JP2018103537A - Discoloration aromatic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a discoloration aromatic material which can confirm a time limit of aroma by color change, can clearly discriminate an expiration date by visual inspection, and is rich in practicability.SOLUTION: A discoloration aromatic material 1 has a porous layer 3 to which a low-refractive-index pigment such as silicic acid and hydrophobic silica produced by a wet method is bound to a binder resin in a dispersed state, and that is opaque in a non-water absorption state and turns transparent in a water-absorbed state, on a support 2, and an aromatic liquid made from perfume, water, an organic solvent, and has a medium selected from water and a water-soluble organic solvent contained in the porous layer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a color-changing fragrance material. Specifically, the present invention relates to a color-changing fragrance material that can visually determine the fragrance expiration date.

Conventionally, as means for discriminating the expiration date of the fragrance material, it has been disclosed that the fragrance is discriminated by contraction (see, for example, Patent Document 1).
However, since the fragrance gradually contracts, the expiration date for use cannot be clearly recognized.
There is also disclosed an impregnated body for an aromatic liquid in which a color-changing substance that changes color by contact with an alcohol-based aromatic liquid and returns to the original color by volatilization of the alcohol-based aromatic liquid is adhered to the impregnation part.
Although it is disclosed that the impregnated body for an aromatic liquid returns to its original color when the alcohol volatilizes, it is possible to prevent running out of the fragrance, but only a specific medium can be used and the color change of the impregnated discoloration substance The practicality was not satisfied.

JP 2002-35100 A Microfilm of actual application No.59-90187 (No. 61-8050)

  The present invention is intended to provide a color-changing fragrance material that can clearly distinguish the fragrance expiration date visually.

The present invention comprises, on a support, a porous layer in which a low refractive index pigment is fixed in a binder resin in a dispersed state, is opaque in a non-absorbing state, and is transparent in the absorbing state. A discolorable fragrance material comprising a fragrance liquid composed of a fragrance and a medium in the quality layer is a requirement.
Furthermore, the medium is an organic solvent, the low refractive index pigment is hydrophobic silica, the porous layer contains an electron donating color-forming organic compound, the porous layer It is necessary to contain an electron-accepting compound therein, to provide a non-color-changing colored layer between the support and the porous layer, and to provide an adhesive layer as the lowermost layer.

  According to the present invention, since the expiration date of the fragrance can be confirmed by a color change, it is possible to provide a color-changing fragrance material rich in practicality that can clearly determine the expiration date by visual observation.

It is a longitudinal cross-sectional view of one Example of the color-change fragrance | flavor of this invention. It is a longitudinal cross-sectional view of the other Example of the color-change fragrance | flavor of this invention. It is a longitudinal cross-sectional view of the other Example of the color-change fragrance | flavor of this invention.

  The present invention comprises, on a support, a porous layer in which a low refractive index pigment is fixed in a binder resin in a dispersed state, is opaque in a non-absorbing state, and is transparent in the absorbing state. A discolorable fragrance material comprising a fragrance liquid comprising a fragrance and a medium in a quality layer.

The support is not particularly limited, and for example, paper, synthetic paper, woven fabric, knitted fabric, braided fabric, non-woven fabric, natural or synthetic leather, plastic, glass, ceramics, metal, wood, stone, etc. are used. Fabric, leather, synthetic paper, and plastic are preferably used. Further, the shape may be a planar shape or a three-dimensional shape.
In addition, the said support body may be what the support body itself was colored, and what provided the non-discoloring colored layer on the support body.
Examples of the colorant for coloring the support or the colorant contained in the non-color-changing colored layer include general dyes, fluorescent dyes, and color pigments. Among these, as color pigments, general pigments, fluorescent pigments, In addition to metal powder, a transparent metallic luster pigment (pearl pigment) in which a core material such as mica, alumina, glass or the like is coated with titanium oxide can be exemplified.

The porous layer is a layer in which a low refractive index pigment is fixed in a dispersed state together with a binder resin, and is a layer having different transparency in a dry state and a liquid absorption state.
The low refractive index pigment has a refractive index in the range of 1.4 to 1.8 and exhibits good transparency when water is absorbed.
Examples of the low refractive index pigment include silicic acid and its salts, barite powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, talc, alumina, alumina white, magnesium carbonate, etc., and silicic acid and its salts are preferred. Used.
Examples of the silicic acid salts include aluminum silicate, aluminum potassium silicate, sodium aluminum silicate, aluminum calcium silicate, potassium silicate, calcium silicate, calcium sodium silicate, sodium silicate, magnesium silicate, and magnesium potassium silicate.
Two or more of the low refractive index pigments can be used in combination.
The particle size of the low refractive index pigment is not particularly limited, but 0.03 to 10.0 μm is preferably used.
In addition, silicic acid is mentioned as a low refractive index pigment used suitably.
The silicic acid may be a silicic acid produced by a dry process, but a silicic acid produced by a wet process (hereinafter referred to as a wet process silicic acid) is particularly effective. To explain this point, silicic acid is amorphous. Amorphous silicic acid produced by a dry process using a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride (hereinafter referred to as dry process silicic acid), and sodium silicate. It is roughly divided into those using a wet method using a liquid phase reaction such as decomposition by an acid such as a dry method, and the structure of a dry method silicic acid is different from that of a wet method silicic acid. The dry method silicic acid has a three-dimensional structure in which silicic acid is closely bound. In contrast, wet-process silicic acid has a so-called two-dimensional structure part in which silicic acid is condensed to form a long molecular arrangement.
Therefore, since the molecular structure becomes rough compared to the dry method silicic acid, when wet method silicic acid is applied to the porous layer, it is excellent in the diffused reflection of light in the dry state compared to the system using the dry method silicic acid, Therefore, it is guessed that the concealment property in a normal state becomes large.
In the porous layer, when absorbing an aromatic liquid using water as a medium, the wet process silicic acid has more hydroxyl groups present as silanol groups on the particle surface than the dry process silicic acid, and has a hydrophilicity degree. It is large and is preferably used.
In addition, in order to adjust the concealability in the normal state of the porous layer and the transparency in the liquid absorption state, other general-purpose low-refractive index pigments can be used in combination with the wet process silicic acid.

The low refractive index pigment in the porous layer depends on properties such as particle diameter, specific surface area, oil absorption, etc., in order to satisfy both the concealability in the normal state and the transparency in the liquid absorption state, preferably the coating amount is 1 to 30 g / ^{m 2,} more preferably 5 to 20 g / ^{m 2.} If it is less than 1 g / m ² , it is difficult to obtain sufficient concealability in a normal state, and if it exceeds 30 g / m ² , it is difficult to obtain sufficient transparency during liquid absorption.
The low refractive index pigment is dispersed in a vehicle containing a binder resin as a binder, applied to a support, and then the volatile matter is dried to form a porous layer.
Examples of the binder resin include urethane resin, nylon resin, vinyl acetate resin, acrylic ester resin, acrylic ester copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic resin, polyester resin, styrene. Resin, styrene copolymer resin, polyethylene resin, polycarbonate resin, epoxy resin, styrene-butadiene copolymer resin, acrylonitrile-butadiene copolymer resin, methyl methacrylate-butadiene copolymer resin, butadiene resin, chloroprene resin, melamine resin, and the above Each resin emulsion, casein, starch, cellulose derivative, polyvinyl alcohol, urea resin, phenol resin and the like can be mentioned.
The mixing ratio of the low refractive index pigment and these binder resins depends on the type and properties of the low refractive index pigment, but preferably the binder resin solid content is 0.5 to 1 part by mass with respect to 1 part by mass of the low refractive index pigment. 2 parts by mass, and more preferably 0.8 to 1.5 parts by mass. When the binder resin solid content is less than 0.5 parts by mass with respect to 1 part by mass of the low refractive index pigment, it is difficult to obtain a practical film strength of the porous image, and the content exceeds 2 parts by mass. In this case, the permeability of the medium into the porous layer is deteriorated.
Since the porous layer has a smaller mixing ratio of the binder resin to the colorant than a general coating film, it is difficult to obtain sufficient film strength. Therefore, in order to increase the scratch resistance, it is effective to use a nylon resin or a urethane resin among the binder resins.
Examples of the urethane resin include a polyester urethane resin, a polycarbonate urethane resin, and a polyether urethane resin, and two or more of them can be used in combination. In addition, a urethane emulsion resin in which the resin is emulsified and dispersed in water, or a colloid in which the resin is self-emulsified without the need for an emulsifier by an ionic group of the ionic urethane resin (urethane ionomer) itself and dissolved or dispersed in water. A dispersion type (ionomer type) urethane resin can also be used.
The urethane resin may be either a water-based urethane resin or an oil-based urethane resin, but a water-based urethane resin, in particular, a urethane emulsion resin or a colloidally dispersed urethane resin is preferably used.
The urethane resin can be used alone, but other binder resins can be used in combination depending on the type of support and the performance required for the coating. When a binder resin other than the urethane resin is used in combination, in order to obtain a practical film strength, it is preferable to contain 30% or more of the urethane resin in a solid mass ratio in the binder resin of the porous layer.
In the binder resin, the crosslinkable resin can be further improved in film strength by adding an arbitrary crosslinking agent and crosslinking.
The binder resin has a large or small affinity with a medium. By combining these, the penetration time into the porous layer, the degree of penetration, and the slow speed of drying after the penetration can be adjusted. Furthermore, the said adjustment can be controlled by adding a dispersing agent and surfactant suitably.
A colorant may be contained in the porous layer.

Moreover, when using the aromatic liquid which used the organic solvent as a medium, hydrophobic silica can also be used as a low refractive index pigment.
The hydrophobic silica contained in the porous layer will be described.
Silica is classified into a dry method and a wet method depending on the production method, and both have a structure in which silanol groups are arranged on the surface.
Hydrophobic silica reacts silanol groups with silanes such as methylchlorosilane, siloxanes such as polydimethylsiloxane, hexamethyldisilazane, etc. to change the hydrophilicity of silanol groups to hydrophobic, so it not only absorbs water. Shows water repellency.
As general-purpose hydrophobic silica, trade names Nippil SS-10, SS-20, SS-70, SS-40, SS-50, SS-50, SS-100, Nippon Aerosil Co., Ltd. manufactured by Tosoh Silica Co., Ltd. Product names AEROSIL R972, RY50, R812, R805, RX200, RY200, trade names TS-530, TS-610, TS-720, manufactured by Degussa Japan Co., Ltd. Names AEROSIL R202, R805, R812, trade names REOLOSIL MT-10, DM-10, DM-20S made by Tokuyama Corporation, trade names SYLOPHOBIC100, 200, 704, made by Fuji Silysia Chemical Co., Ltd. 4004, 507, 702, 505, 603, and the like.
The hydrophobic silica has a refractive index in the range of 1.4 to 1.8 and exhibits good transparency when liquid is absorbed.
The particle diameter of the hydrophobic silica is not particularly limited, but 0.03 to 10.0 μm is preferably used.
Two or more hydrophobic silicas can be used in combination.

The hydrophobic silica is preferably dispersed in an organic solvent because it is difficult to disperse in an aqueous emulsion as well as water dispersion by ordinary methods.
The binder resin is dissolved or dispersed in an organic solvent, and a liquid material containing hydrophobic silica is applied entirely or partially on a support and dried to obtain a porous layer.
Examples of the organic solvent include n-paraffin solvents, isoparaffin solvents, naphthene solvents, aromatic solvents, α-olefin solvents and other petroleum solvents, light oil, spindle oil, machine oil, cylinder oil, turpentine oil, Examples include mineral spirit, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, ethyl lactate, xylene, toluene, ethanol, isopropyl alcohol, butanol and the like.
Examples of the binder resin include urethane resin, nylon resin, vinyl acetate resin, acrylic ester resin, acrylic ester copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic resin, polyester resin, styrene. Resin, styrene copolymer resin, polyethylene resin, polycarbonate resin, epoxy resin, styrene-butadiene copolymer resin, acrylonitrile-butadiene copolymer resin, methyl methacrylate-butadiene copolymer resin, butadiene resin, chloroprene resin, melamine resin, and the above Each resin emulsion, casein, starch, cellulose derivative, polyvinyl alcohol, urea resin, phenol resin and the like can be mentioned.
The binder resin soluble in the organic solvent includes acrylic resin, urethane resin, polyester resin, alkyd resin, epoxy resin, melamine resin, styrene resin, nylon resin, vinyl acetate resin. , Vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, high impact polystyrene, acrylonitrile-butadiene-styrene copolymer resin, cellulose resin and the like.
The mixing ratio of the hydrophobic silica and the binder resin depends on the type and properties of the hydrophobic silica, but is preferably 0.5 to 2 parts by mass of the binder resin solid content with respect to 1 part by mass of the hydrophobic silica. More preferably, it is 0.8 to 1.5 parts by mass. When the binder resin solid content is less than 0.5 parts by mass with respect to 1 part by mass of the hydrophobic silica, it is difficult to obtain a practical film strength of the porous layer to be formed, and it exceeds 2 parts by mass. In this case, the permeability of the liquid into the hydrophobic silica tends to be impaired.
Since the porous layer has a smaller mixing ratio of the binder resin to the colorant than a general coating film, it is difficult to obtain sufficient film strength. Therefore, among the binder resins, it is preferable to increase the scratch resistance using a nylon resin, a urethane resin, or an acrylic resin.
Examples of the urethane resin include a polyester urethane resin, a polycarbonate urethane resin, and a polyether urethane resin, and two or more of them can be used in combination.
The urethane resin can be used alone, but other binder resins can be used in combination depending on the type of support and the performance required for the coating.
In the binder resin, the crosslinkable resin can be further improved in film strength by adding an arbitrary crosslinking agent and crosslinking.
The binder resin has a large or small affinity with the liquid. By combining these, the permeation time into the porous layer, the degree of permeation, and the slow speed of drying after permeation can be adjusted. Furthermore, the said adjustment can be controlled by adding a dispersing agent suitably.
A colorant may be contained in the porous layer.

The porous layer using the hydrophobic silica does not absorb water even when water (interfacial tension value 72 mN / m) is attached, and repels water on the surface. And no discoloration occurs.
On the other hand, when ethanol (interfacial tension value 22 mN / m) is attached as an organic solvent, the porous layer absorbs the organic solvent and becomes transparent, and the color of the lower layer becomes visible.
When the organic solvent contained in the porous layer evaporates, the porous layer becomes opaque and returns to its original state.
The low refractive index pigment is dispersed in a solvent containing a binder resin to prepare a liquid material such as paint or printing ink, and printing methods such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, A porous layer is provided on the support surface by a method such as brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, or dip coating.

In the porous layer, an electron-donating reaction between the aromatic liquid containing an electron-accepting compound that imparts an electron-accepting reaction and an electron-donating colorable organic compound by containing an electron-donating colorable organic compound. As a result, the electron-donating color-forming organic compound develops and decolorizes, so that the expiration date due to the fragrance can be further clarified by visual observation and the accuracy of the fragrance can be improved.
Examples of the electron-donating color-forming organic compounds include diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl indolyl azaphthalides, fluorans, styrinoquinolines, Examples thereof include diazarhodamine lactones, pyridines, quinazolines, bisquinazolines.
Examples of these compounds are given below.
3,3-bis (p-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-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-propylindol-3-yl) -4-azaphthalide,
3,6-bis (diphenylamino) fluorane,
3,6-dimethoxyfluorane,
3,6-di-n-butoxyfluorane,
2-methyl-6- (N-ethyl-Np-tolylamino) fluorane,
3-chloro-6-cyclohexylaminofluorane,
2-methyl-6-cyclohexylaminofluorane,
2- (2-chloroamino) -6-dibutylaminofluorane,
2- (2-chloroanilino) -6-di-n-butylaminofluorane,
2- (3-trifluoromethylanilino) -6-diethylaminofluorane,
2- (3-trifluoromethylanilino) -6-dipentylaminofluorane,
2- (dibenzylamino) -6-diethylaminofluorane,
2- (N-methylanilino) -6- (N-ethyl-Np-tolylamino) fluorane,
1,3-dimethyl-6-diethylaminofluorane,
2-chloro-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-diethylaminofluorane,
2-anilino-3-methoxy-6-diethylaminofluorane,
2-anilino-3-methyl-6-di-n-butylaminofluorane,
2-anilino-3-methoxy-6-di-n-butylaminofluorane,
2-xylidino-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6- (N-ethyl-Np-tolylamino) fluorane,
1,2-benz-6-diethylaminofluorane,
1,2-benz-6- (N-ethyl-N-isobutylamino) fluorane,
1,2-benz-6- (N-ethyl-N-isoamylamino) fluorane,
2- (3-methoxy-4-dodecoxystyryl) quinoline,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (diethylamino) -8- (diethylamino) -4-methyl ,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (di -N-butylamino) -4-methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (diethylamino) ) -4-methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (N -Ethyl-Ni-amylamino) -4-methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (dibutylamino) -8- (dipentylamino) -4 -Methyl,
4,5,6,7-Tetrachloro-3- [4- (dimethylamino) -2-methoxyphenyl] -3- (1-butyl-2-methyl-1H-indol-3-yl) -1 (3H ) -Isobenzofuranone,
4,5,6,7-tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl] -3- (1-ethyl-2-methyl-1H-indol-3-yl) -1 (3H) -Isobenzofuranone,
4,5,6,7-tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl] -3- (1-pentyl-2-methyl-1H-indol-3-yl) -1 (3H) -Isobenzofuranone,
4,5,6,7-tetrachloro-3- [4- (diethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indol-3-yl) -1 (3H) -Isobenzofuranone,
3 ', 6'-bis [phenyl (2-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -3-one,
3 ', 6'-bis [phenyl (3-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -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- (4'-dimethylaminophenyl) -4-methoxy-quinazoline,
4,4 ′-(ethylenedioxy) -bis [2- (4-diethylaminophenyl) quinazoline]
Etc.
In addition to the above compounds having a substituent on the phenyl group forming the xanthene ring, the fluoranes include a substituent on the phenyl group forming the lactone ring as well as the phenyl group forming the xanthene ring (for example, Or a blue or black compound having an alkyl group such as a methyl group or a halogen atom such as a chloro group.
When the aromatic liquid does not contain an electron-accepting compound that imparts an electron-accepting reaction, an electron-donating color-forming organic compound and an electron-accepting compound are contained in the porous layer. Since the color is changed by the transfer reaction, the expiration date due to the fragrance can be further clarified by visual observation, and the accuracy of the fragrance can be improved.
Examples of the electron-accepting compound include a group of compounds having active protons, a group of pseudo-acidic compounds (a compound group that is not an acid but acts as an acid in the composition to develop an electron-donating color-forming organic compound), an electron There is a group of compounds having pores.
Examples of compounds having active protons include monophenols to polyphenols as compounds having phenolic hydroxyl groups, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as substituents. Alternatively, those having an amide group, a halogen group, etc., and bis-type and tris-type phenols, phenol-aldehyde condensation resins and the like can be mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.
Specific examples are given below.
Phenol, o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate N-octyl p-hydroxybenzoate, resorcin, dodecyl gallate, 4,4-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 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- Droxyphenyl) 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) -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-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1-phenyl-1,1-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, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis [2- ( 4-hydroxyphenyl) -2-propyl] benzene, bis (2-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, 3,3-bis (3-methyl-4-hydroxyphenyl) ) Butane etc.
The compound having a phenolic hydroxyl group can develop the most effective thermochromic property, but aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and their It may be a compound selected from metal salts, 1,2,3-triazole and derivatives thereof.

By providing an adhesive layer as the lowermost layer in the lower layer of the support, the adhesion to the object can be facilitated.
The pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive mainly composed of a general-purpose acrylic resin, urethane resin, styrene-butadiene copolymer, vinyl ether copolymer, natural rubber, or the like.
The adhesive layer may be provided with a release layer such as a release paper for convenience during use.

An aroma liquid composed of the fragrance and the medium will be described.
Although the said fragrance | flavor is divided into food fragrance | flavor (flavor) and cosmetics fragrance | flavor (fragrance), use of food fragrance | flavor with higher safety | security is preferable. The form of the fragrance includes a water-soluble fragrance, an oil-soluble fragrance, and an emulsified fragrance. In the case of an oil-soluble fragrance, the fragrance can be emulsified or included by cyclodextrin.
Examples of the perfumes include grapefruit oil, orange oil, lemon oil, lime oil, jasmine oil, peppermint oil, rosemary oil, nutmeg oil, cassia oil, lavender oil, cypress oil, hiba oil, fennel oil and other essential oils, hexyl Alcohols such as alcohol, phenylethyl alcohol (rose P), furfuryl alcohol, cycloten, geraniol, aldehydes such as heptanal, octanal, dodecanal, tetradecanal, hexadecanal, octadecanal, benzaldehyde, furfural, ethyl aceto Esters such as acetate, propyl acetate, amyl acetate, linalyl acetate, benzyl acetate, dimethylbenzylcarbinyl acetate, benzylpropionate, nootkatone, ethylpyra Emissions, lemon terpene-less, orange terpene-less, Wanirin, Echiruwanirin, furfuryl mercaptan, aromatic compounds such as Boneoru and heliotrope, alpha-pinene, exemplified β- pinene, terpene oils such as limonene.
In addition, blended fragrances such as banana fragrance, blueberry fragrance, vanilla fragrance, mint fragrance, apple fragrance, peach fragrance, melon fragrance, pineapple fragrance, grape fragrance, lilac fragrance, jasmine fragrance are used. You can also

Examples of the medium include water, an organic solvent, and a combination of water and a water-soluble organic solvent.
Examples of the water-soluble organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolide And the like can be given.

In a state in which the aromatic liquid composed of the fragrance and the medium is impregnated in the porous layer, the porous layer is transparent by liquid absorption and the color of the lower layer is visually recognized, and the aromatic liquid is in the porous layer. It can be confirmed that it is present and fragrant.
As the fragrance liquid volatilizes, the fragrance of the fragrance decreases, and the porous layer dries so that the color of the lower layer is not visually recognized. Therefore, the expiration date of the fragrance can be clearly determined visually.
Here, by setting the color of the image of the fragrance and the color of the lower layer of the porous layer to the same color or similar colors, the color perceived by the scent can be linked to enhance the merchantability.

Examples of the present invention will be described below. In addition, the part in an Example shows a mass part.
Example 1 (see FIG. 1)
As a support 2, on the surface of a green polyethylene terephthalate film, 15 parts of wet method fine particle silica [trade name: Nipseal E-220, manufactured by Nippon Silica Industry Co., Ltd.], urethane emulsion [trade name: Hydran AP-10, Dainippon Ink & Chemicals, Inc.] Industrial Co., Ltd., 30% solid content] 45 parts, 40 parts water, 0.5 parts silicone antifoam, 3 parts thickener for aqueous ink, 1 part ethylene glycol, 3 parts isocyanate crosslinker Using the screen printing ink thus formed, the entire surface was solid-printed with a 100-mesh screen plate and dried and cured at 60 ° C. for 30 minutes to form the porous layer 3 to obtain a discolored body.
Next, an aromatic liquid consisting of 0.2 part of mint fragrance [trade name: Super Emulsion Peppermint 106] manufactured by Taiyo Kagaku Co., Ltd. and 99.8 parts of water was obtained.
The aromatic liquid was impregnated in the porous layer of the discolored body to obtain a discolorable aromatic material 1.
In the discolorable fragrance material, since the porous layer is made transparent by absorbing the fragrance liquid, the green color by the support is visually recognized.
When the discolorable aromatic material was placed indoors, the medium of the aromatic liquid evaporated with the aroma and became white as the porous layer dried, and the expiration date of the aromatic material could be clearly determined visually.

Example 2 (see FIG. 2)
A non-discoloring colored layer 4 was provided on the surface of a white polyethylene terephthalate film as a support 2 using a printing ink containing an orange pigment.
Next, 15 parts of wet method fine particle silica [trade name: NIPSEAL E-220, manufactured by Nippon Silica Kogyo Co., Ltd.], urethane emulsion [trade name: Hydran AP-10, Dainippon Ink Chemical Co., Ltd.] Industrial Co., Ltd., 30% solid content] 45 parts, 40 parts water, 0.5 parts silicone antifoam, 3 parts thickener for aqueous ink, 1 part ethylene glycol, 3 parts isocyanate crosslinker Using the screen printing ink, the entire surface was solid-printed with a 100-mesh screen plate and dried and cured at 60 ° C. for 30 minutes to form the porous layer 3 to obtain a discolored body.
Next, an aromatic liquid consisting of 0.2 part of mango fragrance (manufactured by San-Ei Gen FFI Co., Ltd., trade name: Mango Flavor) and 99.8 parts of water was obtained.
The aromatic liquid was impregnated in the porous layer of the discolored body to obtain a discolorable aromatic material 1.
In the color-changing fragrance material, since the porous layer is made transparent by absorbing the aromatic liquid, orange color due to the non-color-changing colored layer is visually recognized.
When the discolorable fragrance material was placed in a vehicle, the medium of the fragrance liquid was evaporated together with the fragrance and became white as the porous layer was dried, and the expiration date of the fragrance material could be clearly determined visually.

Example 3 (see FIG. 3)
10 parts of hydrophobic silica (manufactured by Tosoh Silica Co., Ltd., product name: NipSeal SS20), vinyl chloride-vinyl acetate copolymer resin (manufactured by Nissin Chemical Industry Co., Ltd., product name) on the surface of yellow cast coated paper as support 2 : Solvain A) Using a screen printing ink in which 10 parts, 25 parts of cyclohexanone and 1 part of a nonionic additive were mixed, the entire surface was solid-printed on a 100-mesh screen plate and dried and cured at 60 ° C. for 30 minutes to be porous. Layer 3 was formed to obtain a discolored body.
An adhesive layer 5 is provided on the back surface of the support.
Next, an aromatic liquid consisting of 5 parts of lemon scented perfume [manufactured by Takasago International Corporation, trade name: LEMON TJP-F-000765] and 95 parts of ethyl alcohol was obtained.
The aromatic liquid was impregnated in the porous layer of the discolored body to obtain a discolorable aromatic material 1.
In the color-changing fragrance material, since the porous layer is made transparent by absorbing the aromatic liquid, yellow color due to the non-color-changing colored layer is visually recognized.
When the discolorable aromatic material is attached to the wall surface of the room, the medium of the aromatic liquid evaporates with the aroma and becomes white as the porous layer dries, and the expiration date of the aromatic material can be clearly identified visually. It was.

Example 4
12 parts of hydrophobic silica (manufactured by Fuji Silysia Chemical Co., Ltd., product name: Silo Hovic 200), acrylic resin 50% toluene / butyl acetate solution (DIC Corporation) on a yellow ABS resin molding in the shape of lemon as a support Manufactured, product name: Acrydic A-817) 20 parts, 15 parts of methyl ethyl ketone and 15 parts of xylene were mixed and spray-coated using a spray ink to form a porous layer to obtain a discolored body.
Next, an aromatic liquid consisting of 5 parts of lemon scented perfume [manufactured by Takasago International Corporation, trade name: LEMON TJP-F-000765] and 95 parts of ethyl alcohol was obtained.
The aromatic liquid was impregnated into the porous layer of the color changing body to obtain a color changing aromatic material.
In the color-changing fragrance material, since the porous layer is made transparent by absorbing the aromatic liquid, yellow color due to the non-color-changing colored layer is visually recognized.
When the discolorable aromatic material was placed indoors, the medium of the aromatic liquid evaporated with the aroma and became white as the porous layer dried, and the expiration date of the aromatic material could be clearly determined visually.

Example 5
10 parts of hydrophobic silica (manufactured by Tosoh Silica Co., Ltd., product name: Nipseal SS20), vinyl chloride-vinyl acetate copolymer resin (manufactured by Nissin Chemical Industry Co., Ltd., product name: Solvine) A) Using a screen printing ink in which 10 parts, 25 parts of cyclohexanone, and 1 part of a nonionic additive were mixed, the entire surface was printed on a 100 mesh screen plate, dried and cured at 60 ° C. for 30 minutes, and then a porous layer In addition, 1 part of 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide and 100 parts of butyl acetate were mixed. The porous layer was spray-coated and dried to contain an electron-donating color-forming organic compound in the porous layer to obtain a pale yellow discolored body.
Subsequently, an aromatic liquid composed of 2 parts of hinokitiol, 3 parts of eugenol and 95 parts of ethyl alcohol was obtained.
The aromatic liquid was impregnated into a bird-shaped stamp, and the porous layer was impregnated to obtain a color-changing aromatic material having a bird-shaped image.
In the discolorable aromatic material, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide in the porous layer is colored blue. At the same time, since the porous layer is made transparent by absorbing the aromatic liquid, a green bird image is visually recognized.
When the color-changing fragrance is allowed to stand, 1,2-benz-6- (N-ethyl-N-isoamylamino) fluorane becomes colorless as the medium of the fragrance liquid evaporates with the fragrance and the porous layer dries. The porous layer became pale yellow, and the expiration date of the fragrance material could be clearly discriminated visually.

Example 6
As a support, on the surface of white synthetic paper, 10 parts of hydrophobic silica (manufactured by Tosoh Silica Co., Ltd., product name: Nipseal SS20), vinyl chloride-vinyl acetate copolymer resin (manufactured by Nissin Chemical Industry Co., Ltd., product name: sorbine) A) Using a screen printing ink in which 10 parts, 25 parts of cyclohexanone and 1 part of a nonionic additive are mixed, it is printed in a heart shape on a 100-mesh screen plate, dried and cured at 60 ° C. for 30 minutes, and then a porous layer In addition, 2 parts of 1,2-benz-6- (N-ethyl-N-isoamylamino) fluorane, 5 parts of 1,1-bis (4-hydroxyphenyl) n-nonane and 100 parts of methyl ethyl ketone were mixed. The porous layer is formed by spray-coating a porous layer and then drying to contain an electron-donating color-forming organic compound and an electron-accepting compound in the porous layer. To obtain a color change of ink color.
Next, an aromatic liquid consisting of 5 parts of lemon scented perfume [manufactured by Takasago International Corporation, trade name: LEMON TJP-F-000765] and 95 parts of ethyl alcohol was obtained.
The aromatic liquid was impregnated into the porous layer of the color changing body to obtain a color changing aromatic material.
In the discolorable aromatic material, 1,2-benz-6- (N-ethyl-N-isoamylamino) fluorane in the porous layer became colorless, and the porous layer was made transparent by absorbing the aromatic liquid. Due to the state, the white color of the support is visible.
When the color-changing fragrance is allowed to stand, 1,2-benz-6- (N-ethyl-N-isoamylamino) fluorane becomes pink as the medium of the fragrance liquid evaporates with the fragrance and the porous layer dries. At the same time, the porous layer turned white, and the expiration date of the fragrance material could be clearly discriminated visually.

DESCRIPTION OF SYMBOLS 1 Discolorable aromatic material 2 Support body 3 Porous layer 4 Non-discoloring colored layer 5 Adhesive layer

Claims (7)

  On the support, a low refractive index pigment is fixed in a binder resin in a dispersed state, and is provided with a porous layer that is opaque in a non-liquid-absorbing state and transparent in the liquid-absorbing state. A discolorable fragrance material comprising a fragrance liquid comprising a fragrance and a medium.   The discolorable aromatic material according to claim 1, wherein the medium is an organic solvent.   The discolorable aromatic material according to claim 1 or 2, wherein the low refractive index pigment is hydrophobic silica.   The discolorable aromatic material according to any one of claims 1 to 3, wherein the porous layer contains an electron-donating color-forming organic compound.   The discolorable aromatic material according to claim 4, wherein the porous layer contains an electron-accepting compound. The color-changing aromatic material according to any one of claims 1 to 5, wherein a non-color-changing colored layer is provided between the support and the porous layer.   The discolorable aromatic material according to any one of claims 1 to 6, wherein an adhesive layer is provided in the lowermost layer.

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