JP2001120651A - Fragrant microcapsule, and fragrant and thermally discoloring laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a microcapsule emitting fragrance by rubbing with a finger and a fragrant and thermally discoloring laminate simultaneously bringing about fragrant and thermally discoloring properties. SOLUTION: In a microcapsule, a film wall is broken by an external force to emit fragrance. A fragrant and thermally discoloring laminate constituted by laminating a layer on the surface of a supporting body, the layer comprising the fragrant microcapsule and thermally discoloring microcapsule pigment which are mixed or independent are fixed in a binder resin in a dispersed state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a fragrance releasing microcapsule and a fragrance releasing thermochromic laminate using the same. Specifically, the capsule wall membrane is destroyed by external force,
The present invention relates to a scent-release microcapsule that emits a scent due to a fragrance component contained therein, and a scent-release thermochromic laminate in which the scent-release microcapsules and the thermochromic microcapsules coexist to generate scent and thermal discoloration simultaneously. .

[0002]

2. Description of the Related Art Several proposals have conventionally been made with respect to fragrance capsules which release a fragrance by breaking a capsule wall film by an external force (JP-A-3-39300).

[0003]

SUMMARY OF THE INVENTION The present inventor has studied the above-mentioned external force-destructible fragrance releasing microcapsules, and is not destroyed by an external force applied in a production and secondary processing step or a distribution step. Disclosed is a low-pressure destructive fragrance releasing microcapsule that is broken by finger or eraser or the like to release fragrance. Further, by allowing the aroma releasing microcapsules and thermochromic microcapsule pigment to coexist,
Providing aroma-dissipating thermochromic laminates that simultaneously produce scent and heat discoloration, and achieve the combined effect of visual effects due to heat discoloration and odor effects due to fragrance, for toys, training fields, special printing fields, etc. Is intended to be applied.

[0004]

The present invention will be described with reference to the drawings (see FIGS. 1 to 9). The present invention provides a microcapsule in which a capsule wall film is broken by an external force and emits a fragrance due to a fragrance component contained therein, wherein the fragrance composition comprises a fragrance and a retaining agent, wherein the retaining agent is a hydrocarbon, a halogenated hydrocarbon. , Sulfides, ethers, ketones, esters, acid amides, alcohols, or waxes, and fragrance / retention agent = 1-50 /
The perfume composition contained therein is blended at a ratio of 99 to 50 (weight ratio), and the perfume composition is contained in the wall film 11.
And the average particle diameter [(minor axis / major axis) / 2] is 5
The fragrance releasing microcapsules 1 are required to be in the form of microcapsules having a circularity (minor axis / major axis) of 0.6 or more and a circularity of 0.6 to 500 μm (see FIG. 1). Furthermore, the capsule wall film 11 is broken by an external force, and the fragrance releasing microcapsules 1 and the thermochromic microcapsule pigments 2 releasing the fragrance of the fragrance composition 10 contained therein are dispersed in the binder resin in a mixed state or an individual state. A requirement is a scentable thermochromic laminate 3 in which a layer fixed in a state is laminated on the surface of the support 30 (see FIG. 7). Further, the odor releasing thermochromic laminate 3 includes the odor releasing layer 31 in which the odor releasing microcapsules 1 are fixed in a dispersed state in a binder resin, and the thermochromic microcapsule pigment 2 in the binder resin. A thermochromic layer 32 fixed in a dispersed state; furthermore, the fragrance releasing layer 31 is in a laminated state on the thermochromic layer 32 (see FIG. 8). That the layers 32 are in a juxtaposed state;
And the thermochromic microcapsule pigment 2 are fixed in a dispersed state in a binder resin in a mixed state to form a scentable thermochromic layer 3
3 (see FIG. 7). Further, the thermochromic microcapsule pigment 2 comprises (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) A pigment obtained by enclosing the thermochromic composition 20 containing a reaction medium for determining the temperature at which both of the color reactions take place in a microcapsule; The reaction medium of the microcapsule pigment 2 is
A compound selected from hydrocarbons, halogenated hydrocarbons, sulfides, ethers, ketones, esters, acid amides, alcohols, or waxes; and thermochromic microcapsule pigment 2 Has a non-circular cross-sectional shape (see FIGS. 3 to 6). Further, the thermochromic microcapsule pigment 2 is heated by heating from the color-developing state and developing by cooling from the decoloring state. A decoloring type, a color storage state that alternately stores and retains a colored state or a decolored state in a specific temperature range, or a color is developed by heating from a decolored state and returns to a decolored state by cooling from the colored state. To be selected from any of the heating and coloring types.

[0005] The fragrance releasing microcapsules in the above,
A fragrance composition comprising a fragrance and a retaining agent is formed by forming a wall film by a known means and encapsulating the same. The fragrance is effective for those conventionally used widely, and the retaining agent is for retaining the fragrance and releasing the capsule properly when the capsule is broken, and the eutectic temperature of the fragrance and the retaining agent is − The range of 20 ° C. to + 60 ° C. satisfies the simple destructibility intended by the present invention, which is destroyed by a pressing operation by rubbing with a finger or an eraser or the like and releases fragrance. Further, the eutectic temperature is in the range of 10 to 60C (more preferably, 20 to 60C).
(50 ° C.), it is solid under normal conditions, has an external pressure buffering action, and is hard to break. However, when it is liquefied by heating due to scratching or the like, the external pressure buffering property is reduced, and it cooperates with external force due to scratching. Then, the wall film is destroyed by the load of a relatively low pressure during the rubbing process by a finger or the like, and the fragrance can be released.
The fragrance / retention agent = 1 to 50/99 to 50 (weight ratio);
Further, preferably, the range of 5 to 25/95 to 75 (weight ratio) satisfies the retention and aroma emission. The retaining agent is a hydrocarbon, a halogenated hydrocarbon, a sulfide, an ether, a ketone, an ester, an acid amide,
It is a compound selected from alcohols and waxes, and one or more of these compounds can be used as a mixture. The retention agent can be selected and applied from the same compounds as the reaction medium of the thermochromic material described later. The microencapsulation is conventionally formed by a general-purpose means, and an average particle diameter [(minor axis / major axis) / 2] of 5 to 500 μm, preferably about 10 to 50 μm satisfies the practicality, In a microcapsule-type system having a circularity (minor axis / major axis) of 0.6 or more, the tolerance to elastic deformation due to external stress is poor, and therefore, external stress is directly received and rubbing of fingers and the like is performed. It functions effectively for easy destruction. In a system in which the circularity is less than 0.6, the degree of elastic deformation due to external stress is large, and the elastic deformation is appropriate to relieve the stress and suppress destruction.

Next, the fragrance will be described. As the flavor, an oil-soluble general-purpose flavor can be suitably used. The fragrance is generally a mixture of compounds as exemplified below, and the use thereof alone is not applied except for special examples. The compounds are exemplified below, but the compounds are not limited to these, and any compounds that exhibit perfume characteristics are effective. Ethyl acetoacetate, acetophenone, anisaldehyde, jasminal, isoamyl anthranilate, isoeugenol, isoamyl isovalerate, ethyl isovalerate, allyl isothiocyanate, undecalactone, ethylvalinine, ethyl enanthate, eugenol, octylaldehyde, Ethyl caprate, ethyl caprate, caproic acid, allyl caproate, ethyl caproate, isoamyl formate, geranyl formate, citronellyl formate, cinnamic alcohol, cinnamic aldehyde, cinnamic acid, ethyl cinnamate, methyl cinnamate, geraniol. Ethyl acetate, isoamyl acetate, geranyl acetate, cyclohexyl acetate, citronellyl acetate, cinnamyl acetate, terpinyl acetate, phenylethyl acetate, butyl acetate, benzyl acetate, menthyl acetate, linalyl acetate, methyl salicylate, allyl cyclohexylpropionate, citronellal, citronellol, citral , Terpineol, decyl alcohol, decyl aldehyde, nonalactone, p-methylacetophenone, vanillin, hydroxycitronellal, hydroxycitronellal dimethyl acetal, piperonal, isoamyl phenylacetate, isobutyl phenylacetate, ethyl phenylacetate, isoamyl propionate, propionic acid Ethyl, benzyl propionate, perilaldehyde, benzyl alcohol, benzaldehyde, bornene Lumpur, maltol, methyl β Nafuchiruketon, N-methylstyrene anthracite sulfonyl methyl, menthol, cineole, ionone, isoamyl butyrate, ethyl butyrate, cyclohexyl butyrate, butyl butyrate, linalool, and the like. The aforementioned fragrance ingredients are natural,
It can be used regardless of the synthetic compound.

The fragrance component prepared by combining the above-mentioned compounds is blended with a retention agent to constitute a fragrance composition, and the composition is encapsulated in microcapsules by a general-purpose microencapsulation means to produce a fragrance releasing microparticle. Make up the capsule. The retention agent is selected from hydrocarbons, halogenated hydrocarbons, sulfides, ethers, ketones, esters, acid amides, alcohols, and waxes. Specific examples are described below.

[0008] Retaining agents are exemplified below. As hydrocarbons, there are chain hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and the like, and as saturated chain hydrocarbons, pentadecane, hexadecane, heptadecane, octadecane,
Nonadecane, eikosan, heneikosan, dokosan,
Examples include trichosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, and triacontan. Examples of unsaturated chain hydrocarbons include 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracocene, 1-pentacocene, 1-hexacocene, 1-heptacocene, 1-octacocene, 1
-Nonacocene, 1-triaconten and the like can be exemplified. Examples of the alicyclic hydrocarbons include cyclooctane, cyclododecane, n-pentadecylcyclohexane, n-octadecylcyclohexane, n-nonadecylcyclohexane,
Decahydronaphthalene and the like can be exemplified. As aromatic hydrocarbons, dodecylbenzene, biphenyl, ethylbiphenyl, 4-benzylbenzene, phenyltolylmethane, diphenylethane, 1,3-diphenylbenzene,
Examples thereof include dibenzyltoluene, methylnaphthalene, 2,7-diisopropylnaphthalene, methyltetralin, and naphthylphenylmethane.

The halogenated hydrocarbons include 1-bromodecane, 1-bromoundecane, 1-bromododecane, 1-bromotridecane, 1-bromotetradecane,
1-chlorotetradecane, 1-bromopentadecane, 1
-Bromohexadecane, 1-chlorohexadecane, 1-
Examples thereof include iodohexadecane, 1-bromoheptadecane, 1-bromooctadecane, 1-chlorooctadecane, 1-iodooctadecane, 1-bromoeicosane, 1-chloroeicosane, 1-bromodocosan, and 1-chlorodocosane.

As the sulfides, di-n-octyl sulfide, di-n-nonyl sulfide, di-n-decyl sulfide, di-n-dodecyl sulfide, di-n-
Tetradecyl sulfide, di-n-hexadecyl sulfide, di-n-octadecyl sulfide, octyldodecyl sulfide, diphenyl sulfide, dibenzyl sulfide, ditolyl sulfide, diethyl phenyl sulfide, dinaphthyl sulfide, 4,4'-dichloro-
Examples thereof include diphenyl sulfide and 2,4,5,4'-tetrachloro-diphenyl sulfide.

As the ethers, aliphatic ethers having a total carbon number of 10 or more, for example, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether, Ditridecyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decanediol dimethyl ether, undecanediol dimethyl ether, dodecanediol dimethyl ether, tridecanediol dimethyl ether, decanediol diethyl ether, undecanediol diethyl ether, etc. . Alicyclic ethers such as s-trioxane; As aromatic ethers, phenyl ether, benzyl phenyl ether, dibenzyl ether, di-p
-Tolyl ether, 1-methoxynaphthalene, 3,4
Examples thereof include 5-trimethoxytoluene.

The ketones include aliphatic ketones having a total carbon number of 10 or more, for example, 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, 6-undecanone, 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8
Pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2-pentadecanone,
-Octadecanone, 2-nonadecanone, 10-nonadacanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, lauron, stearone and the like. Arylalkyl ketones having a total carbon number of 12 to 24, for example, n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecanophenone; 4-n-
Dodecaacetophenone, n-tridecanophenone, 4-
n-undecanoacetophenone, n-laurophenone,
4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n-decanophenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4 -N-hexylacetophenone, 4-n-
Cyclohexyl acetophenone, 4-tert-butyl propiophenone, n-heptaphenone, 4-n-pentyl acetophenone, cyclohexyl phenyl ketone,
Benzyl-n-butyl ketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonaphthone, 2-acetonaphthone,
Cyclopentyl phenyl ketone and the like. Aryl aryl ketones, for example, benzophenone, benzyl phenyl ketone, dibenzyl ketone and the like. Alicyclic ketones, for example, cyclooctanone, cyclododecanone, cyclopentadecanone, 4-tert-butylcyclohexanone and the like can be exemplified.

As the esters, esters having 10 or more carbon atoms are effective, and include monohydric carboxylic acids having aliphatic and alicyclic or aromatic rings and monohydric alcohols having aliphatic and alicyclic or aromatic rings. Esters and aliphatics obtained from any combination of esters, aliphatic and alicyclic or aromatic polyhydric carboxylic acids and aliphatic and alicyclic or aromatic monohydric alcohols obtained from any combination And esters obtained from any combination of a monovalent carboxylic acid having an alicyclic or aromatic ring and a polyhydric alcohol having an aliphatic and an alicyclic or aromatic ring, and specifically, ethyl caprylate and caprylic acid. Octyl, stearyl caprylate, myristyl caprate,
Stearyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n-stearate Butyl, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, n-undecyl stearate, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate, Behenyl behenate, cetyl benzoate, p-
Stearyl tert-butyl benzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate, dilauryl azelate, di-lauryl sebacate (n −
Nonyl), dineopentyl 1,18-octadecylmethylenedicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-pentanediol dimyristate,
1,2,6-hexanetriol trimiristate,
Examples thereof include 1,4-cyclohexanediol didecyl, 1,4-cyclohexane dimethanol dimyristate, xylene glycol dicaprinate, and xylene glycol distearate.

An ester of a saturated fatty acid and a branched aliphatic alcohol; an unsaturated fatty acid or an ester of a branched or substituted saturated fatty acid or an aliphatic alcohol having 16 or more carbon atoms; cetyl butyrate; Ester compounds selected from stearyl butyrate and behenyl butyrate are also effective. Specifically, 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl caprate, lauric acid 3,
5,5-trimethylhexyl, palmitic acid 3,5,5
-Trimethylhexyl, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate,
1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behenate, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-caproic acid
Methylpentyl, 2-methylpentyl caprylate, 2-methylpentyl caprate, 2-methylpentyl laurate, 2-methylbutyl stearate, 2 stearic acid
-Methylbutyl, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate, 1-ethylpentyl caproate, palmitin 1-ethylpentyl acid, 1-methylpropyl stearate, 1 stearic acid
-Methyloctyl, 1-methylhexyl stearate,
1,1-dimethylpropyl laurate, 1-capric acid
Methylpentyl, 2-methylhexyl palmitate, 2-methylhexyl stearate, 2-methylhexyl behenate, 3,7-dimethyloctyl laurate, 3,7-dimethyloctyl myristate, 3,7 palmitate
-Dimethyloctyl, 3,7-dimethyloctyl stearate, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate Isostearyl erucate, cetyl isostearate, stearyl isostearate, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, 2
-Isostearyl ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, behenyl butyrate and the like.

Further, carboxylic acid ester compounds disclosed in Japanese Patent Publication No. 4-17154, for example, a carboxylic acid ester having a substituted aromatic ring in the molecule, a carboxylic acid having an unsubstituted aromatic ring in the molecule and a carboxylic acid having 10 or more carbon atoms. Of aliphatic alcohols, carboxylic acid esters containing a cyclohexyl group in the molecule, esters of fatty acids having 6 or more carbon atoms and unsubstituted aromatic alcohols or phenols, esters of fatty acids having 8 or more carbon atoms and branched aliphatic alcohols, dicarboxylic acids Esters of acids and aromatic or branched aliphatic alcohols, benzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin ,
Dimyristin, distearin and the like.

A fatty acid ester compound obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an aliphatic carboxylic acid having an even carbon number, n-pentyl alcohol or n-heptyl alcohol, and an even aliphatic compound having 10 to 16 carbon atoms. Fatty acid ester compounds having a total of 17 to 23 carbon atoms obtained from aliphatic carboxylic acids are also effective. Specifically, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecyl caprylate, N-tridecyl caprylate, n-pentadecyl caprylate, n-caprate
Heptyl, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, n-laurate
Heptyl, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-undecyl myristate, N-tridecyl myristate, n-pentadecyl myristate, n-pentyl palmitate,
N-heptyl palmitate, n-nonyl palmitate,
N-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n-stearate
-Nonyl, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undersi eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate , N-undecyl behenate,
Examples include n-tridecyl behenate and n-pentadecyl behenate.

Examples of alcohols include decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol,
Aliphatic monohydric saturated alcohols such as pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol, allyl alcohol, aliphatic unsaturated alcohols such as oleyl alcohol, cyclopentanol, cyclopentyl Examples thereof include alicyclic alcohols such as hexanol, cyclooctanol, cyclododecanol and 4-tert-butylcyclohexanol; aromatic alcohols such as 4-methylbenzyl alcohol and benzhydrol; and polyhydric alcohols such as polyethylene glycol.

Examples of the acid amides include the following compounds. Acetamide, propionamide, butyric amide, caproic amide, caprylic amide, capric amide, lauric amide, myristic amide,
Palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, benzamide, caproic anilide, caprylic anilide, capric anilide, lauric anilide, myristic anilide, palmitic anilide, stearic anilide,
Behenic acid anilide, oleic acid anilide, erucic acid anilide, caproic acid N-methylamide, caprylic acid N-
Methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristic acid N-methylamide,
Palmitic acid N-methylamide, stearic acid N-methylamide, behenic acid N-methylamide, oleic acid N-
Methylamide, erucic acid N-methylamide, lauric acid N-ethylamide, myristic acid N-ethylamide, palmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide, lauric acid N-
Butylamide, N-butylamide myristic acid, N-butylamide palmitic acid, N-butylamide stearate, N-butylamide oleate, N-octylamide laurate, N-octylamide myristic acid, N-octylamide palmitate, N-stearic acid -Octylamide, oleic acid N-octylamide, lauric acid N
-Dodecylamide, myristic acid N-dodecylamide,
Palmitic acid N-dodecylamide, stearic acid N-dodecylamide, oleic acid N-dodecylamide, dilauric acid amide, dimyristic acid amide, dipalmitic acid amide, distearic acid amide, dioleic acid amide,
Trilauric amide, Trimyristic amide, Tripalmitic amide, Tristearic acid amide, Trioleic amide, Succinamide, Adipamide,
Glutaramide, malonamide, azelaic amide, maleic amide, succinic N-methylamide, adipic N-methylamide, glutaric N-methylamide, malonic N-methylamide, azelaic N-methylamide, succinic N- Ethylamide, adipic acid N-
Ethylamide, glutaric acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, succinic acid N-butylamide, adipic acid N-butylamide, glutaric acid N-butylamide, malonic acid N-butylamide, adipic acid N-octylamide , Adipic acid N
-Dodecylamide and the like.

Examples of the waxes and medium molecular weight polymers include paraffin wax having a melting point of 50 to 120 ° C., microcrystalline wax, petrolactam, oxidized paraffin wax, and petrolactam oxide. Shellac, sugar cane wax, carnauba wax, candelilla wax,
Castor wax, hardened tallow oil, hardened fish oil, hardened rapeseed oil, montan wax, palm wax, chuhokuro, hazelou, wool fat, etc. Polyethylene wax, montanic acid wax, ethylene-vinyl acetate copolymer wax, ethylene acrylic copolymer wax, vinyl ether wax, etc.
Examples include palm oil, babassu oil, liquid paraffin, polybutene, polybutadiene, polystyrene oligomer, and the like.

The fragrance releasing microcapsules are dispersed in an aqueous or oily vehicle containing a binder resin to form a printing ink or a paint to form an aromatic layer. Here, the proportion of the fragrance releasing microcapsules is 5 to 100 parts by weight (preferably 10 parts by weight) based on 100 parts by weight of the binder resin.
６０60 parts by weight). When the amount is 5 parts by weight or less, the fragrance is insufficient, and when the amount is 100 parts by weight or more, it is excessive,
It is uneconomical.

Specific examples of the binder resin include an ionomer resin, an isobutylene-maleic anhydride copolymer resin, an acrylonitrile-acrylic styrene copolymer resin, an acrylonitrile-butadiene-styrene copolymer resin, and an acrylonitrile-chlorinated polyethylene-styrene copolymer. Polymerized resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinylidene chloride, vinyl chloride resin, chlorinated vinyl chloride resin,
Vinyl chloride-vinylidene chloride copolymer resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, polystyrene resin, high-impact polystyrene resin, polypropylene resin, polymethylstyrene resin, polyacrylic acid resin, polymethylmethacrylate resin, epoxy resin , Epoxy acrylate resin, alkyl phenol resin, rosin modified phenol resin, rosin modified alkyd resin, phenol resin modified alkyd resin, styrene modified alkyd resin, acryl modified alkyd resin, amino alkyd resin, vinyl chloride-vinyl acetate resin, styrene-butadiene resin, Unsaturated polyester resin, polyurethane resin, vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylate emulsion tree , Water-soluble melamine resins, water soluble urea resins, water-soluble phenolic resin, water-soluble epoxy resin, water-soluble polybutadiene resins, cellulose acetate, the cellulose derivatives such as ethyl cellulose and the like.

The thermochromic microcapsule pigment is
(A) an electron-donating color-forming organic compound, (b) an electron-accepting compound that colors the compound, and (c) a reaction medium that determines the temperature at which a color reaction between the two occurs. Conventionally known ones are effective, and specifically, those described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29898, etc. proposed by the present applicant. Is available. The color change occurs before and after a predetermined temperature (color change point) as a boundary, a decolored state occurs at a temperature range higher than the color change point, and a color developed state occurs at a temperature range lower than the color change point. Only one of the states can exist. That is, the other state is maintained while the heat or cold required to develop the state is applied, but returns to the state exhibited in the normal temperature range when the application of the heat or cold is stopped, hysteresis. can be mentioned width is relatively small characteristic (ΔH _a = 1~7 ℃) heating decolorizable with (a), particularly [Delta] H _a is 3 ° C. following systems [KOKOKU 1-
No. 29398, a fatty acid ester having a ΔT value (melting point-cloud point) of 3 ° C. or less is used as the component (c)]. It shows heat decoloring properties and can be applied effectively according to the purpose.

Also, Japanese Patent Publication No. 4-171 proposed by the present applicant.
No. 54, JP-A-7-179777, JP-A-7-179777
-33997 discloses a large hysteresis characteristic described in JP-A 8-39936 Patent Publication (ΔH _B = 8~
50 ° C.), that is, the shape of the curve plotting the change in the coloring density due to the temperature change is different from the case where the temperature is increased from a temperature lower than the color change temperature range and conversely, the temperature is decreased from a temperature higher than the color change temperature range. The color changes following a route that is significantly different from the case where the color changes, a color-developing state is exhibited below the low-temperature discoloration point, a decoloring state is exhibited above the high-temperature discoloration point, and the temperature between the low-temperature side discoloration point and the high-temperature side discoloration point. A color storage and retention type (B) that alternately stores and retains the color-developed state and the decolored state can be applied.

Further, as a composition of the heat-coloring type (C), a color is developed by heating from a decolored state and proposed by the present applicant (JP-A-11-129623, JP-A-11-5973).
(B), a system to which a specific alkoxyphenol compound having a linear or branched alkyl group having 3 to 18 carbon atoms is applied as the electron accepting compound.

By selecting and applying pigments containing the three types (A, B, and C) of the thermochromic compositions according to the purpose, thermochromic elements having various discoloration forms are constituted. it can.

(C) Compounds which are reaction media for causing the electron transfer reaction according to the above (a) and (b) to occur reversibly in a specific temperature range include hydrocarbons, halogenated hydrocarbons, sulfides, and ethers. , Ketones, esters, acid amides, alcohols, waxes and other conventional reaction media are all effective, and semi-liquid substances such as medium molecular weight polymers may be used. One or more compounds can be applied. The compounds exemplified as the retaining agent can be applied as they are. The thermochromic composition applied to the present invention is a general-purpose (A), (B),
The component (C) is an essential component, and the proportion of each component depends on the concentration, the color change temperature, the color change form, and the type of each component. (B) component 0.1 to 50, preferably 0.5 to 2
0, component (c) is in the range of 1 to 200, preferably 5 to 100 (all the above parts are parts by weight).

The microcapsule pigment containing the thermochromic composition satisfies the practicality if it has a particle size of 0.1 to 100 μm, preferably 3 to 30 μm. The average particle diameter of the thermochromic pigment [(major axis + minor axis) / 2] is 0.5 μm to 3 μm.
A range of 0 μm, preferably 0.5 to 15 μm, and more preferably 0.5 to 10 μm is effective in terms of sensitivity to discoloration, endurance, workability, and the like.

The microcapsule pigments having a perfect circular cross section are not refused, but those having a non-circular cross-sectional shape, more specifically, those having a non-circular cross-sectional shape having a depression on at least a part of the outer surface. (See FIGS. 3 to 6) can be effectively applied. That is, since the pigment is a non-circular flat pigment, it can be appropriately elastically deformed under stress of heat or pressure to relieve stress, and thus has an effect of suppressing destruction of the capsule wall film. In the encapsulated thermochromic pigment of the present invention, the reversible thermochromic composition / wall film is preferably in the range of 7/1 to 1/1 (weight ratio). If the ratio of the thermochromic composition is larger than the above range, the thickness of the wall film becomes too thin, and the protective function of the contained thermochromic composition is reduced. On the other hand, if the ratio of the wall film is larger than the above range, the color density must be reduced, which is not preferable.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The fragrance releasing microcapsules of the present invention can be used by being blended in a dispersed state in a binder resin and fixed to the surface of a support, but can be used in combination with a thermochromic microcapsule pigment. It is put to practical use as a form.

[0030]

Examples are shown below. The parts in the examples are parts by weight.

Example 1 5 parts of an epoxy resin was dissolved in 100 parts of a fragrance component consisting of 50 parts of lemon oil and 50 parts of myristyl alcohol (melting point of 33.0 ° C. in a eutectic state).
Emulsified in a 10% aqueous gelatin solution, adjusted and stirred to an outer diameter of 5 μm, and added 2.5 parts of an amine-based curing agent.
The scented microcapsules obtained by reacting at 3 ° C. for 3 hours were isolated by centrifugation.
Ethylene-vinyl acetate copolymer resin emulsion 6
7 parts were added to obtain a scented ink. Using a thermochromic ink composed of 40 parts of thermochromic microcapsule pigment (colorless at 33 ° C. or higher, heat-decolorable type exhibiting yellowish green at 33 ° C. or lower) and 60 parts of an ethylene-vinyl acetate resin emulsion,
Screen printing was performed on a lemon pattern printed in a general color to form a thermochromic layer, and then a scent-release ink was applied by gravure printing to form a scent-release layer. At room temperature, the printed matter has the appearance of a yellow-green immature lemon, but at the same time it changes color to yellow by rubbing with the fingertips, simultaneously emits the scent of lemon, as if the lemon were fully ripe. Presented.

Example 2 55 parts of an isocyanate resin was dissolved in 100 parts of a fragrance component consisting of 2 parts of synthetic apple fragrance and 98 parts of lauryl stearate (melting point of 42 ° C. in a eutectic state of both), and 3% of 60 ° C. Emulsified in gelatin aqueous solution, outer diameter 30
The mixture was stirred and adjusted to 0 μm, then heated to 80 ° C. and reacted for 3 hours, and then filtered to isolate a fragrant microcapsule. 20 parts of thermochromic microcapsule pigment (colorless at 42 ° C. or higher, pinkish at 42 ° C. or lower), 20 parts of the fragrance releasing microcapsules, and 60 parts of acrylic emulsion are mixed, and a fragrance thermochromic cloth is mixed. Ink was obtained.
Screen printing on the surface of the cotton towel using the scent-release thermochromic ink, pink color at room temperature, changes to colorless by bath temperature, emits the fragrance of apple by wiping the body, unique bathing I was able to get a towel.

Example 3 25 parts of natural lavender fragrance, stearyl caprate 75
25 parts of an isocyanate resin was dissolved in 100 parts of a fragrance component composed of 3 parts (melting point of 33 ° C. in a eutectic state of both) and emulsified in a 3% aqueous gelatin solution at 60 ° C.
The mixture was stirred and adjusted to a thickness of μm.
Allowed to react for hours. After standing overnight, the floating fragrant microcapsules were isolated. 20 parts of thermochromic microcapsule pigments (colorless at 33 ° C. or higher and heat decoloring type exhibiting green at 33 ° C. or lower), 20 parts of the fragrance releasing microcapsules
30 parts of a urethane-based emulsion and 30 parts of water were mixed to obtain an aroma releasing thermochromic aqueous spray ink. The fragrance thermochromic aqueous spray ink was spray-coated on the flower part of the artificial lavender flower to obtain a fragrance thermochromic artificial flower. The artificial flower emitted a lavender aroma at the same time as the flower portion changed from green to purple when touched by hand.

Example 4 10 parts of an isocyanate resin was dissolved in 100 parts of a fragrance component consisting of 40 parts of sausage flavor and 60 parts of cetyl caprate (melting point of 30 ° C. in the eutectic state of both). The mixture was emulsified in an aqueous alcohol solution, stirred to an outer diameter of 50 μm, and then heated to 90 ° C. and reacted for 3 hours. After the reaction, the fragrance releasing microcapsules were isolated by centrifugation. 20 parts of thermochromic microcapsule pigment (colorless at 30 ° C. or higher, heat-decoloring type that exhibits black at 30 ° C. or lower), 10 parts of the above-mentioned fragrance microcapsules, and 70 parts of SBR-based emulsion Concealment printing was performed on a printed matter on which a sausage pattern was printed using a general color using a water-based ink. The printed matter had a black color at room temperature, but when rubbed with a fingertip, the sausage pattern appeared and the sausage scent was released at the same time.

[0035]

The fragrance releasing microcapsules of the present invention do not release fragrance in the normal state, but release the fragrance by breaking the capsule by simple means such as rubbing with a finger or the like. Discolored at 30 ℃ -60
The laminate of the present invention, which is combined with a thermochromic element having a discoloration point in the temperature range of ° C., simultaneously develops an odor effect due to fragrance and a visual effect due to thermal discoloration to provide a new fragrance having a combined effect. Various thermochromic laminates include toys, educational materials, picture books, stationery, fancy goods, fabrics, garments such as yarn, decorative elements such as artificial flowers and paintings, calendars, greeting cards and other cards, and forgery prevention. Applicable to the field.

[Brief description of the drawings]

FIG. 1 is an enlarged explanatory view of (A) an external appearance and (B) a cross section of one embodiment of a fragrance releasing microcapsule applied to the present invention.

FIG. 2 is an enlarged explanatory view of (A) the appearance and (B) a cross section of another embodiment of the fragrance releasing microcapsule applied to the present invention.

FIG. 3 is an enlarged explanatory view of (A) the appearance and (B) a cross section of one embodiment of the thermochromic microcapsule pigment applied to the present invention.

FIG. 4 is an enlarged explanatory view of (A) the appearance and (B) a cross section of another example of the thermochromic microcapsule pigment applied to the present invention.

FIG. 5 is an enlarged explanatory view of (A) the appearance and (B) a cross section of another example of the thermochromic microcapsule pigment applied to the present invention.

FIG. 6 is an enlarged explanatory view of (A) the appearance and (B) a cross section of another example of the thermochromic microcapsule pigment applied to the present invention.

FIG. 7 is an explanatory longitudinal sectional view of one embodiment of the scented thermochromic laminate of the present invention.

FIG. 8 is an explanatory longitudinal sectional view of another embodiment of the scented thermochromic laminate of the present invention.

FIG. 9 is an explanatory longitudinal sectional view of another embodiment of the scented thermochromic laminate of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 fragrance releasing microcapsule 10 fragrance composition 11 wall film 2 thermochromic microcapsule pigment 20 thermochromic composition 21 wall film 3 fragrance thermochromic laminate 30 support 31 fragrance layer 32 thermochromic layer 33 Perfuming thermochromic layer

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4C080 AA04 BB03 HH05 HH10 JJ03 LL03 QQ03 4F100 AK01A AK68 AR00A AR00C AS00A AS00C AT00B BA02 BA03 BA07 BA10A BA10B CA13A CA13C CA30A DE04A DE04C GB90 HB01BA00 J20A00A20A00 BA30 BA49 BA64 BB51 CA54 CA72 DA08 DA09 DA15 EA31

Claims (11)

[Claims] 1. The capsule wall membrane is broken by an external force,
In a microcapsule that emits a fragrance due to a fragrance component contained therein, the fragrance composition comprises a fragrance and a retention agent, and the retention agent is a hydrocarbon, a halogenated hydrocarbon, a sulfide, an ether, a ketone, an ester, Acid amides,
A compound selected from alcohols or waxes, blended at a ratio of fragrance / retention agent of 1 to 50/99 to 50 (weight ratio), and covering the fragrance composition contained therein with a wall film to form an average particle The diameter [(minor axis / major axis) / 2] is 5 to 500
μm and a microcapsule having a roundness (minor axis / major axis) of 0.6 or more, wherein the microcapsules are in the form of a fragrance. 2. The capsule wall membrane is broken by an external force,
A fragrance in which a layer in which a fragrance releasing microcapsule and a thermochromic microcapsule pigment that emit an aroma due to the contained perfume composition are fixed in a mixed or individual state in a dispersed state in a binder resin is laminated on the surface of the support. Thermochromic laminate. 3. A scent releasing layer in which a fragrance releasing microcapsule is fixedly dispersed in a binder resin, and a thermochromic layer in which a thermochromic microcapsule pigment is fixedly dispersed in a binder resin. Item 4. An aroma releasing thermochromic laminate according to Item 2. 4. The odor releasing thermochromic laminate according to claim 3, wherein the odor releasing layer is in a laminated state on the thermochromic layer. 5. The odor releasing thermochromic laminate according to claim 3, wherein the odor releasing layer and the thermochromic layer are arranged side by side. 6. The fragrance according to claim 2, wherein the fragrance releasing microcapsules and the thermochromic microcapsule pigment are fixed in a dispersed state in a binder resin in a mixed state to form a fragrance releasing thermochromic layer. Thermochromic laminate. 7. The fragrance releasing microcapsules according to claim 1 are applied to the fragrance releasing microcapsules.
The scented thermochromic laminate according to any one of the preceding claims. 8. The thermochromic microcapsule pigment comprises:
A thermochromic composition containing (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that determines the temperature at which the color reaction of the two occurs, is encapsulated in microcapsules. The scent-released thermochromic laminate according to claim 2, 3 or 6, which is a pigment comprising: 9. A retention medium for the fragrance releasing microcapsules and a reaction medium for the thermochromic microcapsules are hydrocarbons, halogenated hydrocarbons, sulfides, ethers, ketones, esters, acid amides. 3. The odor-dissipating thermochromic laminate according to claim 2, which is a compound selected from the group consisting of alcohols, waxes, and the like. 10. The thermochromic microcapsule pigment according to any one of claims 2, 3, 6, 7, 8, and 9, has a non-circular cross-sectional shape. 11. A thermochromic microcapsule pigment, which is decolorized by heating from a color-developing state and changes color by heating from a decolored state to a color at a specific temperature by changing the color-developed state or the decolored state to a specific temperature. Color memory holding type that stores and holds in the area, or
The scent-release thermochromic according to any one of claims 2 to 10, wherein the color is formed by heating from the decolored state, and is selected from a heating and coloring type which returns to the decolored state by lowering the temperature from the colored state. Laminate.