JP3306608B2 - Thermochromic pearl luster - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermochromic pearl luster. More specifically, the present invention relates to a thermochromic pearl luster product exhibiting a color change rich in pearl luster.

[0002]

2. Description of the Related Art Conventionally, with regard to ornaments and ornaments that exhibit pearl luster, a luminescent material such as a phosphorescent pigment is mixed with a base made of a synthetic resin, and a coating layer made of artificial pearls is formed on the outer surface of the base. An attempt has been disclosed (Japanese Utility Model Publication No. 4-26005). Japanese Patent Application Laid-Open No. 5-137849 discloses an attempt to increase the color change by laminating a pearlescent layer on a thermochromic layer.

[0003]

The system in which the luminescent material is mixed cannot provide various pearl luster effects by simple means such as temperature change, even if it can provide a luminous effect. On the other hand, in a system in which a pearlescent layer is laminated on a thermochromic layer, those that become blackish when colored due to temperature changes have a metallic luster, lacking the freedom of color selection, and have a rich pearly luster. Difficult to change. The present invention is intended to solve the above-mentioned problem and to provide a thermochromic pearl luster processed body in which the thermochromic layer is in both the colored state and the decolored state, and in which the appearance rich in pearl luster is visually recognized. is there.

[0004]

The present invention will be described with reference to the drawings (see FIGS. 1 and 2). The present invention relates to a pearlescent pigment.
An electron-donating color-forming organic compound on the pearlescent layer 2 containing
The temperature at which the color reaction between the electron-accepting compound and the two occurs.
The heat consisting of three essential compatibilities of the organic compound medium
The color-change pigment is fixed in a dispersed state in the binder;
A thermochromic layer 3 having a thickness of 0 to 400 μm is laminated, and the thermochromic layer 3 is represented by the following formulas when coloring and decoloring.
The thermochromic pearl luster processed body 1 is characterized in that the apparent transmittance (T) of the light to be applied is at least 5% or more. Apparent transmittance T (%) = [500 × P (% · μm)] ÷ [C (%) × D (μm)] [C is the content of the thermochromic pigment in the dried film of the thermochromic layer.
, D indicates the thickness of the dried film, and P indicates that C is 10%.
Shows the transmittance of light when colored when the film thickness is 50 μm.
The apparent transmittance T (%) at the time is expressed by P
Is 10% and the light transmittance at the time of decoloring when the film thickness is 50 μm.
Required by replacing

[0005] To illustrate a specific configuration of the present invention, a pearlescent layer 2 is formed on a support 4 (transparent or opaque support), and a thermochromic layer 3 is laminated on the pearlescent layer 2. A pearlescent pigment is blended with the support 4, the support itself constitutes the pearlescent layer 2, a thermochromic layer 3 is formed on the back of the transparent support, and the pearlescent layer 2 is formed on the thermochromic layer 3. Are laminated, and the surface side of the transparent support is an outer surface. In the above configuration, a non-thermochromic layer may be appropriately provided below the thermochromic layer 3 so that the color change of the thermochromic layer 3 in the color change can be more variously visualized. It should be noted that a clear coat layer or a laminate layer can be appropriately laminated on the front or back surface of the processed body, and a light stabilizer such as an ultraviolet absorber or an antioxidant can be compounded in the clear coat layer on the front surface. Alternatively, a transparent clear coat layer or a laminate layer can be interposed between the thermochromic layer 3 and the pearlescent layer 2.

The thermochromic layer 3 comprises a thermochromic material containing a conventionally known thermochromic dye, for example, an electron-donating color-forming organic compound, an electron-accepting compound, and a reversible color-forming reaction between the two. A thermochromic material containing a three-component homogeneous compatibilizer of an organic compound medium or a thermochromic material exhibiting thermochromic properties in the form of fine particles of a resin solid solution of the component (for example, JP-B-51-35414; JP-B-51-44706, JP-B-1-29398 and the like. The color changes at a predetermined temperature (discoloration point) at that temperature, and only one specific state can exist in the normal temperature range between the two states before and after the change. That is, the other state is maintained while the heat or cold required for the state to develop is applied, but returns to the state exhibited in the normal temperature range when the heat or cold is no longer applied (the so-called state). The color changes due to a small hysteresis width for temperature / color density due to temperature change). In addition, a thermochromic material containing a color memory thermochromic dye which exhibits a large hysteresis characteristic and discolors, which is described in Japanese Patent Publication No. Hei. The shape of the curve plotting the change in coloring temperature follows a path that differs greatly when the temperature is increased from a temperature lower than the discoloration temperature range and conversely, when the temperature is decreased from a temperature higher than the discoloration temperature range. Heat-colored type: in a normal temperature range between the low-temperature side discoloration point and the high-temperature side discoloration point, it is possible to memorize and retain the aspect changed at the temperature below the low-temperature side color change point or above the high-temperature side color change point). And a discoloration layer.

The thermochromic dye or the color-memory thermochromic dye described above is usually encapsulated in microcapsules, dispersed in a medium containing a binder, applied as a coloring material such as ink or paint, and supported. A desired thermochromic layer 3 is formed on the body surface. Further, the microcapsules may be dispersed in a thermoplastic or thermosetting resin. Incidentally, a pearlescent pigment can be dispersed in the thermochromic layer 3 as appropriate.

The pearlescent layer 2 can be formed by coating with a printing ink or paint containing a pearlescent pigment. A film formed by blending a pearlescent pigment with a transparent or translucent resin or the like or a relatively thin molded body It may be formed as. As the pearlescent pigment, conventionally known titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate, lead acid arsenate, bismuth oxychloride and the like can be applied. It is dispersed in a medium containing a binder and applied in the form of a paint, ink or the like. Alternatively, the pigment may be contained in a dispersed state in a thermoplastic resin or a thermosetting resin. As the means for dispersing the pearlescent pigment and fixing the pearlescent pigment to the surface of the support, conventional means are conventionally appropriately selected and put to practical use.

Examples of a medium for forming the thermochromic layer 3 and the pearlescent layer 2 are described below. As evaporative drying type (resin / solvent type), rosin, shellac, casein, rosin-maleic acid resin, alkyd resin, cellulose derivative, petroleum resin, low molecular weight polyethylene, polystyrene,
Resins such as polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyacrylate copolymer, modified rubber, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylpyrrolidone-vinyl acetate copolymer are used as petroleum solvents and aromatic solvents. , Aliphatic hydrocarbon solvents, alcohol solvents,
Examples thereof include a solution dissolved in a ketone solvent, an ester solvent, and water. Examples of the cooling solidification type (hot melt type) include carnauba wax, paraffin wax, and microcrystalline wax. Examples of the infiltration drying type (resin / petroleum-based solvent type) include a solution in which a resin such as rosin or a rosin-based derivative is dissolved in machine oil, spindle oil, kerosene, or the like. Examples of the emulsion type include a polyvinyl acetate type, a styrene-butadiene type, and an acrylic type. Oxidative polymerization type, polymerized linseed oil, tung oil, dry oil such as dehydrated castor oil and soybean oil-modified alkyd resin,
An oil-modified alkyd resin such as a coconut oil-modified alkyd resin, a linseed oil-modified alkyd resin and the like can be mentioned. As thermosetting type, epoxy resin, alkyd resin, acrylic resin, xylene resin, guanamine resin, phenol resin,
Examples include unsaturated polyester resins, polyurethane resins, maleic acid resins, melamine resins, urea resins, acryl-urethane resins, and the like. Examples of the photocurable type include a photopolymerizable acrylic resin, a photocurable epoxy resin, and the like.
Examples of the water-soluble synthetic resin paint include a water-soluble alkyd resin, a water-soluble melamine resin, a water-soluble urea resin, a water-soluble phenol resin, a water-soluble acrylic resin, a water-soluble epoxy resin, and a water-soluble polybutadiene resin. As the resin for holding and molding the thermochromic material or the pearlescent pigment in a dispersed state, various general-purpose transparent thermoplastic or thermosetting resins have conventionally been used. According to the present invention, in the above-described configuration, it is a main feature that the light transmissivity of the thermochromic layer at the time of coloring and at the time of decoloring are both in a region of at least 5% or more and less than 95%. By preparing the thermochromic layer 3 having the light transmittance range described above, the light transmissivity of the thermochromic layer at the time of generation and decoloration is appropriate, and visual perception can be made effectively without impairing the pearl luster.

The above requirement is specifically achieved by satisfying the following expression. Apparent transmittance T (%) = [500 × P (% · μm)] ÷
[C (%) × D (μm)] Here, C indicates the content of the thermochromic pigment in the dried film of the thermochromic layer, D indicates the film thickness of the dried film, and P indicates the C value.
Is 10%, and shows the light transmittance at the time of coloring when the film thickness is 50 μm. Incidentally, the apparent transmittance T ′ (%) at the time of decoloring is obtained by calculating P ′ to P ′ (C is 10% and the film thickness is 50%) in the above equation.
(indicating the transmittance of light at the time of decoloring at μm). In a system in which the thickness of the thermochromic layer 3 is less than 10 μm, it is difficult to clearly see the color change, while
In a system exceeding μm, increasing the blending amount of the thermochromic pigment is not preferable because residual color at the time of decoloring is observed. Therefore, a thickness of 20 μm to 300 μm is practically preferable.

[0011]

The thermochromic layer 3 is formed on the pearlescent layer 2, and develops and decolors in response to a temperature change. here,
The thermochromic layer 3 is provided with a light transmittance of at least 5% at the time of coloring and decoloring, so that it has a colored pearly luster without impairing the pearl luster. And a pearlescent appearance in the decolored state. At this time, in the system in which the pearlescent layer 2 is a spherical or hemispherical surface layer, the pearly luster is enhanced and visually perceived. In a system in which the thermochromic layer 3 is made of a thermochromic material containing a color-memorizing thermochromic dye, even after removing the application of heat or cold required for discoloration, the appearance is retained in the room temperature range. The two aspects before and after the change can be stored alternately and visualized.

[0012]

EXAMPLES In the following examples, parts are parts by weight. Example 1 2 parts of pearlescent pigment (fine lead carbonate fine crystal), 5 parts
0% acrylic resin / xylene solution 50 parts, xylene 30
Parts and 30 parts of methyl isobutyl ketone were stirred and mixed,
The surface of a white spherical acrylic molded product as a support 4 was uniformly spray-coated with a spray gun to provide a pearlescent layer 2. Next, a reversible thermochromic color memory microcapsule pigment in which a reversible thermochromic material comprising 3 parts of 1,2-benz-6-diethylaminofluoran, 5 parts of bisphenol A, and 50 parts of neopentyl stearate is encapsulated with an epoxy resin film. (Decoloring temperature 30 ° C, coloring temperature 15 ° C) (P = 5
5, P '= 60 pigment) 10 parts, 50% acrylic resin /
50 parts of a xylene solution, 30 parts of xylene and 30 parts of methyl isobutyl ketone are stirred and mixed, and spray-coated evenly with a spray gun on the surface of the spherical substance provided with the pearlescent layer. To obtain a thermochromic pearl luster processed product 1 (imitation pearl). Here, T = 3
2%, T '= 35%. The obtained thermochromic pearlescent product 1 exhibits a pink color with pearly luster when colored, and when heated to 30 ° C. or more, the thermochromic material is decolorized and white with pearly luster. When cooled to 15 ° C. or lower, the thermochromic material is colored to exhibit a pearlescent pink color. Each of the above aspects could be stored alternately at room temperature of 25 ° C.

Example 2 A white urea resin was mixed with 4 parts of a pearlescent pigment (pearl essence (such as scales)) and nitrocellulose 20.
And 80 parts of ethyl acetate were immersed 5 times in a mixture obtained by stirring and mixing to form a pearlescent layer. Next, 1 part of 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 5 parts of bisphenol A, and cetyl alcohol 2
5 parts, reversible thermochromic microcapsule pigment containing 25 parts of stearyl caprate in an epoxy resin film (blue at about 30 ° C. or less, colorless at about 30 ° C. or more), 10 parts of fluorescent pink pigment 1 part, (P = 55, P '= 60 in the mixed pigment), 50 parts of 50% acrylic resin / xylene solution, 30 parts of xylene and 30 parts of methyl isobutyl ketone are stirred and mixed to be uniform on the surface of the pearlescent layer. Was spray-coated with a spray gun to provide a thermochromic layer having a dry film thickness of 20 μm to obtain a thermochromic pearl luster. Here, T = 45% and T ′ = 49%. The obtained processed product has a nacreous blue color at about 30 ° C. or lower, and has a nacreous pink color at 30 ° C. or higher.

Example 3 After 20 parts of pearlescent pigment and 1000 parts of polypropylene having a Vicat softening point of 100 ° C. were uniformly mixed, the mixture was molded using an extruder at a cylinder temperature of 165 ° C. and a gate temperature of 160 ° C. Pellets of 2-3 mm were obtained by the method. The pellet having the pearl luster was formed into a hemispherical material having a diameter of 10 mm by using an injection molding machine at a cylinder temperature of 170 ° C. A reversible thermochromic color-memory microcapsule pigment in which a reversible thermochromic material comprising 3 parts of 2-anilino-3-methyl-6-dibutylaminofluorane, 4 parts of bisphenol A, and 50 parts of neopentyl stearate is encapsulated with an epoxy resin film. (Decoloring temperature 30 ° C, coloring temperature 15
C) (Pigment of P = 55, P '= 60) 10 parts, 50 parts of 50% acrylic polyol resin / xylene solution, 30 parts of xylene, 30 parts of methyl isobutyl ketone, and 10 parts of isocyanate curing agent were stirred and mixed. The surface of the molded product having pearl luster was spray-coated with a spray gun to provide a thermochromic layer having a dry film thickness of 40 μm, to obtain a thermochromic pearl luster. Here, T = 31% and T ′ = 34%. The obtained processed product has a black color with a pearly luster when colored, and when heated to 30 ° C. or more, the thermochromic material is decolorized to a white with a pearly luster, and cooled to 15 ° C. or less. Then, the thermochromic material developed a color and exhibited a black color with a pearly luster, and at room temperature of 25 ° C., both the above aspects could be stored alternately.

Example 4 A reversible thermochromic pigment containing a reversible thermochromic material comprising 1,2-benz-6-diethylaminofluoran, bisphenol A, myristyl alcohol, and decyl myristate in an epoxy resin film (about 10 ° C.) Below, colored pink, decolored at about 15 ° C. or higher) 10 parts, fluorescent yellow pigment 5
, 50 parts of a 50% acrylic resin / xylene solution, 30 parts of xylene, and 30 parts of methyl isobutyl ketone were stirred and mixed, and a hemispherical hollow transparent molded product (bowl) The inner surface of the mold was spray-coated with a spray gun to provide a thermochromic layer having a dry film thickness of 20 μm.
Next, pearlescent pigments (Ultra Fine O, manufactured by Marl)
FS) 2 parts, 50% acrylic resin / xylene solution 50
Parts, 30 parts of xylene and 30 parts of methyl isobutyl ketone were stirred and mixed, and spray-painted on the inner surface of the thermochromic layer with a spray gun to provide a pearlescent layer to obtain a thermochromic pearlescent product. Here, T = 37% and T ′ = 40%. When the obtained processed body is viewed from the outside (transparent resin molded body side), it shows a red color with pearl luster at about 10 ° C. or less, and a fluorescent yellow color with pearl luster at about 15 ° C. or more.

Example 5 A one-component polyurethane resin solution [for dry transfer leather, solid content: about 25%, solid content: Dainippon Ink Chemicals Co., Ltd.] Co., Ltd.) was applied with a doctor knife to a concentration of 130 g / m ² and dried. Next, 5 parts of a pearl pigment (Iriodin 120, manufactured by Merck) and 60 parts of a urethane emulsion (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content: 30%) were stirred and mixed, and the mixture was coated on the coating layer with a doctor knife. Coating was performed so as to be 130 g / m ² . Subsequently, a 40D polyester tricot was joined by wet lamination, and after drying, the release paper was removed to obtain a synthetic leather having pearl luster. A reversible thermochromic color memory microcapsule pigment in which a reversible thermochromic material comprising 3 parts of 2-chloro-3-methyl-6-diethylaminofluoran, 5 parts of bisphenol A, and 50 parts of neopentyl stearate is encapsulated with an epoxy resin film [ Decoloring temperature 30 ° C, coloring temperature 1
5 ° C., (Pigment of P = 55, P ′ = 60)] 5 parts, vinyl chloride-vinyl acetate copolymer resin (Vinylite VMCH, manufactured by Union Carbide Co., Ltd.) 15 parts, silicone defoamer (NUC silicone SAG-47) 1 part of Toshiba Silicone Co., Ltd.), 40 parts of cyclohexanone, and 5 parts of a hydrocarbon-based medium boiling point solvent (Shellsol A, manufactured by Shell Chemical Co., Ltd.), and mixed. It was printed thereon and provided with a thermochromic layer having a dry film thickness of 40 μm to obtain a thermochromic pearl luster. The obtained processed product has a vermilion color with pearl luster when colored,
When heated above ℃, the thermochromic material is decolorized to white with pearl luster, and when cooled to 15 ° C or lower, the thermochromic material is colored and exhibits vermilion with pearl luster, At room temperature of 25 ° C., the compound had a tautomerism and could be stored.
Here, T = 28% and T ′ = 30%.

Comparative Example 1 A white urea resin was mixed with 4 parts of a pearlescent pigment (pearl essence (such as scale)) and nitrocellulose 20.
And 80 parts of ethyl acetate were immersed 5 times in a mixture obtained by stirring and mixing to form a pearlescent layer 2. Next, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide (1 part), bisphenol A (5 parts), cetyl alcohol (25 parts), capric acid 10 parts of a reversible thermochromic Microscapsule pigment (blue at about 30 ° C. or less, colorless at about 30 ° C. or more), 5 parts of white pigment, 5 parts of a white pigment, At P = 1
3, P '= 17) 50% acrylic resin / xylene solution 5
0 parts, xylene 30 parts and methyl isobutyl ketone 30
The mixture was stirred and mixed, and the surface of the pearlescent pigment layer was uniformly spray-coated with a spray gun to provide a thermochromic layer having a dry film thickness of 60 μm, thereby obtaining a thermochromic pearl processed body. Where T
= 3%, T '= 4%. The obtained processed body is about 3
The color is blue at 0 ° C or lower, and pink at 30 ° C or higher. This painted product does not have pearl luster at the time of coloring and decoloring.

[0018]

According to the present invention, when the thermochromic layer is colored and decolored,
It is possible to provide a thermochromic pearl luster that satisfies the decorative and intriguing properties that allow the appearance of pearl luster to be developed and that develops a variety of pearl luster due to temperature changes. , Hairpins, tie pins, cow buttons and other small items, fabrics,
It can be processed into plastic materials and can be applied to various fields such as decoration, accessories, dolls and toys.

[Brief description of the drawings]

FIG. 1 is an enlarged cross-sectional explanatory view of a thermochromic pearl luster of one embodiment of the present invention.

FIG. 2 is an enlarged cross-sectional explanatory view showing a state after discoloration of the thermochromic pearl luster product of FIG. 1;

[Explanation of symbols]

Reference Signs List 1 thermochromic pearl luster processed body 2 pearl luster layer 3 thermochromic layer 4 support

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-111957 (JP, A) JP-A-50-1258171 (JP, A) JP-A-5-137849 (JP, A) 141297 (JP, U) Japanese Utility Model Showa 64-42100 (JP, U) Japanese Utility Model Showa 62-116900 (JP, U) Japanese Utility Model Utility Model No. 5-44004 (JP, U) (58) Field surveyed (Int. ⁷ , DB name) B41M 5/28-5/34 B32B 1/00-35/00 A44C 17/00

Claims (1)

(57) [Claims] 1. A pearlescent layer comprising pearlescent pigments, electrostatic
Child-providing color-forming organic compound, electron-accepting compound and the aforementioned
An organic compound medium that determines the temperature at which both color reactions occur
Thermochromic pigments composed of miscible components in the binder
Has a thickness of 10 to 400 μm fixed in a dispersed state
An apparent transmittance (T) of light represented by the following formula at the time of color development and decoloration of the thermochromic layer:
Are both at least 5% or more. Apparent transmittance T (%) = [500 × P (% · μm)] ÷ [C (%) × D (μm)] [C is the content of the thermochromic pigment in the dried film of the thermochromic layer.
, D indicates the thickness of the dried film, and P indicates that C is 10%.
Shows the transmittance of light when colored when the film thickness is 50 μm.
The apparent transmittance T (%) at the time is expressed by P
Is 10% and the light transmittance at the time of decoloring when the film thickness is 50 μm.
Required by replacing