JPH08300539A - Thermally discolorable laminate - Google Patents

Abstract

PURPOSE: To invisibly form a multi-color and various image and to enhance the remarkability and the design effect in a thermally discolorable printed matter in which an non-thermally discoloring image is invisibly formed by discoloring a thermally discolorable concealing layer due to temperature change. CONSTITUTION: A thermally discolorable laminate 1 comprises a thermally discolorable concealing layer 4 for invisibly forming non-thermally discoloring image 3 formed on the surface of a support 2, and a thermally discolorable shielding and light transmission image 5 exhibiting the interchangeability between white opaque state and colorless transparent state according to the temperature change on the layer 4.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermochromic laminate. More specifically, the thermochromic shading-translucent image that exhibits a hysteresis characteristic due to temperature change and changes color, and exhibits the alternation of both the white opaque state and the colorless transparent state, and the color change due to the temperature change The present invention relates to a thermochromic laminate in which a non-thermochromic image can be concealed by a discoloration of a thermal masking layer.

[0002]

2. Description of the Related Art Conventionally, several attempts have been disclosed to provide a thermochromic masking layer on a non-thermochromic image so that the nonthermochromic image can be concealed by a temperature change (Act 3). -3
No. 429, Jpn. 3-45829, J. S. 59-68
972). Several proposals have been disclosed regarding thermochromic materials for forming the thermochromic hiding layer. For example, regarding the reversible thermochromic material exhibiting a color-colorless reversible color change or a color [1] -color [2] reversible color change, some proposals by the present applicants have been disclosed ( JP-B-51-44706, JP-B-51-44708, JP-B-1-29398, etc.). The thermochromic material discolors at a discoloration temperature,
Of the two states before and after the change, only one particular state exists at room temperature. That is, the other state returns to the state exhibited in the normal temperature range when the application of heat or cold heat required for the development of the state disappears. It is a reversible thermochromic material of a type that exhibits a small hysteresis width (ΔH) with respect to a temperature-color density curve due to so-called temperature change and changes color (see FIG. 7). As the other thermochromic material, it exhibits a large hysteresis width (ΔH) due to temperature change, and when the temperature is increased from the low temperature side of the discoloration temperature range, it is decreased from the high temperature side of the discoloration temperature range. In the case where the color changes along a path that is significantly different from that in the case, and even after removing the application of heat or cold heat required for the color change, the low temperature side color point or less in the normal temperature range between the low temperature side color change point and the high temperature side color change point. Alternatively, a color memory thermochromic type of a type having so-called tautomerism between a colored state and a colorless state or tautomerism between a colored [1] and a colored [2], which retains a state of being discolored at a high temperature side discoloration point or higher. Examples of the material include [(Japanese Patent Publication No. 4-17154, etc.), (see FIG. 6)]. The thermochromic material described above exhibits the hysteresis characteristics illustrated in FIGS. 6 and 7 in the color density-temperature curve, and changes color. The change in color density due to the temperature change progresses along the arrow. Here, A is the minimum temperature T at which the completely decolored state is reached.
₄ is a point showing the density at (coloring and erasing branch temperature), and B
Is a point showing the density at the maximum temperature T ₃ (maximum holding temperature) where the completely colored state can be maintained, and C is a point showing the density at the lowest temperature T ₂ (minimum holding temperature) where the completely decolored state can be maintained. , D is the maximum temperature T that reaches a completely colored state
_The temperature width (ΔH), which is the point showing the density at ₁ (complete coloring temperature) and the length of the line segment HG shows the degree of hysteresis.
In the system where ΔH is less than about 6 ° C., the former type of reversible thermochromic material is used, and in the system where ΔH is 8 ° C. or more, the latter functions as the color memory thermochromic material. However, as shown in the above drawings (FIGS. 6 and 7), a thermochromic light-shielding / translucent material satisfying the practicality of exhibiting reversible behavior of white opaque-colorless transparent has not yet been disclosed.

Recently, as a heat-sensitive recording material for image formation by a thermal head or the like, an attempt to form a heat-sensitive layer by dispersing microcapsules containing an organic low-molecular substance in a resin medium has been disclosed (special feature. Kaihei 5-116452
No. The microcapsules show a cloudy opaque state and a colorless and transparent state depending on the temperature, but the color change characteristics are different from those of the thermochromic material described above, and the third state in which the temperature of the colorless and transparent state is exceeded is exceeded. That is, in a system that exhibits an intermediate state (translucent state) of the above states and expresses the intermediate state, the state changes by following a route different from those of the two states. This point will be described with reference to FIG. T
₀ 'following a normal temperature is in the cloudy opaque state, which the temperature T _2' becomes transparent when heated to again T ₀ 'in this state
Even if cooled below and returned to room temperature, it remains as it is. When heated above T ₃ ', it becomes a semitransparent state between the maximum transparency and the maximum opacity, and when the temperature is lowered in this state, It returns to the initial cloudy opaque state without taking the transparent state again. This cloudy opaque state is T ₁ '
After being heated to a temperature between T ₂ ′ and cooled to room temperature, that is, a temperature of T ₀ ′ or less, an intermediate state between transparent and opaque can be obtained. Also, if the transparent material at room temperature is heated to a temperature of T ₃ 'or higher and then returned to room temperature,
It returns to cloudy and opaque again. That is, it assumes both an opaque and transparent state and an intermediate state at room temperature. As described above, the state change due to the temperature change of the microcapsules in the heat-sensitive recording material used for image formation with a thermal head or the like behaves differently from the thermochromic material that causes the above two conventional states to appear alternately. Present.

[0004]

The microcapsules in the above-mentioned heat-sensitive recording material are effective when applied to a system for developing and erasing an image by a thermal head or the like, but are in a transparent state at a temperature of T ₂ '. After that, no matter how much it is cooled, it does not return to the cloudy and opaque state but remains in the transparent state, and in the high temperature region of T ₃ 'or higher, the third state (translucent state) as described above appears. , The color change characteristic due to temperature change is different from the conventional thermochromic material,
It is difficult to use both of them together. The present invention exhibits the same color change characteristics as the above-mentioned conventional thermochromic material, has a reversibility of a white opaque state-a colorless transparent state with an arbitrary hysteresis width (ΔH), and has a conventional thermochromic property. A thermochromic light-shielding / translucent material satisfying the combined use with the material is first disclosed in Japanese Patent Application No. 6-292.
No. 326, which is a novel thermochromic material that is rich in distinctiveness, saliency, and unexpectedness that reveals various color tones and various images using the thermochromic light-shielding / translucent material. It is intended to provide a laminate.

[0005]

According to the present invention, a thermochromic concealing layer 4 for concealing a non-thermochromic image 3 formed on the surface of a support 2 is provided.
And a thermochromic light-shielding / translucent image 5 exhibiting the alternation of a white opaque state and a colorless transparent state by a temperature change on the thermochromic hiding layer 4. The body 1 is a requirement (see FIG. 1). Further, the thermochromic shading-translucent image 5 contains one or more crystalline compounds having a melting point in the range of -40 ° C to + 90 ° C and selected from esters, ethers and ketones. An image formed by encapsulating microcapsule pigments having a particle size of 0.1 to 50 μm in a resin in a dispersed state, and further non-thermochromic on the upper layer of the thermochromic shading-translucent image 5. The image 3 or the thermochromic image 6 is formed, and the microcapsule pigment has a total carbon number of 13 or more in which the esters are monohydric fatty acids and aliphatic monohydric alcohols or monohydric alcohols having an alicyclic ring. Of the above, an aliphatic dihydric or polyhydric carboxylic acid and an aliphatic monohydric alcohol or an alicyclic monohydric alcohol having a total carbon number of 18 or more, an aliphatic dihydric or polyhydric alcohol or an alicyclic dicarboxylic acid. Valuable and polyvalent Ester having a total carbon number of 18 or more consisting of a carboxylic acid and a monovalent fatty acid, a dihydric alcohol having an aromatic ring and a total carbon number of 24 or more consisting of a monovalent fatty acid, a monovalent carboxylic acid having an aromatic ring and a fat An ester having a total carbon number of 15 or more consisting of a group monohydric alcohol or a monohydric alcohol having an alicyclic ring, an ester having a total carbon number of 14 or more consisting of a monovalent carboxylic acid having an aromatic ring and a monohydric alcohol having an aromatic ring, The ethers selected from an ester having a total carbon number of 15 or more composed of a divalent fatty acid and a monohydric alcohol having an aromatic ring, and an ester having a total carbon number of 16 or more composed of a divalent fatty acid and a monohydric alcohol having an aromatic ring. Are selected from aliphatic ethers having a total carbon number of 16 or more or ethers having an aromatic ring having a total carbon number of 11 or more, and the ketones are aliphatic ketones having a total carbon number of 10 or more. , A ketone having an aromatic ring or an alicyclic ring having a total carbon number of 10 or more, and a hysteresis width (Δ
H) and the temperature rises in the white opaque state, the state begins to change when the temperature T _C is reached, and the colorless and transparent state is maintained in the temperature range above the temperature T _D. In the process of decreasing the temperature in the colorless and transparent state, when the temperature T _B lower than the temperature T _D is reached, the above state starts to change, and the microcapsule pigment completely changes to a white opaque state in the temperature range below the temperature T _A. (Fig. 3
To refer to FIG. 4), further, the microcapsule pigment is the temperature is lower than T _C T _B, in a temperature range between T _B and T _C, the white opaque state and a colorless transparent state can coexist Furthermore, the microcapsule pigment has a hysteresis width (Δ
H) and an average particle size of 1 to less than 2 μm has a larger hysteresis width (ΔH) than a system having a particle size of 2 μm or more, and the microcapsule pigment is oil-soluble in the inclusions as necessary. The fluorescent whitening agent is mixed in a dissolved or dispersed state, and the thermochromic masking layer 4 exhibits a hysteresis width (ΔH) in the relationship of temperature-color density, and a coloring material containing a thermochromic material. In the process in which the thermochromic material is in the first hue state and the temperature rises,
Upon reaching the second temperature T _3, the first color begins to discolor, become completely second color at a second higher temperature T ₄ or more temperature range than the temperature T _3, the thermochromic material is a second color In the process of decreasing the temperature in the state, when the first temperature T ₂ lower than the second temperature T ₃ is reached, the second hue starts to change color,
The thermochromic light-shielding and translucent image 5 is composed of a thermochromic material that completely exhibits the first hue in a temperature range lower than the first temperature T ₂ and lower than the temperature T ₁ (see FIG. 6). The thermochromic concealing layer 4 exhibits substantially the same discoloration temperature and substantially the same hysteresis width (ΔH), and the non-thermochromic image 3 and the thermochromic light-shielding / translucent image 5 are related to each other. It is a requirement that it is an image. Further, the non-thermochromic image 3 or the thermochromic image 6 can be appropriately provided on the thermochromic light-shielding / translucent image 5 (see FIG. 2). The thermochromic shading of the present invention described above
The translucent microcapsule pigment is a microcapsule containing one or more crystalline compounds selected from esters, ethers, and ketones. Is a pigment having a size of 1 to 20 μm, and microencapsulation is performed by a conventionally known interfacial polymerization method, in-situ polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting. There are a dispersion cooling method, an air suspension coating method, a spray drying method and the like, which are appropriately selected depending on the application, but generally, the interfacial polymerization method and the in situ polymerization method are preferably used,
As film agents, polyamide, polyurethane, polyurea,
Epoxy, polycarbonate, melamine-formalin condensate, urea-formalin condensate and the like can be mentioned. It should be noted that, if necessary, one or two selected from oil-soluble optical brighteners such as coumarin-based, naphthalimide-based, oxazole-based, and thiophene-based oil-soluble optical brighteners with respect to 100 parts by weight of the inclusion. The fluorescent whitening property can be imparted to the microcapsule pigment itself by dissolving or dispersing 0.001 to 20 parts by weight (more preferably 0.01 to 10 parts by weight) of one or more compounds. . The surface of the microcapsules may be provided with a secondary resin film depending on the purpose to impart durability, or the surface characteristics may be modified for practical use. The microcapsule pigment is fixed in a dispersed state in a resin and applied to the present invention. A thermochromic light-shielding / translucent resin composition which is applied to the present invention and exhibits a mutual change between a white opaque state and a colorless transparent state due to a temperature change. And an image 5 of characters, symbols, dots, lines, geometric patterns, patterns, etc. is formed on the thermochromic hiding layer 4 by an appropriate printing technique.

Next, the inclusion of the microcapsule pigment applied to the present invention will be described. Among the esters applied to the present invention, the total carbon number 1 consisting of a monohydric fatty acid and an aliphatic monohydric alcohol or an alicyclic monohydric alcohol.
Pentadecyl acetate, butyric acid n as 3 or more esters
-Tridecyl, n-pentadecyl butyrate, n-caprylate
Nonyl, n-undecyl caprylate, n-lauryl caprylate, n-tridecyl caprylate, n-pentadecyl caprylate, cetyl caprylate, stearyl caprylate, n-propyl caprate, n-heptyl caprate, n-caprate. Undecyl, n-lauryl caprate, n-tridecyl caprate, n-pentadecyl caprate, cetyl caprate, stearyl caprate, n-undecyl caproate, n-tridecyl caproate,
N-pentadecyl caproate, n-nonyl caproate,
N-Undecyl caproate, stearyl caproate, n-hexyl caprylate, n-heptyl caprylate, n-octyl caprylate, methyl laurate, n-laurate
-Heptyl, n-pentyl laurate, neopentyl laurate, 2-ethylhexyl laurate, n-lauric acid
-Octyl, n-nonyl laurate, n-decyl laurate, n-undecyl laurate, lauryl laurate, n-tridecyl laurate, myristyl laurate, n-pentadecyl laurate, stearyl laurate, cyclohexylmethyl laurate, Methyl myristate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-decyl myristate, n-undecyl myristate, lauryl myristate, n-tridecyl myristate, myristyl myristate, myristate n-pentadecyl, cetyl myristate, stearyl myristate, cyclohexyl myristate, methyl palmitate, ethyl palmitate,
N-propyl palmitate, n-pentyl palmitate, neopentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-decyl palmitate, n-undecyl palmitate, lauryl palmitate, n-tridecyl palmitate, Myristyl palmitate n-pentadecyl palmitate, cetyl palmitate, cyclohexylmethyl stearyl palmitate, methyl stearate, n-amyl stearate, n-heptyl stearate, neopentyl stearate, n-octyl stearate, n stearate n -Nonyl, n-decyl stearate, n-undecyl stearate, n-tridecyl stearate, myristyl stearate, n-pentadecyl stearate, cetyl stearate, steari Stearyl, eicosyl stearate, stearic acid n- docosyl, cyclohexylmethyl stearate, oleyl stearate, isostearyl stearate, cyclohexylmethyl stearate, methyleicosanoic, eicosanoic acid n- amyl, Eiko acid n
-Heptyl, n-octyl eicoate, n-nonyl eicoate, n-decyl eicoate, n-undecyl eicoate, n-tridecyl eicoate, n-pentadecyl eicoate, ethyl behenate, n-amyl behenate, behen Acid n-heptyl, neopentyl behenate, n-octyl behenate,
Behenate n-nonyl, behenate n-decyl, behenate n
-Undecyl, n-tridecyl behenate, myristyl behenate, n-pentadecyl behenate, cetyl behenate,
Examples thereof include stearyl cyclohexyl acetate, stearyl 2-cyclohexylpropionate, and neopentyl octylate.

Esters having a total of 18 or more carbon atoms, which are composed of an aliphatic divalent or polyvalent carboxylic acid and an aliphatic monohydric alcohol or an alicyclic monohydric alcohol, include di-n-butyl sebacate and diadipic acid. n-hexyl, di-n-nonyl oxalate, di-n-decyl oxalate, di-n-undecyl oxalate, dilauryl oxalate, di-n-tridecyl oxalate, dimyristyl oxalate, di-n-pentadecyl oxalate, dicetyl oxalate , Di-n-heptadecyl oxalate, distearyl oxalate, dilauryl malonate, di-n-tridecyl malonate, dimyristyl malonate, di-n-pentadecyl malonate, dicetyl malonate, di-n-heptadecyl malonate, distearyl malonate , Di-n-nonyl succinate, di-n-decyl succinate, di-n-undecyl succinate, succinic acid Lauryl, di-n-tridecyl succinate, dimyristyl succinate, di-n-pentadecyl succinate, dicetyl succinate, diheptadecyl succinate, distearyl succinate, di-decyl glutarate, di-n-undecyl glutarate, dilauryl glutarate. , Di-n-tridecyl glutarate, dimyristyl glutarate, di-n-pentadecyl glutarate, dicetyl glutarate, di-n-heptadecyl glutarate, distearyl glutarate,
Di-n-decyl adipate, di-n-undecyl adipate, dilauryl adipate, di-n-tridecyl adipate, dimyristyl adipate, di-n-pentadecyl adipate, dicetyl adipate, di-n-heptadecyl adipate, di-adipate Stearyl, di-n-docosyl adipate, di-n-decyl pimelic acid, di-n-undecyl pimelic acid, dilauryl pimelic acid, di-n-tridecyl pimelic acid, dimyristyl pimelic acid, di-n-pimelic acid.
Pentadecyl, dicetyl pimelic acid, di-n-pimelic acid
Heptadecyl, distearyl pimelic acid, di-n-decyl suberate, di-n-undecyl suberate, dilauryl suberate, di-n-tridecyl suberate, dimyristyl suberate, di-nonyl sebacate, di-n-decyl sebacate, Di-n-undecyl sebacate, dilauryl sebacate, di-n-tridecyl sebacate, dimyristyl sebacate, di-n-pentadecyl sebacate, dicetyl sebacate, di-n-heptadecyl sebacate, distearyl sebacate, di-suberate di- Pentadecyl, dicetyl suberate, di-n-heptadecyl suberate, distearyl suberate, di-n-decyl azelate, di-n-undecyl azelate, dilauryl azelate, di-tridecyl azelate, dimyristyl azelate, azelai Acid di n-pentadecyl, azelaic acid dicetyl, azelaic acid di n-heptadecyl, azelaic acid distearyl, 1,18 octadecyl methylene dicarboxylic acid di n-octyl, 1,18 octadecyl methylene dicarboxylic acid dicyclohexyl, 1,18 octadecyl methylene dicarboxylic acid Dyneopentyl and the like can be mentioned.

As the esters having a total carbon number of 18 or more, which are composed of an aliphatic dihydric or polyhydric alcohol or an alicyclic dihydric or polyhydric alcohol and a monohydric fatty acid, there are ethylene glycol dicaprylic acid ester and ethylene glycol dicaprin. Acid ester, ethylene glycol diundecanoate ester, ethylene glycol dilaurate ester,
Ethylene glycol ditridecanoate, ethylene glycol dimyristate, ethylene glycol dipentadecanoate, ethylene glycol dipalmitate, ethylene glycol diheptadecanoate, ethylene glycol distearate, 1,3-propanediol dicaprylic acid Ester, 1,3-propanediol dicapric acid ester,
1,3-propanediol diundecanoate,
1,3-propanediol dilaurate, 1,
3-Propanediol ditridecanoate, 1,3
-Propanediol dimyristate, 1,3-
Propanediol dipentadecanoate, 1,3-
Propanediol dipalmitate, 1,3-propanediol diheptadecanoate, 1,3-propanediol distearate, 1,4-butanediol dicaprylate, 1,4-butanediol dicaprate, 1,4-butanediol diundecanoate, 1,4-butanediol dilaurate, 1,4-butanediol ditridecanoate, 1,4-butanediol dimyristate, 1,4-butanediol Dipentadecanoic acid ester, 1,4-butanediol dipalmitic acid ester, 1,4-butanediol diheptadecanoic acid ester, 1,4-butanediol distearic acid ester,
1,5-pentanediol dicapric acid ester, 1,
5-pentanediol diundecanoate, 1,5
-Pentanediol dilaurate, 1,5-pentanediol ditridecanoate, 1,5-pentanediol dimyristate, 1,5-pentanediol dipentadecanoate, 1,5-pentanediol dipalmitate Ester, 1,5-pentanediol diheptadecanoic acid ester, 1,5-pentanediol distearic acid ester, 1,6-hexanediol dicapric acid ester, 1,6-hexanediol diundecanoic acid ester, 1,6- Hexanediol dilaurate, 1,6-hexanediol ditridecanoate, 1,6-hexanediol dimyristate, 1,6-hexanediol dipentadecanoate, 1,6-hexanediol dipalmitate , , 6-hexanediol diheptadecanoic acid ester, 1,6-hexanediol distearic acid ester, 1,7-pentanediol dicapric acid ester, 1,7-pentanediol diundecanoic acid ester, 1,7-pentanediol diester Laurate, 1,7-pentanediol ditridecanoate, 1,7-pentanediol dimyristate, 1,7-pentanediol dipentadecanoate, 1,7-pentanediol dipalmitate, 1, 7-pentanediol diheptadecanoic acid ester, 1,7-pentanediol distearic acid ester, 1,8-octanediol dicapric acid ester,
1,8-octanediol diundecanoic acid ester,
1,8-octanediol dilaurate, 1,
8-octanediol ditridecanoic acid ester, 1,8
-Octanediol dimyristate ester, 1,8-
Octanediol dipentadecanoate, 1,8-
Octanediol dipalmitate, 1,8-octanediol diheptadecanoate, 1,8-octanediol distearate, 1,9-nonanediol dicaprate, 1,9-nonanediol diundecanoate 1,9-nonanediol dilaurate, 1,9-nonanediol ditridecanoate, 1,9-nonanediol dimyristate, 1,9-nonanediol dipentadecanoate, 1,9-nonane Diol dipalmitic acid ester, 1,9-nonanediol diheptadecanoic acid ester, 1,9-nonanediol distearic acid ester, 1,10-decanediol dicaprylic acid ester,
1,10-decanediol dicapric acid ester, 1,
10-decanediol diundecanoate, 1,1
0-decanediol dilaurate, 1,10-
Decanediol ditridecanoate, 1,10-decanediol dimyristate, 1,10-decanediol dipentadecanoate, 1,10-decanediol dipalmitate, 1,10-decanediol diheptadecanoate Ester, 1,10-decanediol distearate ester, 1,5-pentanediol distearate, 1,2,6-hexanetriol dimyristate, pentaerythritol trimyristate, pentaerythritol tetralaurate, 1, 4-cyclohexanediol dimyristyl, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanediol dimyristyl, 1,4-cyclohexanediol distearyl, 1,4-cyclohexanedimethanol dilaurate, 1, - Jimirisuteto etc. cyclohexanedimethanol.

As the esters having a total carbon number of 24 or more, which consist of a dihydric alcohol having an aromatic ring and a monovalent fatty acid,
Xylylene glycol dicaprylate, xylylene glycol dicaprate, xylylene glycol diundecanoate, xylylene glycol dilaurate, xylylene glycol ditridecanoate, xylylene glycol dimyristate, xylylene glycol Examples thereof include dipentadecanoic acid ester, xylylene glycol dipalmitic acid ester, xylylene glycol diheptadecanoic acid ester, and xylylene glycol distearic acid ester.

Esters having a total carbon number of 15 or more and composed of a monovalent carboxylic acid having an aromatic ring and an aliphatic monohydric alcohol or an alicyclic monohydric alcohol include hexyl 3,5-dimethylbenzoate and 2- Decyl methyl benzoate,
Lauryl 2-methylbenzoate, myristyl 2-methylbenzoate, stearyl 2-methylbenzoate, 4-tert.
-Butyl cetyl benzoate, behenyl 4-cyclohexyl benzoate, myristyl 4-phenyl benzoate, 4-octyl lauryl benzoate, stearyl 3-ethyl benzoate, decyl 4-isopropyl benzoate, stearyl 4-benzoyl benzoate, 4- Stearyl chlorobenzoate,
Myristyl 3-bromobenzoate, Stearyl 2-chloro-4-bromobenzoate, Decyl 3,4-dichlorobenzoate, Octyl 2,4-dibromobenzoate, Cetyl 3-nitrobenzoate, Cyclohexylmethyl 4-aminobenzoate Cetyl 4-diethylaminobenzoate, Stearyl 4-anilinobenzoate, Decyl 4-methoxybenzoate, 4
-Cetyl methoxybenzoate, octyl 4-butoxybenzoate, cetyl 4-hydroxybenzoate, stearyl p-chlorophenylacetate, cetyl p-chlorophenylacetate,
Neopentyl salicylate, stearyl 2-naphthoate,
Examples thereof include cetyl benzylate, stearyl benzylate, decyl 3-benzoylpropionate, stearyl benzoate, myristyl benzoate, cyclohexylmethyl 2-benzoylpropionate, cyclohexylmethyl cinnamate and the like.

Examples of esters having a total carbon number of 14 or more, which consist of a monovalent carboxylic acid having an aromatic ring and a monohydric alcohol having an aromatic ring, include benzyl salicylate and salicylic acid 4
-Methoxymethylphenylmethyl, 4-chlorophenylmethyl benzoate, benzyl cinnamate, phenyl 4-tert-butylbenzoate, 4-chlorobenzyl 2-methylbenzoate, 4-methoxyphenylmethyl benzoate and the like.

Esters having a total carbon number of 15 or more, which are composed of a monovalent fatty acid and a monohydric alcohol having an aromatic ring, include:
4-Chlorophenylmethyl caprylate, 4-capric acid
Chlorophenylmethyl, 4-methoxyphenylmethyl laurate, 4-methoxyphenylmethyl myristate,
4-Nitrophenylmethyl stearate, capric acid 4
-Methylphenylmethyl, 2-chlorophenylmethyl myristate, 4-chlorophenyl 11-bromolaurate, 4-isopropylphenyl stearate, stearyl 2-naphthoate, cetyl benzylate, stearyl benzylate, benzyl caproate, benzyl palmitate,
Examples thereof include 3-phenylpropyl stearate and phenyl 11-bromolaurate.

As the esters having a total carbon number of 16 or more, which are composed of divalent fatty acids and monohydric alcohols having an aromatic ring,
Examples thereof include dibenzyl sebacate, and dineopentyl 4,4′-diphenyldicarboxylate.

Next, the ethers applicable to the present invention will be described. Examples of aliphatic ethers having 16 or more carbon atoms include dioctyl ether, diniethylhexyl ether, didecyl ether, didodecyl ether, ditridecyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, diheptadecyl ether. Examples thereof include ether and dioctadecyl ether.

Examples of ethers having an aromatic ring having a total carbon number of 11 or more include benzyl isoamyl ether, diphenyl ether, ethylene glycol diphenyl ether,
Diisopropylbenzyl ether and the like can be mentioned.

Next, the ketones applied to the present invention will be described. Examples of the aliphatic ketones having a total carbon number of 10 or more include 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-heptadecane, 2-pentadecanone, 2-octadecanone,
2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-heneicosanone, 2-docosanone, lauron, stearone, cyclodecanone and the like can be mentioned.

As the ketones having an aromatic ring or alicyclic ring having a total carbon number of 10 or more, benzyl acetophenone, benzyl phenyl ketone, n-octadecanophenone, n
-Heptadecanophenone, n-hexadecanophenone,
n-tetradecanophenone, n-tridecanophenone,
Laurophenone, n-undecanophenone, n-decanophenone, 4'-n-octylacetophenone, n-nonanophenone, 4'-n-heptylacetophenone, n
-Octanophenone, 4'-n-hexylacetophenone, 4'-cyclohexylacetophenone, 2-methylbenzophenone, dicyclohexylketone, 4-ter
t-butylpropiophenone, n-heptanophenone,
4'-n-pentylacetophenone, cyclohexylphenylketone, 2-benzylidenecyclohexanone, benzophenone, cyclodecanone, 2-n-heptylcyclohexanone, 2-cyclohexylcyclohexanone,
2- (1-cyclohexyl) cyclohexanone, benzyl n-butyl ketone, 4'-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, cyclopentylphenyl ketone, 4-phenylcyclohexanone, 1-acetothephthalone, 2-acetothephthalone, 4-n-pentylcyclohexanone, benzyl isopropyl ketone, 4'-n-propyl acetophenone, 2 ', 4', 6'-trimethyl acetophenone,
Cyclobutyl phenyl ketone, 2 ', 4'-dimethylacetophenone, 2', 5'-dimethylacetophenone,
4'-ethylacetophenone, isopropyl phenyl ketone, 4'-methylpropiophenone, 1-phenyl-
2-butanone, phenyl n-propioketone, cyclopropylphenyl ketone, phenylpropenyl ketone, 2
-Amino-4'-chlorobenzophenone, 2-amino-
5-chlorobenzophenone, 4-fluorobenzophenone, 2-amino-2 ′, 5-chlorobenzophenone, 4
-Chloro-4'-hydroxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 2,
4'-difluorobenzophenone, 4,4'-difluorobenzophenone, 2,4-dichlorobenzophenone,
2,4'-dichlorobenzophenone, 4,4'-dichlorobenzophenone, 2,3,4,5,6, -pentafluorobenzophenone, decafluorobenzophenone, 3
-3'diaminobenzophenone, 3-4 diaminobenzophenone, 4,4'diaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 3,4
-Dimethoxyphenyl cisetone, 2 ', 3', 4'-trimethoxyacetophenone, 3 ', 4', 5'-trimethoxyacetophenone and the like.

Next, specific examples of the fluorescent whitening agent applied to the present invention will be described. As a coumarin oil-soluble optical brightener,
A 7-triazinylamino-3-phenylcoumarin derivative and a 3-phenyl-7-allyltriazolylcoumarin derivative are preferably used.

Next, the resin will be described. The microcapsule pigment according to the present invention is dispersed in an appropriate vehicle containing a general-purpose printing or coating resin and applied as a printing ink form. The resins are exemplified below. Polyacrylic acid ester, acrylic acid ester-styrene copolymer,
Ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, methacryl-maleic acid copolymer, α-olefin-maleic acid copolymer, ethylene-methacrylic acid copolymer, polyurethane copolymer, carboxymethyl cellulose, Methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone,
Sodium alginate, hydroxypropyl cellulose, arabic rubber, casein, petroleum resin, low molecular weight polyethylene, polystyrene, alkyd resin, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, synthetic rubber,
Examples thereof include epoxy resin, amino resin, heat-reactive unsaturated hydrocarbon resin, and ultraviolet curable resin. The occupancy of the microcapsule pigment in the thermochromic light-shielding / translucent image is effective in the range of 5 to 80% by weight (preferably 10 to 60% by weight) in view of the thermochromic effect. That is, when the amount is less than 5% by weight, the color density is low, and the color change cannot be clearly seen. The thickness of the thermochromic hiding layer 4 is at least 3 μm.
Or more, preferably 1 to 400 μm, more preferably 10
It is ˜100 μm, and the color change effect can be satisfied within the above range. If it is less than 0.3 μm, the vividness of color change is poor, while
A system exceeding 400 μm is not preferable because the appearance is impaired. The thermochromic hiding layer 4 is for concealing the non-thermochromic image 3 by a temperature change, and may be an appropriate image and has a darker visual density than the nonthermochromic image 3 or a color tone when colored. Combinations of the same or similar tones are effective.

[0020]

In the resin composition in which the microcapsule pigment of the present invention is dispersed, as shown in FIGS. 3 and 4, the curve plotting the change in transparency due to temperature change has a hysteresis width [ΔH].
(T _F −T _E )], exhibiting a tautomerism between a white opaque state and a colorless transparent state, and in the process of increasing the temperature in the white opaque state, when the temperature T _C is reached, the white opaque state is obtained. The state begins to change, and becomes completely colorless and transparent in the temperature range above the temperature T _D , and in the process of falling in the colorless and transparent state, when the temperature T _B lower than the temperature T _C is reached, the colorless and transparent state is reached. Change to a completely white opaque state in a temperature range equal to or lower than the temperature T _A , and the white opaque state and the colorless transparent state can coexist in the temperature range between the temperature T _B and the temperature T _C. give. The above-mentioned behavior depends on the melting point of the inclusion encapsulated in the microcapsule. That is, below the freezing point, it becomes a crystal in the solid state, scatters light to become a white opaque state, and when heated above the melting point, becomes a liquid state, and the incident light becomes transparent and becomes colorless and transparent. The hysteresis width (Δ
H) depends on the melting point of the inclusions encapsulated in the microcapsules and, in the case of the same inclusions, changes the value of ΔH depending on the particle size of the microcapsules. Since the volume is small in the range of the average particle diameter of 1 to 2 μm, the freezing point (crystal temperature) is lowered depending on the small probability that the crystal nuclei of the inclusions are generated, which contributes to the widening of the ΔH value and has a high hysteresis characteristic. (Fig. 3). A system having a particle size of 2 μm or more exhibits substantially the same freezing point regardless of the particle size, its ΔH value is smaller than that of the system having a particle size of less than 2 μm, and the same inclusion exhibits a behavior of a small hysteresis characteristic. The behavior of the aspect change due to the temperature change of the microcapsule pigment of the present invention described above is similar to the behavior of the color density-temperature curve (FIGS. 6 and 7) of the conventional thermochromic material, and the hysteresis widths of the two are By adjusting appropriately, a thermochromic laminate that exhibits a phase change in synchronization can be formed. The thermochromic light-shielding / light-transmitting image 5 of the constitution of the present invention, in which the thermochromic light-shielding / light-transmitting microcapsule pigments are fixed to a transparent resin in a dispersed state, has the same behavior due to the temperature change as described above. And effectively functions as a component of the thermochromic laminate. Since the thermochromic light-shielding-light-transmitting image 5 containing the microcapsule pigment of the present invention exhibits alternation between a white opaque state and a colorless transparent state, the image disposed on the thermochromic hiding layer 4 changes with temperature. Visual combination is further diversified by the combination with the concealment and the concealment of the non-thermochromic image 3 associated with the discoloration of the thermochromic concealing layer 4. Further, the non-thermochromic image 3 or the thermochromic image 6 disposed on the thermochromic light-shielding / translucent image 5 can be hidden to further diversify the visual change.

[0021]

EXAMPLE Next, preparation of the microcapsule pigment for forming the thermochromic light-shielding / light-transmitting image 5 of the present invention will be described. The parts in the following formulations are parts by weight. Microcapsule Pigment A n-Heptyl palmitate 50 parts was dissolved by heating at about 90 ° C., and a mixed solution of 30 parts of methyl ethyl ketone and 15 parts of a polyvalent isocyanate resin (Sumijour L manufactured by Sumitomo Bayer Urethane Co., Ltd.). Add to dissolve evenly. This is mixed in 150 parts of a 5% polyvinyl alcohol (Nippon Gosei Kagaku KK: Gohsenol GM14) aqueous solution, and dispersed using a homomixer until it becomes fine droplets. While maintaining this aqueous suspension at 60 ° C., 50 parts of a 5% aqueous solution of a curing agent (epoxy resin amine adduct, Shell Petroleum Co., Epicure U) was gradually added to the stirring aqueous suspension. 6
Drop the solution over 0 minutes, and after finishing the dropping, raise the solution temperature to 85
The temperature was raised to 0 ° C., and stirring was continued for about 5 hours while maintaining the liquid temperature at 85 ° C. to obtain a dispersion liquid of homogeneous microcapsules having a particle size distribution of 4 to 10 μm (average particle size of about 6 μm). The obtained dispersion was subjected to centrifugal separation treatment and recovered, and the water content was about 4
A 0% microcapsule hydrous composition was obtained. The average particle size of the microcapsule pigment A is 0.1 μm to 5 depending on the stirring power of the homomixer, that is, the rotation speed and stirring time.
It can be arbitrarily set up to 0 μm, and the same applies to the following examples. This water-containing composition changes from white to colorless, starts decoloring at 33 ° C, and completely decolorizes at 36 ° C. Also, coloring starts at 20 ° C. and complete coloring occurs at 15 ° C. to become white.

Microcapsule Pigment B Stearyl caprylate 50 parts and epoxy resin 10 parts [(Shell Petroleum Co .: Epicoat (828)]] were added at 80 ° C.
Was heated and dissolved in to form a homogeneous compatible solution, and 10 parts of methyl ethyl ketone was mixed with this, and then dropped into 100 parts of a 10% gelatin aqueous solution and stirred with a homomixer to form fine droplets. Separately prepared curing agent (epoxy resin amine adduct, manufactured by Shell Sekiyu Co., Ltd .: Epicure U)
50 parts of a 10% aqueous solution of the above is gradually added dropwise to the aqueous suspension maintained at 65 ° C. while stirring, the liquid temperature is maintained at 80 ° C., and stirring is continued for about 5 hours to obtain a particle size distribution of 4 to 10 μm. A uniform dispersion liquid of microcapsules having an average particle diameter of about 6 μm was obtained. The dispersion was subjected to centrifugal separation treatment and recovered to obtain a microcapsule hydrous composition having a water content of about 35%. This hydrated composition changed from white to colorless and started decoloring at 36 ° C,
Complete bleaching at 40 ° C. Also, coloring starts at 33 ° C,
Completely colored at 28 ° C. and turned white.

Example 1 A dinosaur picture 3 was drawn on white wood-free paper 2 with green, pink, and purple non-color-changing inks, and a color-memory thermochromic microcapsule pigment (low-temperature side color changing temperature: 15
℃, high temperature side discoloration temperature: 36 ℃, black, having colorless tautomerism) 40 parts, ethylene vinyl acetate emulsion 60
Part, thickener 2 parts, and antifoaming agent 1 part are uniformly stirred, and the above-mentioned pattern 3 is concealed and printed with a color-memory thermochromic water-based screen ink, and then thermochromic micro Aqueous screen ink vehicle 50 containing 50 parts of a water-containing composition containing capsule pigment A as a main component of acrylic emulsion
The thermochromic laminated print 1 was obtained by printing the dinosaur egg 5 on the upper layer where the dinosaur pattern 3 is located with the ink dispersed in the part (see FIGS. 8 and 9). At room temperature of about 24 ° C., this laminated body 1 has a black surface on which a pattern 5 of white eggs of a dinosaur is visualized.
When heated to 6 ° C. or higher, the dinosaur picture 3 is visible from the above aspect, and this aspect is stored and stored at room temperature of 24 ° C. In addition, the above-mentioned change in appearance due to the change in temperature is repeatedly reproduced.

Example 2 On the dinosaur egg 5 in Example 1, color memory thermochromic microcapsule pigment (low temperature side discoloring temperature: 15 ° C., high temperature side discoloring temperature: 36 ° C., brown, colorless tautomerism) Have)
40 parts, 60 parts of ethylene vinyl acetate emulsion, 2 parts of thickening agent, and 1 part of defoaming agent were uniformly stirred to obtain a realistic pattern with a color-memory thermochromic water-based screen ink. Printing was performed to obtain a laminated body 1 (FIGS. 10 and 11).
reference). The appearance of the laminated body 1 according to the temperature changes in the same manner as in Example 1, but since a brown pattern is added at the time of color development, the realism is further enhanced.

Example 3 On a white polyethylene terephthalate film 2, a crane picture 3 was printed in black, yellow and red, and a color memory thermochromic microcapsule pigment (low temperature side color changing temperature: 28 ° C.) was printed on the upper surface thereof. , High temperature side discoloration temperature: 40 ° C., having black, colorless tautomerism) 40 parts, ethylene vinyl acetate emulsion 60 parts, thickener 2 parts, and defoamer 1 part Color memory obtained by uniformly stirring Thermosensitive color-changing water-based screen ink,
After concealment printing of the pattern 3, a hydrous composition containing the thermochromic microcapsule pigment B is dried thereon by a spray drying method to obtain a dry powder of the microcapsule pigment,
40 parts of this powder was added to vinyl chloride-vinyl acetate copolymer resin 4
0 parts, cyclohexanone 50 parts, aromatic hydrocarbon solvent 5
With a thermochromic light-shielding-translucent oily screen ink that changes from white to colorless, obtained by dispersing it in an oily screen vehicle consisting of 0 part and 0.1 part of a silicone antifoaming agent,
The letter “Kou” was printed to obtain a layered product 1. The laminated body 1
Has a white "jutsu" letter on the black surface at room temperature of about 24 ° C. When heated above 40 ° C, the "jutsu" letter and black surface disappear and the picture 3 of the crane appears. Then, when it was left to cool at room temperature of 24 ° C., the letter “Kou” was visualized again, and the picture 3 of the crane changed to an invisible state (FIG. 12,
(See FIG. 13).

Example 4 A tree trunk and branch pattern 3 was drawn on the outer surface of a white mug 2 with brown and black non-thermochromic ink, and the color memory thermochromic microcapsule pigment (low temperature Side discoloration temperature: 38 ° C., high temperature side discoloration temperature: 50 ° C., 40 parts of green, colorless tautomerized), 60 parts of ethylene vinyl acetate emulsion, 2 parts of thickener, and 1 part of defoaming agent are uniformly stirred. After the pattern 3 was concealed printed with the color memory thermochromic water-based screen ink obtained in the above, a water-containing composition containing the thermochromic microcapsule pigment B was dried thereon by a spray drying method, An image of snow-like appearance with thermochromic light-shielding and translucent ink obtained by dispersing 40 parts of this powder as a dry powder of a microcapsule pigment in an oil vehicle mainly containing epoxy resin. Print 5, and From the upper surface, a pattern 6 of apple was printed with a red and yellow non-thermochromic ink to obtain a laminate 1. At room temperature of about 24 ° C., the laminated body 1 has snow accumulated on the leaves of a green tree and apples are visually recognized on the snow. Pour hot water of about 80 ° C. into a mug and the surface temperature is around 40 ° C. When it turned into, the snow disappeared, and the tree was planted with green leaves and had an apple. When it was further heated and the surface temperature became 50 ° C or higher, the green leaves disappeared and the tree branches appeared to have apples. On the other hand, as the hot water in the mug is allowed to cool,
The opposite of the above was visible again.

Example 5 A pupa pattern 3 is printed in green, black, brown, and yellow on a white cloth 2, and a color-memory thermochromic microcapsule pigment (low-temperature side discoloration temperature: 28 ° C., High temperature discoloration temperature: 40 ° C., black, having a colorless tautomorphism) 40 parts, ethylene vinyl acetate emulsion 60 parts, thickener 2 parts, and defoamer 1 part Color memory obtained by uniformly stirring After the pattern 3 was concealed printed with a thermochromic water-based screen ink, 50 parts of a water-containing composition containing the thermochromic microcapsule pigment B was applied on the dry coating film containing an acrylic emulsion as a main component so that the aqueous coating was transparent. Disperse in 50 parts of the screen vehicle, print the butterfly pattern on the position where the pupa is printed, and on the upper surface of the color memory thermochromic ink (low temperature side discoloration temperature: 26 ° C, high temperature side discoloration temperature: 30 ° C, yellow, colorless It has the alternation of), and is printed on the white butterfly wings.
A laminate 1 was obtained. At room temperature of about 24 ° C., the laminate 1 has a white body on which a butterfly with yellow wings is visualized, but when immersed in warm water at 32 ° C., it changes into a white butterfly. Furthermore, when heated to 40 ° C or higher, the white butterfly and the black color of the back disappear, the pupae are visualized, and when gradually cooled to room temperature of 24 ° C, the white butterfly is visible on the black back at 28 ° C. Butterfly wings turn yellow below ℃ (Fig. 17)
-19).

Method of Measuring Change in Transparency Due to Temperature Change It is practically difficult to confirm in detail the change from a cloudy opaque state to a colorless transparent state with a microcapsule pigment alone, so that the microcapsule pigment is placed in a vehicle containing a resin. A dispersed ink was used, and a screen-printed material was formed using this ink, and the state change due to temperature change and the color change characteristics were examined. The ink was prepared as follows. 4.0 parts of the water-containing composition of the prepared microcapsule pigment was added with 5.2 parts of ethylene vinyl acetate emulsion and 0.5 part of a thickener.
Parts, 0.2 parts of a leveling agent, and 0.1 parts of a defoaming agent were dispersed in a transparent vehicle for an aqueous screen ink to prepare an aqueous screen ink containing microcapsules. The ink was printed on a black woodfree paper having a lightness value of 2.04 using a 109 mesh screen plate to obtain a printed matter having a printing layer having a film thickness of about 25 μm. This film thickness showed almost the same value even when the water-containing composition obtained in each example was used. The change of the microcapsule pigment from the cloudy state to the transparent state due to the temperature change in the printed matter can be visually recognized as a change from white to black. Therefore, by measuring the change in the lightness value due to the temperature change of the printed matter, the behavior of the change from the cloudy opaque state to the transparent state due to the temperature change and its relative whiteness and transparency can be easily measured.

Method for measuring discoloration behavior The printed matter was measured by a color difference meter [TC-3600 type color difference meter, manufactured by Co., Ltd.].
Made by Tokyo Denshoku Co., Ltd.) within a temperature range of 60 ° C / 10 ° C /
The printed matter was heated and cooled at a rate of min. For example, in the system of microcapsule pigment A, the measurement start temperature is 0 ° C.
Warm up to 50 ° C at a rate of 10 ° C / min, then 1
It was cooled to 0 ° C again at a rate of 0 ° C / min. The lightness value displayed on the color difference meter at each temperature at this time is plotted on a graph to create a color change curve as shown in FIG.
T _A , T _B , T _C , T _D , T _E (midpoint temperature of color density during clouding process), T _F (midpoint temperature of color density during transparent process), and ΔH (line segment EF) were obtained. .

Method of Measuring Contrast At the time of measuring the discoloration behavior, for example, in the case of the microcapsule pigment A, the lightness value V _A at 0 ° C. of the lightness value in the turbid opaque state is measured by a color difference meter [TC-3600 color difference meter]. , Made by Tokyo Denshoku Co., Ltd.], and then the brightness value in the transparent state,
The brightness value V _D at 50 ° C. was read in the same manner, and the contrast ΔV was calculated as V _A −V _D.

[0031]

EFFECTS OF THE INVENTION The light-shielding / translucent image of the present invention has a suitable hysteresis width (ΔH) and is a thermochromic material exhibiting alternation between a white opaque state and a colorless transparent state. Conventional reversible thermochromic material and color memory thermochromic material (electron-donating organic compound, electron-accepting compound, A combination with a thermochromic hiding layer by a microcapsule pigment in which a homogeneous compatible solution of three essential components of an organic reaction medium that determines the occurrence temperature of the color reaction of the both is encapsulated in microcapsules),
By combining the combination of different color change characteristics and the combination of different color change characteristics, various thermo color change appearances are revealed, and in combination with the effect of visualizing a white and opaque image during coloring, it is achieved with conventional thermo color change laminates. It brings an effect that cannot be obtained. That is, since it is white and opaque at the time of coloring, a white image is visibly developed on the dark color layer, and at the time of erasing, it becomes a colorless and transparent state, so that the white image becomes invisible and the original dark image. It stays visible in the color layer. Further, the thermochromic light-shielding-translucent image of the present invention is decolored on the high temperature side, so that the colored image provided in the lower layer can be made to appear from the white state,
It is possible to provide a variety of thermochromic laminates that satisfy the nuances of discoloration, unexpectedness, designability, toyability, and the like.

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional explanatory view of an example of a thermochromic laminate of the present invention.

FIG. 2 is a vertical cross sectional view showing another embodiment of the thermochromic laminate of the present invention.

FIG. 3 is a graph showing the behavior of the thermochromic light-shielding-translucent microcapsule pigment of the present invention due to temperature change.

FIG. 4 is another graph showing the behavior of the thermochromic light-shielding-translucent microcapsule pigment of the present invention due to temperature change.

FIG. 5 is a graph showing an example of the behavior of a microcapsule in a thermal recording material due to a temperature change.

FIG. 6 is a graph showing a color density-temperature curve of a color memory thermochromic material that exhibits large hysteresis characteristics and changes color with temperature change.

FIG. 7 is a graph showing a color density-temperature curve of a thermochromic material that changes color with a small hysteresis characteristic due to temperature change.

FIG. 8 is a plan view showing a normal state of an example of the laminated body of the present invention.

9 is a plan view showing a state in which the state of FIG. 8 has changed.

FIG. 10 is a plan view showing an aspect of a laminated body of the present invention in another embodiment.

FIG. 11 is a plan view showing a state in which the state of FIG. 10 is changed.

FIG. 12 is a plan view showing the appearance of another embodiment of the laminated body of the invention.

FIG. 13 is a plan view showing a state in which the state of FIG. 12 is changed.

FIG. 14 is a plan view showing the appearance of another embodiment of the laminated body of the invention.

FIG. 15 is a plan view showing a state in which the state of FIG. 14 is changed.

16 is a plan view showing another aspect changed from the state of FIG.

FIG. 17 is a plan view showing the appearance of another embodiment of the laminated body of the invention.

FIG. 18 is a plan view showing a state in which the state of FIG. 17 is changed.

FIG. 19 is a plan view showing another aspect changed from the state of FIG.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Thermochromic laminate 2 Support 3 Non-thermochromic image 4 Thermochromic masking layer 5 Thermochromic light-shielding / translucent image 6 Thermochromic image T _C Maximum opaque state holding temperature T _D Complete transparency temperature T _E Midpoint temperature during opaque process T _F Midpoint temperature during clearing process T _G Midpoint temperature of color density during decoloring process T _H Midpoint temperature of color density during coloring process V _A White turbidity in opaque state Lightness value V _D Lightness value in transparent state ΔH Hysteresis width T ₁ Full coloration temperature T ₂ Minimum holding temperature in decolored state T ₃ Maximum holding temperature in colored state T ₄ Full decoloring temperature

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location 7416-2H B41M 5/26 102

Claims (10)

[Claims] 1. A thermochromic masking layer for concealing a non-thermochromic image formed on a support surface is provided, and on the thermochromic masking layer, a white opaque state and a colorless transparent state are subjected to alternation by temperature change. A thermochromic laminate provided with a thermochromic light-shielding-translucent image to be presented. 2. A thermochromic shading-translucent image has a melting point of -4.
The resin contains a microcapsule pigment having a particle size of 0.1 to 50 μm and containing one or more crystalline compounds selected from esters, ethers, and ketones in the range of 0 ° C. to + 90 ° C. The thermochromic laminate according to claim 1, which is an image that is fixed in a dispersed state on. 3. The thermochromic laminate according to claim 1, wherein a non-thermochromic image or a thermochromic image is formed on the thermochromic light-shielding-translucent image. 4. The microcapsule pigment according to claim 2, wherein the ester comprises a monohydric fatty acid and an aliphatic monohydric alcohol or a monohydric alcohol having an alicyclic ring, and having a total carbon number of 1
An ester, an aliphatic dihydric or polyhydric alcohol or an alicyclic ring, which is composed of three or more esters, an aliphatic dihydric or polyhydric carboxylic acid and an aliphatic monohydric alcohol or a monohydric alcohol having an alicyclic ring, and having 18 or more carbon atoms in total. An ester having a total carbon number of 18 or more, which comprises a dihydric or polyhydric alcohol and a monovalent fatty acid,
An ester having a total carbon number of 24 or more consisting of an aromatic ring-containing dihydric alcohol and a monovalent fatty acid, a total carbon number consisting of an aromatic ring-containing monovalent carboxylic acid and an aliphatic monohydric alcohol or an alicyclic monohydric alcohol. Ester of 15 or more, monovalent carboxylic acid having aromatic ring and monohydric alcohol having aromatic ring, and total carbon number of 14 or more ester, monovalent fatty acid and monohydric alcohol having aromatic ring, total 15 carbon atoms The above-mentioned ester and an ester having a total carbon number of 16 or more consisting of a divalent fatty acid and a monohydric alcohol having an aromatic ring, wherein the ethers are an aliphatic ether having a total carbon number of 16 or more or a total carbon number of 11 or more. Are selected from ethers having an aromatic ring, and the ketones are aliphatic ketones having a total carbon number of 10 or more, or ketones having an aromatic ring or alicyclic ring having a total carbon number of 10 or more. Selected becomes, the light shielding by the temperature change - with respect to the translucent curve varies with a hysteresis width ([Delta] H), in the course of temperature In the white opaque state is raised, the to reach the temperature T _C state begins to change, Temperature T
_In the temperature range above _D , the colorless and transparent state is maintained, and in the colorless and transparent state, the temperature T
_{When a} temperature T _B lower than _D is reached, the state begins to change,
It is a microcapsule pigment that completely changes to a white opaque state in a temperature range of T _A or lower. 5. The microcapsule pigment according to claim 4 is T
_B is lower than T _C , and the white opaque state and the colorless transparent state can coexist in the temperature range between T _B and T _C. 6. The microcapsule pigment according to claim 2 or 4, which exhibits a hysteresis width (ΔH) depending on the particle size of the microcapsule, and a system having an average particle size of 1 to less than 2 μm is a system having a particle size of 2 μm or more. The hysteresis width (Δ
H) is large. 7. The microcapsule pigment according to claim 2 or 4, wherein an oil-soluble fluorescent whitening agent is mixed in an encapsulated state in a dissolved or dispersed state. 8. The thermochromic hiding layer according to claim 1, which is colored with a color material containing a thermochromic material that exhibits a hysteresis width (ΔH) and changes color in a temperature-color density relationship, In the process in which the thermochromic material is in the first hue state and the temperature rises, when the second temperature T ₃ is reached, the first hue begins to change color, and the first hue is higher than the second temperature T _{3 and} is higher than the temperature T ₄ . In the process in which the thermochromic material is completely in the second hue in the temperature range and the thermochromic material is in the second hue state and the temperature drops,
Of reaches the first temperature T ₂ lower than the temperature T _3, a second color begins to discolor, thermochromic exhibiting a complete first color at a first low temperature T ₁ of the following temperature range than temperature T ₂ It is composed of materials. 9. The thermochromic laminate according to claim 1, wherein the thermochromic shading-translucent image and the thermochromic masking layer exhibit substantially the same discoloration temperature and substantially the same hysteresis width (ΔH). body. 10. The thermochromic laminate according to claim 1, wherein the non-thermochromic image and the thermochromic shading-translucent image are mutually related images.