JPH0781229A - Thermally color-changing light-screening and -transmitting laminate - Google Patents

Abstract

PURPOSE:To obtain a thermally color-changing laminate capable of clearly revealing and hiding a substrate layer having luster, light interference, hologram, and other optical properties by a temperature change. CONSTITUTION:A thermally color-changing light-screening and -transmitting laminate 1 is obtained by laminating a thermally color-changing layer 4, which is formed by firmly bonding a reversibly thermally color-changing material of 0.1-2.0mum particle diameter to a vinyl chloride-vinyl acetate copolymer resin in a dispersed state, has a temperature difference of 10-50 deg.C between a high- temperature side trigger and a low-temperature side trigger, and can change from a colored opaque state to a decolored transparent state and vice versa by a temperature change, on a substrate layer 2 having luster, light interference, hologram, and other optical properties.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermochromic light-shielding / light-transmitting laminate. In detail, it exhibits the mutual alteration of both the colored opaque state and the decolorized transparent state due to the temperature change, and effectively hides the underlying layer having optical properties such as glitter and gloss without impairing the above properties. The present invention relates to a thermochromic light-shielding / light-transmitting laminate to be revealed.

[0002]

2. Description of the Related Art Heretofore, there have been known many laminates in which an underlayer is laminated by a thermochromic layer obtained by fixing a reversible thermochromic material to a binder in a dispersed state, and the underlayer is hidden by a temperature change. And as the thermochromic material applied to the above, in the coexistence of a compound having an alcoholic hydroxyl group in the color-forming reaction between an electron-donating compound and a phenolic compound, a thermochromic material that changes color in response to a change in temperature is It is disclosed in JP-B-51-44706, JP-B-51-44707 and the like. As an attempt to apply this type of thermochromic material, Japanese Patent Publication No. S51-35216 discloses (a) an electron-donating color-forming compound, (b) a compound having a phenolic hydroxyl group, and (c) alcohols. Disclosed is a thermoplastic polymer composition comprising a compound selected from any of the following: an ester, a ketone, and an ether, and (d) a thermoplastic polymer. The above-mentioned conventional techniques all require reversible discoloration. Although it is described that it also has a light transmitting / concealing property with a change in color, in the above invention, the ternary mixture (a), (b) and (c) is contained in the thermoplastic resin polymer as it is. In the case of the one, a marked decrease in color density due to the polar action of the thermoplastic polymer,
There is a drawback that the sensitivity of discoloration is significantly impaired. Furthermore, in the thermoplastic polymer composition of the above invention, (a)
(B) (c) Since most thermochromic materials consisting of three components are already liquid at room temperature or become liquid when discolored,
There is a tendency that a specific component among the three components floats on the surface of the resin, that is, a so-called bleeding phenomenon, in the initial stage of preparation of the thermoplastic polymer composition or by repeated discoloration.
For these reasons, the presence of the above three components in the thermoplastic polymer in a stable manner for a long period of time and with a good discoloring effect even with repeated temperature changes has been a considerable practical problem in the prior art.

Usually, the three-component thermochromic material has a color-changing effect only when the three components are complete. Therefore, in order to impart more stability, the three-component thermochromic material is usually encapsulated by microencapsulation. Protected by the capsule wall. As a result, it can exist stably against chemical action, thermal action, etc. from the outside, and various applications are widely possible. However, in the system in which the thermochromic layer formed by fixing the encapsulated pigment to the transparent resin in a dispersed state is formed by microencapsulating the three components into a kind of solid pigment, Due to the light scattering phenomenon on the surface, its transparency is significantly reduced. Therefore, even in a system in which the underlayer has properties such as luster and gloss, even if the approximate color tone and image can be seen through, the luster and gloss of the underlayer are impaired and it is forced to be seen through. .

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the problems of the laminate due to the thermochromic layer in which the above-mentioned conventional thermochromic material is fixed to a binder in a dispersed state, and is used as a base layer having a luster or gloss. In a combination, it is intended to provide a thermochromic light-shielding-translucent laminated body which has a significantly improved transparency and is visually recognized without impairing the glitter and glossiness, while also having a significantly improved hiding property. To do.

The present inventors have made various studies on the thermochromic composition for forming the thermochromic layer. In the process, the thermochromic composition is composed of the three components (a), (b) and (c). Further studies were carried out, paying attention to the fact that the three components can be directly and stably held in the vinyl chloride-vinyl acetate copolymer resin without encapsulating the reversible thermochromic material. As a result, the three-component reversible thermochromic material was treated with vinyl chloride-
It was found that when dispersed in a fine particle state as a homogenous compatible material in vinyl acetate copolymer resin, it is extremely stable against repeated heating / cooling, and as a result of further diligent research based on this finding, it became fine particles. By distributing
We have developed a thermochromic composition capable of holding the three components extremely stably based on the new knowledge beyond the expectation that a remarkable hysteresis phenomenon is associated with the change of color and the change of transparency.

Conventionally, in order to cause a large hysteresis phenomenon with respect to thermal discoloration, a compound having a special structure or a compound having a special thermal physical property is required as the component (c), and the range is extremely limited. There was (special fair 4-1
7154 publication). The present invention does not strongly depend on the physical properties peculiar to the component (c), but the thermal physical properties of the component (c) itself, in other words, (b)
(B) (c) We succeeded in imparting remarkable hysteresis characteristics to the characteristics relating to the change in color and the change in transparency of the thermochromic material consisting of three components. Based on such knowledge, the present inventors did not microencapsulate a thermochromic material consisting of three components, and had a chemical effect on the three components that had a conventional problem, that is, reduction of concentration, deterioration and discoloration. The present invention has completed a thermochromic composition having stable hysteresis characteristics even after repeated operations without lowering the sensitivity.

[0007]

The present invention provides (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, (c) an alcohol, an ester, a ketone, or a carboxylic acid. Of a reversible thermochromic material having a particle size of 0.1 to 2.0 μm, which is composed of a homogeneous compatible solution containing a compound selected from the above, and is fixed in a dispersed state in a vinyl chloride-vinyl acetate copolymer resin matrix at high temperature. The temperature difference between the side trigger and the low temperature side trigger is 10 ° C. to 50 ° C., the temperature changes depending on the temperature with a large hysteresis characteristic, and it exhibits the mutual change of both the colored opaque state and the decolorized transparent state. The color-changing layer and the underlying layer having optical properties such as glitter, light-brightness reflectivity, optical coherence, iris, hologram property, metallic luster, pearl luster, and fluorescence, and the above-mentioned thermal layer The color change layer is not laminated Thermochromic shading - is required for the translucent laminate. Furthermore, the thermochromic layer contains 6 to 5 parts by weight of vinyl chloride-vinyl acetate copolymer resin, (a) 0.05 to 2.0 parts by weight of the electron-donating color-forming organic compound, and (b) phenolic hydroxyl group. 0.1 to 3.0 parts by weight of the compound having
(C) A compound selected from alcohols, esters, ketones, or carboxylic acids is 0.5 to 5.0.
The vinyl chloride-vinyl acetate copolymer resin has an average molecular weight of 7,000 to 50,000.
The constituent monomer weight ratio is 60% to 92% of vinyl chloride and 8% to 40% of vinyl acetate, and the dispersion aid is 0.002 to 0.5 parts by weight with respect to 100 parts by weight of the thermochromic layer. That the compound having a phenolic hydroxyl group is at least 50% by weight of the compound having at least all phenolic hydroxyl groups,

Embedded image [wherein R 1 is H or CH ₃ and R 2 is C _n H
It represents _{2n + 1 (4 <n <} 11) , or R1 = R2 = CF _3, respectively. C _n H _{2n + 1} represents a linear or side chain alkyl group. X represents a substituent on the aromatic ring. Also, X = H or C
H is _3. Further, the component (c) is (a) a monohydric fatty acid and an ester having a total carbon number of 10 or more, which comprises an aliphatic monohydric alcohol or a monohydric alcohol having an alicyclic ring, and (b) an aliphatic Polybasic acid esters having a total carbon number of 28 or more, which are composed of a divalent or polyvalent carboxylic acid and an aliphatic monohydric alcohol or an alicyclic monohydric alcohol, (c) an aliphatic divalent or polyhydric alcohol and a monovalent One or two or more esters selected from the following fatty acid-containing esters having a total carbon number of 26 or more, and (d) an aromatic ring-containing dihydric alcohol and a monohydric fatty acid having a total carbon number of 28 or more. A methacrylic resin layer having a glass transition point of 90 ° C. or higher as an undercoat layer on the surface of the underlayer, and an alcohol-soluble or aliphatic hydrocarbon-soluble transparent meta layer on the thermochromic layer. To Lil resins and acrylic resins, or the like formed by laminating a layer made of a copolymer resin thereof a requirement. In the above configuration, the trigger refers to a temperature at which "change" occurs, a color change temperature, and / or a transparency change temperature. Therefore,
It is colored and opaque at temperatures below the low temperature trigger, and changes to colorless and transparent at temperatures above the high temperature trigger.

The first feature of the present invention is to homogenize the three components in a matrix of vinyl chloride-vinyl acetate copolymer resin in a stable state so as to cope with repeated changes of the three components without being microencapsulated. The first feature of the present invention is that it is dispersed in the form of fine particles as a compatible solution. More specifically,
Regarding the dispersed state of the three-component thermochromic material, the particle size
0.1 μm to 2.0 μm, more preferably 0.2 μm to
If it is within 1.5 μm, the fine particles repeat the change of liquid phase / solid phase upon repeated changes of heating / cooling, but they are extremely stably retained in the matrix of vinyl chloride-vinyl acetate copolymer resin. It In this respect, the vinyl chloride-vinyl acetate copolymer resin exerts an important and effective action in the dispersibility of the ternary thermochromic material. Regarding the point of free energy regarding the stabilization of fine particles of the thermochromic material consisting of the three components held in the resin,
The present inventors consider that since the particle size is more energetically stabilized between 0.1 μm and 2.0 μm, it can be stably present inside the resin. If the thickness exceeds approximately 2 μm, the resin surface tends to bleed due to repeated heating / cooling. Since the free energy increases as the particle size increases, it becomes difficult to stably exist in the matrix resin. On the other hand, 0.
When the thickness is 1 μm or less, visible light is optically transmitted, so the light-shielding property (opacity) is impaired below the low temperature side trigger.
That is, since transparency is increased, a substantially good change in transparency / opacity cannot be obtained. Further, the second feature of the present invention is
By dispersing the three components in the form of fine particles in the matrix,
It has a specific effect on color change and transparency change. That is, it has a certain low temperature side trigger and a certain high temperature side trigger, and it is colored / opaque at a temperature below the low temperature side trigger, and colorless / transparent at a temperature above the high temperature side trigger, but the temperature of the two triggers. The difference is in the range of approximately 10 ° C. or higher and 50 ° C. or lower in the finely divided state, and is characterized by having a very clear hysteresis characteristic.

Regarding the above-mentioned component (c), the present inventors have searched for the thermal physical properties of the compound, and the melting point of the compound is almost uniquely determined by the compound itself. It has been found that (or cloud point) greatly changes depending on the amount of the compound collected collectively, in other words, the capacity of the compound. In short, when 30 ml of compound is present in a 50 ml beaker, and 1 mm in a capillary with an inner diameter of 1 mm.
When it is encapsulated for a length of 0.5 μm, and when it is present in the form of fine particles of 0.5 μm, it means that the smaller the aggregate amount of them is, the lower the freezing point (or cloud point) is. More specifically, the determinants of the freezing point are governed by the crystal nucleus generation rate and the crystal growth rate. However, when the particle size of the compound is about 2 μm or less, the crystal nucleus generation rate decreases, and the crystal growth increases. It becomes more difficult and as a result solidification does not begin unless it is cooled to a lower temperature. In particular, a large change occurs in the freezing point at around 2 μm. Further, in order to satisfactorily exhibit the above-mentioned effects of the present invention, it is preferable that each particle is substantially a single independent particle. In other words, if they are aggregated in the shape of grapes, generally aggregated due to coalescence, or exist in a form with precipitation inside or on the surface, the freezing point fluctuates locally or entirely, resulting in a sharp change. In addition to being difficult to obtain, the particles cannot stably exist in the base resin, causing bleeding and tending to lack stability. The present inventors have used the ternary thermochromic material to disperse in a matrix of vinyl chloride-vinyl acetate copolymer resin with a mononuclear particle size of 0.1 to 2.0 μm in the matrix resin, It was possible to shift the low temperature side trigger to the extremely low temperature side. At the same time, a change in transparency / opacity is almost linked to this, and it succeeded in imparting a specific hysteresis characteristic. In general, the thermochromic layer of the present invention has a hysteresis width of 10 ° C to
It is in the range of 50 ℃.

Next, the matrix matrix resin will be described. As described above, the ternary thermochromic material is susceptible to external chemical influences, and the influence of the matrix resin itself of the matrix is no exception. For example, a 100% vinyl chloride resin is liable to gradually generate hydrogen chloride due to a dechlorination reaction even under ordinary storage conditions, and irreversibly develops an electron-donating color-forming organic compound. In addition, 100% vinyl acetate resin imparts strong desensitization (permanent decolorization) to the three-component thermochromic material due to the strong polarity of the vinyl acetate group, and as a result, it shows almost no thermochromic property. A single resin composition is not suitable as the matrix resin of the present invention. On the other hand, when vinyl chloride resin and vinyl acetate resin are copolymerized with an appropriate monomer ratio, not only is the dechlorination reaction extremely difficult to occur, but a good atmosphere in which the desensitizing effect of the vinyl acetate resin is not substantially exerted is a three-component system. Apply to tarnish materials. This is the reason why the vinyl chloride-vinyl acetate copolymer resin is selected as the matrix resin Marix resin which has neither irreversible color development nor substantially desensitization. Examples of the resin that does not have the permanent desensitizing property and the strong color developing property include a hydrocarbon resin having a small polarity and a halogen-containing resin. Such resins are known to have a three-component thermochromic material dispersed therein. Instead of morphology, it is non-locally dissolved or compatible in the matrix. As a result, in order to diffuse into the matrix resin,
At the same time that the thermochromic effect is significantly reduced, the transparent / opaque effect tends to be impaired. The ternary thermochromic material locally disperses as particles in the matrix resin matrix, resulting in excellent thermochromism and excellent transparency. Furthermore, when they are generally compatible, each compound tends to bleed initially or over time and is extremely unstable. For this reason, dispersion in fine particles is an important factor in the present invention. Therefore, in contrast to a composition in which only an organic compound is dispersed in a matrix matrix resin to change transparency in response to a temperature change, in order to satisfy both changes in color and transparency, the matrix matrix resin is The composition is as follows.

The matrix resin used in the present invention is assumed to be optically substantially transparent. Such a resin has an average molecular weight in the range of 7,000 to 50,000 and a weight ratio of constituent monomers of vinyl chloride. Vinyl chloride-vinyl acetate copolymer resin with 60-92% and vinyl acetate 8-40% is applied. Further, it may contain a small amount of other monomer components such as a hydroxyl group at a constituent monomer ratio of 7% (weight ratio) or less. However, the carboxy group is excluded because it causes irreversible color development. In addition, 30% of other compatible resin to vinyl chloride-vinyl acetate copolymer resin
You may mix in the following weight ratios. Such a small amount of resin component is for the purpose of imparting adhesiveness during secondary processing, improving film strength, etc. within a range that does not impair the basic function of the present invention, that is, color change and transparency change due to temperature change. Can be used. Such other compatible resins include modified alkyd resins, unsaturated polyester resins, saturated polyester resins,
Epoxy resin, amino resin, polyurethane resin, oil-soluble cellulose resin, hydrocarbon resin, vinyl acetate resin, butyral resin, acrylic resin, methyl methacrylate resin, styrene-butadiene copolymer resin, ethylene-vinyl acetate copolymer resin, chlorinated polypropylene Resin, polyamide resin, styrene resin, acrylic-styrene copolymer resin, styrene-maleic acid resin, chlorinated rubber, silicone resin, vinyl chloride-acrylic copolymer resin, ketone resin and the like.

As the electron-donating color-developing organic compound used in the present invention, a so-called leuco dye group which is colored by a compound having a phenolic hydroxyl group is applied, and diphenylmethanephthalides, fluoranes, diphenylmethaneazaphthalide are used. , Indolylphthalide, phenylindolylphthalide, phenylindolylazaphthalide, styrylquinoline, etc.

Next, as the compound having a phenolic hydroxyl group, there are monohydric phenol, dihydric phenol and polyhydric phenol, and further, as a substituent of the benzene ring, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group and a carboxy group. And those having an ester or amide group thereof, halogen and the like, and bis type and tris type phenols. Generally, a phenol compound has relatively high polarity due to its phenolic hydroxyl group, so
(C) Poor solubility in components. If the solubility is poor,
In a thermochromic material composition consisting of three components dispersed in a matrix resin matrix in the form of fine particles, the phenolic compound and the above-mentioned (c) component are likely to cause precipitation and separation phenomena, which may cause bleeding and It does not cause reversible color change and often lacks stability from a practical point of view.

For this reason, it is preferable to use the phenolic compound represented by the following general formula as a component having a phenolic hydroxyl group in a proportion of 100% (weight) or at least 50% (weight) or more. (C)
As the phenol compound having good solubility with respect to the components, a compound having a phenolic hydroxyl group having a structure represented by the following general formula is particularly preferable.

[Wherein R1 is H or CH ₃ and R2 is C _n H _{2n + 1} (
Represents 4 <n <11) or, R1 = R2 = CF _3, respectively.
C _n H _{2n + 1} represents a linear or side chain alkyl group. X
Represents a substituent of an aromatic ring. Also, X = H or CH ₃ . Examples of the compound of the above general formula are shown below, but the invention is not limited thereto. 1,1-bis (4′-hydroxyphenyl) -4-methylbutane, 1,1-bis (4′-hydroxyphenyl) n-pentane, 1,1-bis (4′-hydroxyphenyl) n-hexane, 1 , 1-bis (4 '
-Hydroxyphenyl) n-heptane, 1,1-bis (4'-hydroxyphenyl) n-octane, 1,1-
Bis (4'-hydroxyphenyl) n-nonane, 1,1
-Bis (4'-hydroxyphenyl) n-dodecane,
2,2-bis (4'-hydroxyphenyl) n-heptane, 2,2-bis (4'-hydroxyphenyl) n-nonane, 1,1-bis (3'-methyl-4'-hydroxyphenyl) n -Hexane, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, and the like.

Next, as the alcohol, an aliphatic monovalent saturated alcohol having 10 or more carbon atoms is used. The compounds are exemplified below. Decane 1-all, Undecane 1-
All, lauryl alcohol, tridecane 1-ol myristyl alcohol, pentadecane 1-ol, cetyl alcohol, heptadecane 1-ol, stearyl alcohol, octadecane 2-ol, eicosan 1-ol, docosan 1-ol, 6- (perfluoro-7 -Methyloctyl) hexanol, etc. The ester compounds applicable to the present invention are roughly classified into the following (a) to (d). (A) Esters having a total carbon number of 10 or more and consisting of a monovalent fatty acid and an aliphatic monohydric alcohol or an alicyclic monohydric alcohol. (B) Polybasic acid esters having a total carbon number of 28 or more, which are composed of an aliphatic divalent or polyvalent carboxylic acid and an aliphatic monohydric alcohol or an alicyclic monohydric alcohol. (C) Esters having a total carbon number of 26 or more consisting of an aliphatic dihydric or polyhydric alcohol and a monovalent fatty acid (d) Esters having a total carbon number of 28 or more consisting of a dihydric alcohol having an aromatic ring and a monovalent fatty acid Classes (a) Monoester fatty acid and aliphatic monohydric alcohol or monohydric alcohol having an alicycle and having a total carbon number of 10 or more are exemplified below. In addition, due to the increase in the polarity of the molecule itself, esters with total carbon number of 9 or less
Since it is compatible with the matrix resin, it gives almost no opacity even at the low temperature side trigger temperature or lower. Similarly, an ester containing an aromatic ring has a very low effect.

Ethyl caprylate, n-butyl caprylate, n-octyl caprylate, lauryl caprylate, cetyl caprylate, stearyl caprylate, n-caprate
-Butyl, n-hexyl caprate, myristyl caprate, docosyl caprate, methyl laurate, 2-ethylhexyl laurate, n-decyl laurate, stearyl laurate, ethyl myristate, 3-methylbutyl myristate, 2 myristate -Methylpentyl,
N-decyl myristate, cetyl myristate, stearyl myristate, isopropyl palmitate, neopentyl palmitate, n-nonyl palmitate, n-undecyl palmitate, lauryl palmitate, myristyl palmitate, cetyl palmitate, stearyl palmitate, Cyclohexyl palmitate, cyclohexyl methyl palmitate, methyl stearate, ethyl stearate, n-propyl stearate, n-butyl stearate, n-amyl stearate, 2-methylbutyl stearate, n-hexyl stearate, n stearate n -Heptyl, 3,5,5-trimethylhexyl stearate, n-octyl stearate, 2-ethylhexyl stearate, n-nonyl stearate, n-decyl stearate. , N-undecyl stearate,
Lauryl stearate, n-tridecyl stearate,
Myristyl stearate, n-pentadecyl stearate, cetyl stearate, stearyl stearate, eicosyl stearate, n-docosyl stearate, cyclohexyl stearate, cyclohexylmethyl stearate, oleyl stearate, isostearyl stearate, 12-hydroxystearin. N-butyl acid,
N-Methyl behenate, n-ethyl behenate, n behenate
-Propyl, isopropyl behenate, n-butyl behenate, isobutyl behenate, 2-methylbutyl behenate,
N-Amyl behenate, neopentyl behenate, n-hexyl behenate, 2-methylpentyl behenate, n-heptyl behenate, 2-ethylhexyl behenate, n-nonyl behenate, myristyl behenate, n-undecyl behenate. , Lauryl behenate, n-tridecyl behenate, myristyl behenate, n-pentadecyl behenate, cetyl behenate, stearyl behenate, behenyl behenate and the like. An aliphatic divalent or polyvalent carboxylic acid of (b) above,
Examples of polybasic acid esters having a total carbon number of 28 or more, which are composed of an aliphatic monohydric alcohol or a monohydric alcohol having an alicyclic ring, are shown below. Esters having a total carbon number of 27 or less are compatible with the matrix resin of the matrix due to an increase in the polarity of the molecule itself, and therefore do not impart opacity even at temperatures below the low temperature side trigger temperature. Similarly, an ester containing an aromatic ring does not exhibit the above effect.

Di-myristyl oxalate, di-n-pentadecyl oxalate, di-cetyl oxalate, di-lauryl malonate, di-n-pentadecyl malonate, di-cetyl malonate, di-stearyl malonate, di-succinate- Lauryl, di-myristyl succinate, di-cetyl succinate, di-succinate
Stearyl, di-lauryl glutarate, di-adipate
Undecyl, di-lauryl adipate, di-adipate
n-tridecyl, di-myristyl adipate, di-cetyl adipate, di-n-pentadecyl adipate, di-stearyl adipate, di-n-docosyl adipate,
Di-n-decyl azelate, di-lauryl azelate, di-n-tridecyl azelate, di-sebacate
n-nonyl, di-myristyl sebacate, di-stearyl sebacate, di-n-pentyl 1,18-octadecyl methylene dicarboxylic acid, di-n-octyl 1,18-octadecyl methylene dicarboxylic acid 1,18-octadecyl methylene dicarboxylic acid Acid di- (cyclohexylmethyl), 1,18-octadecylmethylylenedicarboxylic acid di-neopentyl, and the like. Examples of the above-mentioned (c) aliphatic dihydric and polyhydric alcohols, alicyclic or dihydric and polyhydric alcohols, and monohydric fatty acid esters having a total carbon number of 26 or more are shown below.

Ethylene glycol di-myristate, ethylene glycol di-palmitate, ethylene glycol di-stearate, propylene glycol di-laurate, propylene glycol di-myristate, propylene glycol di-palmitate, butylene glycol di-stearate, Xylene glycol di-laurate, hexylene glycol di-myristate, hexylene glycol di-palmitate, hexylene glycol di-stearate, 1,5-pentanediol di-stearate, 1,2,6-hexanetriol-dimyristate , Pentaerythritol trimyristate, pentaerythritol tetralaurate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanediol dimyristyl 1,4-cyclohexanediol distearyl, 1,4-cyclohexanedimethanol dilaurate, 1,4-cyclohexanedimethanol Jimirisuteto, and the like. The above-mentioned (d) esters having a total carbon number of 28 or more, which are composed of a divalent alcohol having an aromatic ring and a monovalent fatty acid, are exemplified below. Xylene glycol di-caprinate, xylene glycol di-n-
Undecanoate, xylene glycol di-laurate,
Examples thereof include xylene glycol di-myristate, xylene glycol di-palmitate, xylene glycol di-stearate and the like.

Next, as the ketones, compounds having 10 or more carbon atoms are used, and examples thereof include decan-2-one, undecane-2-one, laurone and stearone. As the carboxylic acids, higher fatty acids having 12 or more carbon atoms are used, and lauric acid, myristic acid, palmitic acid, stearic acid,
Examples include behenic acid. The compounds used as the component (c) are the above-mentioned alcohols, esters, ketones,
You may select and use 1 type (s) or 2 or more types from carboxylic acids. When a plurality of compounds are used together, there is an advantage that the degree of freedom is increased by setting a trigger temperature that causes a change in color and a change in transparency. Next, as a condition that causes a change in transparency as well as a change in color in response to a change in temperature, the ratio of the thermochromic material consisting of three components to the matrix resin matrix is such that the ratio of the change in transparency / opacity and the change in density in color change It has an important factor in the decision. For example, with respect to 6 parts by weight of the base resin, 0.2 parts by weight of the (a) electron-donating color-forming compound and 0.8 parts of the (b) phenolic compound are used.
In the case of parts by weight, when 0.3 parts by weight of stearyl caprylate having 28 carbon atoms is applied as the component (c), the opacity at a temperature below the low temperature side trigger is extremely low and the light shielding property is lacking. On the other hand, when the amount is 7.0 parts by weight, the opacity at the temperature lower than the low temperature side trigger is remarkably increased, but the transparency at the temperature higher than the high temperature side trigger is lowered, and it becomes substantially impossible to see through. Therefore, in order to obtain a thermochromic property with a change in transparency with good contrast, the addition ratio of the thermochromic material consisting of three components is limited to the following range.
The range of such ratio is from 0.05 to 6 parts by weight of vinyl chloride-vinyl acetate resin, and
2.0 parts by weight, a compound having a (b) phenolic hydroxyl group
It is composed of 0.1 to 3.0 parts by weight and 0.5 to 5.0 parts by weight as the component (c). More preferably, with respect to vinyl chloride-vinyl acetate copolymer resin 6 parts by weight,
(A) 0.1 to 0.5 parts by weight of the electron-donating color-forming organic compound, and (b) a compound having a phenolic hydroxyl group 0.2 to 1.
2 parts by weight, 1.0 to 3.0 parts by weight as the component (c) are used.

Next, a method for preparing the thermochromic composition of the present invention will be described. As described above, in order to make the change in color and the change in transparency, which are the greatest features of the present invention, stably function according to the change in temperature, (a), (b), (c)
A reversible thermochromic material composed of three components is a vinyl chloride-vinyl acetate copolymer resin as a matrix resin,
The dispersion is preferably in the range of 0.1 to 2.0 μ. Usually, the matrix resin and the three components are
It is dissolved using one kind or two or more kinds of solvents. From the viewpoint of the solubility of the vinyl chloride-vinyl acetate copolymer resin, it is necessary to use a ketone solvent as the rich solvent. The solvent also works as a rich solvent for the three components. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl isopropyl ketone, and methyl n-propyl ketone. The aromatic solvent works as a poor solvent for the vinyl chloride-vinyl acetate copolymer resin, but it is preferably used in combination with the ketone solvent. As the aromatic solvent, a solvent such as toluene or xylene is used. Other solvents include isopropyl alcohol, alcohol solvents such as n-butanol, ester solvents such as n-ethyl acetate, n-propyl acetate, n-butyl acetate and isobutyl acetate, hexane, cyclohexane, ethylcyclohexane, minerals. Hydrocarbon solvents such as spirit and other glycol monoalkyl ether solvents can be used. Further, as a method of more uniformly dispersing the three-component compatible solution in the matrix of the vinyl chloride-vinyl acetate copolymer resin in a fine shape, the use of a so-called dispersion aid has a remarkable effect. Such a dispersion aid is preferably a substance having a small degree of chemical adverse effect with respect to the above three components. The compound having such a dispersing effect generally has an effect of remarkably reducing the surface tension and the interfacial tension, and exhibits the function of finely dispersing the ternary thermochromic material in the matrix resin in a mononuclear form.

Examples of such compounds are shown below. Polyether-modified dimethylpolysiloxane, polyether-modified methylalkylpolysiloxane, polyester-modified polydimethylsiloxane, polyester-modified methylalkylpolysiloxane, etc. are used as the siloxane derivative, and fluorine-containing compounds such as Florard FC-430 and Florard FC-431 (Sumitomo 3M Fluorinated alkyl esters such as those manufactured by Co., Ltd. as a special polymer system include acrylonitrile- (2-methacryloyloxyethyl) trimethylammonium-methylsulfate-dimethylaminoethylmethacrylate. Thermochromic composition in the base resin 0.1μ
When forming fine particles of m to 2.0 μm, it has an effect of uniformly dispersing in the shape of a single nucleus. In particular, it has a special effect in preventing coalescence and aggregation. Such an additive is added in an amount of 0.002% to 0.05% based on 100 parts by weight of the thermochromic composition.
%, And 0.002% to 0.05% is preferable in order to reduce the chemical influence on the thermochromic composition. (However, the amount of dispersant is solid base)

A solution of the thermochromic composition which is substantially uniformly dissolved by appropriately combining the above-mentioned solvents is attached to the target underlayer by spray coating, screen printing, gravure printing, roll coating, reverse coating or the like. Then, the solvent is completely evaporated and dried by room temperature drying or heat drying. The three components are dispersed in the matrix resin in the form of fine particles through the process of evaporation. In order to maximize the effect of the present invention, it is preferable that the dispersed particles are substantially single particles as described above. It is important to select a solvent that dissolves the thermochromic composition in order to develop a single particle having a particle diameter of 0.1 to 2.0 μm. More specifically, when the solvent evaporates too quickly in the transitional period of drying, of the components of the thermochromic material consisting of three components, the component (c) mainly precipitates first to form a single fine particle. As a result of forming a continuous phase before forming, a phenomenon such as bleeding occurs. Similarly, when the solvent evaporates quickly, or when a poor solvent is mixed in a large amount, the vinyl chloride-vinyl acetate copolymer resin is deposited in advance, so that the thermochromic material is formed into a uniform fine particle. It is often impossible to disperse. Generally, the amount of the solvent used for the thermochromic composition varies depending on the deposition method, but 1 to 50 parts by weight of the solvent is applied to 1 part by weight of the thermochromic light-shielding composition. It is more preferably 3 to 15 parts by weight. The thickness of the thermochromic layer is generally 2 to 100 μm. When the thickness is less than this, there are drawbacks that the fine particles of the thermochromic composition tend to lack stability and that it is difficult to obtain good contrast. In order to physically and uniformly attach the thermochromic composition solution (hereinafter referred to as thermochromic ink), various additives can be added. Known additives are applied as such additives, and an anti-sagging agent, a leveling agent, a defoaming agent, a thickener, a friction resistance improver and the like can be applied. However, it is preferable to use the minimum necessary amount of the additive which has no chemical influence on the above-mentioned three components or has little influence thereof.

In particular, regarding the formation of the thermochromic layer, if the forming layer is not physically smooth, diffuse reflection is caused on the surface of the layer, and needless to say, the appearance remarkably impairs transparency at a temperature above the high temperature side trigger. Therefore, the smoothness of the surface is an important factor for transparency in forming the layer of the thermochromic composition. Various publicly known additives which have little chemical influence and impart smoothness can be used. Further, for the purpose of improving the light resistance and stability of the thermochromic composition, an ultraviolet absorber, an antioxidant, a singlet oxygen quencher and other light stabilizers can be used. Further, the thermochromic layer comprising the thermochromic composition of the present invention is basically colored and opaque at a temperature below the low temperature side trigger, and is colorless and transparent above the high temperature side trigger, but a general dye or transparency. By using a general pigment having
It is also possible to change from colored [1] opaque to colored [2] transparent. In addition, depending on the application, a pigment having a hiding property may be used if transparency is not particularly required.

Next, the underlayer will be described. The base layer is made of a material exhibiting optical properties such as glitter, light brightness reflection, light interference, iris, hologram, metal luster, pearl luster, fluorescence and phosphorescence. Specifically, a bright to bright reflection film formed by laminating a metal thin film layer on one side or both sides of an organic synthetic film base material (for example, a thin silver film formed on an aluminum thin film, an organic synthetic film on which aluminum is formed). , A metal thin film of chromium, silver, copper, etc., further laminated with transparent thin films having different refractive indexes alternately on the surface of the metal thin film to increase the light reflectivity), on the surface of the support. A thin film layer of a transparent metal compound (for example, titanium oxide, silicon oxide, zinc oxide, cadmium sulfide, magnesium fluoride, cerium fluoride, etc.) having a refractive index difference of 0.05 or more with the support is formed, A laminate having an iris pattern in which the thin film and an uneven transparent resin layer having a refractive index difference of 0.05 or more are laminated in this order, and a compound such as zinc sulfide, titanium oxide, oxide, magnesium fluoride and copper iodide. A multi-layer vapor-deposited product, a light-reflecting film, an uneven interference resin film and a semi-transparent metal thin film, and a group of continuous high refractive index glass beads as a lens in an organic resin medium as a binder. A film having retroreflective properties such as a multilayer composite including a layer and a light-reflecting layer behind it, an optical interference film in which multiple layers of transparent plastic thin films having different refractive indices are laminated to provide iris, Hologram having a light-reflecting layer on at least one side of a rough pattern,
Colored or colorless paint on the surface of the metallic mirror surface to form a transparent film with a thickness that is thin enough to cause light interference, or a part of the transparent film is used as radiation centered on a desired point. The light ray reflected on the metal film surface and the light ray reflected on the transparent film surface, such as an iris pattern or a radiation pattern in which a thick line portion is formed as a thick line, overlap with each other, so-called "thin film interference" That generate fine aluminum, copper, brass,
Metal powder of gold, silver, nickel or the like, or plastic vapor deposition powder, for example, polyester resin, phenol resin, vinyl chloride resin metal vapor deposited by a conventional method, coated with pulverized powder, leafing type aluminum,
Copper, zinc, copper alloy coated with a binder, metal foil such as gold foil, silver foil, metallic luster pigment (for example,
Examples thereof include gold, silver, metallic red, metallic blue, metallic green and other metallic colors in which the surface of natural mica is coated with titanium oxide, and colored supports such as pearlescent pigments, fluorescent dyes and phosphorescent pigments. The present invention is not limited by the material and form as long as it is a support that effectively exhibits the optical properties of the underlayer.
A transparent or opaque support is used depending on the application. Examples of the transparent support include polyester film (amorphous polyester), polycarbonate, polystyrene, styrene-butadiene block copolymer resin, acrylonitrile-styrene copolymer resin, acrylic resin, methyl methacrylate resin, epoxy resin, polypropylene resin, hard or soft chloride. There are vinyl resin, acrylonitrile-butadiene-styrene copolymer resin (transparent grade), polypropylene resin and the like. Opaque or translucent resins and materials include medium and low pressure polyethylene, acrylonitrile-butadiene-styrene copolymer resin, nylon resin, and resins obtained by coloring or shielding the above transparent resin with pigments, papers, synthetic papers, fibers. , Cloth, filaments, glass, wood, and the like.

When the thermochromic composition of the present invention is laminated on a support, it is dissolved in a solvent and coated as described above. The solvent dissolves and swells the support resin to give a thermochromic property. It often happens that the composition is adversely affected by chemical effects related to thermochromism and physical effects related to transparency. For example, when a thermochromic composition dissolved in methyl isobutyl ketone is applied to a support of polystyrene resin by spraying, the solvent dissolves the support resin and the polystyrene resin migrates into the thermochromic composition. As a result, the thermochromic property of the thermochromic composition is easily affected chemically. For this reason, it is preferable to apply an undercoat to the surface of the support in advance and then laminate the thermochromic composition. As the undercoat resin, a methacrylate resin exerts a preferable effect and is coated on the support with a solvent composition that does not attack the support depending on the coating method. As a more preferable resin, a methacrylic resin having a glass transition point of 90 ° C. or higher is preferable, and as such a resin, polymethyl methacrylate (Tg: 125 ° C.), polyisopropyl methacrylate (Tg: 95 ° C.), and a copolymer obtained. A resin having a glass transition point of 90 ° C. or higher can be used. Further, a top coat layer can be laminated on the thermochromic layer. Even when applying the top coat layer,
The solvent for the top coat is a thermochromic layer (thermochromic composition layer)
Redissolving not only changes the composition ratio of the thermochromic composition, but also significantly affects the thermochromic function and the transparency / opacity function. Therefore, the solvent applied to the top coat must be a composition that does not substantially dissolve or swell the thermochromic composition layer. Water as a suitable solvent,
They are alcohols, glycol ethers, and aliphatic hydrocarbon solvents. Easily soluble in such solvents, or a resin of a dispersion system, and a vinyl chloride-vinyl acetate copolymer resin as a good adhesive resin soluble methacrylic resin, vinyl-modified alkyd resin, oil-soluble polyurethane resin, Examples thereof include acrylic resin, acrylic copolymer resin, epoxy resin and the like. Among them, a solvent composition in which an alcohol solvent and / or an aliphatic hydrocarbon solvent accounts for 40% or more of the total solvent of a methacrylic resin and an acrylic resin having transparency of an alcohol soluble or an aliphatic hydrocarbon soluble, or a copolymer resin thereof When it is dissolved and laminated, the thermochromic composition is not adversely affected and proper coatability is satisfied, and a transparent topcoat layer having adhesion is provided. In the undercoat and topcoat resins, an ultraviolet absorber, an antioxidant, a singlet oxygen quencher, a colorant, and other light stabilizers are effectively used for the purpose of improving the light resistance of the thermochromic layer. .

[0026]

[Function] Dispersing a thermochromic material consisting of three components (a), (b) and (c) into a fine particle of 0.1 to 2.0 μm in a vinyl chloride-vinyl acetate copolymer resin matrix. Thus, any of the above components is stably held without bleeding on the resin surface, the transparency reversibly changes with color change due to temperature change, and the change between colored opaque and decolored transparent is reversible and reversible. Specifically, the thermochromic light-shielding / transparent function having a large hysteresis characteristic in which the temperature difference between the high temperature side trigger and the low temperature side trigger is at least 10 ° C. or more and 50 ° C. or less is exhibited. In the above, since the thermochromic material is not in the form of a microencapsulated pigment, there is no adverse effect on the transparency due to the light scattering phenomenon and the transparency is high. Therefore, the thermochromic layer formed by laminating the composition of the present invention is excellent in light transmission and transparency, and allows clear visibility without impairing the optical characteristics of the underlayer having optical properties such as glitter and gloss. .

[0027]

EXAMPLES The optical characteristics of the thermochromic composition forming the thermochromic layer of the laminate of the invention will be described in more detail with reference to examples. All parts in the examples are parts by weight. Regarding the hysteresis width, when changing from colored opaque to colorless and transparent and then cooling to the low temperature side, the hysteresis width becomes small if the temperature during temperature rise is in the vicinity of the high temperature side trigger or less. The hysteresis width of the present invention refers to the maximum hysteresis width for one thermochromic composition. In the following examples, the color change temperature, the absorbance and the transmittance were measured according to the following methods. (1) Discoloration temperature Regarding Examples 1 to 6, white synthetic paper having a thickness of 60 μm was attached to the back surface of the PET film coated with the thermochromic composition, to prepare a measurement sample. The measurement sample is further attached to the bottom of the heating / cooling container using double-sided tape. The thermochromic composition side is a color difference meter (TC-
Set toward the light source side of Model 3600 color difference meter, made by Tokyo Denshoku Co., Ltd. Put water in a heating / cooling container, 1 per minute
Under the condition of 0 ° C, the temperature decrease (from 50 ° C to 0 ° C) and the temperature increase (from 0 ° C to 50 ° C) were changed as one cycle, and the brightness of the sample at each temperature was plotted in the graph. (2) Absorbance and transmittance At room temperature of 20 ° C., the same PET film as the film used in the example was used for the control side, and the thermochromic printed matter obtained according to each example was set on the sample side, and the spectrum was analyzed. Photometer (U
-3210: Absorbance (by a reflection method) and transmittance of light having a wavelength of 400 to 700 nm were measured with a self-recording spectrophotometer manufactured by Hitachi, Ltd. The measurement sample was measured at 20 ° C. for absorbance and transmittance in two states of colored opaque and decolorized transparent. In the figure, the solid line shows the absorbance and the transmittance at 20 ° C. when the color is opaque, and the broken line shows the absorbance and the transmittance at 20 ° C. when the color is transparent.

Example 1 1,2-Benz-6-dibutylaminofluorane 1.
3 parts, 1,1-bis (4′-hydroxyphenyl) hexane 5 parts, stearyl caprate 5 parts, stearyl laurate 15 parts VYHH (vinyl chloride-vinyl acetate copolymer resin, polymer composition: vinyl chloride / vinyl acetate = 86/14,
Union Carbide made in Japan) 20% MIBK solution 30
Dissolved in 0 parts. Further, 0.2 part of Byk-310 (polyester-modified dimethylpolysiloxane, manufactured by Byk chemie) was added to prepare a thermochromic ink (A). PET film (100 μm thick, manufactured by Lintec Co., Ltd., trade name: NF) using the above ink using an applicator
PET Tomei 100 [A]) was coated so that the film thickness when dried was about 15 μm, and dried at 80 ° C. for 30 minutes to form a thermochromic layer. It was observed that the thermochromic material was dispersed in the thermochromic layer in the range of about 0.2 to 1.0 μm. The obtained printed matter had two triggers, a low temperature side trigger: about 12 ° C and a high temperature side trigger: about 39 ° C, and the hysteresis width was about 20 ° C. When the temperature was higher than the high temperature side trigger, the color disappeared and became transparent, and when the temperature was lower than the low temperature side trigger, it became pink and became opaque. In the temperature range between the low temperature side trigger and the high temperature side trigger, the above two states can be selectively taken. The change could be stably repeated without bleeding even after 500 times of repetition. Further, the same change and stability were confirmed even when left in a constant temperature room at 60 ° C. for 1 week. The color change curve of the printed matter is shown in FIG. 1, the absorbance during coloring / opacity and the color disappearance / transparency is shown in FIG. 2, and the transmittance is shown in FIG.

Example 2 2-chloro-3-methyl-6-diethylaminofluorane 2 parts, 2,2-bis (4'-hydroxyphenyl)
5 parts of propane and 20 parts of myristyl alcohol are added to Denka vinyl 1000D (vinyl chloride-vinyl acetate copolymer resin, polymer composition: vinyl chloride / vinyl acetate = 68/32, manufactured by Denki Kagaku Kogyo) MIBK / xylene (1/1). Solution 3
It was dissolved in 00 parts. Furthermore, Byk-325 (polyether-modified dimethylpolysiloxane, Byk chemie
(Manufactured by the company) was added to prepare a thermochromic ink (B). A PET film (100 μm thick, manufactured by Lintec Co., Ltd., product name:
After coating NF PET Tomei 100 [A]) so that the film thickness when dried will be about 20 μm, then at 80 ° C. × 30
After drying for a minute, a thermochromic layer was formed. In the thermochromic layer,
It was observed that the thermochromic material was dispersed in the resin in the range of about 0.2-2.0 μm. The obtained printed material has a low temperature side trigger: about 4 ° C, a high temperature side trigger: about 33 ° C.
The hysteresis width with two triggers was about 20 ° C. When the temperature was higher than the high temperature side trigger, the color disappeared and became transparent, and when the temperature was lower than the low temperature side trigger, it became vermilion and became opaque. In the temperature range between the low temperature side trigger and the high temperature side trigger, the above two states can be selectively taken. The same change could be stably repeated without bleeding even after 500 times of repetition. 60 more
The same change and stability were confirmed even when left in a thermostatic chamber at ℃ for 1 week. The color change curve of the printed matter is shown in FIG. 4, the absorbance when colored (opaque) and decolored (transparent) is shown in FIG. 5, and the transmittance is shown in FIG.

Example 3 3-Cyclohexylamino-6-chlorofluorane 2
Part, 1,1-bis (4′-hydroxyphenyl) octane 5 parts, 2,2-bis (4′-hydroxyphenyl)
20% MIBK / of Denka vinyl 1000 MT3 (vinyl chloride-vinyl acetate copolymer resin, polymer composition: vinyl chloride / vinyl acetate = 70/30, manufactured by Denki Kagaku Kogyo Co., Ltd.) with 2 parts of propane, 10 parts of cetyl alcohol, and 10 parts of stearyl caprate.
It was dissolved in 300 parts of a xylene (1/1) solution. Further By
0.2 parts of k-300 (polyether-modified dimethylpolysiloxane, manufactured by Byk chemie) was added to prepare a thermochromic ink (C). A PET product name: NF PET Tomei 100 [A]) was coated using the above ink and applicator so that the film thickness when dried was about 15 μm, and dried at 80 ° C. for 30 minutes to form a thermochromic layer. It was observed that in the thermochromic layer, the thermochromic material was dispersed in the resin in the range of about 0.1 to 1.0 μm. The obtained printed matter has a low temperature side trigger: about 6
C, high temperature side trigger: The hysteresis width having two triggers of about 30 ° C was about 16 ° C. When the temperature was above the high temperature side trigger, the color disappeared and became transparent, and when the temperature was below the low temperature side trigger, it became orange and became opaque. In the temperature range between the low temperature side trigger and the high temperature side trigger, the above two states can be selectively taken. The same change could be stably repeated without bleeding even after 500 times of repetition. Further, the same change and stability were confirmed even when left in a constant temperature room at 60 ° C. for 1 week. The color change curve of the printed matter is shown in FIG. 7, the absorbance when colored (opaque) and the color erased (transparent) is shown in FIG. 8, and the transmittance is shown in FIG.

Example 4 1.5 parts of 2-phenyl-6- (N-ethyl-N-hexylamino) fluorane, 8 parts of 2,2-bis (4'-hydroxyphenyl) decane and 20 parts of lauryl stearate. Denka vinyl 1000 MT3 (vinyl chloride-vinyl acetate copolymer resin, polymer composition: vinyl chloride / vinyl acetate = 70
/ 30, manufactured by Denki Kagaku Kogyo Co., Ltd.) was dissolved in 300 parts of a 20% MIBK / xylene (1/1) solution. Further FC-430
(Fluorine-based leveling agent, manufactured by Sumitomo 3M Ltd.)
1 part was added to prepare a thermochromic ink (D). The above ink was applied to a PET film (100
μm thickness, Lintec Co., Ltd., trade name: NF PET
Tomei 100 [A]) has a dry film thickness of about 15 μm
And the coating was dried at 80 ° C. for 30 minutes to obtain a thermochromic layer. It was observed that in the thermochromic layer, the thermochromic material was dispersed in the resin in the range of about 0.2 to 1.5 μm. The resulting printed material has a low temperature side trigger:
About 6 ° C., high temperature side trigger: The hysteresis width having two triggers of about 38 ° C. was about 28 ° C. When the temperature was higher than the high temperature side trigger, the color disappeared and became transparent, and when the temperature was lower than the low temperature side trigger, it became green and became opaque. In the temperature range between the low temperature side trigger and the high temperature side trigger, the above two states can be selectively taken. The change could be stably repeated without bleeding even after 500 times of repetition. 1 in a constant temperature room at 60 ℃
Similar changes and stability were confirmed even when left for a week. The color change curve of the printed matter is shown in FIG. 10, the absorbance at the time of coloring (opaque) and the color erasing (transparent) is shown in FIG. 11, and the transmittance is shown in FIG.

Example 5 1,2-Benz-6-diethylaminofluorane 1.
5 parts, 2,2-bis (4'-hydroxyphenyl) octane 5 parts, neopentyl glycol dipalmitate 20 parts VYHD (vinyl chloride-vinyl acetate copolymer resin, polymer composition: vinyl chloride / vinyl acetate = 86) / 14, Union Carbide made in Japan 20% MIBK / xylene (1
/ 1) It was dissolved in 300 parts of the solution. Further Byk-310
(Polyester modified dimethyl polysiloxane, Byk
Chemie) was added 0.2 parts to prepare a thermochromic ink (E). A PET film (100 μm thick, Lintec Co., Ltd.) was applied to the above ink using an applicator.
Product name: NF PET Tomei 100 [A]) coated to a dry film thickness of about 15 μm,
The thermochromic layer was formed by drying at 80 ° C for 30 minutes. The composition of the printed matter is about 0.2 to 1.0 μm in the resin.
It was observed that they were dispersed in the range. The obtained printed material has a low temperature side trigger: about 0 ° C, a high temperature side trigger: about 3
Hysteresis width with two triggers of 7 ℃ is about 33
It was at ℃. In the temperature range between the low temperature side trigger and the high temperature side trigger, which becomes transparent when the temperature is higher than the high temperature side trigger and becomes transparent, and becomes pink when the temperature is lower than the low temperature side trigger, and becomes opaque, the two states can be selectively taken. The change could be stably repeated without bleeding even after 500 times of repetition. Further, the same change and stability were confirmed even when left in a constant temperature room at 60 ° C. for 1 week. The color change curve of the printed matter is shown in FIG.
FIG. 14 shows the absorbance when colored (opaque) and decolorized (transparent).
The transmittance is shown in FIG.

Example 6 2- (3'-trifluoromethylphenyl) amino-6
-Diethylaminofluorane 2 parts, 2,2-bis (4'-hydroxyphenyl) octane 5 parts, dimyristyl didipicate 10 parts, cetyl alcohol 10 parts V
20% MIBK / xylene (1/1) solution of YHD (vinyl chloride-vinyl acetate copolymer resin, polymer composition: vinyl chloride / vinyl acetate = 86/14, Union Carbide Japan)
It was dissolved in 300 parts. Further, Byk-310 (polyester-modified dimethylpolysiloxane, Byk chemie
0.3 part was added to prepare a thermochromic ink (F). A PET film (100 μm thick, manufactured by Lintec Co., Ltd., trade name: N
F PET Tomei 100 [A]) was coated so that the film thickness when dried was about 15 μm, and dried at 80 ° C. for 30 minutes to form a thermochromic layer. It was observed that the composition in the printed matter was dispersed in the resin in the range of about 0.2 to 1.5 μm. The obtained printed matter had a hysteresis width of about 33 ° C. with two triggers of low temperature side trigger: about −6 ° C. and high temperature side trigger: about 37 ° C. When the temperature was higher than the high temperature side trigger, the color disappeared and became transparent, and when the temperature was lower than the low temperature side trigger, it became dark gray gray and became opaque. In the temperature range between the low temperature side trigger and the high temperature side trigger, the above two states can be selectively taken. The change could be stably repeated without bleeding even after 500 times of repetition. Further, the same change and stability were confirmed even when left in a constant temperature room at 60 ° C. for 1 week. The color change curve of the printed matter is shown in FIG. 16, and the absorbances when colored (opaque) and decolorized (transparent) are shown in FIG.
The same transmittance is shown in FIG.

Example 7 (thermochromic shading-translucent laminate) [1] Adjustment of each ink (1) Undercoat ink Acrypet VK (methyl methacrylate resin: manufactured by Mitsubishi Rayon Co., Ltd.) 10 parts MIBK (methyl) 60 parts of isobutyl ketone) and 30 parts of propylene glycol monomethyl ether were dissolved to prepare an undercoat ink (a). (2) Thermochromic ink 300 parts of the thermochromic ink (A) of Example 1 was mixed with MIBK2.
50 parts and 50 parts of cyclohexanone were mixed to obtain a thermochromic ink (A '). (3) Topcoat ink Plus size CB-2 (alcohol-soluble acrylic resin: 50% ethanol solution, manufactured by Kyowa Chemical) 20 parts, Tinuvin 328 (ultraviolet absorber, manufactured by Ciba Geigy) 0.5
Parts were dissolved in 50 parts of isopropanol and 30 parts of n-butanol to prepare a top coat ink (b). [2] Preparation of Laminated Body Aluminum-deposited polyester film (trade name: # 1
The undercoat ink (a) was spray coated on the surface of 25 METAL ME TS, manufactured by Toyo Metalizing Co., Ltd., and dried at 80 ° C. for 30 minutes. The undercoat layer of the obtained coated product had a film thickness when dried of about 5 μm. Subsequently, the thermochromic ink (A ') was applied to the upper layer by spraying and dried at 80 ° C for 30 minutes. The thermochromic layer of the obtained coated product had a film thickness when dried of about 10 μm. Furthermore,
The top coat ink (b) was applied as a protective layer by spraying, and then dried at 80 ° C. for 30 minutes. The topcoat layer of the obtained coated product had a film thickness when dried of about 10 μm. When the obtained laminate was wetted with cold water at 10 ° C. using an applicator, it became pink and, at the same time, the metallic luster of the underlayer disappeared. Next, when this was wetted with warm water of 45 ° C. using an applicator, the pink color disappeared and at the same time the metallic luster of the underlayer appeared. This at room temperature 25 ℃
There was no change when left in place. Change 5
Repeated 00 times, the same change was confirmed.

Example 8 (thermochromic, light-shielding and translucent laminate) [1] Preparation of inks (1) Undercoat ink DIALAL BR-80 (methyl methacrylate resin:
Undercoat ink (c) by dissolving 10 parts of Mitsubishi Rayon Co., Ltd.) in 60 parts of MIBK and 30 parts of cyclohexanone.
Was adjusted. (2) Thermochromic ink 300 parts of thermochromic ink (B) of Example 2 was mixed with MIBK1.
50 parts were mixed and diluted to obtain a thermochromic ink (B '). (3) Topcoat ink: DIALAL BR-102 (alcohol-soluble acrylic resin: manufactured by Mitsubishi Rayon Co., Ltd.) 10 parts, Tinuvin PS (ultraviolet absorber, manufactured by Ciba Geigy Co., Ltd.) 1 part, isopropyl alcohol 60 parts, n-butanol 30 parts And was dissolved in to prepare a top coat ink (d). [2] Fabrication of laminated body MEARL IRI which exhibits iris due to the phenomenon of optical interference
DESCENT FILM (Brand name: IF-8101)
The same coating method and drying conditions as in Example 7 were applied to the surface of
The above inks (c), (B ') and (d) were sequentially applied.
When the obtained laminate was put in a freezer at -5 ° C, a vermillion color was developed instantaneously and the iris pattern and iris character of the base were not visually observed at all. Further, when this was heated with a hair styling blower, the vermillion color disappeared and the brilliant pattern and brilliance of the base appeared. It was allowed to stand at room temperature for 3 days without any change. The same change was confirmed even after 500 repetitions.

Example 9 (thermochromic light-shielding / transparent laminate) The same undercoat as in Example 8 was formed on the surface of a gold-colored aluminum vapor-deposited polyester film (trade name: # 50 Metalmy CCC, manufactured by Toyo Metalizing Co., Ltd.). The same coating was performed using ink, thermochromic ink, and topcoat ink. When the obtained laminate was placed in a freezer at -5 ° C, a vermillion color was developed instantaneously, and the underlying metallic metallic luster was not visible at all. Furthermore, when this was heated with a hair styling blower, the vermilion disappeared and the underlying metallic metallic luster appeared. It was allowed to stand at room temperature for 3 days without any change. The same change was confirmed even after 500 repetitions.

Example 10 (thermochromic light-shielding / light-transmitting laminate) [1] Preparation of each ink (1) Undercoat ink Dynar BR-85 (metl methacrylate resin:
20 parts of Mitsubishi Rayon Co., Ltd.) dissolved in 80 parts of MIBK,
The undercoat ink (e) was adjusted. (2) Thermochromic ink The thermochromic ink (C) of Example 3 was used as it was. (3) Topcoat Ink 70 parts of Acridic A-188 (Turpen-soluble acrylic resin: manufactured by Dainippon Ink and Chemicals, Inc.) was dissolved in 30 parts of mineral terpen to prepare a topcoat ink (f). [2] Preparation of Laminated Body Holographic film having a glossy and three-dimensional effect (trade name:
Undercoat ink (e) on the surface of hologlaster 101 Surf whisper, Lintec Co., Ltd.
Was coated using an applicator so that the film thickness when dried was about 5 μm, and dried at 80 ° C. for 30 minutes to form an undercoat layer. Subsequently, the thermochromic ink (C) was coated on the upper layer using an applicator so that the film thickness when dried was about 10 μm, and then 30 ° C. at 80 ° C.
It was dried for a minute to form a thermochromic light-shielding ink layer. Further, as a protective layer, the top coat ink (f) was coated using an applicator so that the film thickness when dried was about 10 μm, and then dried at 80 ° C. for 30 minutes to form a top coat layer. The obtained laminate has a low temperature side trigger:
Approximately 6 ° C, high temperature side trigger: It has two discoloration points of approximately 30 ° C. It develops orange color below the low temperature side trigger, hides the underlying hologram pattern and glossiness, and erases above the high temperature side trigger. At the same time, the underlying hologram pattern and the glossy feeling were visualized. The same change was confirmed even after 500 repetitions.

Example 11 (thermochromic light-shielding / light-transmitting laminate) [1] Preparation of each ink (1) Undercoat ink DIALAL BR-83 (methyl methacrylate resin:
20 parts of Mitsubishi Rayon Co., Ltd.) dissolved in 80 parts of MIBK,
The undercoat ink (g) was adjusted. (2) Thermochromic ink The thermochromic ink (F) of Example 6 was used as it was. (3) Topcoat ink plus size L-53 (alcohol-soluble acrylic resin: 50% ethanol solution, manufactured by Kyowa Kagaku) 50 parts, Tinuvin PS (ultraviolet absorber, manufactured by Ciba Geigy) 1.5
Parts were dissolved in 50 parts of n-propyl alcohol to prepare a top coat ink (h). [2] Preparation of Laminated Body Holographic film having a glossy and three-dimensional effect (trade name:
The inks (g), (F), and (h) described above were sequentially applied to the polyester film side of the original fabric obtained by laminating Sparkles and SPECTRATE) with a nylon tricot by the same coating method and drying conditions as in Example 10. . The obtained laminate has two discoloration points of a low temperature side trigger: about 10 ° C. and a high temperature side trigger: about 35 ° C., and a dark gray gray color is formed below the low temperature side trigger, and a hologram pattern and a glossy feeling of the base are obtained. It was concealed and erased when the temperature was higher than the trigger, and the underlying hologram pattern and glossiness were visualized. The same change was confirmed even after 500 repetitions.

Comparative Example A laminate was prepared in the same manner as in Example 7 except that the ink shown below was used in place of the thermochromic ink (A ') of Example 7. 1,2-Benz-6-dibutylaminofluorane 1.3 parts, 1,1-bis (4'-hydroxyphenyl) hexane 5 parts, stearyl caprate
5 parts and 15 parts of stearyl laurate were microencapsulated by an ordinary method by an epoxy-amine interfacial polymerization method.
30 parts of this microcapsule is VYHH (vinyl chloride-vinyl acetate copolymer resin, polymer composition: vinyl chloride / vinyl acetate =
86/14, Union Carbide) 20% MIB
The K solution was dispersed in 300 parts and further mixed with 250 parts of MIBK and 50 parts of cyclohexanone to prepare a thermochromic ink. The obtained laminate has a pink color at 10 ° C. or lower and conceals the metallic luster of the base, but at 45 ° C. or higher, the pink color disappears, but it remains clouded due to diffuse reflection of the microcapsules. The metallic luster was not visible at all.

[0040]

In the thermochromic light-shielding / translucent laminate of the present invention, the thermochromic surface layer alternately exhibits both a colored opaque state and a decolorized transparent state depending on temperature. The color change is visually recognized and the underlying layer having optical properties such as glitter, iris and gloss is hidden without impairing the optical properties. Furthermore, even after removing the heat or cold heat required to change to the colored opaque state or the decolorized transparent state described above, either one is selectively applied in the temperature region between the low temperature side trigger and the high temperature side trigger. The state of can be stored and retained, and the change in the aspect can be reversibly and repeatedly reproduced. Thus, toys, dolls, entertainment equipment, exercise equipment, papers, stationery, printed materials, clothing, cloth personal items, as a thermochromic laminate satisfying toy properties, unexpectedness, decorativeness, taste, etc. Jewelry, buttons, bags, bags, jewelry imitations,
Applicable to various fields such as makeup tools, footwear, shoes, eyeglass parts, mirror parts, cloths, film fabrics, fittings, indoor equipment items, wallpaper, commemorative cups, packaging containers, packaging materials, daily sundries, kitchen utensils, etc. As a result, saliency and peculiarity can be imparted to enhance the commercialability.

[0041]

[Brief description of drawings]

FIG. 1 shows a color change curve due to a temperature change of Example 1, which shows characteristics of a thermochromic layer formed of a thermochromic composition applied to the present invention. The solid line shows the state when colored and opaque, and the dotted line shows the state when decolorized and transparent (the same applies to FIGS. 2 to 18 below).

FIG. 2 shows coloring of the printed matter of Example 1, opacity and erasing,
The absorbance curve when transparent is shown.

FIG. 3: Coloring of printed matter of Example 1, opacity and decolorization,
The transmission spectrum at the time of transparency is shown.

FIG. 4 shows a color change curve due to temperature change in Example 2 of a printed matter to which the composition of the present invention is applied.

FIG. 5: Coloring of printed matter of Example 2, opacity and decolorization,
The absorbance curve when transparent is shown.

FIG. 6 shows coloring of the printed matter of Example 2, opacity and erasing,
The transmission spectrum at the time of transparency is shown.

FIG. 7 shows a color change curve due to a temperature change of Example 3 of a printed matter to which the thermochromic composition of the present invention is applied.

FIG. 8 shows the absorbance curves of the printed matter of Example 3 when it was colored, opaque, decolored, and transparent.

FIG. 9: Coloring of printed matter of Example 3;
The transmission spectrum at the time of transparency is shown.

FIG. 10 shows a color change curve due to temperature change in Example 4 of a printed matter to which the thermochromic composition of the present invention is applied.

FIG. 11 shows absorbance curves of the printed matter of Example 4 when it was colored, when it was opaque, when it was decolored, and when it was transparent.

FIG. 12 shows the transmission spectra of the printed matter of Example 4 when it was colored, when it was opaque, when it was decolored, and when it was transparent.

FIG. 13 shows a color change curve due to a temperature change of Example 5 of a printed matter to which the thermochromic composition of the present invention is applied.

FIG. 14 shows absorbance curves of the printed matter of Example 5 when it was colored, when it was opaque, when it was decolored, and when it was transparent.

FIG. 15 shows the transmission spectra of the printed matter of Example 5, when it was colored, when it was opaque, when it was decolored, and when it was transparent.

FIG. 16 shows a color change curve due to a temperature change of Example 6 of a printed matter to which the thermochromic composition of the present invention is applied.

FIG. 17 shows the absorbance curves of the printed matter of Example 6 when it was colored, when it was opaque, when it was decolored, and when it was transparent.

FIG. 18 shows transmission spectra of the printed matter of Example 6 when it was colored, when it was opaque, when it was decolored, and when it was transparent.

FIG. 19 is an enlarged vertical sectional view of an example of the laminated body of the present invention.

[Explanation of symbols]

 1 Laminated body 2 Support body 3 Underlayer 4 Thermochromic layer

Claims (8)

[Claims] 1. (a) an electron-donating color-forming organic compound,
(B) A compound having a phenolic hydroxyl group, (c) a reversible particle size of 0.1 to 2.0 μm, which is composed of a homogeneous compatible solution containing a compound selected from alcohols, esters, ketones, and carboxylic acids. The thermochromic material is fixed in a dispersed state in the vinyl chloride-vinyl acetate copolymer resin matrix, and the temperature difference between the high temperature side trigger and the low temperature side trigger is 10 ° C to 50 ° C, which is large depending on the temperature. A thermochromic layer that exhibits hysteretic characteristics and changes, and exhibits mutual change of both colored opaque state and decolorized transparent state, and glitter, light brightness reflection, light coherence, iris, hologram, metallic luster A thermochromic light-shielding-translucent laminate comprising an underlayer exhibiting optical properties such as pearl luster and fluorescence, and the thermochromic layer being laminated on the underlayer. 2. The thermochromic layer comprises 0.05 to 2.0 parts by weight of (a) an electron-donating color-developing organic compound, and (b) a phenolic compound, based on 6 parts by weight of a vinyl chloride-vinyl acetate copolymer resin. 0.1 to 3.0 parts by weight of a compound having a hydroxyl group, and (c) 0.5 to 5.0 parts by weight of a compound selected from alcohols, esters, ketones, or carboxylic acids. The thermochromic light-shielding material according to claim 1, wherein
Translucent laminate. 3. The vinyl chloride-vinyl acetate copolymer resin has an average molecular weight of 7,000 to 50,000, and the constituent monomer weight ratio is 60% to 92% of vinyl chloride and 8% to 40% of vinyl acetate. The thermochromic light-shielding-translucent laminate described. 4. The heat discoloration layer is 0.00 relative to 100 parts by weight.
The thermochromic light-shielding / light-transmitting laminate according to claim 1, wherein a dispersion aid is added in a ratio of 2 to 0.5 parts by weight. 5. The thermochromic light-shielding / light-transmitting according to claim 1, wherein the compound having a phenolic hydroxyl group is a compound selected from the following general formulas in a proportion of at least 50% by weight of the compound having a total phenolic hydroxyl group. Laminate. [Chemical 1] [However, R1 is H or CH ₃ and R2 is C _n H _{2n + 1} (4
<Represents n <11), or R1 = R2 = CF _3, respectively.
C _n H _{2n + 1} represents a linear or side chain alkyl group. X
Represents a substituent of an aromatic ring. Also, X = H or CH ₃ . ] 6. The component (c), wherein the component (a) is a monohydric fatty acid and an aliphatic monohydric alcohol or a monohydric alcohol having an alicyclic ring and having 10 or more carbon atoms in total, (b)
An aliphatic dihydric or polyhydric carboxylic acid and a polybasic acid ester having a total carbon number of 28 or more, which comprises an aliphatic monohydric alcohol or a monohydric alcohol having an alicyclic ring, and (c) an aliphatic dihydric or polyhydric alcohol Total carbon number consisting of monovalent fatty acids 26
The ester according to claim 1, which is one or two or more esters selected from the above esters and (d) an ester having a total carbon number of 28 or more, which comprises a dihydric alcohol having an aromatic ring and a monovalent fatty acid. Thermochromic shading-translucent laminate. 7. The thermochromic light-shielding-translucent laminate according to claim 1, wherein a methacrylic resin layer having a glass transition point of 90 ° C. or higher is provided as an undercoat layer on the surface of the underlayer. 8. The thermochromic light-shielding film according to claim 1, wherein a layer made of an alcohol-soluble or aliphatic hydrocarbon-soluble transparent methacrylic resin and acrylic resin or a copolymer resin thereof is laminated on the thermochromic layer. -Translucent laminate.