JP2001098171A - Metallic lustered thermochromism liquid composition and laminated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a metallic lustered thermochromism liquid composition and a laminated material rich in brilliance, exhibiting a glittery unique metallic luster color and imparting a sight of colorful appearances by a temperature change. SOLUTION: This metallic lustered thermochromism liquid composition is composed of a metallic luster pigment (A) obtained by coating the surface of an oblate glass piece with titanium oxide, a thermochromism material (B) and a vehicle (C) containing a resin. The metallic lustered thermochromism laminated material is obtained by making the liquid composition adhere on a base material and drying.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a metallic gloss thermochromic liquid composition and a laminate. More specifically, the present invention relates to a liquid composition exhibiting a variety of aspects, in which a color change due to a temperature change is visually observed together with a metallic luster color rich in glitter, and a metallic luster thermochromic laminate using the same.

[0002]

2. Description of the Related Art Several proposals have already been disclosed by the present applicant for a thermochromic paint exhibiting a metallic glossy color and a coated body obtained using the same (Japanese Patent Application Laid-Open No. 6-107974). JP-A-6-107975, JP-A-6-107976, etc.). The proposal is
It is based on a combination of a metallic luster pigment coated with titanium oxide on the surface of natural mica and a thermochromic material, which allows visualization of various color changes in metallic luster, temperature indication, decoration, toy elements, etc. It has applicability in various fields.

[0003]

SUMMARY OF THE INVENTION The present inventors have further pursued the visual effect of this type of metallic luster thermochromic material,
Compared to the above-described conventional system, a thermochromic liquid composition which is rich in glitter and has a unique metallic luster color that shines, and a metallic gloss thermochromic laminate obtained using the same. It is.

[0004]

According to the present invention, there is provided a metallic luster pigment (A) in which the surface of a flat glass piece is coated with titanium oxide,
A thermochromic material (B) containing, as essential three components, an electron-donating color-forming organic compound, an electron-accepting compound, and an organic compound medium for reversibly causing a color reaction between the two, and a vehicle containing a resin ( The requirement is a metallic glossy thermochromic liquid composition comprising C). Further, the metallic luster pigment (A)
Is that the average thickness is in the range of 1 to 10 μm and the average particle size is in the range of 5 to 500 μm. The thermochromic material (B) is obtained by encapsulating the composition containing the essential three components in microcapsules. Pigment in the form of microcapsules, a non-thermochromic colorant is added as necessary, and 100 parts by weight of the resin, 0.1 parts of the metallic luster pigment (A).
1 to 39 parts by weight, and 0.5 to 39 parts by weight of the thermochromic material (B).
(B) = 0.1 / 1 to 40/1 (weight ratio). Further, the liquid composition is required to be in the form of a paint, a printing ink, a writing ink, a cosmetic lacquer, a fiber coloring liquid, or a paint. Further, a metal glossy thermochromic laminate which is reversibly heat-discolored from a metallic glossy color to a colorless or colored color by attaching and drying the liquid composition on a support is required. still,
The non-thermochromic coloring agent described above is a general-purpose dye or pigment, and can be appropriately compounded to diversify the color change.

The present invention is characterized by the application of a metallic luster pigment (A) in which the surface of a flat glass piece is coated with titanium oxide, and a conventional metallic luster pigment in which the surface of natural mica is coated with titanium oxide. Compared to the applied system, it produces a glittering, metallic luster luminous effect, and the luminous effect is visually perceived as having a perspective and a three-dimensional effect, and the color change effect due to the temperature change of the coexisting thermochromic material. A variety of appearances that weaving are brought out. To supplement the effect,
Since the metallic luster pigment (A) exists in a non-planar state due to the partial overlap of individual pigments, the glitter and the color tone are slightly changed, and various forms having a three-dimensional effect as a whole are visually recognized. Let it. Here, even if the individual pigments are present in the overlapping portion, the color change due to the thermochromic material (B) can be achieved without impairing the original metallic luster brilliant effect depending on the transparency of the pigments themselves. Can be seen through, and the appearance of change can be diversified and visualized.

As the metallic luster pigment (A), Nippon Glass Fiber Co., Ltd. obtained by coating a scale-like glass piece with titanium oxide.
Product name "Metashine" part number: RCFSX-545
0TS (6041) [average thickness 5 ± 2 μm, average particle size 4
50 ± 145 μm, gold], RCF0X-5200TS
(6042) [average thickness 5 ± 2 μm, average particle size 200 ±
70 μm, silver color], RCFSX-5140TS (604
3) [average thickness 5 ± 2 μm, average particle size 140 ± 45 μm
m, silver], RCFSX-5080TS (6044)
[Average thickness 5 ± 2 μm, average particle size 80 ± 30 μm, silver color], RCFSX-2080TS (6046) [Average thickness 2 ± 1 μm, average particle size 80 ± 30 μm, silver color], RC
FSX-K120TS (6043) [Average thickness 20 ± 5
μm, average particle size 120 ± 20 μm, silver color], RCFSX
-5090RC (8052) [Average thickness 5 ± 2 μm, average particle size 90 ± 30 μm, gold color], RCFSX-5090
RC (8053) [average thickness 5 ± 2 μm, average particle size 90
± 30 μm, metallic green], RCFSX-50
90RC (8069) [average thickness 5 ± 2 μm, average particle size 90 ± 30 μm, metallic blue], RCFSX-5
090RC (8070) [Average thickness 5 ± 2 μm, average particle size 90 ± 30 μm, metallic purple], RCFSX
-5090RC (8071) [average thickness 5 ± 2 μm, average particle size 90 ± 30 μm, metallic red] and the like.

The thermochromic material (B) contains, as essential three components, an electron-donating color-forming organic compound, an electron-accepting compound, and an organic compound medium which reversibly causes a color reaction between the two. Conventionally known thermochromic compositions are effective. For example, Japanese Patent Publication No. 51-44 proposed by the present applicant is effective.
No. 706, JP-B-51-44707, JP-B-1-29398 and the like can be used. The color changes before and after a predetermined temperature (color change point) as a boundary, shows a decolored state in a temperature range higher than the color change point, and a color developed state in a temperature range lower than the color change point. Only one particular state can exist. That is, the other state is maintained while the heat or cold required for the state to appear is applied, but returns to the state exhibited in the normal temperature range when the application of the heat or cold disappears, the hysteresis width. Is a heat-decoloring type thermochromic material exhibiting relatively small thermochromic behavior. In addition, Japanese Patent Publication No. 4-1715 proposed by the present applicant.
4, JP-A-7-179777, JP-A-7-179
No. 33997, Japanese Unexamined Patent Publication No. 8-39936, etc. exhibit a large hysteresis characteristic, that is, the shape of the curve plotting the change in the coloring density due to the temperature change shows that the temperature rises from a lower temperature side than the discoloration temperature range. The color changes in a temperature range below the low-temperature side discoloration point, or the temperature above the high-temperature side discoloration point. A color storage type thermochromic material that can be stored alternately in a normal temperature range between the two color changing points even if the decolored state in the region is after removing the application of cold or heat required for the color change. Can be used. Japanese Patent Application Laid-Open No. 11-129 proposed by the present applicant
No. 623, Japanese Unexamined Patent Publication No. 11-5973, etc., and a heat-coloring-type thermochromic method using a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms as an electron accepting compound. A conductive material can be applied.

The thermochromic material (B) can be effectively applied as it is to the composition comprising the essential three components.
Pigment form, for example, fine granules obtained by blending the composition with a binder resin, those obtained by coating the surface of the fine granules with another resin, and microcapsules in which the composition is encapsulated in microcapsules Pigments are effective. Among them, pigments in the form of microcapsules satisfy vivid and high-concentration color development, homogeneity, dispersion stability, chemical resistance and the like, and are practically suitable. The microencapsulation is carried out by a conventionally known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method, air suspension. It can be carried out by applying a coating method, a spray drying method or the like. Depending on the purpose, a secondary resin film may be further provided on the surface of the pigment to impart durability, or the surface properties may be modified for practical use. In the pigment in the microcapsule form, the average particle diameter [(major axis + minor axis) / 2]
It is effective in the range of 0.5 to 100 μm, preferably 1 to 30 μm, more preferably 3 to 10 μm, in terms of the sharpness of discoloration, endurance, workability and the like.

As the resin contained in the above-mentioned vehicle (C), those conventionally applied to general-purpose paints, printing inks, inks for writing implements, cosmetic lacquers, and other coloring materials are effective. Specifically, ionomer resin, isobutylene-maleic anhydride copolymer resin, acrylonitrile-acrylic styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-chlorinated polyethylene-styrene copolymer resin, ethylene-vinyl acetate copolymer resin Polymerized resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinylidene chloride, vinyl chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, Polystyrene resin, high impact polystyrene resin, polypropylene resin, polymethylstyrene resin, polyacrylic acid resin,
Polymethyl methacrylate resin, epoxy resin, epoxy acrylate resin, alkyl phenol resin, rosin-modified phenol resin, rosin-modified alkyd resin, phenol resin-modified alkyd resin, styrene-modified alkyd resin, acryl-modified alkyd resin, amino alkyd resin,
Vinyl chloride-vinyl acetate resin, styrene-butadiene resin, unsaturated polyester resin, polyurethane resin, vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylate emulsion resin, water-soluble melamine resin, water-soluble urea resin, Water-soluble phenol resins, water-soluble epoxy resins, water-soluble polybutadiene resins, and cellulose derivatives such as cellulose acetate and ethyl cellulose are exemplified.

The above resin is dissolved or dispersed in water, an organic solvent or the like to form a vehicle (C), and the above metallic luster pigment (A) and thermochromic material (B) are dispersed to form a metallic luster. A thermochromic liquid composition is obtained. Incidentally, in the vehicle, an ultraviolet absorber, an infrared absorber, an antioxidant,
Add additives such as singlet oxygen quenchers, antioxidants, antistatic agents, thixotropic agents, defoamers, plasticizers, extenders, lubricants, and foaming agents as necessary to improve their functions. Can be.

The metallic luster pigment (A) is used in an amount of 0.1 to 39 parts by weight (preferably 1 to 100 parts by weight of the resin).
10 to 10 parts by weight), 0.5 to 39 parts by weight (preferably 1 to 10 parts by weight) of the thermochromic material (B), and (A) / (B) = 0. 1/1 to 4
0/1 (weight ratio), preferably 0.5 / 1 to 30/1
Weight ratio, etc. (A),
By satisfying the weight ratio between (B) and (C), a unique aspect in which the glittering effect and the thermochromic effect are fused can be effectively exhibited.

The metallic glossy thermochromic laminate of the present invention is obtained by adhering the above-mentioned liquid composition to the surface of a support by a known means and drying it. For example, screen printing, offset printing, gravure printing, coater, tampo printing,
By printing means such as transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc., or by handwriting with an application tool with a coating body, writing instrument, etc. An appropriately shaped film can be formed at a desired position on the support. The support is not particularly limited in material, and is all effective. Paper, synthetic paper, cloth, synthetic leather,
Leather, plastic, glass, porcelain, metal, wood,
A stone material or the like can be exemplified, and the shape is not limited to a flat shape, but may be an uneven shape, or may be a fibrous shape or the like. In the case where a non-thermochromic coloring layer (including an image) is previously formed on the support, the coloring layer can be hidden by a temperature change, and the aspect of the change can be further varied. Can be changed.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid composition of the present invention is used in the form of paints, printing inks, writing implement inks, cosmetic lacquers, coloring liquids for fibers, paints, and the like. The liquid composition is deposited on a support by a suitable means and dried to form a film. The film is laminated to form a metallic gloss thermochromic laminate.

[0014]

EXAMPLES Examples will be described below, but the present invention is not limited to these examples. The parts in the examples are parts by weight.

EXAMPLE 1 A golden metallic luster pigment in which the surface of a flaky glass piece is coated with titanium oxide [RCFSX-, manufactured by Nippon Glass Fiber Co., Ltd.
5090RC (8052), average thickness 5 ± 2 μm, average particle size 90 ± 30 μm] 15 parts, thermosetting material in the form of microcapsules having an average particle diameter of 8 μm 8 parts, acrylate resin (50% xylene solution) 50 parts, Xylene 3
0 parts and 30 parts of methyl isobutyl ketone were uniformly mixed to obtain a metallic glossy thermochromic paint. The paint was spray-coated on a white styrene-based resin plate to obtain a metallic glossy thermochromic laminate. Here, the thermochromic material is a phase composed of 3 parts of 2-anilino-3-methyl-6-dibutylaminofluorane, 6 parts of 4,4 ′-(2-methyl-propylidene) bisphenol, and 50 parts of neopentyl stearate. It is a microcapsule pigment obtained by encapsulating a thermochromic composition composed of a solution by an interfacial polymerization method of an epoxy resin / amine curing agent, and has two color changing points (a low-temperature color changing point: 15 ° C., a high-temperature color changing point: (30 ° C.). When the thermochromic material develops a black color at 15 ° C. or less, reflects light having a wavelength of 550 to 600 nm, which is a part of incident light, and absorbs light having other wavelengths, the metallic material has a gold color. Glossy color, 30 ° C
When the thermochromic material decolorizes and reflects transmitted light,
Since all the incident light is reflected, the golden metallic glossy color disappears and becomes colorless, and at room temperature of 25 ° C., each aspect in the coloring state or the decoloring state is alternately stored and held. Seen all the way.

Example 2 Metallic blue metallic luster pigment (trade name RCFSX-5090RC (8069), manufactured by Nippon Glass Fiber Co., Ltd., average thickness 5 ± 2 μm, average) Particle size 90 ± 30 μm] 10 parts, thermochromic material 10 in the form of microcapsules having an average particle size of 8 μm
Parts, 2 parts of a fluorescent pink pigment, 50 parts of an acrylate resin (50% xylene solution), 30 parts of xylene and 30 parts of methyl isobutyl ketone were uniformly mixed to obtain a metallic glossy thermochromic paint. Using the above-mentioned paint, spray-coat on a white styrene-based resin molded body and have a thickness of about 100
A μm metallic glossy thermochromic laminate was obtained. Here, the thermochromic material is 1 part of 3- (diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 4,4 ′-( 2
-Methyl-propylidene) a microcapsule pigment obtained by encapsulating a thermochromic composition comprising a compatibilizer of 6 parts of bisphenol and 50 parts of neopentyl stearate by an interfacial polymerization method of an epoxy resin / amine curing agent. It is a color memory type thermochromic material having a discoloration point (low-temperature side discoloration point: 15 ° C., high-temperature side discoloration point: 30 ° C.). When the thermochromic material develops a blue color at 15 ° C. or less, reflects light having a wavelength of 430 to 500 nm, which is a part of incident light, and absorbs light having other wavelengths, it has a metallic blue color. When the thermochromic material decolorizes at 30 ° C. or more and reflects transmitted light, it reflects all incident light, the metallic blue metallic gloss disappears and becomes pink, At room temperature of 25 ° C., the respective aspects in the color-developed state or the decolored state are alternately stored and held, and are visually observed alternatively.

Example 3 A metallic purple color in which the surface of a flaky glass piece is coated with titanium oxide [RCFS, manufactured by Nippon Glass Fiber Co., Ltd.
X-5090RC (8070), average thickness 5 ± 2μ
m, average particle size 90 ± 30 μm] 15 parts, average particle size 8 μ
8 parts of the thermochromic material in the form of microcapsules, 50 parts of an acrylate resin (50% xylene solution), 30 parts of xylene and 30 parts of methyl isobutyl ketone are uniformly mixed to obtain a metallic gloss thermochromic paint. Was. The paint was spray-coated on a fluorescent yellow styrene resin plate to obtain a metallic glossy thermochromic laminate. Here, the thermochromic material is composed of 3 parts of 2-anilino-3-methyl-6-dibutylaminofluorane, 6 parts of 4,4 ′-(2-methyl-propylidene) bisphenol, and 2 parts of cetyl alcohol.
This is a microcapsule pigment (discoloration point: 30 ° C.) obtained by encapsulating a thermochromic composition comprising 5 parts and 25 parts of stearyl caprate by an interfacial polymerization method of an epoxy resin / amine curing agent. In the laminate, the thermochromic material develops a black color at 30 ° C. or lower, and 380 which is a part of the incident light.
Reflecting light having a wavelength of ４430 nm and absorbing light of other wavelengths, the color becomes a metallic-purple metallic glossy color. At 30 ° C. or higher, the thermochromic material loses its color, and when transmitting light is reflected, incident light is reflected. All are reflected, the metallic purple metallic luster color disappears and becomes fluorescent yellow, and each aspect in the color-developed state or the decolored state is visually reversible.

Example 4 Metallic blue metallic luster pigment (trade name RCFSX-5090RC (8069), manufactured by Nippon Glass Fiber Co., Ltd., average thickness 5 ± 2 μm, average) Particle size: 90 ± 30 μm] 20 parts, 10 parts of the thermochromic material in the form of microcapsules having an average particle diameter of 8 μm used in Example 2, 70 parts of an acrylate resin emulsion, 1 part of a crosslinking agent, and 0.5 part of an antifoaming agent It was dispersed to obtain a metallic glossy thermochromic printing ink. The ink was screen-printed on pink paper to obtain a metallic glossy thermochromic laminate. In the laminate, the thermochromic material develops a blue color at 15 ° C. or less, and 430 to 500 which is a part of the incident light.
Reflecting light of nm wavelength and absorbing light of other wavelengths, it becomes a metallic blue metallic glossy color. The thermochromic material loses its color at 30 ° C or higher, and when transmitted light is reflected, all incident light is reflected. Will be reflected, the metallic blue metallic glossy color will disappear and become pink, and at room temperature of 25 ° C., the respective aspects in the coloring state or the decoloring state are alternately stored and held, Visually viewed as an alternative.

[0019]

According to the present invention, there is provided a unique metal having a variety of appearances in which a color change due to a temperature change and a glittering effect of metallic luster are interwoven, and the change in appearance is seen as an appearance accompanied by transparency and a three-dimensional effect. Glossy thermochromic liquid composition, and a metal gloss thermochromic laminate having the same effect by attaching the liquid composition on a support can be provided, and toy properties, decorative properties, thermodynamic properties, It can be applied to various fields that require saliency, design, etc.

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Claims (7)

[Claims] 1. A reversible color reaction between a metallic luster pigment (A) in which the surface of a flat glass piece is coated with titanium oxide, an electron-donating color-forming organic compound and an electron-accepting compound, and both of them. A metallic luster thermochromic liquid composition comprising a thermochromic material (B) containing, as essential three components, an organic compound medium to be made, and a vehicle (C) containing a resin. 2. The metallic luster pigment (A) has an average thickness of 1
-10 μm, average particle size is 5-500 μm
The metallic glossy thermochromic liquid composition according to claim 1, wherein 3. The thermochromic liquid having metallic luster according to claim 1, wherein the thermochromic material (B) is a pigment in the form of microcapsules in which the composition containing the essential three components is encapsulated in microcapsules. Composition. 4. The metallic glossy thermochromic liquid composition according to claim 1, further comprising a non-thermochromic colorant. 5. A metal luster pigment (A) in an amount of 0.1 to 39 parts by weight and a thermochromic material (B) 0.5 in 100 parts by weight of a resin.
The composition according to any one of claims 1 to 4, wherein the composition is blended in a proportion of up to 39 parts by weight and satisfies the ratio (A) / (B) = 0.1 / 1 to 40/1 (weight ratio). The metallic glossy thermochromic liquid composition according to the above. 6. A paint, a printing ink, a writing implement ink,
The metallic luster thermochromic liquid composition according to any one of claims 1 to 5, which is in the form of a cosmetic lacquer, a coloring liquid for fibers, or a paint. 7. A metallic luster that is reversibly heat-discolored from a metallic luster color to colorless or colored by applying and drying the liquid composition according to any one of claims 1 to 6 on a support. Thermochromic laminate.