JP3306601B2 - Thermochromic shading-translucent laminate - Google Patents

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, the color changing opaque state and the decoloring transparent state are changed by a change in temperature, so that the underlying layer having optical properties such as brilliancy and glossiness is effectively hidden without impairing the properties. The present invention relates to a thermochromic light-shielding-light-transmitting laminate to be exposed.

[0002]

2. Description of the Related Art Hitherto, there have been known a large number of laminates in which an underlayer is laminated by a thermochromic layer in which a reversible thermochromic material is fixed to a binder in a dispersed state, and the underlayer is hidden by a temperature change. As the thermochromic material applied to the above, a thermochromic material that changes color in response to a change in temperature in the presence of a compound having an alcoholic hydroxyl group in a color-forming reaction between an electron-donating compound and a phenolic compound. It is disclosed in JP-B-51-44706, JP-B-51-44707 and the like. As an attempt to apply this kind of thermochromic material, Japanese Patent Publication No. 51-35216 discloses (a) an electron donating color compound, (b) a compound having a phenolic hydroxyl group, and (c) alcohols. And (d) a thermoplastic polymer composition containing a compound selected from any of esters, ketones, and ethers and a thermoplastic polymer. All of the above conventional techniques require reversible discoloration. Although it is described that it also has light transmittance / hiding properties with the change in color, in the above invention, the three-component mixture (a), (b), and (c) is directly contained in a thermoplastic resin polymer. The remarkable decrease in color density due to the polar action of the thermoplastic polymer,
There is a disadvantage that the sharpness of discoloration is significantly impaired. Further, in the thermoplastic polymer composition of the invention, (a)
(B) (c) Since the thermochromic material composed of three components is already liquid at room temperature or is often liquid at the time of discoloration,
The initial stage of the preparation of the thermoplastic polymer composition or the repetition of discoloration tended to cause a so-called bleed phenomenon in which a specific component among the three components floated on the surface of the resin.
For this reason, there has been a considerable practical problem in the prior art in that the three components are stably present in the thermoplastic polymer for a long period of time and have a good discoloration effect even at repeated temperature changes.

[0003] Usually, the three-component thermochromic material has a color-changing effect only when the three components are aligned. Therefore, in order to provide more stability, the three-component thermochromic material is usually encapsulated in a capsule film by microencapsulation. Protected by capsule wall. As a result, it is possible to stably exist in response to external chemical action, thermal action, and the like, and various applications are widely possible. However, when the three components are microencapsulated, they become a kind of solid pigment, and in a system in which a thermochromic layer in which the encapsulated pigment is fixedly dispersed in a transparent resin is formed, a pigment pigment specific to the capsule pigment is formed. Due to the phenomenon of light scattering on the surface, its transparency is significantly reduced. Therefore, even in a system in which the underlayer has properties such as brilliancy and gloss, even if a rough color tone and an image can be seen through, the brilliancy and glossiness of the underlayer are impaired and it is necessary to be seen through. .

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problem of the laminate by the thermochromic layer in which the thermochromic material is fixed in a binder in a dispersed state, and provides a glittering or glossy underlayer. In a combination, it is intended to provide a thermochromic light-shielding-light-transmitting laminate in which the transparency is remarkably improved, the luster and gloss are visually observed without loss, and the concealing property is also remarkably improved. Is what you do.

The inventors of the present invention have made various studies on a thermochromic composition for forming a thermochromic layer. In the course of the study, the thermochromic composition was composed of the three components (a), (b) and (c) described above. Focusing on the fact that the three components can be directly and stably retained in a vinyl chloride-vinyl acetate copolymer resin without microencapsulating the reversible thermochromic material, further investigations were made. As a result, the ternary reversible thermochromic material was converted to vinyl chloride-
The knowledge that, when dispersed in a fine particle state as a homogeneous compatibilizer in a vinyl acetate copolymer resin, it is extremely stable against repeated heating / cooling. By dispersing,
A thermochromic composition capable of holding three components extremely stably was developed based on a new finding that surpassed the expectation that the change in color and the resulting change in transparency was accompanied by a remarkable hysteresis phenomenon.

Conventionally, in order to cause a large hysteresis phenomenon with respect to thermal discoloration, a compound having a special structure or a compound having special thermal properties is required for the component (c), and its range is extremely limited. There was (Tokuhei 4-1
No. 7154). The present invention provides the thermal properties of the component (c) itself, in other words, (a) by the action and effect of micronization without strongly depending on the physical properties specific to the component (c).
(B) (c) A remarkable hysteresis characteristic was successfully imparted to the characteristics relating to the color change and the transparency change of the thermochromic material composed of three components. The present inventors, based on such knowledge, without microencapsulating the thermochromic material consisting of three components, and the chemical effect on the three components which had a problem in the past, that is, decrease in concentration, deterioration and discoloration. Without reducing the sensitivity, a thermochromic composition having stable hysteresis characteristics even in repeated operations was completed.

[0007]

DISCLOSURE OF THE INVENTION The present invention relates to a method for producing brilliant, brilliant
Degree reflection, light interference, iris, hologram, metallic luster
Presents optical properties selected from properties, pearl luster, and fluorescence
That on the base layer, (b) an electron-donating coloring organic compound,
(B) a compound having a phenolic hydroxyl group, (c) a reversible thermochromic material comprising a homogenous solution of the three components, including a compound selected from any of alcohols, esters, ketones, or carboxylic acids. But the constituent monomer weight
The ratio is 60% to 92% for vinyl chloride and 8% to 40% for vinyl acetate.
Vinyl acetate-vinyl acetate having an average molecular weight of 7,000 to 50,000
In the copolymer resin, the particle diameter is in the range of 0.1 to 2.0 μm .
The temperature difference between the high temperature side trigger and the low temperature side trigger fixed in a dispersed state in size is in the range of 10 ° C to 50 ° C,
Exhibits a colorless and transparent state at temperatures higher than the high-temperature trigger, and
Shows a colored opaque state at a temperature below the side trigger, and
In the temperature range between the trigger and the hot side trigger, the colorless transparent
Large enough to hold either bright or colored opaque state
A thermochromic light-shielding / light-transmitting laminate in which thermochromic layers exhibiting hysteresis characteristics and discoloring are laminated is required. Furthermore, the thermochromic layer contained 6 parts by weight of the vinyl chloride-vinyl acetate copolymer resin, and (a) 0.1% of the electron-donating color-forming organic compound.
(B) 0.1 to 3.0 parts by weight of a compound having a phenolic hydroxyl group, (c) a compound selected from any of alcohols, esters, ketones, and carboxylic acids There is a requirement that you become configured at a ratio of 0.5 to 5.0 parts by weight. In the above configuration, the trigger indicates a temperature at which “change” occurs, a temperature at which color changes, and / or a temperature at which transparency changes. Therefore, at a temperature lower than the low-temperature side trigger, it is colored and opaque, and at a temperature higher than the high-temperature side trigger, it changes colorless and transparent.

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

In the search for the thermal properties of the compound (C), the present inventors have found that the melting points of the compounds are almost uniquely determined by the compounds themselves, while the freezing points It has been found that (or the cloud point) varies greatly depending on the amount of 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 encapsulated with a length of 0.5 μm or even as fine particles of 0.5 μm, the smaller the amount of aggregation in a stepwise manner, the lower the freezing point (or cloud point). More specifically, the determinant of the freezing point is governed by the crystal nucleation rate and the crystal growth rate. However, when the particle size of the compound is approximately 2 μm or less, the crystal nucleation rate decreases, and crystal growth is reduced. It becomes more difficult and consequently solidification will not start unless it is further cooled to a lower temperature. In particular, a large change occurs in the freezing point around 2 μm. Further, in order to achieve the above-mentioned advantageous effects of the present invention, it is preferable that each particle is substantially a single independent particle. That is, if it is aggregated in a grape-like manner, aggregated by coalescence generally, or present in a form that involves precipitation on the inside or on the surface, it has local or global fluctuations in the freezing point, so a sharp change Not only is difficult to obtain, but also the particles cannot be stably present in the base resin, causing bleeding and lacking stability. The present inventors disperse a mononuclear particle of the vinyl chloride-vinyl acetate copolymer resin in the matrix of the vinyl resin-vinyl acetate copolymer resin in the matrix resin using the ternary thermochromic material, The cold trigger could be shifted significantly to the cold side. At the same time, the change in transparency / opacity is also substantially linked to this, thereby succeeding in imparting a specific hysteresis characteristic. In general, the thermochromic layer of the present invention has a hysteresis width of 10 ° C.
It is in the range of 50 ° C.

Next, the matrix resin will be described. As described above, the three-component thermochromic material is easily affected by external chemicals, and the influence of the matrix resin itself is no exception. For example, a 100% vinyl chloride resin easily generates hydrogen chloride by a dechlorination reaction gradually even in a normal storage state, and irreversibly develops an electron-donating color-forming organic compound. Also, 100% vinyl acetate resin imparts strong desensitization (permanent decoloration) to the ternary thermochromic material due to the strong polarity of the vinyl acetate group, and as a result, shows almost no thermochromic property. The composition of a single resin is unsuitable as the matrix resin of the present invention. On the other hand, when the vinyl chloride resin and the vinyl acetate resin are copolymerized at an appropriate monomer ratio, not only is the dechlorination reaction extremely unlikely to occur, but also a good atmosphere in which the desensitization of the vinyl acetate resin is not substantially exerted is a three-component system. Give to discolorable materials. This is the reason why the vinyl chloride-vinyl acetate copolymer resin is selected as the base resin, the marix resin, which has no irreversible coloring and substantially no desensitization. Examples of the resin having no permanent desensitizing property and strong coloring property include a hydrocarbon-based resin having a small polarity and a halogen-containing resin, and such resins are known to disperse a three-component thermochromic material. It is not localized but is dissolved or compatible in the parent matrix in a non-local manner. As a result, because it is diffused into the base resin,
At the same time, the effect of the thermochromic property is significantly reduced, and at the same time, the effect of the transparency / opacity tends to be impaired. The ternary thermochromic material provides excellent thermochromic properties and excellent transparency by being locally dispersed as particles in the matrix resin. Furthermore, when they are generally compatible, each compound tends to bleed initially or over time and is extremely unstable. For this reason, dispersion into fine particles is an important factor in the present invention. Therefore, it is completely different from a composition in which only an organic compound is dispersed in a base matrix resin to change the transparency in response to a change in temperature.To satisfy both changes in color and transparency, the base matrix resin is The composition is as follows.

The matrix matrix resin used in the present invention is premised on being optically substantially transparent. Such a resin has an average molecular weight in the range of 7,000 to 50,000, and the constituent monomer weight ratio is vinyl chloride. A vinyl chloride-vinyl acetate copolymer resin of 60-92% and vinyl acetate 8-40% is applied. Further, a small amount of other monomer components, for example, a hydroxyl group, may be contained at a constituent monomer ratio of 7% (weight ratio) or less. However, carboxy groups are excluded because they cause irreversible color development. In addition, the other compatible resin is 30% of the vinyl chloride-vinyl acetate copolymer resin.
You may mix by the following weight ratios. Such a small amount of the resin component is used for the purpose of imparting adhesiveness at the time of secondary processing and improving the film strength within a range not impairing the basic function of the present invention, that is, the change in color and the change in transparency due to the change in temperature. Can be used. As such other compatible resin, modified alkyd resin, unsaturated polyester resin, saturated polyester resin,
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, acryl-styrene copolymer resin, styrene maleic acid resin, chlorinated rubber, silicone resin, PVC-acryl copolymer resin, ketone resin, and the like.

As the electron-donating color-forming organic compound used in the present invention, a group of so-called leuco dyes, which are colored by a compound having a phenolic hydroxyl group, are used. Diphenylmethanephthalides, fluorans, diphenylmethaneazaphthalide , Indolylphthalides, phenylindolylphthalides, phenylindolylazaphthalides, styrylquinolines, and the like.

The compounds having a phenolic hydroxyl group include monohydric phenols, dihydric phenols and polyhydric phenols. Alkyl, aryl, acyl, alkoxycarbonyl, carboxy and benzene ring substituents are also exemplified. And those having an ester or amide group, a halogen, etc., and bis-type and tris-type phenols. Generally, phenolic compounds are relatively polar because of their phenolic hydroxyl groups,
(C) Poor solubility in components. Poor solubility,
In a thermochromic material composition composed of three components dispersed in fine particles in a matrix resin matrix, the phenolic compound and the component (c) are liable to cause precipitation / separation phenomena, causing bleeding, In many cases, reversible color change does not occur and stability is lacking in practical use.

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

## STR1 However, R1 is H or CH _3, 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. X = H or CH ₃ . Hereinafter, the compounds of the above general formula will be exemplified, but 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-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 alcohols, aliphatic monovalent saturated alcohols having 10 or more carbon atoms are used. The compounds are exemplified below. Decane 1-ol, 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; The ester compounds applied to the present invention are roughly classified into the following (a) to (d). (A) Esters having a total carbon number of 10 or more comprising a monovalent fatty acid and an aliphatic monohydric alcohol or a monohydric alcohol having an alicyclic ring. (B) Polybasic acid esters having a total of 28 or more carbon atoms comprising an aliphatic dihydric or polyhydric carboxylic acid and an aliphatic monohydric alcohol or an alicyclic monohydric alcohol. (C) Esters having a total of 26 or more carbon atoms composed of an aliphatic dihydric or polyhydric alcohol and a monovalent fatty acid. (D) Esters having a total of 28 carbon atoms or more composed of a dihydric alcohol having an aromatic ring and a monovalent fatty acid. Kinds Esters having a total carbon number of 10 or more composed of the monovalent fatty acid (a) and an aliphatic monohydric alcohol or an alicyclic monohydric alcohol are exemplified below. Esters having a total carbon number of 9 or less are caused by an increase in the polarity of the molecule itself.
Since it is compatible with the base matrix resin, it hardly imparts opacity even at or below the low-temperature trigger temperature. Similarly, the ester containing an aromatic ring also has a very low degree of the effect.

Ethyl caprylate, n-butyl caprylate, n-octyl caprylate, lauryl caprylate, cetyl caprylate, stearyl caprylate, n-capric acid
-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, cyclohexylmethyl palmitate, methyl stearate, ethyl stearate, n-propyl stearate, n-butyl stearate, n-amyl stearate, 2-methylbutyl stearate, n-hexyl stearate, n-stearate -Heptyl, 3,5,5-trimethylhexyl stearate, n-octyl stearate, 2-diethylhexyl 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. (B) the aliphatic divalent or polyvalent carboxylic acid,
Polybasic acid esters having a total of 28 or more carbon atoms, which are composed of aliphatic monohydric alcohols or monohydric alcohols having an alicyclic ring, are exemplified below. Esters having a total carbon number of 27 or less do not impart opacity even at or below the low-temperature trigger temperature because they are compatible with the matrix resin due to an increase in the polarity of the molecule itself. 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-saryl 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-octadecylmethylenedicarboxylate, di-n-octyl 1,18-octadecylmethylenedicarboxylate 1,18-octadecylmethylenedicarboxylate Di- (cyclohexylmethyl) acid; di-neopentyl 1,18-octadecylmethylylene dicarboxylate; The above-mentioned (c) esters of aliphatic dihydric and polyhydric alcohols or alicyclic or dihydric and polyhydric alcohols and monohydric fatty acids having 26 or more carbon atoms in total are exemplified 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 didistearate, 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. Examples of the above-mentioned (d) esters having a total carbon number of 28 or more composed of a dihydric alcohol having an aromatic ring and a monovalent fatty acid are shown below. Xylene glycol di-caprinate, xylene glycol di-n-
Undecanoate, xylene glycol di-laurate,
Xylene glycol di-myristate, xylene glycol di-palmitate, xylene glycol di-stearate and the like.

Next, compounds having 10 or more carbon atoms are used as ketones, and examples thereof include decane 2-one, undecane 2-one, laurone, and stearone. As carboxylic acids, higher fatty acids having 12 or more carbon atoms are used, and lauric acid, myristic acid, palmitic acid, stearic acid,
Behenic acid and the like. (C) Compounds used as components include the above-mentioned alcohols, esters, ketones,
One or more carboxylic acids may be selected and used. When a plurality of compounds are used in combination, 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 for causing a change in transparency together with a change in color in accordance with a change in temperature, the ratio of the three-component thermochromic material with respect to the matrix resin is determined by the change in transparency / opacity and the density in the color change. It has important factors in the decision. For example, based on 6 parts by weight of the base resin, 0.2 parts by weight of (a) the electron-donating color-forming compound and 0.8 parts by weight of (b) the phenolic compound are used.
In the case of using parts by weight, (iii) when 0.3 parts by weight of stearyl caprate having 28 carbon atoms is used as the component, the opacity at a temperature lower than the low-temperature side trigger is extremely low and the light-shielding property is lacking. On the other hand, when the content is 7.0 parts by weight, the opacity at a temperature lower than the low-temperature trigger is remarkably increased, but the transparency at a temperature higher than the high-temperature trigger is reduced, and substantially no see-through is possible. Therefore, in order to obtain thermochromic properties together with change in transparency with good contrast, the addition ratio of the thermochromic material composed of three components is limited to the following range.
The range of this ratio is 0.05 to 5 parts by weight of (a) the electron-donating color-forming organic compound per 6 parts by weight of the vinyl chloride-vinyl acetate resin.
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, the 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) compound having a phenolic hydroxyl group of 0.2 to 1.
2 parts by weight, and 1.0 to 3.0 parts by weight as the component (c).

Next, a method for preparing the thermochromic composition of the present invention will be described. As described above, in order to allow the color change and the transparency change, which are the most significant features of the present invention, to function stably according to the temperature change, (a), (b), (c)
The reversible thermochromic material composed of three components is contained in a vinyl chloride-vinyl acetate copolymer resin as a matrix resin.
Is fixed in a dispersed state in the size range of 0.1 to 2.0 mu m
You. Usually, the matrix resin and the three components are dissolved using one or more of the following solvents. In view of the solubility of the vinyl chloride-vinyl acetate copolymer resin, it is necessary to use a ketone-based solvent as a rich solvent. The solvent also functions 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, methyl n-propyl ketone, and the like. The aromatic solvent functions as a poor solvent for the vinyl chloride-vinyl acetate copolymer resin, but 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 alcohol solvents such as isopropyl alcohol and n-butanol, n-ethyl acetate, n-propyl acetate, and n-acetic acid.
Ester solvents such as -butyl and isobutyl acetate; hydrocarbon solvents such as hexane, cyclohexane, ethylcyclohexane and mineral spirit; and other solvents such as glycol monoalkyl ethers. Further, as a method for dispersing the three-component compatible solution more uniformly and in a fine shape in the matrix of the vinyl chloride-vinyl acetate copolymer resin, the use of a so-called dispersing agent has a remarkable effect. Such a dispersing aid is preferably a substance having a small degree of chemical adverse effect on the three components. Compounds having such a dispersing effect generally have an effect of significantly reducing surface tension and interfacial tension,
The effect shows that the three-component thermochromic material is finely dispersed in the base resin into a mononuclear shape.

The following are examples of such compounds. As siloxane derivatives, polyether-modified dimethylpolysiloxane, polyether-modified methylalkylpolysiloxane, polyester-modified polydimethylsiloxane, polyester-modified methylalkylpolysiloxane, etc., and as fluorine-based compounds, Florad FC-430 and Florad FC-431 (Sumitomo 3M) Fluorinated alkyl esters such as a fluorine compound (manufactured by Co., Ltd.), and acrylonitrile- (2-methacryloyloxyethyl) trimethylammonium-methylsulfate @ dimethylaminoethyl methacrylate as a special polymer. The thermochromic composition is 0.1 μm in the base resin.
When forming fine particles of m to 2.0 μm, it has an effect of uniformly dispersing in the form of a single nucleus. In particular, it has a special effect in preventing coalescence and aggregation. Such additives are used in an amount of 0.002% to 0.05% based on 100 parts by weight of the thermochromic composition.
%, And preferably 0.002% to 0.05% in order to reduce the chemical influence on the thermochromic composition. (However, the amount of dispersant is based on solid content)

The solution of the thermochromic composition dissolved substantially uniformly by appropriately combining the above-mentioned solvents adheres to the target underlayer by spray coating, screen printing, gravure printing, roll coating, reverse coating or the like. The solvent is completely evaporated and dried by drying at room temperature or drying by heating. The three components are dispersed in the form of fine particles in the matrix resin through the process of evaporation. In order to maximize the effects of the present invention, the dispersed particles are preferably substantially single particles as described above. It is important to select a solvent that dissolves the thermochromic composition in order to make a single particle exhibit a particle diameter of 0.1 to 2.0 μm. More specifically, in the transitional period of drying, if the solvent evaporates too quickly, of the three components of the thermochromic material, the component (c) mainly precipitates first, and single fine particles are formed. The formation of a continuous phase before formation results in bleeding and other phenomena. Similarly, when the solvent evaporates rapidly or when a poor solvent is incorporated in a large amount, the vinyl chloride-vinyl acetate copolymer resin is deposited in advance, so that the thermochromic material is formed into uniform fine particles. Dispersion often becomes impossible. In general, the amount of the solvent used for the thermochromic composition varies depending on the method of attachment, but 1 to 50 parts by weight of the solvent is applied to 1 part by weight of the thermochromic light-shielding composition. More preferably, it is 3 to 15 parts by weight. The thickness of the thermochromic layer is generally from 2 to 100 μm. If the thickness is less than this, there are disadvantages that the stability of the fine particles of the thermochromic composition tends to be lacking and that it is difficult to obtain good contrast. Various additives can be added to physically and uniformly adhere the thermochromic composition solution (hereinafter, referred to as thermochromic ink). Known additives are applied as such additives, and anti-sagging agents, leveling agents, antifoaming agents, thickeners, and friction resistance improvers can be applied. However, it is preferable to use an additive which does not have a chemical influence on the above-mentioned three components or has a minimal effect on the three components in a minimum necessary amount.

In particular, regarding the formation of the thermochromic layer, if the formed layer is not physically smooth, irregular reflection will occur on the surface of the layer, so that the transparency will be significantly impaired at a temperature higher than the high temperature side trigger, not to mention the appearance. Therefore, in forming a layer of the thermochromic composition, the smoothness of the surface is an important factor for the transparency. Various known additives having little chemical influence and imparting 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 composed of the thermochromic composition of the present invention is basically colored and opaque at a temperature lower than the low-temperature trigger, and is colorless and transparent at a temperature higher than the high-temperature trigger, but is more generally a dye or a transparent material. By using a general pigment having
A change of colored [1] opaque〕 colored [2] transparent is also possible. In addition, if transparency is not required depending on the use, a pigment having a hiding property may be used.

Next, the underlayer will be described. Underlayer bright, light intensity reflecting, iridescent, iris properties, holographic property, metallic luster, pearlescent, made of a material exhibiting fluorescence properties of the optical properties. Specifically, a brilliant-brightness reflective film comprising a metal thin film layer laminated on one or both sides of an organic synthetic film base material (for example, a silver thin film formed on an aluminum thin film, , Chrome, silver, copper, etc. laminated metal thin film,
Further, a transparent thin film having a different refractive index is alternately multilayered on the surface of the metal thin film to increase light reflectivity), and the surface of the support has a difference of 0.05 or more in refractive index from 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.) is formed, and the thin film layer has a refractive index of 0.05.
A laminate having an iris pattern in which transparent resin layers having irregularities having the above differences are laminated in order, a compound such as zinc sulfide, titanium oxide, oxide, magnesium fluoride and copper iodide, which is deposited in multiple layers, a light reflecting film Provided with a concave-convex interference resin film and a semi-transparent metal thin film, including a single layer of a group of continuous high refractive index glass beads as a lens in an organic resin medium as a binder and a light reflecting layer behind the same Films with retroreflective properties such as those composed of multilayer composites, optical interference films with multiple layers laminated on transparent plastic thin films with different refractive indices to give iris, and a light reflecting layer on at least one side of fine uneven patterns A hologram having a metallic mirror surface formed by coating a transparent film having a thickness small enough to cause light interference with a colored or colorless paint on the surface of a metallic mirror surface, or A part of the film is thickened along the radiation centered on the desired point to form a thick strip, which produces an iris pattern and a radiation pattern. What overlaps with the light beam, what causes the so-called `` thin film interference '', fine aluminum, copper, brass, gold, silver, nickel, etc. metal powder in a transparent resin solution, or plastic deposited powder, for example,
Polyester resin, phenolic resin, vinyl chloride resin metal deposited by a conventional method, coated with crushed powder,
Leafing type aluminum, copper, zinc, copper alloy coated with a binder, gold foil, silver foil or other metal foil, metallic luster pigment (for example, gold, silver, metallic with natural mica surface coated with titanium oxide) Red,
Metallic blue, metallic green and other metallic color) and pearlescent pigments, mention may be made of a colored support or the like due to the fluorescent Somekao fee. The present invention is not limited to a material and a form as long as it is a support that effectively expresses the optical properties of the underlayer described above. A transparent or opaque support is used depending on the application. As a transparent support, 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 Examples include vinyl resin, acrylonitrile-butadiene-styrene copolymer resin (transparent grade), and polypropylene resin. As the opaque or translucent resin and material, medium and low pressure polyethylene, acrylonitrile-butadiene-styrene copolymer resin, nylon resin, and resin obtained by coloring or shielding the above transparent resin with a pigment, paper, synthetic paper, fiber , Fabric,
Filaments, glass, wood and the like can be mentioned.

When the thermochromic composition of the present invention is laminated on a support, the composition is dissolved in a solvent as described above, and the solution is applied. The solvent dissolves and swells the resin of the support to form a thermochromic composition. The composition often has a chemical adverse effect on thermochromic properties and a physical adverse effect on transparency. For example, when a thermochromic composition dissolved in methyl isobutyl ketone is applied to a polystyrene resin support by spraying, the solvent dissolves the support resin and the polystyrene resin migrates into the thermochromic composition. As a result, the thermochromic composition 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 resin for the undercoat, a methacrylate resin exhibits a preferable effect, and is coated on the support with a solvent composition that does not attack the support according to a coating method. As a more preferable resin, a methacrylic resin having a glass transition point of 90 ° C. or more is preferable. Such a resin is obtained by polymethyl methacrylate (Tg: 125 ° C.), polyisopropyl methacrylate (Tg: 95 ° C.), and copolymerization. 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. When coating the top coat layer,
The solvent for the top coat is a thermochromic layer (thermochromic composition layer)
Remelting not only fluctuates the composition ratio of the thermochromic composition, but also has a significant effect on the thermochromic function and the transparency / opacity function. For this reason, it is necessary to apply a solvent which does not substantially dissolve or swell the thermochromic composition layer as the solvent applied to the top coat. Preferred solvents are water,
Alcohols, glycol ethers, and aliphatic hydrocarbon solvents. A methacrylic resin, a vinyl-modified alkyd resin, a vinyl-modified alkyd resin, an oil-soluble polyurethane resin, which is easily soluble in such solvents, or a resin of a dispersion system, and a resin having good adhesiveness with a vinyl chloride-vinyl acetate copolymer resin, Acrylic resin, acrylic copolymer resin, epoxy resin and the like can be mentioned. Above all, a solvent composition in which an alcohol solvent and / or an aliphatic hydrocarbon solvent accounts for 40% or more of the total solvent in a methacrylic resin and an acrylic resin or a copolymer resin thereof having alcohol-soluble or aliphatic hydrocarbon-soluble transparency. When melt | dissolving and laminating | stacking, a suitable top coat property is satisfy | filled, without giving a bad influence to a thermochromic composition, and a transparent topcoat layer with adhesiveness 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] Constituent monomer weight ratio is 60% to 92% vinyl chloride,
Average molecular weight 7,000-50,000, vinyl acetate 8% -40%
In a vinyl chloride-vinyl acetate copolymer resin matrix of
(A), (B) and (C) By dispersing the thermochromic material composed of three components in a size in the range of 0.1 to 2.0 μm , there is no bleeding of any of the above components on the resin surface. It is held stably, and the transparency changes reversibly with the color change due to the temperature change, and the color opacity and the decoloration transparent change and the reversible change, more specifically, the temperature difference between the high temperature trigger and the low temperature trigger Exhibit a thermochromic light-shielding / light-transmitting function having a large hysteresis characteristic of at least 10 ° C or more and 50 ° C or less. In the above, since the thermochromic material is not in the form of a microencapsulated pigment, there is no adverse effect on 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 transparent see-through without impairing the optical properties of the underlayer having optical properties such as brilliancy and gloss. .

[0027]

EXAMPLES The optical characteristics of the thermochromic composition forming the thermochromic layer of the laminate of the present invention will be described in more detail with reference to Examples. All parts in the examples are parts by weight. In addition, regarding the hysteresis width, when cooling to a low temperature side after changing from colored opaque to colorless and transparent, if the temperature at the time of temperature rise is in the vicinity of the high temperature side trigger or less, the hysteresis width becomes small. The hysteresis width of the present invention refers to the maximum hysteresis width for one thermochromic composition. Hereinafter, the measurement of the discoloration temperature, absorbance and transmittance in the examples was carried out according to the following methods. (1) Discoloration Temperature In Examples 1 to 6, a double-sided tape of 60 μm thick white synthetic paper was adhered to the back surface of the PET film coated with the thermochromic composition to obtain a measurement sample. The measurement sample is further adhered to the bottom of the heating / cooling container using a double-sided tape. The thermochromic composition side is a color difference meter (TC-
It is set facing the light source side of a 3600 type color difference meter (manufactured by Tokyo Denshoku Co., Ltd.). Pour water into a heating / cooling container,
The temperature was lowered (from 50 ° C. to 0 ° C.) and the temperature was raised (from 0 ° C. to 50 ° C.) as one cycle under the condition of 0 ° C., and the brightness of the sample at each temperature was plotted on a graph. (2) Absorbance and transmittance At room temperature of 20 ° C., using the same PET film as the film used in the examples on the control side, the thermochromic printed matter obtained according to each example was set on the sample side, and the spectroscopy was performed. Photometer (U
-3210: Absorbance (based on a reflection method) and transmittance of light having a wavelength of 400 to 700 nm were measured by using a self-recording spectrophotometer manufactured by Hitachi, Ltd. In addition, the measurement sample measured the absorbance and the transmittance | permeability in 20 states of 2 states of color opacity and decoloration transparent. The solid line in the figure indicates the absorbance and transmittance at 20 ° C. when colored and opaque, and the broken line indicates the absorbance and transmittance at 20 ° C. when decolorized and transparent.

Example 1 1,2-benz-6-dibutylaminofluoran
3 parts, 1,1-bis (4′-hydroxyphenyl) hexane, 5 parts, stearyl caprate, 5 parts, and stearyl laurate, 15 parts, were treated with VYHH (vinyl chloride-vinyl acetate copolymer resin, polymer composition: PVC / vinyl acetate = 86/14,
20% MIBK solution 30 of Union Carbide made in Japan)
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). A PET film (100 μm thick, manufactured by Lintec Co., Ltd., trade name: NF)
PET Tomei 100 [A]) was coated to a thickness of about 15 μm when dried, and dried at 80 ° C. for 30 minutes to form a thermochromic layer. In the thermochromic layer, it was observed that the thermochromic material was dispersed in a range of about 0.2 to 1.0 μm. The resulting printed material had two triggers, a low temperature side trigger: about 12 ° C. and a high temperature side trigger: about 39 ° C., and a hysteresis width of about 20 ° C. The color disappeared and became transparent above the high temperature side trigger, and it became pink and opaque below the low temperature side trigger. 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 was able to be repeated stably without bleeding even after 500 repetitions. Further, the same change and stability were confirmed even when left in a constant temperature room at 60 ° C. for one week. FIG. 1 shows the discoloration curve of the printed matter, FIG. 2 shows the absorbance at the time of coloring / opacity, and the absorbance at the time of decoloring / transparency, and FIG. 3 shows the transmittance.

Example 2 2-Chloro-3-methyl-6-diethylaminofluoran 2 parts, 2,2-bis (4'-hydroxyphenyl)
5 parts of propane and 20 parts of myristyl alcohol were mixed with 20% MIBK / xylene (1/1) of Denkavinyl 1000D (vinyl chloride-vinyl acetate copolymer resin, polymer composition: polyvinyl chloride / vinyl acetate = 68/32, manufactured by Denki Kagaku Kogyo). Solution 3
Dissolved in 00 parts. Furthermore, Byk-325 (polyether-modified dimethylpolysiloxane, Byk chemie
Was added to prepare a thermochromic ink (B). A PET film (100 μm thick, manufactured by Lintec Co., Ltd., trade name:
NF PET Tomei 100 [A]) is coated so that the film thickness at the time of drying becomes about 20 μm.
After drying for a minute, a thermochromic layer was formed. In the thermochromic layer,
The thermochromic material was observed to be dispersed in the resin in the range of about 0.2-2.0 μm. The obtained printed matter was a low temperature side trigger: about 4 ° C. and a high temperature side trigger: about 33 ° C.
The hysteresis width with two triggers was about 20 ° C. The color disappeared above the high temperature side trigger and became transparent, and the color became vermilion and opaque below the low temperature side trigger. 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 repetitions. Further 60
The same change and stability were confirmed even when left in a constant temperature room at ℃ for one week. FIG. 4 shows the discoloration curve of the printed matter, FIG. 5 shows the absorbance at the time of coloring (opaque) and at the time of erasing (transparent), and FIG. 6 shows the transmittance.

Example 3 3-Cyclohexylamino-6-chlorofluorane 2
Part, 1,1-bis (4'-hydroxyphenyl) octane 5 parts, 2,2-bis (4'-hydroxyphenyl)
2 parts of propane, 10 parts of cetyl alcohol, and 10 parts of stearyl caprate were mixed with 20% MIBK / denka vinyl 1000MT3 (vinyl chloride-vinyl acetate copolymer resin, polymer composition: PVC / vinyl acetate = 70/30, manufactured by Denki Kagaku Kogyo).
It was dissolved in 300 parts of a xylene (1/1) solution. More By
0.2 parts of k-300 (polyether-modified dimethylpolysiloxane, manufactured by Byk Chemie) was added to prepare a thermochromic ink (C). Using the above ink and applicator, PET was coated on a PET trade name: NF PET Tomei 100 [A]) to a thickness of about 15 μm when dried, and then dried at 80 ° C. for 30 minutes to form a thermochromic layer. In the thermochromic layer, it was observed that 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 trigger: The hysteresis width with two triggers of about 30 ° C was about 16 ° C. The color disappeared above the high temperature side trigger and became transparent, and became orange and opaque below the low temperature side trigger. 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 repetitions. Further, the same change and stability were confirmed even when left in a constant temperature room at 60 ° C. for one week. FIG. 7 shows the discoloration curve of the printed matter, FIG. 8 shows the absorbance at the time of coloring (opaque) and at the time of erasing (transparent), and FIG. 9 shows the transmittance.

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 were used. Denka Vinyl 1000MT3 (vinyl chloride-vinyl acetate copolymer resin, polymer composition: PVC / vinyl acetate = 70)
/ 30, manufactured by Denki Kagaku Kogyo) in 300 parts of a 20% MIBK / xylene (1/1) solution. In addition, FC-430
(Fluorine leveling agent, Sumitomo 3M).
One part was added to prepare a thermochromic ink (D). The above ink was applied to a PET film (100
μm thickness, manufactured by Lintec Corporation, Product name: NF PET
Tomei 100 [A]) has a thickness of about 15 μm when dried.
After coating, the mixture was dried at 80 ° C. for 30 minutes to obtain a thermochromic layer. In the thermochromic layer, it was observed that the thermochromic material was dispersed in the resin in the range of about 0.2 to 1.5 μm. The resulting print is the low temperature trigger:
Approximately 6 ° C., high-side trigger: The hysteresis width having two triggers of approximately 38 ° C. was approximately 28 ° C. The color disappeared above the high temperature side trigger and became transparent, and became green and opaque below the low temperature side trigger. 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 was able to be repeated stably without bleeding even after 500 repetitions. In addition, 1
The same change and stability were confirmed even after leaving for a week. FIG. 10 shows the discoloration curve of the printed matter, FIG. 11 shows the absorbance at the time of coloring (opaque) and the time of decoloring (transparent), and FIG. 12 shows the transmittance.

Example 5 1,2-Benz-6-diethylaminofluoran
5 parts, 2,2-bis (4'-hydroxyphenyl) octane, 5 parts, and neopentyl glycol dipalmitate (20 parts) were mixed with 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) Dissolved in 300 parts of solution. Byk-310
(Polyester-modified dimethylpolysiloxane, Byk
Chemie) (0.2 part) was added to prepare a thermochromic ink (E). A PET film (100 μm thick, Lintec Co., Ltd.)
After coating on NF PET Tomei 100 [A]) so that the film thickness when dried becomes about 15 μm,
After drying at 80 ° C. for 30 minutes, a thermochromic layer was formed. The composition in the printed matter is about 0.2 to 1.0 μm in the resin.
Was observed to be dispersed in the range. The obtained printed matter has a low-temperature trigger: about 0 ° C. and a high-temperature trigger: about 3
Hysteresis width with two triggers of 7 ° C. is about 33
° C. In the temperature range between the low-temperature trigger and the high-temperature trigger where the color is erased and transparent above the high temperature side trigger and becomes pink and opaque below the low temperature side trigger and becomes opaque, the above two states can be selectively taken. The same change was able to be repeated stably without bleeding even after 500 repetitions. Further, the same change and stability were confirmed even when left in a constant temperature room at 60 ° C. for one week. FIG. 13 shows the discoloration curve of the printed matter.
FIG. 14 shows the absorbance when colored (opaque) and when decolored (transparent).
FIG. 15 shows the transmittance.

Example 6 2- (3'-trifluoromethylphenyl) amino-6
2 parts of diethylaminofluorane, 5 parts of 2,2-bis (4′-hydroxyphenyl) octane, 10 parts of dimyristyl didipinate, and 10 parts of cetyl alcohol
20% MIBK / xylene (1/1) solution of YHD (vinyl chloride-vinyl acetate copolymer resin, polymer composition: PVC / vinyl acetate = 86/14, manufactured by Union Carbide Japan)
Dissolved in 300 parts. Further, Byk-310 (polyester-modified dimethylpolysiloxane, Byk chemie
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 to a thickness of about 15 μm when dried, and then dried at 80 ° C. for 30 minutes to form a thermochromic layer. It was observed that the composition in the print was dispersed in the resin in the range of about 0.2-1.5 μm. The obtained printed matter had a hysteresis width of about 33 ° C. having two triggers, a low-temperature side trigger: about -6 ° C. and a high-temperature side trigger: about 37 ° C. The color disappeared above the high temperature side trigger and became transparent, and the color became dark gray gray and opaque below the low temperature side trigger. 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 was able to be repeated stably without bleeding even after 500 repetitions. Further, the same change and stability were confirmed even when left in a constant temperature room at 60 ° C. for one week. FIG. 16 shows the discoloration curve of the printed matter, and FIG. 17 shows the absorbance at the time of coloring (opaque) and at the time of decoloring (transparent).
FIG. 18 shows the transmittance.

Example 7 (thermochromic shading-translucent laminate) [1] Preparation of each ink (1) Undercoat ink Acrypet VK (methyl methacrylate resin: manufactured by Mitsubishi Rayon Co., Ltd.) (Isobutyl ketone) and 30 parts of propylene glycol monomethyl ether to prepare an undercoat ink (a). (2) Thermochromic ink 300 parts of the thermochromic ink (A) of Example 1 was replaced with MIBK2
50 parts and 50 parts of cyclohexanone were mixed to prepare a thermochromic ink (A ′). (3) Topcoat ink plus size CB-2 (alcohol-soluble acrylic resin: 50% ethanol solution, manufactured by Kyo Chemical) 20 parts, Tinuvin 328 (ultraviolet absorber, manufactured by Ciba-Geigy) 0.5
Was 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
25 Metal Me TS (manufactured by Toyo Metallizing Co., Ltd.) was coated with the undercoat ink (a) by spraying and dried at 80 ° C. for 30 minutes. The undercoat layer of the obtained coated product had a thickness of about 5 μm when dried. Subsequently, the thermochromic ink (A ') was applied on the upper layer by spraying and dried at 80 ° C for 30 minutes. The thermochromic layer of the obtained coating had a thickness of about 10 μm when dried. Furthermore,
As a protective layer, the top coat ink (b) was applied by spraying and then dried at 80 ° C. for 30 minutes. The top coat layer of the obtained coated product had a thickness of about 10 μm when dried. When the obtained laminate was wetted with cold water of 10 ° C. using an applicator, the laminate turned pink, and at the same time, the metallic luster of the underlying layer became invisible. Next, when this was wetted with warm water of 45 ° C. using an applicator, the pink color disappeared and the metallic luster of the underlayer appeared at the same time. This is at room temperature 25 ° C
There was no change even if left in the place. The change is 5
This was repeated 00 times, and a similar change was confirmed.

Example 8 (thermochromic shading-translucent laminate) [1] Preparation of each ink (1) Undercoat ink Dianal BR-80 (methyl methacrylate resin:
10 parts of Mitsubishi Rayon Co., Ltd. dissolved in 60 parts of MIBK and 30 parts of cyclohexanone, and the undercoat ink (c)
Was adjusted. (2) Thermochromic ink In 300 parts of thermochromic ink (B) of Example 2, MIBK1 was added.
50 parts were mixed and diluted to prepare a thermochromic ink (B '). (3) Top Coat Ink 10 parts of Dianal BR-102 (alcohol-soluble acrylic resin: manufactured by Mitsubishi Rayon Co.), 1 part of Tinuvin PS (ultraviolet absorbent, manufactured by Ciba Geigy), 60 parts of isopropyl alcohol, 30 parts of n-butanol To prepare a top coat ink (d). [2] Fabrication of laminate MEARL IRI exhibiting iris by optical interference phenomenon
DESCENT FILM (trade name: IF-8101)
By the same coating method and drying conditions as in Example 7 on the surface of
The inks (c), (B ') and (d) were sequentially applied.
When the obtained laminate was placed in a freezer at -5 ° C, vermilion was instantaneously formed, and the iris pattern and properties of the base were not visually observed at all. Further, when this was heated with a hairdressing blower, the vermilion disappeared, and the glow pattern and glow of the base appeared. It was left at room temperature for 3 days without any change. The same change was confirmed even after 500 repetitions.

Example 9 (thermochromic shading-translucent laminate) The same undercoat as in Example 8 was applied to the surface of a gold-colored aluminum-evaporated polyester film (trade name: # 50 Metal Me CCC, manufactured by Toyo Metallizing Co., Ltd.). The same coating was performed using ink, thermochromic ink, and top coat ink. When the obtained laminate was placed in a freezer at -5 ° C, a vermilion color was instantaneously formed and no golden metallic luster on the underlayer was observed. Further, when this was heated with a hair-blowing blower, the vermilion disappeared, and a golden metallic luster on the underlayer appeared. It was left 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 Dianal BR-85 (Methol methacrylate resin:
Dissolve 20 parts of Mitsubishi Rayon Co. in 80 parts of MIBK,
The undercoat ink (e) was prepared. (2) Thermochromic ink The thermochromic ink (C) of Example 3 was used as it was. (3) Top coat ink 70 parts of Acridic A-188 (tarpene-soluble acrylic resin: manufactured by Dainippon Ink and Chemicals, Inc.) was dissolved in 30 parts of mineral turpen to prepare a top coat ink (f). [2] Production of laminated body Holographic film having glossiness and three-dimensional appearance (trade name:
Undercoat ink (e) on the surface of Holographic Star 101 Surf Whisper (manufactured by Lintec Corporation)
Was coated using an applicator to a thickness of about 5 μm when dried, and then dried at 80 ° C. for 30 minutes to form an undercoat layer. Subsequently, the upper layer is coated with a thermochromic ink (C) using an applicator so that the film thickness when dried becomes about 10 μm, and then applied at 80 ° C. for 30 minutes.
After drying for a minute, a thermochromic light-shielding ink layer was formed. 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 resulting laminate is cold trigger:
Approximately 6 ° C., high temperature side trigger: It has two discoloration points of about 30 ° C., develops orange color below the low temperature side trigger, conceals the underlying hologram pattern and glossiness, and decolors above the high temperature side trigger. At the same time, the underlying hologram pattern and glossiness were visually recognized. 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 Dianal BR-83 (methyl methacrylate resin:
Dissolve 20 parts of Mitsubishi Rayon Co. in 80 parts of MIBK,
An undercoat ink (g) was prepared. (2) Thermochromic ink The thermochromic ink (F) of Example 6 was used as it was. (3) Topcoat ink 50 parts of plus size L-53 (alcohol-soluble acrylic resin: 50% ethanol solution, manufactured by Ryo Kagaku Co., Ltd.), tinuvin PS (ultraviolet absorber, manufactured by Ciba Geigy) 1.5
Was dissolved in 50 parts of n-propyl alcohol to prepare a top coat ink (h). [2] Production of laminated body Holographic film having glossiness and three-dimensional appearance (trade name:
(G), (F), and (h) inks were sequentially applied to the polyester film side of the raw material obtained by bonding Sparkles, SPECTRATEK) 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 trigger: about 10 ° C. and a high-temperature trigger: about 35 ° C., and develops a dark gray-gray color below the low-temperature trigger, and exhibits a hologram pattern and glossiness of the base. It was concealed, decolored above the high-temperature side trigger and visualized the hologram pattern and the glossiness of the base. The same change was confirmed even after 500 repetitions.

Comparative Example A laminate was produced in the same manner as in Example 7, except that the following ink was used instead of the thermochromic ink (A ') of Example 7. 1.3 parts of 1,2-benz-6-dibutylaminofluorane, 5 parts of 1,1-bis (4′-hydroxyphenyl) hexane, stearyl caprate
5 parts and 15 parts of stearyl laurate were microencapsulated by an epoxy-amine interfacial polymerization method in a conventional manner.
30 parts of the microcapsules were mixed with VYHH (vinyl chloride-vinyl acetate copolymer resin, polymer composition: PVC / vinyl acetate =
86/14, manufactured by Union Carbide)
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 less and conceals the metallic luster of the substrate, but at 45 ° C. or more, the pink color disappears, but the substrate remains cloudy due to irregular reflection of microcapsules. No metallic luster was visible.

[0040]

According to the thermochromic light-shielding / translucent laminate of the present invention, the surface thermochromic layer alternately exhibits both a colored opaque state and a decolored transparent state depending on the temperature. The color change is visually recognized, and the underlying layer having optical properties such as brilliancy, iris, and glossiness is concealed without impairing the optical properties. Furthermore, even after removing the heat or cold required for changing the color to the opaque state or the decolored transparent state, any one of them can be selectively used in the temperature region between the low-temperature trigger and the high-temperature trigger. Can be stored and stored, and the change in the aspect is repeatedly and reversibly reproduced. Thus, as a thermochromic laminate that satisfies toy properties, surprisingness, decorativeness, interest, etc., toys, dolls, entertainment tools, sports equipment, papers, stationery, printed matter, clothing, cloth personal belongings, Jewelry, buttons, bags, bags, jewelery imitations,
Applicable to various fields such as cosmetic tools, footwear, shoes, eyeglass parts, mirror parts, fabrics, film fabrics, fittings, indoor equipment, wallpapers, commemorative cups, packaging containers, packaging materials, daily necessities, kitchenware, etc. As a result, saliency and specificity can be imparted, and the marketability can be enhanced.

[0041]

[Brief description of the drawings]

FIG. 1 shows a color change curve due to a temperature change in Example 1 showing characteristics of a thermochromic layer formed by 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 transparent and erased (the same applies to FIGS. 2 to 18 below).

FIG. 2 shows coloring, opacity and decoloring of the printed matter of Example 1,
3 shows an absorbance curve when transparent.

FIG. 3 shows coloring, opacity and decoloring of the printed matter of Example 1,
The transmission spectrum when transparent is shown.

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

FIG. 5 shows coloring, opacity and decoloring of the printed matter of Example 2,
3 shows an absorbance curve when transparent.

FIG. 6 shows coloring, opacity and decoloring of the printed matter of Example 2,
The transmission spectrum when transparent is shown.

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

FIG. 8 shows an absorbance curve of the printed matter of Example 3 when colored, opaque and decolored, and transparent.

FIG. 9 shows coloring, opacity and decoloring of the printed matter of Example 3;
The transmission spectrum when transparent is shown.

FIG. 10 shows a color change curve according to a 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 colored, opaque, decolored, and transparent.

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

FIG. 13 shows a color change curve according to a temperature change in 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 colored, opaque, decolored, and transparent.

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

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

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

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

FIG. 19 is an enlarged longitudinal sectional view of one embodiment of the laminate of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Laminated body 2 Support 3 Underlayer 4 Thermochromic layer

Continuation of the front page (56) References JP-A-5-137849 (JP, A) JP-A-7-25251 (JP, A) JP-A-6-135144 (JP, A) (58) Fields investigated (Int) .Cl. ⁷ , DB name) B41M 5/28-5/34 B32B 1/00-35/00 C09K 9/02 C09D 11/00-11/02

Claims (2)

(57) [Claims] 1. Brightness, brightness reflection, light interference, iris
Properties, hologram properties, metallic luster, pearl luster, fluorescent
(A) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, (c) alcohols, esters, ketones, or carboxylic acids on the underlayer exhibiting the selected optical property. A reversible thermochromic discoloration comprising a homogenous solution of the three components containing a compound selected from the group consisting of:
The weight ratio of the constituent monomers is 60% to 92%.
, Vinyl acetate 8% -40%, average molecular weight 7,000-50,
000 chloride vinyl - during vinyl acetate copolymer resin, the temperature difference is secured to the dispersed state in the size range of particle size 0.1 to 2.0 [mu] m, and the high-temperature side trigger and low-temperature side trigger 1
Temperature in the range of 0 ° C to 50 ° C , higher than the high temperature trigger
At the temperature below the low temperature trigger.
Presents color opaque state, low temperature trigger and high temperature trigger
In the temperature range between the colorless transparent state or the colored opaque state
Shows a large hysteresis characteristic that can hold either of
A thermochromic light-shielding / light-transmitting laminate in which thermochromic layers that change color are laminated. 2. A thermochromic layer comprising 6 parts by weight of a vinyl chloride-vinyl acetate copolymer resin, (a) 0.05 to 2.0 parts by weight of an electron-donating color-forming organic compound, and (b) phenolic 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. 2. The thermochromic shading according to claim 1, which is constituted.
Translucent laminate.