JP2003011260A - Metallic luster style heat discolorative laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metallic luster style heat discolorative laminate which can visually recognize a metallic luster color having a highly glittering luminance and a color change by a clearly reversible heat discoloring layer and which has a various application development. SOLUTION: The metallic luster style heat discolorative laminate 1 laminates a metallic luster layer 3 containing a metallic luster pigment obtained by coating a metal oxide on a front surface of a synthetic mica, and a reversible heat discoloring layer 2 containing a heat discoloring composition made of an organic compound medium for reversibly bringing about a color reaction of both an electron donative color reactive organic compound and an electron acceptive compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a metallic luster color thermochromic laminate. More specifically, due to temperature change, gold color,
The present invention relates to a metal-gloss-like thermochromic laminate which is configured to exhibit a metallic luster of high brightness such as silver or metallic color and to make a color change visible.

[0002]

2. Description of the Related Art Conventionally, some proposals by the present applicants have already been disclosed regarding a thermochromic laminate having a metallic luster tone (JP-A-6-1067 and JP-A 6-1).
068, JP 6-8628, JP 9-
193279, etc.). The above-mentioned proposal is a laminate in which a metallic luster layer containing a metallic luster pigment in which the surface of natural mica is coated with titanium oxide is provided on a reversible thermochromic layer, and the metallic luster color of gold, silver or metallic color is changed depending on the temperature change. It shows the color change from the color change of the conventional thermochromic material and has a unique color change compared with the conventional color change of the thermochromic material, so it has applicability not only in the temperature indicating field but also in various fields such as decoration and toys. ing.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have further pursued the visual effect of this type of metallic luster color thermochromic laminate and have a metallic luster color which is rich in glitter and has a glittering appearance. However, it is intended to provide a metal-gloss-like thermochromic laminate capable of exhibiting a more distinct color change due to the color change of the reversible thermochromic layer.

[0004]

The present invention provides a synthetic mica table.
Metallic luster including metallic luster pigment whose surface is coated with metal oxide
Layer, electron-donating color-forming organic compound and electron-accepting compound
And organic compound media that reversibly cause color reaction between the two
And a reversible thermochromic layer containing a thermochromic composition comprising
The requirement is a metallic luster color thermochromic laminate. Further
Is that the synthetic mica is represented by the following general formula (1), X_{1/3 ~ 1} Y_2-3 Z_Four O_TenF₂     (1) (In the formula, X is Na⁺ , Li⁺ , K⁺ , Ca²⁺, Sr²⁺,
Ba²⁺, And Y is Mg ²⁺, Li⁺ , Ni²⁺, Co²⁺,
Zn²⁺, Mn²⁺, Al³⁺, Cr³⁺, Ti³⁺A kind of
2 or more types, Z is Al³⁺, Si⁴⁺, Ge⁴⁺, B³⁺of
Indicates one or more types) Furthermore, the surface of the synthetic mica is made of gold containing titanium oxide as the main component.
Being coated with a group oxide, the metallic luster pigment is an average
Has a thickness of 0.1 to 5 μm and an average particle diameter of 2 to 10
00 μm, transparent resin layer on top of metallic luster layer
Is required.

The metallic luster layered laminate previously proposed by the present applicant is a pigment in which the metallic luster pigment to be applied is a pigment in which the surface of natural mica is coated with titanium oxide. Depending on the titanium oxide coverage, gold, silver, or , Metallic metallic luster. Therefore, it is possible to present a glittering appearance and also to see a different appearance due to the color change of the reversible thermochromic layer due to temperature change.

As a result of further studies on the above-mentioned metallic luster and a laminate exhibiting a color change due to a temperature change, the present inventors have found that the use of a metallic luster pigment in which the surface of synthetic mica is coated with a metal oxide causes reversible heat. It was found that a metal glossy thermochromic laminate having a more distinct aspect change due to the color change of the color-change layer can be obtained. That is, since the metallic luster pigment used in the present invention uses synthetic mica as the core substance,
Compared with general-purpose natural mica, the content of metal ions showing a tendency to color impurities such as iron and iron is low, the transparency is excellent, and the metallic luster is coated with a metal oxide typified by titanium oxide. The obtained metal oxide exhibits a metallic luster of gold, silver or metallic depending on the coverage of the metal oxide. Therefore, the metallic luster pigment obtained by coating the synthetic mica with the metal oxide is also excellent in glitter and excellent in transparency, so that the color tone of the reversible thermochromic layer can be clearly recognized. The synthetic mica used as the core substance of the metallic luster pigment is preferably the synthetic mica represented by the general formula (1), and one example thereof is KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ . The shape of the synthetic mica is not particularly limited, but may be a flat shape or a scale shape. The metal oxide coating the surface of the synthetic mica, titanium,
Examples thereof include metal oxides such as zirconium, chromium, vanadium, and iron, but metal oxides containing titanium oxide as a main component are preferable. The metallic luster pigment has an average thickness of 0.1 to 5 μm and an average particle diameter of 2 to 1000 μm.
m, preferably 2 to 500 μm, more preferably 2 to 2
It is 00 μm. By using the metallic luster pigment exhibiting the above-mentioned thickness and average particle diameter, it is possible to exhibit uniform glitter of the metallic luster layer and a clear color change due to discoloration of the reversible thermochromic layer. The average particle size is the average particle size by the laser diffraction method, and the volume-based median size corresponds to 50% of the cumulative distribution.

As the metallic luster pigment in which the surface of the synthetic mica is coated with a metal oxide, specifically, the product name "Ultimica" manufactured by Nippon Kogaku Kenkyu Co., Ltd. product number: SB-100 (5-3)
0 μm: silvery), SD-100 (10 to 60 μm: silvery), SE-100 (15 to 100 μm: silvery), SF
-100 (44 to 150 μm: silver), SH-100
(150 to 600 μm: silver), YB-100 (5 to 3)
0 μm: gold), YD-100 (10-60 μm: gold), YE-100 (15-100 μm: gold), YF
-100 (44 to 150 μm: gold color), RB-100
(5-300 μm: metallic red), RD-100
(10-60 μm: metallic red), RE-100
(15 to 100 μm: metallic red), RF-10
0 (44 to 150 μm: metallic red), RBB-
100 (5-30 μm: metallic purple), RBD
-100 (10-60 μm: metallic purple), R
BE-100 (15 to 100 μm: metallic purple), RBF-100 (44 to 150 μm: metallic purple), VB-100 (5 to 30 μm: metallic violet), VD-100 (10 to 60 μm: metallic violet), VE- 100 (15-100μ
m: metallic violet), VF-100 (44-
150 μm: metallic violet), BB-100
(5 to 30 μm: metallic blue), BD-100
(10-60 μm: metallic blue), BE-100
(15 to 100 μm: metallic blue), BF-10
0 (44 to 150 μm: metallic blue), GB-1
00 (5 to 30 μm: metallic green), GD-1
00 (10-60 μm: metallic green), GE-
100 (15 to 100 μm: metallic green), G
F-100 (44 to 150 μm: metallic green)
Can be illustrated. The average particle diameter and color tone are shown in parentheses.

The laminate of the present invention is formed by laminating a metallic luster layer and a reversible thermochromic layer, and the laminated constitution is not particularly limited, but an upper layer, that is, a metallic luster layer is provided on the visible side, It is preferable to provide a reversible thermochromic layer as the lower layer. With the above structure, a metallic luster can be sufficiently exhibited, and a change in appearance due to a color change of the reversible thermochromic layer provided in the lower layer can be clearly seen. Further, the metallic luster layer also has the effect of improving the light resistance of the reversible thermochromic layer.

Using the ink or paint in which the above-mentioned metallic luster pigment is dispersed in a vehicle, a conventionally known method, for example,
Screen printing, offset printing, gravure printing, coater, tampo printing, printing means such as transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating etc. on the support. A metallic gloss layer can be formed. Further, a molded product formed by blending the metallic luster pigment in a thermoplastic resin or a thermosetting resin may be used as the metallic luster layer. When the metallic luster pigments in the metallic luster layer have a flat shape, the pigments are easily orientated in a plane and have excellent glitter. Even if there is an overlapping portion of the metallic luster pigment, a clear metallic luster color can be visually recognized without impairing the metallic luster depending on the transparency of the pigment.

The reversible thermochromic layer contains a reversible thermochromic composition in the layer, and the composition reversibly causes a color reaction with an electron-donating color-changing organic compound and an electron-accepting compound. A composition containing three components of an organic compound medium to be generated is preferably used. Specifically, JP-B-51-35414, JP-B-51-44706 and JP-A-7-18
The reversible thermochromic composition described in Japanese Patent No. 6540 may be mentioned. In addition, Japanese Patent Publication No. 1-293 proposed by the applicant
As described in JP-A-98, a highly sensitive thermochromic composition having a hysteresis width of 3 ° C. or less with respect to a color density-temperature curve due to temperature change can be mentioned. The above-mentioned color changes before and after a predetermined temperature (color change point) as a boundary, and only one specific state can exist in the normal temperature region of both states before and after the change. That is, the other state is maintained while the heat or cold required to develop that state is applied,
When the heat or cold heat is not applied, the state returns to the state exhibited in the normal temperature range, that is, it is a type that changes color by showing a small hysteresis width (ΔH) with respect to temperature-color density due to temperature change. Further, a reversible thermochromic composition (Japanese Patent Laid-Open No. 11-5973), which uses an alkoxyphenol compound as an electron-accepting compound and exhibits color developability upon heating, can also be used.

Further, Japanese Patent Publication No. 4-171 proposed by the present applicant.
No. 54, the thermosensitive color-changing color-memory thermochromic composition which exhibits a large hysteresis characteristic and changes color, that is, the shape of a curve plotting the change in coloring density due to temperature change changes the temperature. It is a type of discoloring material that changes color when the temperature is increased from the lower temperature side than the temperature range and when it is decreased from the higher temperature side than the discoloration temperature. A thermochromic composition having a feature of being able to store and retain a state of being changed at a temperature below the low-temperature side discoloring point or above the high-temperature side discoloring point in a normal temperature range between the side discoloring points is also effective.

The above-mentioned reversible thermochromic composition is effective when applied as it is, but it is preferable to use it by encapsulating it in microcapsules. This is because the reversible thermochromic composition can be kept in the same composition under various conditions of use, and can exhibit the same effect. By encapsulating in the microcapsules, a chemically and physically stable microcapsule pigment can be formed, and a particle diameter of 0.1 to 10
Practicality is satisfied in the range of 0 μm, preferably 3 to 30 μm. Microencapsulation can be carried out by the conventionally known interfacial polymerization method, in situ polymerization method, submerged curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion cooling method, air suspension method. There are a coating method, a spray drying method and the like, which are appropriately selected depending on the application. Further, the surface of the microcapsules may be provided with a secondary resin film depending on the purpose to impart durability, or the surface characteristics may be modified for practical use.

The reversible thermochromic layer can be formed by the above-mentioned conventionally known method using an ink or a paint in which the reversible thermochromic composition is dispersed in a vehicle. Furthermore, a microcapsule pigment containing the reversible thermochromic composition,
A molded body formed by blending with a thermoplastic resin or a thermosetting resin may be used as the reversible thermochromic layer.

Further, a vinyl chloride-vinyl acetate copolymer resin is prepared by using an electron-donating color-developing organic compound, a compound having a phenolic hydroxyl group, and a three-way homogenous solution of a reaction medium that determines the temperature at which the color reaction of both of them occurs. It is also possible to form the reversible thermochromic layer by using the thermochromic material described in JP-A-6-135144, which is obtained by dispersing it in the form of fine particles.

The reversible thermochromic layer may be mixed with an appropriate amount of non-thermochromic colored dyes and pigments to form various color changes of the thermochromic layer.

A support is not particularly required when at least one of the metallic luster layer and the reversible thermochromic layer is a molded product, but a support is required when both are liquid compositions such as ink and paint. The support is selected from materials such as paper, synthetic paper, metal, ceramics, stone, wood, glass, resin and cloth, and its shape is not particularly limited. When an opaque support is used, a reversible thermochromic layer and a metallic luster layer are provided on the visible side of the support upper layer. In this case, when a metallic gloss layer is provided on the reversible thermochromic layer as described above, a laminate having a high glittering property can be obtained. When the support is transparent, it can be provided on the reversible thermochromic layer and the metallic luster layer, or can be interposed between the reversible thermochromic layer and the metallic luster layer. Examples of the transparent support include glass and resin, and preferably a resin molding or a resin film is used. The transparency may be colorless and transparent, semi-transparent, colored transparent, or colored translucent.

It is preferable to provide a top coat layer on the uppermost layer of the above-mentioned laminate to improve durability and water resistance. Further, a light stabilizer layer can be appropriately provided on the uppermost layer of the above-mentioned laminated body or between each layer. In particular,
The light stabilizer layer is a light stabilizer selected from an ultraviolet absorber, an antioxidant, an antioxidant, a singlet oxygen quencher, a superoxide anion quencher, an ozone quencher, a visible light absorber, and an infrared absorber. It is a layer fixed in a dispersed state, and can be formed according to the preparation of the reversible thermochromic layer or the metallic luster layer described above. In addition, it is more preferable to provide a light stabilizer layer on the uppermost layer because not only durability and water resistance but also light resistance of the reversible thermochromic layer can be imparted.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The metallic luster color thermochromic laminate of the present invention is formed by laminating two layers of a metallic luster layer and a reversible thermochromic layer, and at least one of the above layers serves as a support. As long as it has thickness and strength, no support is required. When the material forming each layer is a liquid material such as paint, it is provided by sequentially coating the support. Furthermore, when each layer is formed by a molded body, each layer is adhered to obtain a laminate.

[0019]

EXAMPLES Next, specific examples will be shown. Parts in the examples are parts by weight.

Example 1 (see FIG. 1) In ABS resin, 3 parts of 2-anilino-3-methyl-dibutylaminofluorane, 6 parts of 4,4 '-(2-methyl-propylidene) bisphenol, neopentyl stearate. A thermochromic composition composed of 50 parts of a compatible solution was blended with a reversible thermochromic microcapsule pigment having an average particle diameter of 8 μm obtained by encapsulation by an interfacial polymerization method of an epoxy resin / amine curing agent, and a fluorescent orange pigment. On the surface of the molded doll (reversible thermochromic layer 3), a purple metallic luster pigment in which the surface of synthetic mica is coated with titanium oxide [manufactured by Nippon Koken Kogyo Co., Ltd., trade name: RBD-100, average particle size 10 60μ
m] and an acrylic ester resin having a thickness of about 40 μm
m metallic luster layer 4 is provided to provide a metallic luster color thermochromic laminate 1
Got

At 15 ° C. or below, a metallic luster color of metallic purple color with a high brightness is visible in the laminate 1. Further, since the reversible thermochromic layer changes color to fluorescent orange at 32 ° C. or higher, a bright fluorescent orange color due to the reversible thermochromic layer is visually recognized without visually recognizing a metallic luster color having high brightness.

Example 2 (See FIG. 2) 2-anilino-3-on a white ABS plate as the support 2.
Methyl-6-dibutylaminofluorane 3 parts, 4,4 '
6 parts of-(2-methyl-propylidene) bisphenol,
A reversible thermochromic microcapsule pigment having an average particle size of 8 μm obtained by encapsulating a thermochromic composition composed of a compatible solution of neopentyl stearate (50 parts) by an interfacial polymerization method of an epoxy resin / amine curing agent and an acrylic ester resin. And a reversible thermochromic layer 3 having a thickness of about 40 μm,
Next, a golden metallic luster pigment in which the surface of synthetic mica is coated with titanium oxide [manufactured by Nippon Koken Kogyo KK, trade name: YD-1
No. 00, average particle diameter 10 to 60 μm] and an acrylic ester resin having a thickness of about 40 μm were provided to obtain a metallic luster thermochromic laminate 1.

In the laminate 1, the reversible thermochromic layer 3 develops a color at 15 ° C. or lower, which is a part of incident light of 550 to 600 nm.
Since the reflected light of the wavelength is reflected and the transmitted light of the other wavelengths is absorbed, a golden metallic luster color with high brightness is visible. Further, since the reversible thermochromic layer disappears at 32 ° C. or higher and reflects transmitted light, all wavelengths of incident light are reflected, and a metallic luster color with high brightness is not visible.
A clear white color is visible due to the support.

Example 3 2-anilino-3-methyl-6-dibutylaminofluorane 3 parts, 4,4'-on a white vinyl chloride resin molding.
Reversible having an average particle size of 8 μm obtained by encapsulating a thermochromic composition composed of a compatible solution of 6 parts of (2-methyl-propylidene) bisphenol and 50 parts of neopentyl stearate by an interfacial polymerization method of an epoxy resin / amine curing agent. A blue metallic luster pigment obtained by laminating a reversible thermochromic layer having a thickness of about 40 μm, which comprises a thermochromic microcapsule pigment and an acrylic ester resin, and then coating the surface of synthetic mica with titanium oxide [Nippon Koken Industrial Co., Ltd. ), Product name: BE-10
0, average particle diameter 15 to 100 μm] and an acrylic ester resin having a thickness of about 40 μm were provided to obtain a metal gloss thermochromic laminate.

In the laminate, the reversible thermochromic layer develops color at 15 ° C. or lower and reflects light which is a part of visible light of incident light,
Since it absorbs light of other wavelengths, a bright metallic luster color of blue with glitter is visible. In addition, since the reversible thermochromic layer disappears at 32 ° C and reflects the transmitted light, all wavelengths of the incident light are reflected, and the metallic luster color with high brightness is not visually recognized and is clear by the molded product. White color is visible.

Example 4 3 parts of 2-anilino-3-methyl-6-dibutylaminofluorane, 4,4 '-(2-methyl-propylidene) bisphenol 6 were placed on a light pink polystyrene molded product in the form of a miniature car. Part, neopentyl stearate 5
A thermochromic composition consisting of 0 parts of a compatible solution was added to
A reversible thermochromic layer having a thickness of about 40 μm, which is composed of a reversible thermochromic microcapsule pigment having an average particle diameter of 8 μm obtained by encapsulation of an amine curing agent by an interfacial polymerization method and an acrylic ester resin, is laminated and then synthesized. Purple metallic luster pigment in which the surface of mica is coated with titanium oxide [Nihon Koken Industry Co., Ltd.]
Product name: RBF-100, average particle size 44-15
0 μm] and an acrylic ester resin having a thickness of about 4
A metal glossy layer having a thickness of 0 μm was provided to obtain a metal glossy thermochromic laminate.

In the laminate, the reversible thermochromic layer develops color at 15 ° C. or lower, reflects reflected light having a wavelength of 380 to 430 nm, which is a part of incident light, and absorbs transmitted light having other wavelengths. , Metallic glitter color of metallic purple color with high brightness is visible. Further, since the reversible thermochromic layer disappears at 32 ° C or higher and reflects the transmitted light, all wavelengths of the incident light are reflected, and the metallic luster color with high brightness is not visible and is clear by the molded product. You can see a nice pink color.

Example 5 (see FIG. 3) 2-anilino-3- was prepared as a support 2 on a yellow ABS plate.
Methyl-6-dibutylaminofluorane 3 parts, 4,4 '
6 parts of-(2-methyl-propylidene) bisphenol,
A reversible thermochromic microcapsule pigment having an average particle size of 8 μm obtained by encapsulating a thermochromic composition composed of a compatible solution of neopentyl stearate (50 parts) by an interfacial polymerization method of an epoxy resin / amine curing agent and an acrylic ester resin. And a reversible thermochromic layer 3 having a thickness of about 40 μm,
Next, a silver metallic luster pigment in which the surface of synthetic mica is coated with titanium oxide [manufactured by Nippon Koken Kogyo Co., Ltd., trade name: SE-1
00, average particle diameter 15 to 100 μm] and a metallic luster layer 4 having a thickness of about 40 μm, which is made of an acrylic acid ester resin, and then, on the upper layer thereof, 4 parts of a benzotriazole-based ultraviolet absorber and 100 parts of an acrylic acid ester resin. The topcoat layer 6 having a thickness of about 40 μm was provided to obtain a metal glossy thermochromic laminate 1.

In the laminate 1, the reversible thermochromic layer develops color at 15 ° C. or lower, reflects light that is a part of the visible light of incident light, and absorbs light of other wavelengths, so that it is glittering. A bright metallic silver-luster color is visible. Also 32
Since the reversible thermochromic layer disappears at ℃ or more and reflects transmitted light, it reflects all wavelengths of the incident light, the metallic luster color with high brightness is not visible, and the clear yellow color by the ABS plate To be seen.

Example 6 (see FIG. 4) A non-color-changing layer 5 having a thickness of 40 μm and comprising 10 parts of a titanium oxide-based white pigment and 50 parts of an acrylic ester resin was provided on a dinosaur-shaped transparent polystyrene molding as the support 2. ,
Next, 2-anilino-3-methyl-6-dibutylaminofluorane 3 parts, 4,4 '-(2-methyl-propylidene) bisphenol 6 parts, neopentyl stearate 5
A thermochromic composition consisting of 0 parts of a compatible solution was added to
A reversible thermochromic layer 3 having a thickness of about 40 μm, which is composed of a reversible thermochromic microcapsule pigment having an average particle diameter of 8 μm obtained by an interfacial polymerization method of an amine curing agent and an acrylic ester resin, is laminated, and synthetic mica is further formed. Green metallic luster pigment whose surface is coated with titanium oxide [Nippon Koken Industry Co., Ltd.
Product name: GE-100, average particle size 15-100
μm] and an acrylic ester resin having a thickness of about 40
A metallic luster layer 4 having a thickness of μm was provided to obtain a metallic luster color thermochromic laminate 1.

In the laminate 1, the reversible thermochromic layer develops color at 15 ° C. or lower, reflects reflected light having a wavelength of 500 to 540 nm, which is a part of incident light, and absorbs transmitted light having other wavelengths. Therefore, the metallic luster color of metallic green color with high brightness is visible. Further, since the reversible thermochromic layer disappears at 32 ° C. or higher and reflects the transmitted light, all wavelengths of the incident light are reflected, and the metallic luster color with high brightness is not seen, and the non-color-changing layer 5 A clear white color is visible.

Example 7 On a white ABS plate, 1 part 2-anilino-3-methyl-dibutylaminofluorane, 2 parts 1,3-dimethyl-6-diethylaminofluorane, 4,4 '-(2-methyl −
Reversible thermochromic microcapsules with an average particle size of 8 μm obtained by encapsulating a thermochromic composition consisting of a propylidene) bisphenol 6 part and neopentyl stearate 50 parts by a interfacial polymerization method with an epoxy resin / amine curing agent. A gold metallic luster pigment in which a reversible thermochromic layer having a thickness of about 40 μm, which is composed of a pigment, a fluorescent pink pigment, and an acrylic ester resin, is laminated, and then the surface of synthetic mica is coated with titanium oxide [Nippon Koken Kogyo Co., Ltd. product name: Y
D-100, average particle diameter 10 to 60 μm] and an acrylic ester resin having a thickness of about 40 μm were provided on the metallic luster layer to obtain a metallic luster thermochromic laminate.

At 15 ° C. or less, the above-mentioned laminated body visually shows a golden metallic luster color with high brightness. Again 3
At 2 ℃ or higher, the reversible thermochromic layer turns pink,
The bright metallic luster color is not visible, but the clear fluorescent pink color due to the reversible thermochromic layer is visible.

Example 8 1.5 parts of 2,6-bis (2'-ethoxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine and 2,2-bis (4'-) on white synthetic paper. (Hydroxyphenyl) hexafluoropropane 8 parts, a reversible thermochromic composition having an average particle size of 8 μm obtained by encapsulating a thermochromic composition composed of a compatible solution of neopentyl stearate by an interfacial polymerization method of an epoxy resin / amine curing agent. Gold metallic luster pigment in which a reversible thermochromic layer having a thickness of about 40 μm, which is composed of a transparent microcapsule pigment and an acrylic ester resin, is laminated, and then the surface of synthetic mica is coated with titanium oxide [Nippon Koken Kogyo KK Product name: YD-100, average particle size 1
0-60 μm] and an acrylic acid ester having a thickness of about 40 μm was provided to obtain a metal glossy thermochromic laminate.

At 15 ° C. or below, a metallic luster color of metallic yellow, which is bright and bright, is visually recognized in the laminate. Further, at 32 ° C. or higher, metallic luster color with high brightness is not visually recognized, and clear white color due to synthetic paper is visually recognized.

Example 9 On a white PET film, 1.5 parts of 6-diethylamino-benzo (a) -fluorane, 6 parts of 4,4 '-(2-methyl-propylidene) bisphenol, 25 parts of myristyl alcohol, capric acid. A reversible thermochromic microcapsule pigment having an average particle diameter of 8 μm obtained by encapsulating a thermochromic composition composed of 25 parts of cetyl by a interfacial polymerization method of an epoxy resin / amine curing agent and an acrylate resin. , A reversible thermochromic layer having a thickness of about 40 μm, and then coated with titanium oxide on the surface of synthetic mica [purple metal luster pigment [manufactured by Nippon Koken Kogyo KK, trade name: R
BE-100, average particle diameter 10-60 μm] and an acrylic ester having a thickness of about 40 μm were provided to obtain a metal gloss thermochromic laminate.

At 20 ° C. or below, a metallic luster color of a metallic magenta color with a high brightness is visible in the laminate. Further, when the temperature exceeds 20 ° C., a metallic luster color having high brightness is not visually recognized, and a clear white color due to the PET film is visually recognized.

Example 10 3- (4-Diethylamino-2-ethoxyphenyl) -3-ethyl-2-methylindol-3-yl) -4-azaphthalide 1 part, 4,4 on a white ABS plate. '-
An average obtained by encapsulating a thermochromic composition composed of a compatible solution of (2-methyl-propylidene) bisphenol 6 parts, myristyl alcohol 25 parts, and cetyl caprate 25 parts by an interfacial polymerization method of an epoxy resin / amine curing agent. A reversible thermochromic microcapsule pigment having a particle size of 8 μm and a reversible thermochromic layer having a thickness of about 40 μm, which is composed of an acrylic acid ester resin, are laminated, and then a blue metallic luster pigment in which the surface of synthetic mica is coated with titanium oxide [ Nippon Koken Kogyo Co., Ltd., trade name: BE-100, average particle size 15-100 μ
m] and an acrylic ester and having a thickness of about 40 μm, a metallic gloss layer was provided to obtain a metallic gloss thermochromic laminate.

At 20 ° C. or below, a metallic luster color of metallic blue color with high brightness which is glittering is visually perceived in the laminate. Further, at 20 ° C. or higher, the metallic luster color with high brightness is not visually recognized, and a clear white color by the ABS plate is visually recognized.

Example 11 On a yellow synthetic paper, a letter "A" was printed with a fluorescent pink non-color-changing ink to form a non-color-changing image, and then the non-color-changing fluorescent yellow ink was used to form the non-color-changing image. A non-color-changing layer was provided on the non-colored portion. Then, 2-anilino-
3-methyl-6-dibutylaminofluorane 3 parts, 4,
4 '-(2-methyl-propylidene) bisphenol 6
Reversible thermochromic microcapsule pigment having an average particle diameter of 8 μm obtained by encapsulating a thermochromic composition composed of 50 parts by weight and a compatible solution of neopentyl stearate by 50 parts by an interfacial polymerization method of an epoxy resin / amine curing agent and acrylic acid. A reversible thermochromic layer having a thickness of about 40 μm, which is composed of an ester resin, is laminated, and a synthetic metallic mica is coated with titanium oxide on the surface of the metallic metallic luster pigment [manufactured by Nippon Koken Kogyo Co., Ltd., trade name: YD-100, average particle diameter 10 to 60 μm] and an acrylic ester having a thickness of about 40 μm were provided to obtain a metal glossy thermochromic laminate.

In the laminate, the reversible thermochromic layer 3 develops a color at 15 ° C. or lower, which is a part of incident light of 550 to 600 nm.
Since the reflected light of the wavelength is reflected and the transmitted light of the other wavelengths is absorbed, a glittering metallic luster of gold color with high brightness is visible. Further, when the reversible thermochromic layer disappears at 32 ° C or higher, the metallic luster color with high brightness is no longer visible, and the pink "A" character due to the non-color-changing image is clearly visible on the yellow background of the non-color-changing layer. .

Example 12 An image of a camouflage pattern was printed on a white paper with three color non-color-changing fluorescent inks (fluorescent orange, fluorescent yellow, fluorescent green), and then 2-anilino-3- was printed thereon. Methyl-6-dibutylaminofluorane 3 parts, 4,4'-
Reversible having an average particle size of 8 μm obtained by encapsulating a thermochromic composition composed of a compatible solution of 6 parts of (2-methyl-propylidene) bisphenol and 50 parts of neopentyl stearate by an interfacial polymerization method of an epoxy resin / amine curing agent. A blue metallic luster pigment obtained by laminating a reversible thermochromic layer having a thickness of about 40 μm, which comprises a thermochromic microcapsule pigment and an acrylic ester resin, and then coating the surface of synthetic mica with titanium oxide [Nippon Koken Industrial Co., Ltd. ), Product name: BE-10
0, average particle diameter 15 to 100 μm] and an acrylic ester having a thickness of about 40 μm were provided to obtain a metal gloss thermochromic laminate.

In the laminate, the reversible thermochromic layer develops color at 15 ° C. or lower, reflects reflected light having a wavelength of 430 to 500 nm, which is a part of incident light, and absorbs transmitted light having other wavelengths. The metallic luster color of metallic blue color with high brightness and glitter is visible. When the reversible thermochromic layer is decolored at 32 ° C. or higher, the metallic luster color with high brightness disappears, and the images of camouflage patterns of fluorescent orange, fluorescent yellow and fluorescent green are clearly visible.

Example 13 (see FIG. 5) A blue metallic luster pigment obtained by coating the surface of a synthetic mica with titanium oxide on the lower layer of a transparent PET film as a support 2 (manufactured by Nippon Koken Kogyo Co., Ltd., trade name). : BE-100, average particle size 15-100 μm] 30 parts, 50% acrylic resin /
50 parts of xylene solution, 30 parts of xylene, and 30 parts of methyl isobutyl ketone are stirred and mixed to form a metallic luster layer 4 by spray-painting a coating material with a spray gun. 3-methyl-6-
A thermochromic composition comprising a compatible solution of 3 parts of dibutylaminofluorane, 6 parts of 4,4 ′-(2-methyl-propylidene) bisphenol and 50 parts of neopentyl stearate was prepared by an interfacial polymerization method of an epoxy resin / amine curing agent. 10 parts of reversible thermochromic microcapsule pigment having an average particle diameter of 8 μm obtained by encapsulation, 50 parts of 50% acrylic resin / xylene solution, 30 parts of xylene, and 30 parts of methyl isobutyl ketone are stirred and sprayed with a coating material. A reversible thermochromic layer 3 was provided by spray coating with a gun to obtain a metal luster color thermochromic laminate 1.

When the laminate 1 is viewed from the side of the support, the reversible thermochromic layer develops color at 15 ° C. or lower to reflect reflected light having a wavelength of 430 to 500 nm, which is a part of incident light, and has a wavelength of other wavelengths. Since it absorbs the transmitted light, a metallic luster color of metallic blue color with a high brightness is visible.
Further, since the reversible thermochromic layer disappears at 32 ° C or higher and reflects transmitted light, all wavelengths of incident light are reflected,
The metallic luster color with high brightness is not visually recognized, and the laminate has transparency.

Example 14 (see FIG. 6) A gold metallic luster pigment having a surface of synthetic mica coated with titanium oxide as an upper layer of a transparent polyvinyl chloride film as a support 2 (manufactured by Nippon Koken Kogyo Co., Ltd., Product Name: YD-10
0, average particle diameter 10 to 60 μm] 30 parts, 50% acrylic resin / xylene solution 50 parts, xylene 30 parts, and
A mixture of 30 parts of methyl isobutyl ketone is mixed and spray-painted with a spray gun to form a metallic luster layer 4. Further, 3 parts of 2-anilino-3-methyl-6-dibutylaminofluorane is provided as a lower layer of the support. , 4, 4 '-(2
-Methyl-propylidene) bisphenol 6 parts, neopentyl stearate 50 parts of thermochromic composition obtained by encapsulation by an interfacial polymerization method of epoxy resin / amine curing agent, a reversible thermochromic composition having an average particle diameter of 8 μm Microcapsule pigment 10 parts, 50% acrylic resin / xylene solution 50 parts, xylene 30 parts, and methyl isobutyl ketone 30 parts are stirred and mixed, and the reversible thermochromic layer 3 is provided by spray-painting a mixed paint. A metal luster tone thermochromic laminate 1 was obtained.

When the laminate 1 is viewed from the side where the metallic luster layer is provided, the reversible thermochromic layer develops color at 15 ° C. or lower to reflect the reflected light having a wavelength of 550 to 600 nm, which is a part of the incident light. Since the transmitted light of other wavelengths is absorbed, a glittering metallic luster color of gold with high brightness is visible.
Further, since the reversible thermochromic layer disappears at 32 ° C and reflects the transmitted light, all wavelengths of the incident light are reflected, and the metallic luster color with high brightness is not visible and the laminated layer has transparency. Become a body.

Comparative Example 1 The same procedure as in Example 2 was repeated except that a golden metallic luster pigment [Merck & Co., trade name: Iriodin 205, average particle size 10 to 60 μm] was used in place of the golden metallic luster pigment of Example 2. As a result, a metal glossy thermochromic laminate was obtained.

In the laminate, the reversible thermochromic layer was colored at 15 ° C. or lower and a metallic metallic luster color was visually recognized as in Example 2, and the reversible thermochromic layer was decolored to white at 32 ° C. or higher. However, the brightness of the metallic luster color is lower than in Example 2, and the transparency is poor. In addition, the white color visible when the reversible thermochromic layer is decolored is not clear.

Comparative Example 2 The procedure of Example 3 was repeated, except that a blue metallic luster pigment [Merck & Co., trade name: Iriodin 225, average particle size 10 to 60 μm] was used in place of the golden metallic luster pigment of Example 3. As a result, a metal glossy thermochromic laminate was obtained.

In the laminate, the reversible thermochromic layer was colored at 15 ° C. or lower and a blue metallic luster color was visually recognized as in Example 3, and the reversible thermochromic layer was decolored to white at 32 ° C. or higher. However, the brightness of the metallic luster color is lower than in Example 3, and the transparency is poor. In addition, the white color visible when the reversible thermochromic layer is decolored is not clear.

[0052]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to visually recognize a metallic luster color having high brightness such as gold, silver, and various metallic colors with high brightness and a color change due to the reversible thermochromic layer.
Further, since the color change of the reversible thermochromic layer is not impaired by the metallic gloss layer at all, it is possible to visually recognize a clear color change, and to impart prominence, specificity, decorativeness, novelty, etc. Therefore, it is possible to provide a metal glossy thermochromic laminate that can be applied in various ways.

[Brief description of drawings]

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

FIG. 2 is a vertical cross-sectional explanatory view of another example of the metallic luster thermochromic laminate of the present invention.

FIG. 3 is a vertical cross-sectional explanatory view of another example of the metallic luster thermochromic laminate of the present invention.

FIG. 4 is a vertical cross-sectional explanatory view of another example of the metallic luster color thermochromic laminate of the present invention.

FIG. 5 is a vertical cross-sectional explanatory view of another example of the metallic luster thermochromic laminate of the present invention.

FIG. 6 is a vertical cross-sectional explanatory view of another example of the metallic luster color thermochromic laminate of the present invention.

[Explanation of symbols]

1 Metallic luster color thermochromic laminate 2 support 3 metallic luster layer 4 Reversible thermochromic layer 5 Non-color-changing layer 6 Top coat layer

Continued front page    F-term (reference) 4F100 AA17A AA21A AC05A AK01C                       AK25A AK25C AK74B AR00B                       BA02 BA03 BA07 BA10B                       BA10C CA07C CA13A CA13B                       DE01A DE04B GB84 GB84B                       JN01C JN24A JN28B

Claims (5)

[Claims] 1. A metallic luster layer containing a metallic luster pigment in which the surface of synthetic mica is coated with a metal oxide, and a color reaction between an electron-donating color-forming organic compound and an electron-accepting compound reversibly occurs. A metal glossy thermochromic laminate comprising a reversible thermochromic layer comprising a thermochromic composition comprising the organic compound medium. 2. The synthetic mica is represented by the following general formula (1):
The metallic luster thermochromic laminate according to claim 1. X_{1/3 ~ 1} Y_2-3 Z_Four O_TenF₂     (1) (In the formula, X is Na⁺ , Li⁺ , K⁺ , Ca²⁺, Sr²⁺,
Ba²⁺, And Y is Mg ²⁺, Li⁺ , Ni²⁺, Co²⁺,
Zn²⁺, Mn²⁺, Al³⁺, Cr³⁺, Ti³⁺A kind of
2 or more types, Z is Al³⁺, Si⁴⁺, Ge⁴⁺, B³⁺of
Indicates one or more types) 3. The metallic luster thermochromic laminate according to claim 1, wherein the surface of the synthetic mica is coated with a metal oxide containing titanium oxide as a main component. 4. The metallic luster pigment has an average thickness of 0.1.
The metallic luster thermochromic laminate according to any one of claims 1 to 3, which has a mean particle size of 2 to 1000 µm. 5. The thermochromic metallic luster color change laminate according to claim 1, wherein a transparent resin layer is provided on the metallic luster layer.