JPH06107851A - Thermochromic molding composition which can reversibly change its color from metallic glossy color and product prepared by molding same - Google Patents

Abstract

PURPOSE:To provide a thermochromic molding composition which can reversibly change its color from a metallic glossy color to colorlessness or other colors and a product prepared by molding the same. CONSTITUTION:A thermochromic molding composition which can reversibly change its color from a metallic glossy color to colorlessness comprises a metallic glossy pigment prepared by coating the surface of natural mica with 45-58wt.% titanium oxide and having an optical thickness of the coating layer of 245-415nm and a particle size of 5-60mum, a thermochromic material comprising an electron-donating compound, an electron-accepting compound and an organic compound medium which causes a reversible color reaction between the both and having a lightness value the color density of 6 below in a colored state and a lightness value of 8 or above in a decolored state, and a molding synthetic resin. A molding is prepared by molding this composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metallic luster thermochromic molding composition having a metallic color, and a molded article using this composition. More specifically, red, green,
The present invention relates to a metallic luster-like thermochromic molding composition exhibiting a color change from metallic colors such as blue and violet, and a molded product 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 have been disclosed in JP-B-51-44706 and JP-B-5-7066.
1-444707, JP-B-51-44708, JP-B-52-7764, JP-B-51-465.
No. 48, Japanese Unexamined Patent Publication No. 62-140881, etc., the thermochromic material colored by utilizing this is put to practical use as a temperature indicating element, a toy element, a magic element and the like.

However, a thermochromic molding composition exhibiting a reversible change from metallic metallic luster color to colorless and a reversible color change to another different color due to a temperature change, and the above-mentioned color change are clearly expressed. The thermochromic moldings to be used have not been known yet. In addition, an attempt to diversify color changes is disclosed in Japanese Utility Model Publication No. 3-14400. The thermochromic material described in this publication covers the thermosensitive liquid crystal with a pearlescent layer to try to develop a pearlescent color change. However, the liquid crystal is essentially colorless and needs to have a dark opaque layer on the back surface because it reflects a specific wavelength that is selective scattering of visible light.
Since it looks black-red-yellow-green-blue-purple-black, even if a pearlescent layer is provided on it, the color change is not clear.
For example, when a metallic color pearlescent pigment is used, the color change is metallic color-red with metallic color-
A metallic color yellow-a metallic color green-a metallic color blue-a metallic color purple-a metallic color, which does not show a clear change to a color not having a metallic color. Moreover, it is not possible to develop a color change from pearlescent to colorless. The metallic color of metallic luster is a gorgeous color, and the change from the metallic color to another color attracts the most attention of the viewer, so that there has been a great demand for such a discolorable molded product.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted research to effectively bring out the color-changing effect of a thermochromic material and to change the color of metallic luster, which is a metallic color, into clear and variegated heat to complete the present invention. I made it. Unlike liquid crystals, the thermochromic material used in the present invention has a characteristic that the thermochromic material itself has a clear color change, so that it is not necessary to provide a blackish opaque layer underneath, and black-white change is possible. . Therefore, by mixing the black-white thermochromic material and the metallic metallic luster pigment, it is possible to visually perceive a color change from metallic metallic luster color to white. It is also possible to make the viewer visually recognize a clear color change from a metallic metallic glossy color to a colored color by mixing a non-discoloring colorant. Furthermore, by using a thermochromic material having a very large hysteresis width as a thermochromic material, that is, a coloring material containing a so-called color-memory thermosensitive dye, the state changed even after the heat or cold heat required for thermochromic is removed. It can be held and also has the effect of making it visible at room temperature. Since the color change due to the heat of the metallic luster color of the metallic color is clearly expressed in this way, the present invention can provide various molded articles, which are widely used in the fields of decoration, interior, toys, stationery, and information. It

[0005]

According to the present invention, "1. A. The surface of natural mica is coated with 45 to 58% by weight of titanium oxide, the optical thickness of the coating layer is from 245 to 415.
B, a metallic metallic pigment having a particle size of 5 to 60 μm and a B.I. 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 both, wherein the lightness value of the color density in the colored state is 6 or less and the colorless state in the decolored state. A thermochromic material having a brightness value of 8 or more; A molding composition comprising a synthetic resin for molding, which reversibly thermally discolors from a metallic metallic color of metallic color to colorless. 2. Metallic metallic luster pigments on the surface of natural mica
Coated with 5 to 58% by weight of titanium oxide and further coated with 4 to 10
The optical thickness of the coating layer coated with wt% iron oxide is 245.
The molding composition according to item 1, which is a metallic luster pigment of metallic color having a particle size of 5 to 60 μm and a particle size of 5 to 60 μm, which is reversibly thermally discolored from a metallic luster color of metallic color to pale yellow. 3. The thermochromic material of component B is a thermochromic material in which a non-thermochromic colored dye or pigment is mixed, and the lightness value (V1) of the color density of the mixed system at the time of color development is 6 or less, and the mixed system at the time of decoloring The color brightness value (V2) is 4 or more, and (V2)-(V
1) A molding composition according to item 1 or 2, wherein reversible heat discolors from a metallic luster color of metallic color to a color of a dye or pigment. 4. Metallic metallic luster pigments on the surface of natural mica
Coated with 5 to 58% by weight of titanium oxide, on which 0.5
The coating layer coated with 10% by weight of the non-thermochromic colored dye / pigment has an optical thickness of 245 to 415 nm and a particle size of 5 to 60.
A molding composition which reversibly changes its color from a metallic luster color of metallic color to a color of a non-thermochromic dye / pigment according to any one of 1 to 3 which is a metallic color luster pigment of μm. 5. The metallic red metallic luster pigment is a metallic red metallic luster pigment having an optical thickness of 245 to 275 nm in which the surface of natural mica is coated with 45 to 47% by weight of titanium oxide. A molding composition which reversibly changes its metallic luster color of metallic red to a colorless or non-thermochromic dye / pigment color. 6. 1. The metallic metallic luster pigment of metallic color is a metallic metallic pigment of metallic purple color having an optical thickness of 280 to 310 nm in which the surface of natural mica is coated with 48 to 50% by weight of titanium oxide. A molding composition which reversibly changes its metallic luster color of metallic purple to a colorless or non-thermochromic dye / pigment color. 7. The metallic blue metallic luster pigment is a metallic blue metallic luster pigment having an optical thickness of 315 to 350 nm obtained by coating the surface of natural mica with 51 to 54% by weight of titanium oxide. A molding composition which reversibly changes its metallic luster color of metallic blue to a colorless or non-thermochromic dye / pigment color. 8. Item 4. The metallic luster pigment of metallic color is a metallic luster pigment of metallic green color having an optical thickness of 375 to 415 nm in which the surface of natural mica is coated with 55 to 58% by weight of titanium oxide. A molding composition which reversibly changes its metallic luster color of metallic green to a colorless or non-thermochromic dye / pigment color. 9. Item 1. The thermochromic material is a thermochromic material in which microcapsules are encapsulated with an electron-donating compound, an electron-accepting compound, and an organic medium that reversibly causes a color reaction between them.
Item 1. A molding composition according to any one of items 1, which reversibly undergoes a thermal discoloration from a metallic color to a colorless or dye / pigment color. 10. Injection molding, extrusion molding, blow molding using the molding composition according to any one of 1 to 9 which reversibly changes the metallic luster color of metallic color to colorless or dye / pigment color. A molded body molded by cast molding or the like. Regarding

The metallic luster pigment of metallic color used in the present invention is specifically a pigment exhibiting metallic color, in which the surface of natural mica particles is coated with titanium oxide. Further, a pigment having a titanium oxide layer coated with iron oxide is also used.
Further, a dichroic metallic luster pigment in which a titanium oxide coating is coated with a non-thermochromic colored dye / pigment is also used. The metallic color referred to in the present invention refers to a metallic luster color such as red, green, blue, and purple.

More specifically, the metallic metallic luster pigment has a metallic metallic luster pigment in which the surface of natural mica particles is coated with 45 to 58% by weight of titanium oxide.
Optical thickness of coating layer 245-415 nm, particle size 5-60
The surface of natural mica particles having a thickness of 45 μm is coated with 45 to 58% by weight of titanium oxide, and the coating layer is coated with 4 to 10% by weight of iron oxide, and the optical thickness is 245 to 415 nm and the particle size is 5 Those having a thickness of -60 μm are also used. The optical thickness of the coating layer is 245 to 415 nm, in which the surface of the natural mica particles is coated with 45 to 58% by weight of titanium oxide, and the upper layer thereof is coated with 0.5 to 10% by weight of the non-thermochromic colored dye and pigment. , Grain size 5
A metallic luster pigment with a dichroic metallic color of up to 60 μm can also be used.

The optical thickness of the coating layer of the metallic metallic luster pigment of the present invention is the refractive index × the geometrical thickness, which is related to the reflection of a certain wavelength. ing. In other words, the specific optical thickness reflects light of a specific wavelength, and the titanium oxide layer of 245 to 415 nm formed on the surface of natural mica has a thickness of 380 to 700 n.
The purple to red light of m is spectrally selected and reflected.
As the thermochromic material, a thermochromic material containing three components, an electron-donating coloring compound, an electron-accepting compound and an organic compound medium that reversibly causes a coloring reaction is used. Development of thermochromic material,
The lightness value at the time of erasing is the lightness of the Munsell color chart system in which, in an achromatic color array, perfect black is 0 and perfect white is 10 and the difference between them is equally spaced. The brightness of a chromatic color indicates the brightness value of an achromatic color having the same sense of brightness of the chromatic color. That is, the smaller the lightness value, the closer it is to black, and the larger the lightness value, the closer to white.

[0009]

The heat-denatured molding composition of the present invention is a composition in which a metallic luster pigment of metallic color and a synthetic resin for molding are mixed in a thermochromic material. It allows the viewer to see through the pigment.
As mentioned above, the mica coated with titanium oxide splits visible light rays of red to violet into light rays of each color according to the coating weight of titanium oxide and the optical thickness of the coating, so that only light of a specific wavelength is emitted. It has a function of reflecting and transmitting other light. On the other hand, mica does not diffusely reflect light but reflects it in parallel rays, so the light has a metallic luster. The light transmitted through the metallic luster pigment is absorbed by the thermochromic material that has undergone thermochromism. In this way, the light of the metallic luster of a specific wavelength is reflected, so that it becomes a metallic color of a specific color. Specifically, the 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, that is, the thickness of the coating layer. For example, titanium oxide-coated mica whose optical thickness is adjusted to selectively reflect light of a specific color and transmit light of another color, the transmitted light is absorbed by the thermochromic material, and the specific color light is absorbed. Since only one is reflected, it exhibits a specific metallic color. On the other hand, when the thermochromic material is white, the transmitted light is also reflected, and not only the metallic color light but also other color light is reflected and all wavelengths of visible light are reflected, so that the material is viewed as white. Therefore, by reversibly changing the thermochromic material to black ← → white, the viewer can see the metallic color ←
→ Visualize the reversible color change of white.

What is important here is that titanium oxide must meet the requirement of an optical thickness of 245 to 415 nm.

When the optical thickness of the titanium oxide coated on the natural mica is within the above range, it is spectrally reflected in each color of red to purple corresponding to the thickness, and the reflected light becomes parallel rays, so that the metallic color light is emitted. Becomes For example titanium oxide coating weight%
Of 45 to 47% and an optical thickness of 245 to 275 nm transmits 500 to 550 nm of green light, and 650
Reflects red light at ~ 700 nm. When the light transmitted through the metallic color pigment is absorbed by the thermochromic material therebelow, only the red metallic color can be seen by the viewer.

When the thermochromic material reflects the light transmitted through the metallic pigment, all visible light is seen as it is in the eyes of the observer, so that it looks white. Therefore, the change of the lightness value due to the discoloration of the thermochromic material causes the disappearance of the metallic color. The expression is reversible. Since the particles of mica are arranged in parallel layers, the reflected light is not diffused and becomes parallel rays. Since such parallel reflected light has a metallic luster color, the reflected light of this pigment is red light with metallic luster, that is, red metallic color.

Similarly, the coating weight percentage of titanium oxide is 55-55.
Pigment with an optical thickness of 375-415 nm at 58% is 63%
Transmitting red light of 0 to 700 nm, 500 to 540n
m of green light is reflected to give a greenish metallic color.

Further, the coating weight% of titanium oxide is 51 to 5
Pigment with an optical thickness of 315-350 nm at 4% is 580
Transmits orange light of ~ 630nm, 430 ~ 500nm
It reflects the blue light of and becomes a blue metallic color.

Pigments having a titanium oxide coating weight percentage of 48-50% and an optical thickness of 280-310 nm are 530-58.
The yellow light of 0 nm is transmitted, and the purple light of 380 to 430 nm is reflected to become a purple metallic color.

As described above, the composition of the present invention reflects the light of a specific wavelength depending on the coating amount of the specific titanium oxide and the optical thickness, and the interference action of mica and the colorless and colorless discoloration action of the thermochromic material. The metallic color can be expressed by.

Further, in the metallic color metallic luster pigment in which the surface of the natural mica particles is coated with titanium oxide and the upper layer thereof is coated with iron oxide, in addition to the above wavelength-selective reflection and transmission effects, iron oxide itself The reversible color change from metallic color to pale yellow is visualized by adding the characteristic of absorbing the purple light and reflecting the yellow light. If the coverage of titanium oxide is less than 45% by weight, it is difficult to obtain a sufficient metallic color. Further, even if the coverage of titanium oxide exceeds 58% by weight, the wavelength selectivity deteriorates, and a sufficient metallic color cannot be obtained. When the iron oxide coverage is less than 4% by weight, the effect of the iron oxide shown above does not sufficiently appear, and when it exceeds 10% by weight, the color is metallic, but the iron oxide coloring is too strong and it is beautiful. I can't get a color change from a metallic color. When iron oxide is used in combination, forming an iron oxide film on the titanium oxide film is most effective in developing the color change from metallic metallic luster color to pale yellow. When titanium oxide is coated on iron oxide, the effect of titanium oxide is large and the effect of iron oxide is small. When titanium oxide and iron oxide are mixed, titanium oxide may block the reflected light of iron oxide as compared with iron oxide in the upper layer, so that the reflection efficiency of iron oxide deteriorates. When an iron oxide film is provided on the titanium oxide film, the iron oxide layer has the property of absorbing purple light and reflecting other light.Since this light appears yellow, it has a metallic luster due to the titanium oxide layer. It has the effect of changing the color from pale yellow. This is because the iron oxide film as the upper layer prevents the reflected light from this iron oxide layer from being interrupted or reflected by other layers.

Further, in the metallic luster pigment of metallic color in which the surface of the natural mica particles is coated with titanium oxide and the upper layer thereof is coated with the non-thermochromic colored dye / pigment, the non-thermochromic colored dye / pigment to be coated is A wide variety of color changes can be expressed by colors, for example, metallic color ← → pink, metallic color ← → blue, etc. in combination with a black ← → white thermochromic layer ← → You can visualize the reversible color change of the color. When the coverage of titanium oxide is less than 45% by weight, a sufficient metallic color is difficult to appear, and therefore when coated with a non-thermochromic colored dye / pigment, it does not look metallic. On the other hand, if the titanium oxide coverage exceeds 58% by weight, the wavelength selectivity deteriorates, and a sufficient metallic color does not appear. When the coverage of the non-thermochromic colored dye / pigment is less than 0.5% by weight, a sufficient color density of colored cannot be obtained. If it exceeds 10% by weight, the color density of the color is too high, and the contrast between the metallic color and the color becomes small. When each of the pigments is within the above range, it is possible to impart the characteristic of selectively transmitting the light of the wavelength of the metallic color and reflecting the light of the wavelength having the complementary color relationship. If the ratio is out of the above range, the wavelength selectivity is lost, or the wavelength selectivity is present but the metallic color is not obtained.

When a thermochromic material containing a non-color-changing dye / pigment colorant is used as the thermochromic material, a reversible color change from a metallic luster color of metallic color to a color of a colorant is visually recognized. Since metallic luster pigments of metallic color are transparent,
The presence of the non-color-changing colorant allows the color of this colorant to be visualized at the same time as the color of the thermochromic layer.

As described above, the thermochromic material comprises three components, an electron-donating color-forming compound, an electron-accepting compound and an organic compound medium. Specifically, for example, the aforementioned Japanese Patent Publication No. 51-3541.
No. 4, etc., (1) (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, and (c) a chain aliphatic 1 having no polar substituent group. A reversible thermochromic material that contains the three components of polyhydric alcohol as essential components. Or (2) (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, and (c) an aliphatic monohydric alcohol having no polar substituent and a polar substituent. A reversible thermochromic material containing, as an essential component, three components of a compound selected from an ester having no polar substituent obtained from an aliphatic monocarboxylic acid. Alternatively, (3) (a) an electron-donating color-developing organic compound, (b) a compound having a phenolic hydroxyl group, (c) a higher aliphatic monohydric alcohol having no polar substituent, and a polar substituent Three components of a compound selected from any one of an aliphatic monocarboxylic acid having no substituent and an ester having no polar substituent obtained from a chain type aliphatic monohydric alcohol having no polar substituent are essential components. And a reversible thermochromic material containing this in microcapsules. Alternatively, (4) (a) an electron-donating color-developing organic compound, (b) a compound having a phenolic hydroxyl group, (c) a higher aliphatic monohydric alcohol having no polar substituent, and a polar substituent Three components of a compound selected from a polar substituent-free ester obtained from a higher aliphatic monocarboxylic acid having no substituent and a chain aliphatic monohydric alcohol having no polar substituent are used as essential components. , A thermochromic material obtained by dissolving or dispersing this in a vehicle. Etc.

The thermochromic material is most preferably used by being encapsulated in microcapsules. This is because the thermochromic materials can be kept in the same composition under the various use conditions and can exhibit the same effect.

In addition to the above, a thermochromic material containing a color-memory thermochromic dye, which exhibits a large hysteresis characteristic and discolors, as described in JP-A-60-264285, that is, a change in color density due to a temperature change. A type in which the shape of the plotted curve changes color by following a route that differs greatly depending on whether the temperature is raised from the low temperature side of the color change temperature range or is lowered from the high temperature side of the color change temperature range. A thermochromic material is also used, which is characterized in that it can store and retain a state of being changed at a temperature below the low temperature side color changing point or above the high temperature side color changing point in the room temperature range between the low temperature side color changing points.

The thermochromic molding composition of the present invention will be specifically described. The thermochromic molding composition of the present invention comprises (A) a composition in which a metallic luster pigment of metallic color and a synthetic resin for molding are mixed in a thermochromic material, and (B) a non-color-changing dye or pigment in the thermochromic material. It is a composition in which a metallic luster pigment of metallic color and a synthetic resin for molding are mixed in a thermochromic material obtained by mixing.

Next, the metallic luster color thermochromic discoloration molding composition of the present invention will be described based on the above (A) and (B). In the composition (A) described above, the metallic luster pigment of metallic color is a metallic luster pigment of metallic color having a particle size of about 5 to 60 μm, and the thermochromic material is an electron-donating color-forming organic compound, an electron-accepting agent. A thermochromic material (hereinafter referred to as a thermochromic material) consisting of a compound and a three-component homogeneous compatible solution of an organic compound medium that reversibly causes a color reaction between the both, and the lightness of the color density of the colored state. If the value is 6 or less,
In the decolored state, the colorless lightness value is 8 or more, and when mixed with a molding synthetic resin, the metallic luster color of the metallic color is colorless,
A metallic luster thermochromic composition of metallic color exhibiting a reversible color change from colorless to metallic metallic luster color is constituted. When the lightness value of the color density in the colored state is 6 or less, it has the ability to sufficiently absorb the light transmitted through the metallic metallic luster pigment. For example, in the case of the metallic metallic luster pigment, the metallic metallic pigment having a clear metallic color is used. Looks shiny. However, when the lightness value of the coloring state exceeds 6, it becomes impossible to sufficiently absorb the light transmitted through the metallic luster pigment of metallic color,
Some will also be reflected so that they will not look like a clear metallic color. On the other hand, when the colorless lightness value in the decolored state is 8 or more, it has the ability to sufficiently reflect the light transmitted through the metallic metallic luster pigment, and therefore the light reflected by the metallic metallic luster pigment and the thermochromic material The light reflected by is mixed,
It returns to white light and appears colorless. However, when the lightness value in the decolored state is less than 8, the light transmitted through the metallic luster pigment of metallic color cannot be sufficiently reflected, and it absorbs a part of it, so that it does not become colorless and the metallic color in the colored state remains.

In the composition (B), the metallic luster pigment of metallic color is about 5 to 60 μm, and the thermochromic material is a mixture of the thermochromic material and a non-chromic colorant (dye, pigment). Lightness value (V ₁ ) of the color density of the developed state
Is 6 or less, the lightness value (V ₂ ) of the color in the decolored state is 4 or more, and the composition satisfies the relationship of the lightness value (V ₂ ) -lightness value (V ₁ )> 1. A metallic luster thermochromic molded article of metallic color exhibiting a reversible color change from metallic color to colored and from colored to metallic color is formed. The reason why the lightness value (V ₁ ) of the color density of the color mixture system in the color-developed state is 6 or less is the same as above. On the other hand, the reason why the lightness value (V ₂ ) of the color in the decolored mixed color system is 4 or more and the V ₂ −V ₁ > 1 needs to be satisfied is that the non-color-changing colorant and the non-thermal colorant are used in this system. Since the discoloring dye and pigment are mixed to form a color, the lightness value becomes small and varies depending on the color of the dye or pigment. For example, the lightness value is relatively large for yellow, orange, etc., and conversely, the lightness value is small for red, purple, etc. However, in order to obtain a satisfactory color change, the lightness value in the decolored state needs to be at least larger than 1 in the color development state, and when it is 1 or less, the contrast is too small and the color change occurs. Not clear. If the lightness value is 4 or more under such conditions, for example, a reversible color change from metallic color to colored or from colored to metallic color can be exhibited. However, if it is less than 4, the color density of the underlying color mixture layer becomes too high, and the metallic color is visible even in the decolored state.

It should be noted that the smaller the lightness value of the thermochromic material at the time of coloring and decoloring is, the closer it is to black, and the larger the lightness value is, the closer it is to white. It can be used as an indicator of how reflective it is, and this indicator
It will show how visible light transmitted through the metallic metallic luster pigment is reflected and absorbed by the underlying thermochromic material.

Therefore, if the thermochromic material has a lightness value of 6 or less, it has the ability to sufficiently absorb the visible light transmitted through the metallic color metallic luster pigment, and as a result, the metallic color reflected by the metallic color metallic luster pigment. Since only colored light is visible, it looks metallic. On the other hand, when the lightness value is 8 or more, the visible light transmitted through the metallic metallic luster pigment is reflected, so that the metallic light reflected by the metallic metallic luster pigment and the light reflected by the thermochromic material are reflected. Both of them will be viewed together, so they will not look metallic.

That is, it is an index of whether or not the thermochromic material has a characteristic of appearing metallic color below the color change temperature and disappearing above the color change temperature. The brightness value of the present invention is a value obtained by measuring a sample prepared as described below using a TC-3600 color difference meter manufactured by Tokyo Denshoku Co., Ltd. 1. Measurement of luminosity value of thermochromic material (including system in which non-chromic dyes and pigments are mixed) (1) Measurement of luminosity value of thermochromic material (colored ← → colorless) Thermochromic material 10 parts, 50% acrylic acid Ester resin /
45 parts of xylene solution, 20 parts of xylene and 20 parts of methyl isobutyl ketone are stirred and mixed, and spray-coated with a spray gun on a white vinyl chloride sheet having a brightness value of 9.1, and a thermochromic material layer having a thickness of 40 μm after drying. To prepare.
The lightness value of the color-developed state and the color-erased state of the obtained thermochromic material layer is measured. (2) Measurement of lightness value of thermochromic material (colored I ← → colored II) 10 parts of thermochromic material, desired amount of non-thermochromic dye / pigment, 50
% Acrylic acid ester resin / xylene solution 45 parts, xylene 20 parts and methyl isobutyl ketone 20 parts by stirring,
Mix and spray-paint with a spray gun on a white vinyl chloride sheet with a brightness value of 9,1 and dry it to a thickness of 40 μm.
A thermochromic material layer is prepared. The lightness value of the color-developed state and the decolored state of the obtained thermochromic material layer is measured. The thermochromic molding composition of the present invention is a powdery, pelletized, or casting liquid composition in which the metallic luster pigment of the metallic color described above and the thermochromic material are mixed with a transparent molding resin. .

Next, the molding synthetic resin used for the powdery or pelletized molding composition will be exemplified. 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 terephthalate resin Rate resins, polycarbonate resins, polystyrene resins, high impact polystyrene resins, polypropylene resins, polymethyl styrene resins, polyacrylate resins, polymethyl methacrylate resin,
An epoxy acrylate resin etc. can be mentioned.

Next, examples of the synthetic resin for molding used in the liquid molding composition for casting will be shown. Alkylphenol resin, rosin modified phenol resin, rosin modified alkyd resin, phenol resin modified alkyd resin, epoxy resin modified alkyd resin, styrene modified alkyd resin, acrylic modified alkyd resin, aminoalkyd resin, vinyl chloride-
Vinyl acetate resin, styrene-butadiene resin, epoxy resin, acrylic ester resin, unsaturated polyester resin, polyurethane resin, vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylic ester emulsion resin, water-soluble alkyd resin, Examples of the synthetic resin include water-soluble melamine resin, water-soluble urea resin, water-soluble phenol resin, water-soluble epoxy resin, water-soluble polybutadiene resin, and cellulose derivative.

UV absorbers, infrared absorbers, antioxidants, singlet oxygen quenchers, antiaging agents, antistatic agents, polarity imparting agents, thixotropic agents, defoamers, stabilizers, plasticizers, Additives such as flame retardants, extender pigments, lubricants, and foaming agents can be added to each layer such as a clear coat layer, a metallic luster pigment layer, and a thermochromic layer, if necessary. The composition of the present invention can be molded into various three-dimensional molded bodies and film sheets by injection molding, extrusion molding, blow molding, compression molding, rolling molding, fluidized dipping method, casting method and the like.

[0032]

【Example】

Example 1 The surface of natural mica was coated with 47% by weight of titanium oxide,
20 parts of metallic red metallic luster pigment having an optical thickness of 265 nm and a particle size of 10 to 60 μm, an average particle diameter of 1 having a lightness value of 2.3 when developed and a brightness value of 8.8 when erased.
20 parts of thermochromic material in the form of 5 μm microcapsules, 2 parts of benzotriazole-based UV absorber, Vicat softening point 1
After uniformly mixing 1000 parts of 19 ° C. high-density polyethylene, the mixture was molded using an extruder under the conditions of a cylinder temperature of 165 ° C. and a gate temperature of 160 ° C.
m pellets were obtained. Using a blow molding machine, the thermochromic pellets have a thickness of about 2 at a cylinder temperature of 175 ° C.
A ball having a diameter of 5 mm and a diameter of 5 cm was blow-molded. In this ball, the thermochromic material develops color at 15 ° C. or lower, reflects light having a wavelength of 650 to 700 nm, which is a part of incident light, and absorbs light having other wavelengths. When the thermochromic material disappears at 30 ° C. or higher and reflects the transmitted light, it reflects all the incident light, and the metallic red metallic luster color disappears and becomes colorless. The thermochromic material is a thermochromic composition composed of a compatible solution of 3 parts of 2-anilino-3-methyl-6-dibutylaminofluorane, 6 parts of bisphenol A, and 50 parts of neopentyl stearate in an epoxy resin / amine. It is obtained by microencapsulation of a system curing agent by an interfacial polymerization method.

Example 2 The surface of natural mica was coated with 48% by weight of titanium oxide,
20 parts of metallic purple metallic luster pigment having an optical thickness of 295 nm and a particle size of 10 to 60 μm, a lightness value at the time of color development of 2.3, and a lightness value at the time of decolorization of 5.3 μm in average particle size 20 parts of thermochromic material in capsule form, 1.5 parts of fluorescent pink pigment, 2 parts of benzotriazole type ultraviolet absorber, polypropylene 1 with Vicat softening point of 100 ° C.
After uniformly mixing 000 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 a conventional method. The thermochromic pellets were heated with an injection molding machine at a cylinder temperature of 170.
Thickness of about 3 mm, length of 10 cm, width of 3.7 c under conditions of ℃
The body of the m miniature car was molded. In this body, the thermochromic material develops color at 15 ° C. or lower, reflects light having a wavelength of 380 to 430 nm, which is the minus part of incident light, and absorbs light having other wavelengths. It becomes a luster color, and when the thermochromic material disappears at 30 ° C or higher, the metallic purple color metallic luster color disappears,
It becomes the color of the fluorescent pink pigment. The thermochromic material is
A thermochromic composition comprising a compatible solution of 3-anilino-3-methyl-6-dibutylaminofluorane (3 parts), bisphenol A (6 parts) and neopentyl stearate (50 parts) was prepared by an interfacial polymerization method using an epoxy resin / amine curing agent. It was obtained by encapsulation.

Example 3 The surface of natural mica was coated with 57% by weight of titanium oxide,
20 parts of metallic green metallic luster pigment having an optical thickness of 395 nm and a particle size of 10 to 60 μm, an average particle diameter of 15 μm with a lightness value of 2.2 in a mixed system and a lightness value of 5.5 when decolored. 20 parts of the thermochromic material in the form of microcapsules, 0.2 part of a blue pigment, 0.6 part of a white pigment, 2 parts of a benzotriazole-based UV absorber, and a Vicat softening point of 10.
After uniformly mixing 1000 parts of linear low-density polyethylene at 5 ° C, a cylinder temperature of 170 was obtained using an extruder.
Molded under the conditions of ℃ and gate temperature 170 ℃
~ 3 mm pellets were obtained. The thermochromic pellets were subjected to sheet molding 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, the thermochromic material develops a color at 15 ° C. or lower, reflects light having a wavelength of 500 to 540 nm, which is a part of incident light, and absorbs light having other wavelengths, resulting in metallic green metallic luster. When the thermochromic material disappears at 30 ° C. or higher, the metallic green metallic luster color disappears and the pastel blue color, which is a mixed color of a blue pigment and a white pigment, is obtained. The thermochromic material is 2-anilino-3-methyl-6-dibutylaminofluorane 3
Part, 6 parts of bisphenol A, and 50 parts of neopentyl stearate. A thermochromic composition obtained by microencapsulation by an interfacial polymerization method of an epoxy resin / amine curing agent.

Example 4 The surface of natural mica was coated with 52% by weight of titanium oxide,
100 parts of metallic blue metallic luster pigment having an optical thickness of 330 nm and a particle size of 10 to 60 μm, an average particle size of a mixed system having a lightness value of 2.2 during color development and a lightness value of 8.9 during decolorization. Thermochromic material 1 in the form of 15 μm microcapsules
After uniformly mixing 00 parts, fluorescent yellow pigment 10.0 parts, benzotriazole type ultraviolet absorber 5 parts, epoxy resin 700 parts and amine curing agent 250 parts, pour it into a star casting mold at 70 ° C. After curing for 1 hour, a star-shaped molded product was obtained. In the star, the thermochromic material develops color at 15 ° C. or lower, reflects light having a wavelength of 430 to 500 nm, which is a part of the incident light, and absorbs light having other wavelengths, resulting in metallic blue metal. When the thermochromic material disappears at 30 ° C. or higher, the metallic blue metallic luster color disappears and the fluorescent yellow pigment color is obtained. The thermochromic material is a thermochromic composition composed of a compatible solution of 3 parts of 2-anilino-3-methyl-6-dibutylaminofluorane, 6 parts of bisphenol A, and 50 parts of neopentyl stearate in an epoxy resin / amine. It 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 47% by weight of titanium oxide, the optical thickness was 265 nm, and the particle size was 10-6.
In place of 0 μm metallic red metallic luster pigment, the surface of natural mica was coated with 45% by weight of titanium oxide, and further with 4% by weight of iron oxide, the optical thickness was 270 nm.
Then, the same procedure as in Example 1 was carried out except that a dichroic metallic reddish purple metallic luster pigment having a particle size of 10 to 50 μm and changing from metallic reddish purple color to yellow was used. In this ball, the thermochromic material develops a color at 15 ° C. or lower, and a part of the incident light is 650 to 70 nm.
When the light of wavelength is reflected and the light of wavelengths other than that is absorbed, it becomes a metallic reddish purple metallic luster color, and when the thermochromic material disappears at 30 ° C or higher, the metallic reddish purple metallic luster color becomes It disappears and becomes yellow.

Comparative Example 1 In place of the thermochromic material of Example 1, the lightness value at the time of color development is 4.
5, 2-anilino-3-having a lightness value of 6.0 when decolorized
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 formed into a fine capsule by interfacial polymerization 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 was used. When the temperature is 15 ° C or lower, the thermochromic material develops color, reflects light having a wavelength of 650 to 700 nm, which is a part of incident light, and absorbs light having other wavelengths, resulting in a metallic red metallic luster color. . In this comparative example, even if the thermochromic material is discolored at 30 ° C. or higher, the transmitted light can still be sufficiently absorbed, so that the metallic red color is slightly thinned and the metallic red metallic luster is still obtained. It looks like a color.

Comparative Example 2 The surface of natural mica was coated with 48% by weight of titanium oxide,
20 parts of metallic purple-colored metallic luster pigment having an optical thickness of 295 nm and a particle size of 10 to 60 μm, a lightness value at the time of color development of 2.4, and a lightness value at the time of decolorization of 3.2, an average particle size which does not become colorless 20 parts of thermochromic material in the form of 15 μm microcapsules, 15 parts of green pigment, 2 parts of benzotriazole-based UV absorber, 1000 parts of polypropylene with a Vicat softening point of 100 ° C. are uniformly mixed, and then a cylinder is formed using an extruder. Molding was performed under the conditions of a 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 pellets were molded with an injection molding machine at a cylinder temperature of 170 ° C. to form a body of a miniature car 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 lower, reflects light having a wavelength of 380 to 430 nm, which is a part of incident light, and absorbs light having other wavelengths. It becomes a glossy color. In this comparative example,
Even if the thermochromic material is decolored at 30 ° C. or higher, it can still sufficiently absorb the transmitted light, so that it is still greenish and still looks like a metallic purple metallic luster color.
The thermochromic material is 2-anilino-3-methyl-
6-dibutylaminofluorane 6 parts, bisphenol A
A thermochromic composition which does not become colorless and comprises a compatible solution of 10 parts and 25 parts of neopentyl stearate is obtained by microencapsulation by an interfacial polymerization method of an epoxy resin / amine curing agent.

[0039]

EFFECTS OF THE INVENTION The thermochromic molding composition of the present invention is reversibly discolored from the metallic luster color of metallic color to the color of a non-thermochromic colorant which is colorless or used in combination with temperature change. The same discoloration occurs in the molded body. When a thermochromic material with a small hysteresis width is used, the color changes in response to temperature changes with high sensitivity.When a thermochromic material with a large hysteresis width is used, even if the heat that has caused the color change is removed, it will change at room temperature. I can keep it.

Claims (10)

[Claims] 1. A. 45-58% by weight on the surface of natural mica
The optical thickness of the coating layer coated with titanium oxide is from 245 to
415 nm and a metallic color metallic luster pigment having a particle size of 5 to 60 μm, and B. 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 both, wherein the lightness value of the color density in the colored state is 6 or less and the colorless state in the decolored state. A thermochromic material having a brightness value of 8 or more; A molding composition comprising a synthetic resin for molding, which reversibly thermally discolors from a metallic luster color of metallic color to colorless. 2. A coating layer in which a metallic color metallic luster pigment coats the surface of natural mica with 45 to 58% by weight of titanium oxide and 4 to 10% by weight of iron oxide on the surface of the coating layer has an optical thickness of 245 to 245. The molding composition according to claim 1, which is a metallic metallic luster pigment having a particle size of 5 to 60 μm and having a particle size of 415 nm, and which is reversibly thermally discolored from a metallic metallic luster color to pale yellow. 3. The thermochromic material of component B is a thermochromic material in which a non-thermochromic colored dye or pigment is blended, and when the lightness value (V1) of the color density of the mixed system at the time of color development is 6 or less, it disappears. The color brightness value (V2) of the mixed system at the time of color is 4 or more (V
2)-(V1)> 1, wherein the molding composition according to claim 1 or 2, which is reversibly thermally discolored from the metallic luster color of metallic color to the color of dye / pigment. 4. A coating in which a metallic color metallic luster pigment covers the surface of natural mica with 45 to 58% by weight of titanium oxide, and 0.5 to 10% by weight of a non-thermochromic colored dye / pigment thereon. The reversibly metallic metallic luster color according to any one of claims 1 to 3, which is a metallic metallic luster pigment having an optical thickness of 245 to 415 nm and a particle size of 5 to 60 µm. A molding composition which undergoes a thermal discoloration to the color of a discolorable dye or pigment. 5. The metallic red metallic luster pigment is a metallic red metallic luster pigment having an optical thickness of 245-275 nm in which the surface of natural mica is coated with 45 to 47% by weight of titanium oxide. 3. A molding composition according to any one of 3 above, which reversibly changes its metallic reddish metallic luster color to a colorless or non-thermochromic dye / pigment color. 6. The metallic luster pigment of metallic color is a metallic luster pigment of metallic purple color having an optical thickness of 280 to 310 nm in which the surface of natural mica is coated with 48 to 50% by weight of titanium oxide. 3. A molding composition according to any one of 3 above, which reversibly changes its metallic luster color of metallic purple to a colorless or non-thermochromic dye / pigment color. 7. The metallic luster pigment of metallic color is a metallic luster pigment of metallic blue color having an optical thickness of 315 to 350 nm in which the surface of natural mica is coated with 51 to 54% by weight of titanium oxide. 3. A molding composition according to any one of 3 above, which reversibly changes its metallic luster color of metallic blue to a colorless or non-thermochromic dye / pigment color. 8. The metallic luster pigment of metallic color is a metallic luster pigment of metallic green color having an optical thickness of 375 to 415 nm in which the surface of natural mica is coated with 55 to 58% by weight of titanium oxide. A molding composition which reversibly changes its metallic luster color of metallic green to a colorless or non-thermochromic dye / pigment color. 9. The thermochromic material according to claim 1, wherein the thermochromic material is a thermochromic material in which microcapsules are encapsulated with an electron-donating compound and an electron-accepting compound, and an organic medium that reversibly causes a color reaction between them. The molding composition according to any one of claims 1 to 3, which is reversibly changed from a metallic color to a colorless color or a dye-pigment color by heat. 10. An injection molding using the molding composition according to any one of claims 1 to 9 which reversibly changes the metallic luster color of metallic color to colorless or dye-pigment color. A molded body molded by extrusion molding, blow molding, cast molding, or the like.