JP6961290B2 - Discoloring fragrance set - Google Patents

Description

The present invention relates to a discolorable fragrance set. More specifically, the present invention relates to a discolorable fragrance material set in which the expiration date of the fragrance can be visually determined.

Conventionally, as a means for determining the expiration date of an aromatic material, it has been disclosed that the expiration date of the aromatic material is determined by shrinkage of the aromatic material (see, for example, Patent Document 1).
However, since the fragrance gradually shrinks, the expiration date cannot be clearly seen.
Further, there is disclosed an impregnated body for an aromatic liquid in which a discoloring substance that changes color due to contact with an alcohol-based aromatic liquid and returns to the original color due to volatilization of the alcohol-based aromatic liquid is adhered to an impregnated portion (for example, Patent Document 2). reference).
Although it is disclosed that the impregnated body for aromatic liquids returns to the original color when alcohol volatilizes and thus can prevent the aroma from being cut off, it can be used only in a specific medium and the color change of the impregnated discoloring substance. It was scarce and did not satisfy the practicality.

JP-A-2002-35100 Microfilm of Jitsusho 59-90187 (Jitsukaisho 61-8050)

The present invention is to provide a discolorable fragrance material set in which the expiration date of fragrance can be clearly discriminated visually.

The present invention comprises a discolored body having a porous layer having a low refractive index pigment fixed to a binder resin in a dispersed state on a support, which is opaque in a non-liquid absorbing state and becomes transparent in a liquid absorbing state. Ri Do and a fragrance solution comprising a perfume and an organic solvent, a low-refractive-index pigment of the porous layer, the coating weight of 5 to 20 g / m ^2, the low-refractive-index pigment is hydrophobic silica, and, the said aromatic liquid requirement discoloring aromatic material set is housed in a container ing.
Furthermore, before Symbol by containing a porous layer electron-donating coloring organic compound in, by containing an electron-accepting compound in the porous layer, the support and the porous layer It is a requirement that a non-discoloring colored layer is provided between them, and that an adhesive layer or a heat-meltable resin layer having a melting point of 60 ° C. to 180 ° C. is provided at the bottom layer of the discolored material.

Since the expiration date of the fragrance can be confirmed by the color change, the present invention can provide a highly practical discolorable fragrance material set in which the expiration date can be clearly determined visually.

It is a perspective view of one reference example of the discoloring fragrance material set of this invention. It is a vertical cross-sectional view of the discolored body used for the discoloring fragrance material set of FIG. It is a longitudinal sectional view of an embodiment of a color change material used in the discoloring aromatic material set of the present invention. It is a vertical cross-sectional view of another Example of the color changer used in the color changeable fragrance material set of this invention.

The present invention comprises a discolored body having a porous layer in which a low refractive index pigment is fixed to a binder resin in a dispersed state on a support, which is opaque in a non-liquid absorbing state and becomes transparent in a liquid absorbing state. It is a discoloring fragrance material set consisting of a fragrance liquid consisting of a fragrance and a medium.

The support is not particularly limited, and for example, cloth such as paper, synthetic paper, woven fabric, knitted fabric, braid, non-woven fabric, natural or synthetic leather, plastic, glass, ceramics, metal, wood, stone and the like are used. Therefore, fabrics, leathers, synthetic papers, and plastics are preferably used. Further, the shape may be a planar shape or a three-dimensional shape.
The support itself may be colored, or may be provided with a non-discoloring colored layer on the support.
Examples of the colorant for coloring the support or the colorant contained in the non-discolorable coloring layer include general dyes, fluorescent dyes and coloring pigments, and among them, the coloring pigments include general pigments and fluorescent pigments. In addition to metal powder, a transparent metal gloss pigment (pearl pigment) in which a core material such as mica, alumina, or glass is coated with titanium oxide can be exemplified.

The porous layer is a layer in which a low refractive index pigment is fixed together with a binder resin in a dispersed state, and has different transparency in a dry state and a liquid absorbing state.
The refractive index of the low refractive index pigment is in the range of 1.4 to 1.8, and exhibits good transparency when it absorbs water.
Examples of the low refractive index pigment include silicic acid and salts thereof, barium powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, talc, alumina, alumina white, magnesium carbonate and the like, and silicic acid and salts thereof are preferable. Used.
Examples of the salt of silicic acid include aluminum silicate, potassium aluminum silicate, sodium aluminum silicate, aluminum calcium silicate, potassium silicate, calcium silicate, sodium calcium silicate, sodium silicate, magnesium silicate, potassium magnesium silicate and the like.
Further, two or more kinds 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 those having a particle size of 0.03 to 10.0 μm are preferably used.
Silicic acid is mentioned as a preferably used low refractive index pigment.
The silicic acid may be a silicic acid produced by a dry method, but a silicic acid produced by a wet method (hereinafter referred to as a wet method silicic acid) is particularly effective. Explaining this point, the silicic acid is amorphous. It is produced as a quality amorphous silicic acid, and depending on the production method, a dry method using a vapor phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride (hereinafter referred to as dry silicic acid) and sodium silicate are used. The dry method silicic acid and the wet method silicic acid have different structures, and the dry method silicic acid has a three-dimensional structure in which silicic acid is tightly bonded. On the other hand, the wet method silicic acid has a so-called two-dimensional structural portion in which silicic acid is condensed to form a long molecular arrangement.
Therefore, since the molecular structure is coarser than that of the dry silicic acid, when the wet silicic acid is applied to the porous layer, the diffuse reflection of light in the dry state is excellent as compared with the system using the dry silicic acid. Therefore, it is presumed that the concealment property under normal conditions will increase.
Further, in the porous layer, when an aromatic liquid using water as a medium is absorbed, the wet method silicic acid has more hydroxyl groups existing as silanol groups on the particle surface than the dry method silicic acid, and the degree of hydrophilicity is higher. It is large and is preferably used.
In addition, in order to adjust the hiding property of the porous layer in a normal state and the transparency in a liquid absorbing state, another general-purpose low refractive index pigment can be used in combination with the wet method silicic acid.

The low refractive index pigment in the porous layer depends on properties such as particle size, specific surface area, and oil absorption, but in order to satisfy both the hiding property in the normal state and the transparency in the liquid absorbing state, it is necessary to satisfy both. 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 concealment under normal conditions, and if it ^{exceeds 30 g / m 2} , it is difficult to obtain sufficient transparency at the time of 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 dried to form a porous layer.
Examples of the binder resin include urethane resin, nylon resin, vinyl acetate resin, acrylic acid ester resin, acrylic acid ester copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic acid resin, polyester resin, and 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. Examples thereof include each resin emulsion, casein, starch, cellulose derivative, polyvinyl alcohol, urea resin, phenol resin and the like.
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 of the low refractive index pigment. It is 2 parts by mass, more preferably 0.8 to 1.5 parts by mass. When the solid content of the binder resin 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 when it exceeds 2 parts by mass. In addition, the permeability of the medium into the porous layer is deteriorated.
Since the mixing ratio of the binder resin to the colorant is smaller in the porous layer than in a general coating film, it is difficult to obtain sufficient film strength. Therefore, it is effective to use a nylon resin or a urethane-based resin among the above-mentioned binder resins in order to increase the scratch resistance.
Examples of the urethane-based resin include polyester-based urethane resin, polycarbonate-based urethane resin, and polyether-based urethane resin, and two or more of them can be used in combination. Further, a colloid in which the resin is emulsified and dispersed in water or self-emulsified by the ionic group of the ionic urethane resin (urethane ionomer) itself without the need for an emulsifier and dissolved or dispersed in water. A dispersed type (ionomer type) urethane resin can also be used.
As the urethane-based resin, either an aqueous urethane-based resin or an oil-based urethane-based resin can be used, but an aqueous urethane-based resin, particularly a urethane-based emulsion resin or a colloid-dispersed urethane-based resin is preferably used.
The urethane-based resin can be used alone, but other binder resins can also be used in combination depending on the type of support and the performance required for the film. When a binder resin other than the urethane resin is used in combination, it is preferable that the urethane resin is contained in the binder resin of the porous layer in a solid content mass ratio of 30% or more in order to obtain a practical film strength.
Among the binder resins, those having a crosslinkable property can be further improved in film strength by adding an arbitrary cross-linking agent and cross-linking.
The binder resin has different affinities with the medium, and 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. Further, the adjustment can be controlled by appropriately adding a dispersant or a surfactant.
A colorant can also be contained in the porous layer.

Further, when an aromatic liquid using an organic solvent as a medium is used, hydrophobic silica can also be used as the low refractive index pigment.
Hydrophobic silica contained in the porous layer will be described.
Silica is classified into a dry method and a wet method according to 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 does not absorb water. Shows water repellency.
As general-purpose hydrophobic silica, trade names Nipsil SS-10, SS-20, SS-70, SS-40, SS-50, SS-100, Nippon Aerosil Co., Ltd. manufactured by Toso Silysia Chemical Ltd. Product names AEROSIL R972, RY50, R812, R805, RX200, RY200, Cabot Carbon products TS-530, TS-610, TS-720, Degussa Japan Co., Ltd. Names AEROSIL R202, R805, R812, Tokuyama Co., Ltd. trade names REOLOSIL MT-10, DM-10, DM-20S, Fuji Silysia Chemical Ltd. trade names SYLPHOBIC 100, 200, 704, 704, same Examples thereof include 4004, 507, 702, 505, and 603.
The hydrophobic silica has a refractive index in the range of 1.4 to 1.8 and exhibits good transparency when it absorbs a liquid.
The particle size of the hydrophobic silica is not particularly limited, but those having a particle size of 0.03 to 10.0 μm are preferably used.
Further, two or more kinds of the hydrophobic silica can be used in combination.

Since it is difficult to disperse the hydrophobic silica not only in water but also in an aqueous emulsion by a usual method, it is preferably dispersed in an organic solvent.
The binder resin is dissolved or dispersed in an organic solvent, and a liquid substance containing hydrophobic silica is coated or partially coated on the support and dried to obtain a porous layer.
Examples of the organic solvent include petroleum solvents such as n-paraffin solvent, isoparaffin solvent, naphthen solvent, aromatic solvent, α-olefin solvent, light oil, spindle oil, machine oil, cylinder oil, and terepine oil. Examples thereof 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 acid ester resin, acrylic acid ester copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic acid resin, polyester resin, and 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. Examples thereof include each resin emulsion, casein, starch, cellulose derivative, polyvinyl alcohol, urea resin, phenol resin and the like.
Examples of the binder resin soluble in the organic solvent include acrylic resin, urethane resin, polyester resin, alkyd resin, epoxy resin, melamine resin, styrene resin, nylon resin, and 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 0.8 to 1.5 parts by mass. When the solid content of the binder resin is less than 0.5 parts by mass with respect to 1 part by mass of hydrophobic silica, it is difficult to obtain a practical film strength of the formed porous layer, and it exceeds 2 parts by mass. In some cases, the permeability of the liquid into the hydrophobic silica is likely to be impaired.
Since the mixing ratio of the binder resin to the colorant is smaller in the porous layer than in a general coating film, it is difficult to obtain sufficient film strength. Therefore, among the binder resins, it is preferable to use nylon resin, urethane resin, or acrylic resin to increase the scratch resistance.
Examples of the urethane-based resin include polyester-based urethane resin, polycarbonate-based urethane resin, and polyether-based urethane resin, and two or more of them can be used in combination.
The urethane-based resin can be used alone, but other binder resins can also be used in combination depending on the type of support and the performance required for the film.
Among the binder resins, those having a crosslinkable property can be further improved in film strength by adding an arbitrary cross-linking agent and cross-linking.
The binder resin has different affinities with the liquid, and 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 adjustment can be controlled by appropriately adding a dispersant.
A colorant can also be contained in the porous layer.

In the porous layer using hydrophobic silica, even if water (interfacial tension value 72 mN / m) is attached, the porous layer does not absorb water and repels water on the surface, so that the porous layer is made transparent. No discoloration occurs.
On the other hand, when ethanol (interfacial tension value 22 mN / m) is attached as the organic solvent, the porous layer absorbs the organic solvent to make it 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 the original state again.
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 a printing method such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, etc. A porous layer is provided on the surface of the support by a method such as brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, and dip coating.

An electron transfer reaction between an aromatic liquid containing an electron accepting compound that imparts an electron transfer reaction and an electron donating color organic compound by containing an electron donating color-forming organic compound in the porous layer. As a result, the electron-donating color-developing organic compound develops and extinguishes the color, so that the expiration date of the fragrance can be visually clarified and the accuracy of the fragrance can be improved.
Examples of the electron-donating color-developing organic compound include diphenylmethanephthalides, phenylindrillphthalides, indolylphthalides, diphenylmethaneazaphthalides, phenylindrillazaphthalides, fluorans, and styrinoxinazolines. Examples thereof include diazarodamine lactones, pyridines, quinazolines, bisquinazolines and the like.
Examples of these compounds are given below.
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide,
3- (4-Diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) phthalide,
3,3-bis (1-n-butyl-2-methylindole-3-yl) phthalide,
3,3-Bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide,
3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3- (2-Hexyloxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3- [2-ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3- (2-Acetamide-4-diethylaminophenyl) -3- (1-propylindole-3-yl) -4-azaphthalide,
3,6-bis (diphenylamino) fluorane,
3,6-dimethoxyfluoran,
3,6-di-n-butoxyfluorane,
2-Methyl-6- (N-ethyl-N-p-trillamino) 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-N-p-trillamino) 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-N-p-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-dodecoxystilyl) quinoline,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran] -3'-on, 2- (diethylamino) -8- (diethylamino) -4-methyl ,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran] -3'-on, 2- (di-n-butylamino) -8- (di-n-butylamino) -8- (di -N-Butylamino) -4-methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran] -3'-on, 2- (di-n-butylamino) -8- (diethylamino) ) -4-Methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran] -3'-on, 2- (di-n-butylamino) -8- (N) -Ethyl-N-i-amylamino) -4-methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran] -3'-on, 2- (dibutylamino) -8- (dipentylamino) -4 -Methyl,
4,5,6,7-Tetrachloro-3- [4- (dimethylamino) -2-methoxyphenyl] -3- (1-butyl-2-methyl-1H-indole-3-yl) -1 (3H) ) -Isobenzofuranone,
4,5,6,7-Tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl] -3- (1-ethyl-2-methyl-1H-indole-3-yl) -1 (3H) -Isobenzofuranone,
4,5,6,7-Tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl] -3- (1-pentyl-2-methyl-1H-indole-3-yl) -1 (3H) -Isobenzofuranone,
4,5,6,7-Tetrachloro-3- [4- (diethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indole-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] xanthene] -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]
And so on.
As fluorans, in addition to the compound having a substituent on the phenyl group forming the xanthene ring, the phenyl group having the substituent on the phenyl group forming the xanthene ring and also forming the lactone ring also has a substituent (for example). , An alkyl group such as a methyl group, or a halogen atom such as a chloro group) may be a compound exhibiting a blue color or a black color.
When the aromatic solution does not contain an electron-accepting compound that imparts an electron transfer reaction, the porous layer contains an electron-donating color-forming organic compound and an electron-accepting compound to generate electrons. Since the color is developed and extinguished by the transfer reaction, the expiration date of the fragrance can be visually clarified, and the accuracy of the fragrance can be improved.
Examples of the electron-accepting compound include 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 acids in the composition to develop an electron-donating color-forming organic compound), and electrons. There are a group of compounds having pores and the like.
Examples of compounds having an active proton include monophenols to polyphenols as compounds having a phenolic hydroxyl group, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as their substituents. Alternatively, those having an amide group, a halogen group and the like, bis-type and tris-type phenols and the like, phenol-aldehyde condensed resins and the like can be mentioned. Further, it may be a metal salt of the compound having a phenolic hydroxyl group.
Specific examples are given below.
Phenol, o-cresol, tertiary butyl catechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate , P-Hydroxybenzoate n-octyl, 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-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) -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-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-nonan, 2,2-bis (4-hydroxyphenyl) n-decane, 2,2-bis (4-hydroxyphenyl) n-dodecane, 2,2-bis (4-hydroxyphenyl) Hydroxyphenyl) ethyl propionate, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) -4-methylhexane, 2,2-bis (4-hydroxyphenyl) 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) ) There is butane etc.
The compound having a phenolic hydroxyl group can exhibit the most effective thermal discoloration property, but is an aromatic carboxylic acid and an aliphatic carboxylic acid having 2 to 5 carbon atoms, a carboxylic acid metal salt, an acidic phosphoric acid ester and theirs. It may be a compound selected from a metal salt, 1,2,3-triazole and a derivative thereof.

The discolored body can be easily adhered to an object by providing an adhesive layer or a heat-meltable resin layer having a melting point of 60 ° C. to 180 ° C. at the bottom layer.
The pressure-sensitive adhesive layer is formed of a general-purpose acrylic resin, urethane-based resin, styrene-butadiene copolymer, vinyl ether copolymer, a pressure-sensitive adhesive mainly composed of natural rubber, and the like.
In addition, a release layer such as a release paper may be provided on the adhesive layer for convenience during use.
The heat-meltable resin layer having a melting point of 60 ° C. to 180 ° C. has a melting point of 60 ° C. to 180 ° C., preferably 70 ° C. to 150 ° C., and is polyamide-based, polyolefin-based, ethylene-vinyl acetate-based, or polyurethane-based. , Or a layer made of a heat-meltable resin selected from polyester-based resins, and the discolored body can be fixed to any part of the object by a heat-bonding means such as a heat iron or a heat press.

The fragrance liquid composed of the fragrance and the medium will be described.
The flavors are divided into food flavors (flavors) and cosmetic flavors (fragrances), and it is preferable to use food flavors with higher safety. The fragrances include water-soluble fragrances, oil-soluble fragrances, and emulsified fragrances. In the case of oil-soluble fragrances, the fragrances can be emulsified or encapsulated with cyclodextrin.
Examples of the fragrance include essential oils such as grapefruit oil, orange oil, lemon oil, lime oil, jasmine oil, peppermint oil, rosemary oil, nutmeg oil, katssia oil, lavender oil, hinoki oil, hiba oil, and fennel oil, and hexyl. Alcohols, phenylethyl alcohols (rose P), furfuryl alcohols, cycloten, geraniol and other alcohols, heptanal, octanal, dodecanal, tetradecaneal, hexadecalal, octadecaneal, benzaldehyde, furfural and other aldehydes, ethylacetate Esters such as acetate, propyl acetate, amyl acetate, linaryl acetate, benzyl acetate, dimethylbenzyl carvinyl acetate, benzyl propionate, nutcaton, ethylpyrazine, lemon tarpenless, orange tarpenless, crocodile, ethyl varnish, furfuryl mercaptan, Examples include aromatic compounds such as Boneol and Heliotrope, and terpene oils such as α-pinene, β-pinene and limonene.
Further, a blended fragrance that combines the above fragrances, for example, a banana fragrance, a blueberry fragrance, a vanilla fragrance, a mint fragrance, an apple fragrance, a peach fragrance, a melon fragrance, a pineapple fragrance, a grape fragrance, a lilac fragrance, and a jasmine fragrance is used. You can also do it.

Examples of the medium include water, an organic solvent, and a combined use 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, and the like. 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-pyrrolidone, etc. Can be mentioned.

In the state where the aromatic liquid composed of the fragrance and the medium is impregnated in the porous layer, the porous layer is made transparent by the 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 also decreases, and the porous layer dries so that the color of the lower layer becomes invisible. Therefore, the expiration date of the fragrance can be clearly determined visually.
Here, by making the color that images the fragrance and the color of the lower layer of the porous layer the same color or a similar color, the fragrance and the visually recognized color can be linked to enhance the commercial value.

Examples of the present invention will be described below. In addition, the part in an Example shows a mass part.
Reference example 1 (see Fig. 1)
Wet method fine particle silica [trade name: Nipseal E-220, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts, urethane emulsion [trade name: Hydran AP-10, Dainippon Ink Chemicals] on the surface of green polyethylene terephthalate film as support 21 Made by Kogyo Co., Ltd., solid content 30%] 45 parts, water 40 parts, silicone-based defoamer 0.5 parts, water-based ink thickener 3 parts, ethylene glycol 1 part, isocyanate-based cross-linking agent 3 parts mixed The entire surface was solid-printed on a 100-mesh screen plate using the above-mentioned screen printing ink, and dried and cured at 60 ° C. for 30 minutes to form a porous layer 22 to obtain a discolored body 2.
Next, a fragrance liquid 3 consisting of 0.2 part of a mint scented fragrance [manufactured by Taiyo Kagaku Co., Ltd., trade name: Super Emulsion Peppermint 106] and 99.8 parts of water was obtained.
The discolored body and the fragrance liquid were combined to obtain a discolorable fragrance material set.
When the porous layer of the discolored body is impregnated with the aromatic liquid, the porous layer is in a state of being made transparent by the absorption of the aromatic liquid, so that the green color due to the support is visually recognized.
When the discolored body was placed indoors, the medium of the fragrance liquid evaporated together with the fragrance and became white as the porous layer dried, and the expiration date of the fragrance material could be clearly discriminated visually.

Reference example 2 (see Fig. 2)
As the support 21, a non-discoloring colored layer 23 was provided on the surface of a white polyethylene terephthalate film using a printing ink containing an orange pigment.
Next, on the non-discolorable colored layer, 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] Made by Kogyo Co., Ltd., solid content 30%] 45 parts, water 40 parts, silicone-based defoamer 0.5 parts, water-based ink thickener 3 parts, ethylene glycol 1 part, isocyanate-based cross-linking agent 3 parts mixed The entire surface was solid-printed on a 100-mesh screen plate using the above-mentioned ink for screen printing, and dried and cured at 60 ° C. for 30 minutes to form a porous layer 22 to obtain a discolored body 2.
Next, a fragrance liquid consisting of 0.2 parts of a mango scented fragrance [manufactured by San-Ei Gen FFI Co., Ltd., trade name: mango flavor] and 99.8 parts of water was obtained.
The discolored body and the fragrance liquid were combined to obtain a discolorable fragrance material set.
When the porous layer of the discolored body is impregnated with the aromatic liquid, the porous layer is made transparent by the absorption of the aromatic liquid, so that the orange color due to the non-color-changing colored layer is visually recognized.
When the discolored body was placed in the vehicle, the medium of the fragrance liquid evaporated together with the fragrance and became white as the porous layer dried, and the expiration date of the fragrance material could be clearly discriminated visually.

Example 1 (see FIG. 3)
As the support 21, on the surface of yellow cast coated paper, 10 parts of hydrophobic silica (manufactured by Tosoh Silica Co., Ltd., product name: Nipseal SS20), vinyl chloride-vinyl acetate copolymer resin (manufactured by Nisshin Chemical Industry Co., Ltd., product name) : Solvain A) Using a screen printing ink that is a mixture of 10 parts, 25 parts of cyclohexanone, and 1 part of nonionic additives, the entire surface is solid-printed on a 100-mesh screen plate, dried and cured at 60 ° C. for 30 minutes to make it porous. The layer 22 was formed to obtain the discolored body 2.
An adhesive layer 24 is provided on the back surface of the support.
Next, an aromatic liquid consisting of 5 parts of a lemon-scented fragrance [manufactured by Takasago Perfume Industry Co., Ltd., trade name: LEMON TJP-F-000765] and 95 parts of ethyl alcohol was obtained.
The discolored body and the fragrance liquid were combined to obtain a discolorable fragrance material set.
When the porous layer of the discolored body is impregnated with the aromatic liquid, the porous layer is made transparent by the absorption of the aromatic liquid, so that the yellow color due to the non-color-changing colored layer is visually recognized.
When the discolored body was attached to the wall surface of the room, the medium of the fragrance liquid evaporated together with the fragrance and became white as the porous layer dried, and the expiration date of the fragrance material could be clearly determined visually.

Example 2
On a lemon-shaped yellow ABS resin molded product as a support, 12 parts of hydrophobic silica (manufactured by Fuji Silysia Chemical Ltd., product name: Silohobic 200), acrylic resin 50% toluene / butyl acetate solution (DIC Corporation) Manufacture, product name: Acrydic A-817) 20 parts, methyl ethyl ketone 15 parts, xylene 15 parts were mixed and spray-painted with spray ink to form a porous layer to obtain a discolored product.
Next, an aromatic liquid consisting of 5 parts of a lemon-scented fragrance [manufactured by Takasago Perfume Industry Co., Ltd., trade name: LEMON TJP-F-000765] and 95 parts of ethyl alcohol was obtained.
The discolored body and the fragrance liquid were combined to obtain a discolorable fragrance material set.
When the porous layer of the discolored body is impregnated with the aromatic liquid, the porous layer is made transparent by the absorption of the aromatic liquid, so that the yellow color due to the non-color-changing colored layer is visually recognized.
When the discolored body was placed indoors, the medium of the fragrance liquid evaporated together with the fragrance and became white as the porous layer dried, and the expiration date of the fragrance material could be clearly discriminated visually.

Example 3
As a support, on the surface of yellow 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 Nisshin Chemical Industry Co., Ltd., product name: solveine) A) Using a screen printing ink that is a mixture of 10 parts, 25 parts of cyclohexanone, and 1 part of a nonionic additive, the entire surface is printed solidly on a 100 mesh screen plate, dried and cured at 60 ° C. for 30 minutes, and the porous layer is formed. 3- (4-Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide and 100 parts of butyl acetate are mixed. The porous layer was spray-coated and dried to contain an electron-donating color-developing organic compound in the porous layer to obtain a pale yellow discolored substance in the porous layer.
Then, an aromatic liquid consisting of 2 parts of hinokitiol, 3 parts of eugenol, and 95 parts of ethyl alcohol was obtained.
A discolorable fragrance material set was obtained by combining the discolored body and a stamping tool obtained by impregnating a bird-shaped stamp with the fragrance liquid.
When the porous layer of the discolored product is impregnated with the aromatic liquid, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl)-in the porous layer 4-Azaphthalide develops a blue color, and the porous layer becomes transparent due to the absorption of aromatic liquid, so that a green bird image can be visually recognized.
When the discoloring aromatic material is left to stand, the medium of the aromatic liquid evaporates together with the aromatic material, and as the porous layer dries, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole) -3-yl) -4-azaphthalide became colorless and the porous layer became pale yellow, and the expiration date of the fragrance material could be clearly discriminated visually.

Example 4
As a support, on the surface of white synthetic paper, 10 parts of hydrophobic silica (manufactured by Toso Silica Co., Ltd., product name: Nipseal SS20), vinyl chloride-vinyl acetate copolymer resin (manufactured by Nisshin Chemical Industry Co., Ltd., product name: solveine) A) Using a screen printing ink that is a mixture of 10 parts, 25 parts of cyclohexanone, and 1 part of a nonionic additive, print in a heart shape on a 100 mesh screen plate, dry and cure at 60 ° C. for 30 minutes, and then dry and cure the porous layer. , And further mixed 1,2-benz-6- (N-ethyl-N-isoamylamino) fluorane (2 parts), 1,1-bis (4-hydroxyphenyl) n-nonane (5 parts), and methyl ethyl ketone (100 parts). The product was spray-coated on the porous layer and dried to contain an electron-donating color-developing organic compound and an electron-accepting compound in the porous layer to obtain a discolored substance having a pink color in the porous layer.
Next, an aromatic liquid consisting of 5 parts of a lemon-scented fragrance [manufactured by Takasago Perfume Industry Co., Ltd., trade name: LEMON TJP-F-000765] and 95 parts of ethyl alcohol was obtained.
The discolored body and the fragrance liquid were combined to obtain a discolorable fragrance material set.
When the porous layer of the discolored body is impregnated with the aromatic liquid, 1,2-benz-6- (N-ethyl-N-isoamylamino) fluorane in the porous layer becomes colorless, and the porous layer becomes aromatic. Since the state is made transparent by absorbing the liquid, the white color of the support is visually recognized.
When the discoloring fragrance material is left to stand, 1,2-Benz-6- (N-ethyl-N-isoamylamino) fluorane turns pink as the medium of the fragrance liquid evaporates together with the fragrance and the porous layer dries. At the same time, the porous layer became white, and the expiration date of the fragrance material could be clearly discriminated visually.

1 Discoloring fragrance material set 2 Discoloring body 21 Support 22 Porous layer 23 Non-discoloring coloring layer 24 Adhesive layer 3 Aroma liquid

Claims (5)

A discolored body having a porous layer in which a low refractive index pigment is fixed to a binder resin in a dispersed state on a support, which is opaque in a non-liquid absorbing state and becomes transparent in a liquid absorbing state, and a fragrance and an organic solvent. Ri Do from an aromatic liquid and consisting of the low-refractive-index pigment in the porous layer, the coating weight of 5 to 20 g / m ^2, the low-refractive-index pigment is hydrophobic silica, and the aromatic liquor discoloring aromatic material set is housed in a container ing. The discolorable fragrance set according to claim 1, wherein the porous layer contains an electron-donating color-developing organic compound. The discolorable fragrance set according to claim 2, wherein the porous layer contains an electron-accepting compound. The discolorable fragrance set according to any one of claims 1 to 3, wherein a non-discolorable colored layer is provided between the support and the porous layer. The discolorable fragrance set according to any one of claims 1 to 4, wherein an adhesive layer or a heat-meltable resin layer having a melting point of 60 ° C. to 180 ° C. is provided on the bottom layer of the discolored body.

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