JP3200692B2 - Molding composition that undergoes reversible thermal discoloration from gold and molded article using this composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding composition capable of thermally discoloring from a gold metallic luster color and a molded article molded using this composition.

[0002]

2. Description of the Related Art Conventionally, thermochromic materials exhibiting a reversible color change of colored ← → colorless and colored [1] ← → colored [2] due to temperature change are disclosed in Japanese Patent Publication No. 51-44706 and Japanese Patent Publication No. Sho 5-5.
JP-A-1-44707, JP-B-51-44708, JP-B-52-7776, and JP-B-51-465.
No. 48, JP-A-62-140881, and the like, and a thermochromic material colored using the thermochromic material is practically used as a temperature indicating element, a toy element, a magic element, or the like.

However, a thermochromic molding composition exhibiting a reversible change from a golden metallic luster color to colorless or a reversible color change to another different color due to a temperature change, and the above-mentioned color change are clearly exhibited. Thermochromic moldings are not yet known. In addition, attempts to diversify color changes are based on actual fairness 3-1.
No. 4,400,400. The thermochromic material described in this publication is intended to cover the thermosensitive liquid crystal with a pearl luster layer so as to develop a pearlescent color change. However, liquid crystals are inherently colorless and reflect a specific wavelength that is the selective scattering of visible light, so a blackish opaque layer is required on the back surface, and thus the color change is black-red-yellow-green-blue. -Because it looks purple-black, even if a pearlescent layer is provided thereon, the color change is not sharp. For example, when a gold pearl luster pigment is used, the color change becomes gold-gold-red-gold-yellow-gold-green-gold-blue-gold-violet-purple-gold. Does not show a change to a non-tingling color. In addition, a color change from pearl luster color to colorless color cannot be developed, and the base cannot be concealed or revealed. Since gold is the most luxurious color and the change from gold attracts the attention of the viewer most, there is a great demand for a molded body that changes color from gold to other colors.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have conducted research to effectively exhibit the discoloration effect of a thermochromic material and to achieve a vivid and colorful thermal discoloration from a golden metallic luster to complete the present invention. It was. Thermochromic material used in the present invention, unlike liquid crystal, because there is a clear color change in the thermochromic material itself, there is no need to provide a dark opaque layer in the lower layer,
In addition, there is a feature that the color-colorless change is possible. Therefore,
By using the above-mentioned composition comprising a colored-colorless thermochromic material and a gold metallic luster pigment, a color change from a golden metallic luster color to a colorless color can be visually recognized. Therefore, for example, by mixing a color-colorless thermochromic material and a gold metallic luster pigment, the light transmitted through the metallic luster pigment layer is reflected or absorbed by the thermochromic material therebelow, causing the thermochromic color to change from the golden metallic luster color. The color change of the material to color can be visualized. Also, a clear color change from a golden metallic glossy color to a colored non-thermochromic material by mixing a non-color-changing colorant can be made visible to a viewer. Such a color change cannot be exhibited in the liquid crystal system. Furthermore, by using a thermochromic material having a very large hysteresis width as a thermochromic material, a so-called color material containing a so-called color memory thermosensitive dye, the state changed even after removing the heat or cold required for thermochromic discoloration. It can be maintained and also has the effect that the state can be visually recognized in a normal temperature range. In this way, the color change due to the heat of the golden metallic gloss is clearly expressed,
INDUSTRIAL APPLICABILITY The present invention is widely used in the field of decorative materials, interiors, toys, ornaments, stationery, and information.

[0005]

According to the present invention, there is provided a composition comprising: "A. Natural optical mica having a surface coated with 41 to 44% by weight of titanium oxide having an optical thickness of 180 to 240.
B. a gold metallic luster pigment having a particle size of 5 to 60 μm; A thermochromic material comprising an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two, and is colorless in a decolorized state when the lightness value of the color density in the colored state is 6 or less B. a thermochromic material having a lightness value of 8 or more; A molding composition comprising a synthetic resin for molding, which is reversibly heat-discolored from gold to colorless. 2. A. The component, a metallic luster pigment, is provided by coating the surface of natural mica with 30 to 48% by weight of titanium oxide,
The optical thickness of the coating layer coated with 10% by weight of iron oxide is 1
4. The molding composition which is a gold metallic glossy pigment having a particle size of 40 to 240 nm and a particle size of 5 to 60 [mu] m, which is reversibly heat-discolored from gold to colorless according to item 1. 3. Coating wherein the surface of natural mica particles is coated with 30 to 48% by weight of titanium oxide, and the upper layer is coated with 0.5 to 10% by weight of a non-thermochromic colored dye / pigment. Optical thickness of layer 140-240 nm, particle size 5-5
2. A molding composition which reversibly heat-discolors from a gold color to a color of a non-thermochromic dyestuff according to item 1, which is a dichroic gold metallic luster pigment of 60 μm. 4. D. A non-thermochromic dye or pigment as a component, wherein the lightness value (V ₁ ) of the color density of the composition at the time of color development is 6 or less and the lightness (V ₂ ) of the composition at the time of decoloration is 4 or more (V ₂ )-
4. A molding for reversibly heat-discoloring from gold to a non-thermochromic colorant described in any one of items 1 to 3, wherein a non-thermochromic colorant satisfying (V ₁ )> 1 is blended. Composition. 5. 5. The thermochromic material according to any one of items 1 to 4, wherein the thermochromic material is a thermochromic material obtained by encapsulating a microcapsule in an organic medium that reversibly causes a color reaction between the electron-donating compound and the electron-accepting compound. A molding composition that undergoes a reversible thermal discoloration from the applied gold color. 6. A molded article formed by injection molding, extrusion molding, blow molding, cast molding, or the like, using the composition described in any one of Items 1 to 5. About.

The golden metallic luster pigment used in the present invention is:
Specifically, the pigment is a gold-colored pigment in which the surface of natural mica particles is coated with titanium oxide. Also, a golden metallic luster pigment in which the surface of natural mica particles is coated with titanium oxide and the upper layer is coated with iron oxide is used. In addition, a dichroic metallic luster pigment in which a titanium oxide coating is coated with a non-thermochromic colored dye or pigment is also used. More specifically, the golden metallic luster pigment is a natural mica particle whose surface is coated with 41 to 44% by weight of titanium oxide. ６０60 μm, or the surface of natural mica particles is coated with 30 to 48% by weight of titanium oxide, and the upper layer is coated with 4 to 10% by weight of iron oxide.
The surface of a gold metallic luster pigment having a particle size of 5 to 60 μm or natural mica particles was coated with 30 to 48% by weight of titanium oxide, and the upper layer was coated with 0.5 to 10% by weight of a non-thermochromic colored dye. Optical thickness of coating layer 140-240 nm, particle size 5
Dichroic gold metallic luster pigments of ６０60 μm can also be used.

[0007] The optical thickness of the titanium coating layer of the golden pigment used in the present invention is a refractive index x a geometric thickness,
This thickness is associated with reflecting certain wavelengths. In other words, the specific optical thickness reflects light of a specific wavelength, and the coating layer formed on the surface of natural mica has a titanium oxide layer having an optical thickness of 180 to 240 nm.
It reflects 50-600 nm gold light. As the thermochromic material, a thermochromic material containing three components of an organic compound medium that reversibly causes a color reaction between the electron-donating color compound and the electron-accepting compound is used.

Further, when a non-color-changing dye / colorant is added in addition to the thermochromic material, a reversible color change from a golden metallic luster color to a colored non-thermochromic colorant is observed. Since the gold metallic luster pigment layer is transparent, the color of the non-discolorable colorant can be visually recognized simultaneously with the thermal discoloration of the thermochromic material. Most preferably, the thermochromic material is used by being encapsulated in microcapsules. This is because the thermochromic materials are maintained at the same composition under various use conditions and can exhibit the same effects. The thermochromic molded article of the present invention is formed of a composition comprising the above-described gold metallic luster pigment, thermochromic material, and transparent synthetic resin for molding.

The lightness values of the thermochromic material at the time of color development and decoloration are as follows. In an achromatic array, complete black is assumed to be 0, complete white is assumed to be 10, and the difference in the sense of brightness is evenly spaced between them. The lightness value of the Munsell color chart system divided as described above is shown, and the lightness of the chromatic color indicates the lightness value of the achromatic color in which the sensation of the brightness of the chromatic color is equal to this. That is, the smaller the brightness value, the closer to black, and the larger the brightness value, the closer to white, it can be used as an index of how much visible light is absorbed and how much it is reflected. It shows how the visible light transmitted through the gloss pigment is reflected and absorbed by the thermochromic material thereunder.

[0010]

The thermochromic molded article of the present invention is formed of a composition obtained by mixing a thermochromic material, a golden metallic luster pigment and a synthetic resin for molding. This is to make the viewer see through. Here, the property of the golden metallic luster pigment, that is, selective interference of the wavelength of visible light due to the fact that the coating of titanium oxide on the surface of natural mica particles is 41 to 44% by weight and the optical thickness is 180 to 240 nm By the synergistic effect of the iris effect, the transmission effect and the visible light reflection and absorption effect of the thermochromic material caused by the action, the multicolored change of the gold metallic gloss can be visually recognized. Specifically, mica has the effect of changing the wavelength of the reflected light at the time of interference by adjusting the coating amount of the coated titanium oxide and the thickness of the coating layer to the above ranges. For example, a titanium oxide-coated mica prepared to have an optical thickness of 180 to 240 nm of the coating layer so as to selectively reflect yellow light and transmit violet light has a thermochromic material underneath which is black. In the case, the transmitted violet light is absorbed by the thermochromic material black,
Since only yellow light of 50 to 600 nm is reflected, it takes on a gold color. On the other hand, when the thermochromic material underneath is white, the transmitted violet light is also reflected by the lower white, so it reflects not only yellow light but also violet light and reflects all wavelengths of visible light. Therefore, it is seen as white. Therefore, by reversibly changing the thermochromic material under the gold metallic luster pigment from black to white, the viewer can visually recognize the reversible color change from gold to white.

What is important here is that titanium oxide must satisfy the requirement of an optical thickness of 180 to 240 nm. If the optical thickness is outside the above range, the reflected light will not be light having a wavelength of 550 to 600 nm and will not be golden.

Further, in the case of a golden metallic luster pigment in which the surface of natural mica particles is coated with titanium oxide and the upper layer is coated with iron oxide, in addition to the wavelength-selective reflection and transmission functions, the iron oxide itself has By adding the characteristic of absorbing violet light and reflecting yellow light, a reversible color change from brighter gold to pale yellow is visualized. However, since the iron oxide itself is colored pale yellow, the coating layer looks pale yellow even when the base is white. If the coating ratio of titanium oxide is less than 30% by weight, it is difficult to produce a sufficient gold color. To make the color gold, it is necessary to coat it with iron oxide in excess of 10% by weight. Even if the color changes, the color is always golden, and a clear color change cannot be obtained. On the other hand, if the coverage of titanium oxide exceeds 48% by weight, the color of the light selectively reflected is not yellow, so that even if it is subsequently coated with iron oxide, it does not become a beautiful gold color. When the iron oxide coverage is less than 4% by weight, the above-mentioned effect of iron oxide is not sufficiently exhibited, and
If it exceeds 0% by weight, the color becomes gold, but even if the thermochromic material changes color, the metallic gloss layer is always golden and a clear color change cannot be obtained. Must.

When iron oxide is used in combination, forming an iron oxide film on a titanium oxide film is most effective for producing a golden metallic luster color. When the titanium oxide is coated on the iron oxide, the reflection effect of the titanium oxide is large, so that the effect of the iron oxide is small. When titanium oxide and iron oxide are mixed, the reflection efficiency of the iron oxide is deteriorated because the titanium oxide may block the reflected light of the iron oxide as compared with the iron oxide being in the upper layer. When an iron oxide film is provided on the titanium oxide film, the iron oxide layer has a property of absorbing purple light and reflecting other light, and since this light looks yellow, a gold color having a metallic luster due to the titanium oxide layer. Has the effect of giving depth. This is because the reflected light from the iron oxide layer is not blocked or reflected by other layers due to the presence of the iron oxide film in the upper layer.

[0014] In addition, in the case of a gold metallic luster pigment in which the surface of natural mica particles used in the present invention is coated with titanium oxide and the upper layer is coated with a non-thermochromic colored dye, the non-thermochromic pigment By the colors of the colored dyes and pigments, a wide variety of color changes can be expressed.For example, in combination with black ← → white thermochromic material, gold color such as gold ← → pink, gold ← → blue, etc. ← → Colored reversible color change can be visualized. When the coverage of titanium oxide is less than 30% by weight, it is difficult to obtain a sufficient gold color, and therefore, when coated with a non-thermochromic colored dye, the color does not look golden. On the other hand, if the coverage of titanium oxide exceeds 48% by weight, the color of the light selectively reflected is not yellow, so that it does not look golden. When the coverage of the non-thermochromic colored dye is less than 0.5% by weight, a sufficient color density of the color cannot be obtained. If it exceeds 10% by weight, the color density of the color is too high and gold cannot be expressed. When each pigment is within the above-mentioned range, it is possible to selectively transmit light having a golden wavelength and reflect light having a wavelength having a complementary color relationship. If the wavelength is outside the above range, the wavelength selectivity is lost, or the color is not golden even though the wavelength selectivity is present.

As described above, the thermochromic material comprises three components of an organic compound medium which reversibly causes a color reaction between the electron donating color compound and the electron accepting compound. Specifically, it is described, for example, in the aforementioned Japanese Patent Publication No. 51-35414. (1) The essential components include (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, and (c) a linear aliphatic monohydric alcohol having no polar substituent. Reversible thermochromic material. Or (2) (a) a compound having an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, (c) an aliphatic monohydric alcohol having no polar substituent, and having a polar substituent. A reversible thermochromic material comprising, as essential components, three components of a compound selected from an ester having no polar substituent obtained from an aliphatic monocarboxylic acid which is not obtained. Or (3) (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, (c) a higher aliphatic monohydric alcohol having no polar substituent, and a polar substituent. The essential component is a compound selected from aliphatic monocarboxylic acids having no polar group and a non-polar substituent-containing ester obtained from a linear aliphatic monohydric alcohol having no polar substituent. And a reversible thermochromic material containing this in a microcapsule. Or (4) (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, (c) a higher aliphatic monohydric alcohol having no polar substituent, and a polar substituent. The essential component is a compound selected from a polar non-substituted ester obtained from a higher aliphatic monocarboxylic acid having no polar group and a linear aliphatic monohydric alcohol having no polar substituent. And a thermochromic material obtained by dissolving or dispersing the same in a vehicle. And so on.

In addition, a thermochromic material containing a color-memorizing thermochromic dye which exhibits a large hysteresis characteristic and is discolored as described in JP-A-60-264285, that is, a change in coloring density due to a temperature change is plotted. The type of discoloration in which the shape of the curved line changes color following a significantly different route depending on whether the temperature rises from a temperature lower than the discoloration temperature range or vice versa. A thermochromic material having a characteristic of being able to memorize and retain a state of a material changed at a temperature equal to or lower than the low-temperature discoloration point or equal to or higher than the high-temperature measurement discoloration point in a normal temperature range between the low-temperature side discoloration points is used.

Next, the thermochromic molding composition of the present invention will be specifically described. The thermochromic molding composition of the present invention includes the following compositions (A) and (B). (A) A composition in which a thermochromic material, a golden metallic luster pigment, and a synthetic resin for molding are mixed. (B) A composition in which a thermochromic material, a non-chromogenic dye / pigment, a golden metallic luster pigment, and a synthetic resin for molding are mixed. The composition for thermochromic molding described above can be used for molding in the form of powder, pellets, dispersions, and the like.

In the molding composition (A) described above,
The gold metallic luster pigment is a gold metallic luster pigment having a particle size of about 5 to 60 μm, an electron-donating color-forming organic compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two. A color-changed material composed of a thermochromic material composed of a three-component homogeneous compatible solution (hereinafter referred to as a thermochromic material) and a synthetic resin for molding. A colorless lightness value of 8 or more, wherein a golden metallic gloss thermochromic molded body exhibiting a reversible color change from a golden metallic glossy colorless to a colorless to a golden metallic glossy color is formed. You. When the lightness value of the color density in the color-developed state is 6 or less, there is a capability of sufficiently absorbing the light transmitted through the gold metallic luster pigment. appear. However, when the lightness value of the colored state exceeds 6, the light transmitted through the gold metallic luster pigment cannot be sufficiently absorbed, and a part of the light is reflected again, so that it becomes impossible to see a clear golden metallic luster color. On the other hand, if the colorless lightness value of the decolored state is 8 or more, it has the ability to sufficiently reflect the light transmitted through the gold metallic luster pigment, so that the light reflected by the gold metallic luster pigment is reflected by the thermochromic material. The mixed light returns to white light and appears colorless. However, when the lightness value in the decolored state is less than 8, light transmitted through the gold metallic luster pigment cannot be sufficiently reflected,
It does not become colorless because it absorbs partly, and the gold metallic color in the colored state remains.

In the composition (B), the golden metallic luster pigment is a mixture of the golden metallic luster pigment of about 5 to 60 μm, the thermochromic material and a dye or pigment which is a non-chromogenic colorant. The lightness value (V ₁ ) of the color density in the color development state is 6
Hereinafter, a composition in which the lightness value (V ₂ ) of the color in the decolored state is 4 or more, and which satisfies the relationship of (V ₂ ) − (V ₁ )> 1, and is a composition from a gold metallic glossy color to a colored Thus, a gold metallic gloss thermochromic molded body exhibiting a reversible color change from colored to golden metallic gloss is formed. The reason why the lightness value (V ₁ ) of the color density of the color mixture in the color development state is 6 or less is the same as described above.
On the other hand, the reason that the color value (V ₂ ) of the mixed color system in the decolored state needs to be 4 or more and the above-mentioned V ₂ −V ₁ > 1 needs to be satisfied is that in this system, a non-color-changing colorant, Since the thermochromic dyes and pigments are mixed and become colored, the lightness value becomes small and fluctuates depending on the colors of the dyes and pigments. For example, the brightness value is relatively large for yellow, orange, and the like, and is small for red, purple, and the like. However, in order to obtain a satisfactory color change, the lightness value in the decolored state needs to be at least greater than 1 in the color development state. Not clear. If there is a lightness value of 4 or more under such conditions, for example, a reversible color change from gold to color and from color to gold can be exhibited. However, when it is less than 4, the color density of the color mixing layer becomes too high, and the transmitted light is absorbed, so that the gold color can be seen even in the decolored state.

The lightness value referred to in the present invention is an index as to whether or not the material has such a characteristic that the thermochromic material looks golden below the color change temperature of the thermochromic material and disappears above the color change temperature. The lightness value of the present invention is a value obtained by measuring a sample adjusted as described below using a TC-3600 color difference meter manufactured by Tokyo Denshoku Co., Ltd. 1. Measurement of lightness value of thermochromic material (including a system mixed with non-color-changing dye / pigment) (1) Measurement of lightness value of thermochromic material (colored ← → colorless) Thermochromic material 10 parts, 50% acrylic acid Ester resin /
45 parts of a xylene solution, 20 parts of xylene and 20 parts of methyl isobutyl ketone were stirred and mixed, spray-coated on a white vinyl chloride sheet having a lightness value of 9.1 with a spray gun, and dried to form a thermochromic layer having a thickness of 40 μm. Prepare. The lightness value of the color-developed state and the decolored state of the obtained thermochromic layer is measured. (2) Measurement of lightness value of thermochromic material (color I ← → color II) 10 parts of thermochromic material, desired amount of non-thermochromic dye, 50 parts
% Acrylate resin / 45 parts of xylene solution, 20 parts of xylene and 20 parts of methyl isobutyl ketone were stirred,
The mixture was mixed, spray-coated on a white vinyl chloride sheet having a lightness value of 9.1 with a spray gun, and dried to a thickness of 40 μm.
Is prepared. The lightness value of the color-developed state and the decolored state of the obtained thermochromic layer is measured.

Next, examples of the molding synthetic resin used in the molding composition in the form of pellets and powders will be described. Ionomer resin, isobutylene-maleic anhydride resin copolymer resin, acrylonitrile-acrylic styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-chlorinated polyethylene-styrene copolymer resin, ethylene- Vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinylidene chloride resin, vinyl chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer resin, chlorine Polyethylene resin, chlorinated polypropylene resin, polyamide resin, high density polyethylene resin, medium and low density polyethylene resin, linear low density polyethylene resin, polyethylene terephthalate resin, polybutylene terev Rate resins, polycarbonate resins, polystyrene resins, high impact polystyrene resins, polypropylene resins, polymethyl styrene resins, polyacrylate resins, polymethyl methacrylate resins, epoxy acrylate resins.

Next, examples of the synthetic resin used in the liquid molding composition used for the casting molding will be described. Alkyl phenol resin, rosin modified phenol resin, rosin modified alkyd resin, phenol resin modified alkyd resin, epoxy resin modified alkyd resin, styrene modified alkyd resin, acryl modified alkyd resin, amino alkyd resin, vinyl chloride-vinyl acetate resin, styrene-butadiene resin , Epoxy resin, acrylate ester resin, unsaturated polyester resin, polyurethane resin, vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylate ester emulsion resin, water-soluble alkyd resin, water-soluble melamine resin, water-soluble urea Resins, water-soluble phenolic resins, water-soluble epoxy resins, water-soluble polybutadiene resins, resins such as cellulose derivatives, etc., which are used by dissolving or dispersing in a vehicle such as water or an organic solvent. Door can be.

The molding composition of the present invention is used in the form of pellets for injection molding, extrusion molding, blow molding, compression molding, etc.
The powder is used for the fluidized immersion method. Use in liquid form for the casting method. The molded article of the present invention is, in addition to a three-dimensional three-dimensional molded article,
Sheets and films are also included. In addition, an ultraviolet absorber, an infrared absorber, an antioxidant, a singlet oxygen quencher, an antioxidant, an antistatic agent, a polarity imparting agent, a thixotropic agent, an antifoaming agent,
Additives such as stabilizers, plasticizers, flame retardants, extenders, lubricants, and foaming agents can be added to the composition as needed.

[0024]

Next, the present invention will be described specifically with reference to examples. Parts are parts by weight. Example 1 The surface of natural mica was coated with 43% by weight of titanium oxide.
20 parts of a golden metallic luster pigment having an optical thickness of 210 nm and a particle size of 10 to 60 μm, a microcapsule having an average particle diameter of 15 μm having a lightness value of 2.3 when coloring and a lightness value of 8.8 when decoloring. After uniformly mixing 20 parts of the thermochromic material described above, 2 parts of a benzotriazole-based ultraviolet absorber, and 1000 parts of high-density polyethylene having a Vicat softening point of 119 ° C., the cylinder temperature is 165 ° C. and the gate temperature is 160 using an extruder.
The pellets were molded under the conditions of ° C. to obtain pellets of 2 to 3 mm by a conventional method. The thermochromic pellet was blown with a blow molding machine at a cylinder temperature of 175 ° C and a thickness of about 2 mm and a diameter of 5c.
m were blow molded. In this ball, 1
When the thermochromic material develops color at 5 ° C. or less, reflects light 3 having a wavelength of 550 to 600 nm, which is a part of incident light, and absorbs light 4 having other wavelengths, it becomes a gold metallic glossy color,
When the thermochromic material loses its color at 30 ° C. or more and reflects the transmitted light 4, all the incident light is reflected, and the golden metallic gloss disappears and becomes colorless. The thermochromic material is 2-anilino-3-methyl-6-dibutylaminofluoran 3
, A thermochromic composition comprising a compatible solution of 6 parts of bisphenol A and 50 parts of neopentyl stearate was obtained by microencapsulation by an interfacial polymerization method of an epoxy resin / amine-based curing agent.

Example 2 The surface of natural mica was coated with 43% by weight of titanium oxide.
20 parts of a golden metallic luster pigment having an optical thickness of 210 nm and a particle size of 10 to 60 μm, and a lightness value at the time of color development of a mixed system of 2.
3. Average particle size 15 μm with a lightness value of 5.3 when decolorized
20 parts of thermochromic material in the form of microcapsules, 1.5 parts of a fluorescent pink pigment, and a benzotriazole ultraviolet absorber 2
Part, polypropylene 100O with Vicat softening point 100 ° C
After uniformly mixing the portions, the mixture was molded using an extruder under the conditions of a cylinder temperature of 165 ° C and a gate temperature of 160 ° C, and pellets of 2 to 3 mm were obtained by a conventional method. The thermochromic pellet was molded by an injection molding machine at a cylinder temperature of 170 ° C. to form a miniature car body having a thickness of about 3 mm, a length of 10 cm and a width of 3.7 cm. In this body, the thermochromic material develops color at 15 ° C. or less, and reflects light 3 having a wavelength of 550 to 600 nm, which is a part of the incident light,
When the light 4 of other wavelengths is absorbed, the color becomes a golden metallic luster color. When the thermochromic material is decolored at 30 ° C. or higher, the golden metallic luster color disappears and the color becomes a fluorescent pink pigment. The thermochromic material is a thermochromic composition comprising a compatibilizer of 3-anilino-3-methyl-6-dibutylaminofluoran (3 parts), bisphenol A (6 parts), and neopentyl stearate (50 parts). This is obtained by microencapsulation of a system curing agent by an interfacial polymerization method.

Example 3 The surface of natural mica was coated with 43% by weight of titanium oxide.
20 parts of a golden metallic luster pigment having an optical thickness of 210 nm and a particle size of 10 to 60 μm, and a lightness value at the time of color development of a mixed system of 2.
2. Average particle size of 15 μm with a lightness value of 5.5 when decolorized
20 parts of thermochromic material in the form of microcapsules, 0.2 parts of blue pigment and 0.6 parts of white pigment, 2 parts of benzotriazole-based ultraviolet absorber, and 1000 parts of linear low density polyethylene having a Vicat softening point of 105 ° C. After mixing, the cylinder temperature was 170 ° C. and the gate temperature was 17 using an extruder.
Molding was performed under the condition of 0 ° C., and pellets of 2 to 3 mm were obtained by an ordinary method. The thermochromic pellet was formed into a sheet with an extruder at a cylinder temperature of 180 ° C. to obtain a thermochromic sheet having a thickness of about 1 mm. In this sheet, when the thermochromic material develops color at 15 ° C. or less, reflects light 3 having a wavelength of 550 to 600 nm, which is a part of incident light, and absorbs light 4 having other wavelengths, a gold metal When the thermochromic material loses its color at 30 ° C. or higher, the golden metallic gloss disappears, and it becomes a pastel blue color which is a mixed color of a blue pigment and a white pigment. In addition, the thermochromic material is 2-
Microencapsulation of a thermochromic composition comprising a compatibilizer of 3 parts of anilino-3-methyl-6-dibutylaminofluoran, 6 parts of bisphenol A and 50 parts of neopentyl stearate by an interfacial polymerization method of an epoxy resin / amine curing agent It was obtained in

Example 4 The surface of natural mica was coated with 36% by weight of titanium oxide and further coated with 8% by weight of iron oxide, having an optical thickness of 200.
Gold metallic luster pigment 10 having a particle size of 10 to 60 μm in nm
0 parts, 100 parts of a thermochromic material in the form of microcapsules having an average particle diameter of 15 μm and a lightness value of 2.2 when the color value of the mixed system is 2.2 and a lightness value of 8.9 when the color is erased, and 10.0 parts of a fluorescent yellow pigment
Parts, 5 parts of a benzotriazole-based ultraviolet absorber, 700 parts of an epoxy resin, and 250 parts of an amine-based curing agent are uniformly mixed, and then poured into a star-shaped casting mold, cured at 70 ° C. for 1 hour, and star-shaped. Was obtained. In the star, the thermochromic material develops a color below 15 ° C., and 550 which is a part of the incident light
When light 3 having a wavelength of ~ 600 nm is reflected and light 4 having other wavelengths is absorbed, the color becomes a golden metallic gloss, and when the thermochromic material decolorizes at 30 ° C or more, the golden metallic gloss disappears,
The color of the fluorescent yellow pigment. The thermochromic material is a thermochromic composition comprising a compatibilizer of 3-anilino-3-methyl-6-dibutylaminofluoran (3 parts), bisphenol A (6 parts), and neopentyl stearate (50 parts). This is obtained by microencapsulation of a system curing agent by an interfacial polymerization method.

Example 5 The surface of the natural mica of Example 1 was coated with 43% by weight of titanium oxide, having an optical thickness of 210 nm and a particle size of 10-6.
The surface of natural mica was replaced with 4 μm
Coated with 2% by weight of titanium oxide and then with 2.5% by weight of navy blue, optical thickness 210 nm, particle size 1
Example 1 was the same as Example 1 except that a dichroic gold-colored metallic luster pigment of 0 to 50 μm in which the color changed from gold to blue was used. In this ball, when the thermochromic material develops color at 15 ° C. or less, reflects light 3 having a wavelength of 550 to 600 nm, which is a part of incident light, and absorbs light 4 having other wavelengths, a gold metal When the thermochromic material loses its color at 30 ° C. or higher, the golden metallic gloss disappears and becomes blue.

Comparative Example 1 In place of the thermochromic material of Example 1, the lightness value at the time of coloring was 4.0.
5. 2-anilino-3- having a lightness value at the time of decoloration of 6.0.
A non-colorless thermochromic composition comprising a compatible solution of 6 parts of methyl-6-dibutylaminofluorane, 10 parts of bisphenol A and 25 parts of neopentyl stearate is microencapsulated by an interfacial polymerization method of an epoxy resin / amine curing agent. Example 1 is the same as Example 1 except that the obtained thermochromic material in the form of microcapsules having an average particle diameter of 15 μm is used. At 15 ° C. or lower, the thermochromic material develops color and reflects light 3 having a wavelength of 550 to 600 nm, which is a part of incident light,
When the light 4 of other wavelengths is absorbed, the color becomes a golden metallic luster color. In this comparative example, even if the thermochromic material decolorizes at 30 ° C. or higher, the transmitted light 4 can still be sufficiently absorbed, so that the gold color is slightly reduced, but still appears as a gold metallic gloss color. .

Comparative Example 2 The surface of natural mica was coated with 43% by weight of titanium oxide.
20 parts of a golden metallic luster pigment having an optical thickness of 210 nm and a particle size of 10 to 60 μm, and a lightness value at the time of color development of a mixed system of 2.
4. The thermochromic material 20 in the form of microcapsules having an average particle diameter of 15 μm and having a lightness value of 3.2 at the time of decoloring and not colorless and having an average particle size of 15 μm
Parts and green pigment 15 parts, benzotriazole type ultraviolet absorber 2 parts, Vicat softening point 100 ° C. polypropylene 10
After uniformly mixing 00 parts, the mixture was molded using an extruder under the conditions of a cylinder temperature of 165 ° C. and a gate temperature of 160 ° C., and pellets of 2 to 3 mm were obtained by an ordinary method. The thermochromic pellet was subjected to injection molding at a cylinder temperature of 170.
Under conditions of ° C, thickness about 3mm, length 10cm, width 3.7c
m miniature car body was molded. In this body, the thermochromic material develops a color at 15 ° C. or lower, reflects light 3 having a wavelength of 550 to 600 nm, which is a part of the incident light, and absorbs light 4 having other wavelengths. It becomes a glossy color. In this comparative example, even if the thermochromic material is decolored at 30 ° C. or higher, the transmitted light 4 can still be sufficiently absorbed, so that the material is merely greenish and still looks like a gold metallic glossy color. The thermochromic material is 6 parts of 2-anilino-3-methyl-6-dibutylaminofluoran, 10 parts of bisphenol A, and neopentyl stearate 25.
The thermochromic composition which does not become colorless and which is composed of a compatible part is obtained by microencapsulation by an interfacial polymerization method of an epoxy resin / amine-based curing agent.

The thermochromic molding composition of the present invention is reversibly changed from a golden metallic luster color to a colorless color or a non-thermochromic colorant used in combination with a temperature change. The molded article undergoes the same discoloration. If a thermochromic material with a small hysteresis width is used, the color changes in response to temperature changes with high sensitivity, and if a thermochromic material with a large hysteresis width is used, the state changed at room temperature even if the heat that caused the color change is removed. Can be kept.

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Claims (6)

(57) [Claims] 1. A. First Embodiment 41-44% by weight of natural mica surface
The optical thickness of the coating layer coated with titanium oxide is 180 to
B. a golden metallic luster pigment having a particle size of 240 nm and a particle size of 5 to 60 μm; A thermochromic material comprising an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two, and is colorless in a decolorized state when the lightness value of the color density in the colored state is 6 or less B. a thermochromic material having a lightness value of 8 or more; A molding composition comprising a synthetic resin for molding, which is reversibly heat-discolored from gold to colorless. 2. A. The optical thickness of the coating layer in which the surface of natural mica is coated with 30 to 48% by weight of titanium oxide and further coated with 4 to 10% by weight of iron oxide is 140 to 240 nm. The molding composition according to claim 1, which is a golden metallic luster pigment having a particle size of 5 to 60 µm, which is reversibly heat-colored from gold to colorless. 3. A natural metallic mica pigment of the component A coats the surface of natural mica particles with 30 to 48% by weight of titanium oxide,
The upper layer is coated with 0.5 to 10% by weight of a non-thermochromic colored dye, the optical thickness of the coating layer is 140 to 240 nm,
2. The molding composition according to claim 1, which is a dichroic gold metallic luster pigment having a particle size of 5 to 60 [mu] m. D. A non-thermochromic dye or pigment as a component, wherein the lightness value (V ₁ ) of the color density of the composition at the time of color development is 6 or less and the lightness (V ₂ ) of the composition at the time of decoloration is 4 or more (V ₂ ) A non-thermochromic colorant that satisfies ( ₁ )-(V1)> 1 is reversibly thermochromically changed from gold to a non-thermochromic dye according to any one of claims 1 to 3. Molding composition. 5. The thermochromic material is a thermochromic material in which microparticles are wrapped in an organic medium which reversibly causes a color reaction between an electron-donating compound and an electron-accepting compound and both.
5. A molding composition which reversibly heat-discolors from gold as described in any one of the above items 4 to 4. 6. A molded article formed by injection molding, extrusion molding, blow molding, cast molding, or the like, using the composition according to any one of claims 1 to 5.