R2 in general formula (1) are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and it is preferable that at least one of them is an organic group, and in consideration of high color density when color is developed, it is more preferable that both are organic groups. When R1 and R2 in general formula (1) are both organic groups, it becomes easy to cause the water-discoloring composition to develop a color with high color density upon contact with water without reducing the reactivity and interaction between the electron-donating color-forming organic compound and the electron-accepting compound.

[0033] These organic groups include hydrocarbon groups and derivatives thereof. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The hydrocarbon group may be linear or branched, and may be saturated or unsaturated. The derivative of a hydrocarbon group means a group having at least one nitrogen atom, oxygen atom, sulfur atom, sulfonyl group, carbonyl group, etc. at the end of the hydrocarbon group or in the molecule, and examples thereof include a dimethylaminopropyl group, a hydroxyethyl group, and a dimethyloxobutyl group. Furthermore, R1 and R2 may together form a heterocycle, for example, a morpholine skeleton and its derivatives. Of these organic groups, in consideration of the long-term stability of the water-discoloring composition and color development at high color density, aliphatic hydrocarbon groups are preferred, and it is more preferred that the aliphatic hydrocarbon group is an alkyl group.

[0034] The alkyl groups of R1 and R2 may be linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. From the viewpoint of amphiphilicity between water and the electron-donating organic color-forming compound or the electron-accepting compound, the alkyl group preferably has 1 to 5 carbon atoms, more preferably has 1 to 3 carbon atoms, is further preferably a methyl group or an ethyl group, and is particularly preferably a methyl group.

[0035] R3 in the general formula (1) is selected from an alkoxyalkyl group, an alkyl group, an alkenyl group, or a hydrogen atom. The alkoxyalkyl group, alkyl group, and alkenyl group are not particularly limited in the number of carbon atoms and may be either linear or branched, but in consideration of high solubility in water, the alkoxyalkyl group preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 5 carbon atoms. The alkyl group preferably has 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms. The alkenyl group preferably has 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms, and even more preferably is a vinyl group.

[0036] The amide compound may be appropriately synthesized or may be a commercially available product. Specific examples include alkoxyalkylamides, acrylamides, alkylamides, alkenylamides, and formamides. These amide compounds may be used singly or in combination of two or more.

[0037] Among the above amide compounds, a dimethylamide compound in which R1 and R2 in general formula (1) are both methyl groups is preferred, as it develops color immediately upon contact with moisture and has excellent color development properties with high color density. Specific examples of the dimethylamide compound include 3-methoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, 3-n-propoxy-N,N-dimethylpropionamide, 3-iso-propoxy-N,N-dimethylpropionamide, 3-tert-butoxy-N,N-dimethylpropionamide, and N,N-dimethylacrylamide.

[0038] R4 and R5 in general formula (2) are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms, and it is preferable that at least one of them is an organic group, and in consideration of high color density when color is developed, it is more preferable that both are organic groups. When R4 and R5 in general formula (2) are both organic groups, it becomes easy to cause the water-discoloring composition to develop a color with high color density upon contact with water without reducing the reactivity and interaction between the electron-donating color-forming organic compound and the electron-accepting compound.

[0039] Examples of the imidazolidinone compound include 2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, 1,3-dibutyl-2-imidazolidinone, and derivatives thereof, with 1,3-dimethyl-2-imidazolidinone being preferred since it provides higher color density during color development.

[0040] <Other additives> In addition to the three components, alcohols and glycols may be added to impart drying properties to the water-discoloring composition applied to the surface. In addition, the composition may further contain an ultraviolet absorber, an antioxidant, and the like.

[0041] <Applicator> As a means for applying the water-chromatic composition of the present invention, a sponge, puff, paintbrush, paintbrush, cotton swab, etc. that does not contain the water-chromatic composition inside can be used, but an applicator that contains the water-chromatic composition inside can also be used because it has low viscosity and does not produce precipitates.

[0042] The applicator of the present invention is characterized by containing the water-discoloring composition having the above-described structure. The applicator is not particularly limited as long as the water-discoloring composition is stored inside the applicator (hereinafter sometimes referred to as the "storage section") and can be applied to the target area such as paper or cloth from the application section provided at the front end.The water-discoloring composition may be stored directly in the storage section, or may be impregnated into a padding or storage body provided in the storage section. For example, the container may be made of paper or plastic, and the application part may be made of a brush, paint brush, sponge, felt, fiber bundle, roller, comb, or the like. Specific examples include a brush-equipped container type, a paintbrush-equipped container type, a scraper-equipped container type, a roller-equipped container type, a sponge-head bottle type, a tube type, a stamp type, a marking pen type, and a ballpoint pen type. When using a cotton-filled applicator that utilizes capillary force, if a conventional water-discoloring composition with high viscosity is used, it may not be ejected stably from the application part, and precipitates may form in the application part and storage part. However, when the water-discoloring composition of the present invention is used, no precipitates are formed and high fluidity can be maintained in the storage part, making it possible to eject the composition stably. [Example]

[0043] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Table 1 shows the compositions of the water-discoloring compositions of Examples and Comparative Examples. The composition values ​​in the table are in parts by mass.

[0044] [Table 1]

[0045] The contents of the ingredients in the table are explained according to the note numbers. (1) Crystal violet lactone (2) 2-anilino-3-methyl-6-(N-ethyl-Np-tolylamino)fluoran (3) 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane (4) 1,1,1-tris(4-hydroxyphenyl)ethane (5) 4-Methyl-N-[[[3-[[(4-methylphenyl)sulfonyl]oxy]phenyl]amino]carbonyl]benzenesulfonamide (6) 3-Methoxy-N,N-dimethylpropionamide (7) N,N-Dimethylacrylamide (8) N,N-Dimethylacetamide (9) N,N-Dimethylformamide (10) N,N-Diethylacrylamide (11) 1,3-Dimethyl-2-imidazolidinone

[0046] [Preparation of Water-Discoloring Composition] The raw materials were mixed in the amounts given in the examples and comparative examples, and the mixture was stirred and dissolved at 25° C. for 30 minutes to obtain a water-discoloring composition.

[0047] The water-discoloring compositions prepared in the Examples and Comparative Examples were subjected to the following tests and evaluations. The results obtained are shown in Table 1. <Dissolution stability test> The prepared water-discoloring composition was placed in a glass bottle and allowed to stand at 25°C for one day, after which the presence or absence of precipitates was visually confirmed. The results obtained are shown in Table 1. ○: No precipitate was observed. ×: Precipitation was observed.

[0048] <Evaluation of color change> 0.5 g of each of the water-discoloring compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 3 was uniformly applied to filter paper (manufactured by Toyo Roshi Kaisha, Ltd., product name: Qualitative Filter Paper No. 2) to obtain samples for optical density measurement. Each optical density measurement sample in the colored state was measured at three points for yellow, magenta, cyan, and black using a fluorescent spectrodensitometer (product name: FD-7 model, manufactured by Konica Minolta, Inc.), and the average values ​​for each were calculated. The sum of the average values ​​for each of the four colors was used to evaluate the color density, with 5.0 or more being rated as ◎, 4.0 or more but less than 5.0 being ◯, and less than 4.0 being ×. The samples for optical density measurement obtained from Examples 1 to 10 and Comparative Examples 1 to 3, which were colorless when applied, were immersed in a beaker filled with tap water to develop color.

[0049] [Preparation of applicator] The water-discoloring compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were impregnated into an occlusion body made of polyester sliver covered with a synthetic resin film, and housed in a barrel made of polypropylene resin. A resin-processed polyester fiber pen body (bullet-shaped) was attached to the tip of the barrel in a connected state via a resin holder, and a cap was attached to produce an applicator.

[0050] The following tests and evaluations were carried out using each of the prepared applicators. The results obtained are shown in Table 2. [Evaluation using an applicator] Using the prepared applicator, three circles were applied consecutively to a piece of report paper (writing paper A conforming to the old JIS P3201), and each piece of coated report paper was immersed in a plastic basin filled with tap water to allow the color to develop. The state of the colored circles was then visually inspected to evaluate the applicability. <Coating property evaluation> ○: The product was discharged smoothly from the application area, and all three circles were visible when the color developed. ×: The viscosity was high, the product was not discharged from the application site, and no circle was observed.

[0051] [Table 2]

Claims

1. A water-color-changing composition comprising at least an electron-donating chromogenic organic compound, an electron-accepting compound, and an amide compound represented by general formula (1) and / or an imidazolidinone compound represented by general formula (2). 【Chemistry 1】 [In general formula (1), R1 and R2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R3 is one of an alkoxyalkyl group, an alkyl group, an alkenyl group, or a hydrogen atom.] 【Chemistry 2】 [In general formula (2), R4 and R5 are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms.]

2. The water-color-changing composition according to claim 1, wherein in the general formula (1), both R1 and R2 are organic groups having 1 to 30 carbon atoms.

3. The water-color-changing composition according to claim 1, wherein in the general formula (1) above, both R1 and R2 are methyl groups.

4. An applicator containing the water-color-changing composition described in claims 1 to 3.

Images