JP7437121B2 - Glittering reversible photochromic flat yarn and products using the same - Google Patents

Description

The present invention relates to a glittering reversible photochromic flat yarn and products using the same. More specifically, the present invention relates to a glittering, reversible photochromic flat thread that changes color when irradiated with light, and in which the color change and glittering properties are visible from both the front and back sides, and products using the same.

Conventionally, reversible photochromic gold and silver threads have been disclosed in which a resin layer (photochromic layer) dyed with a photochromic dye is provided on the side where the metal vapor deposition layer is visible (for example, see Patent Document 1).
The reversible photochromic gold and silver thread is made by providing a photochromic layer on a metal vapor deposited layer, and the color change from a metallic luster color to another tone can be reversibly visually recognized by irradiation with light of a predetermined wavelength. However, the color change is only visible on the side where the photochromic layer is provided on the metal vapor deposited layer, and by sequentially providing the metal vapor deposited layer and the photochromic layer on both sides of the base material, the color change when irradiated with light can be observed on both sides. Although it was visible on both sides, the gold and silver threads became thicker and sometimes lost the soft texture of the threads.

Japanese Unexamined Patent Publication No. 139839/1983

The present invention aims to provide a glittering, reversible photochromic flat yarn that has a flexible texture, and whose color change and glittering properties are visible from both the front and back sides when irradiated with light, and products using the same. .

The present invention provides reversible light on one wide surface of a flat thread made of a transparent glittering resin film having optical properties selected from metallic luster, pearl luster, hologram, iris, and light reflectivity. A glittering reversible photochromic flat thread provided with a first reversible photochromic layer containing a color-changing material,
The metallic luster is a transparent metallic luster pigment obtained by coating the surface of a glass piece with a metal oxide, a cholesteric liquid crystal type metallic luster pigment, or a transparent metallic luster obtained by coating silicon oxide with one or more kinds of metal oxides. It is due to any of the pigments,
The pearlescent property is achieved by a transparent pearlescent pigment obtained by coating the surface of natural mica, synthetic mica, or flaky aluminum oxide with a metal oxide, or by using 10 or more layers of polymers with different refractive indexes. A transparent multilayer film exhibiting a light interference phenomenon provided in an intermediate layer is a transparent pearlescent resin film containing a translucent dye in the multilayer film,
The hologram property is based on a relief hologram in which a transparent reflective layer is formed on the surface of the uneven pattern on a transparent hologram forming layer provided with a fine uneven pattern, or a volume hologram,
The iris has a polypropylene layer on the front and back outermost layers, and 113 thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene are alternately formed inside , and has blue reflected light and green interference light. A transparent multilayer film with a thickness of 15 μm , the outermost layers on the front and back are polypropylene layers, and the inside has 113 alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layers on the front and back are polypropylene layers, and the inside is made up of 226 alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene , blue reflection. A transparent multilayer film with a thickness of 28 μm that emits light and green interference light , the outermost layer on the front and back is a polypropylene layer, and the inside has 226 layers of alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene. , a transparent multilayer film with a thickness of 31 μm that has red reflected light and green interference light, the outermost layer on the front and back is a polyester layer, and the inside has 113 alternating thin layers of polyester and thin layers of polyolefin , a blue film. A transparent multilayer film with a thickness of 15 μm that has reflected light of A transparent multilayer film with a thickness of 17 μm that has light and green interference light, the outermost layer on the front and back is a polypropylene layer , and the inside has 113 alternating thin layers of polyolefin and thin layers of polyester. A transparent multilayer film with a thickness of 15 μm that has green interference light , the outermost layer on the front and back is a polypropylene layer, and the inside has 113 alternating thin layers of polyolefin and thin layers of polyester. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 alternating thin layers of polyester and thin layers of acrylic resin , and has blue reflected light and green light. A transparent multilayer film with a thickness of 15 μm that has interference light , the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 layers of alternating polyester thin layers and acrylic resin thin layers, red reflected light and green reflected light. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 alternating thin layers of polyester and thin layers of acrylic resin, and has blue reflected light and green light. A transparent multilayer film with a thickness of 30 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 layers of alternating polyester thin layers and acrylic resin thin layers, red reflected light and green reflected light. A 34 μm transparent multilayer film with interference light, the outermost layers on the front and back are acrylic resin layers, and the inside is made up of 226 alternating thin layers of polyester and thin layers of acrylic resin , blue reflected light and green interference light. A transparent multilayer film with a thickness of 28 μm , the front and back outermost layers are acrylic resin layers, and the inside is made up of 226 alternating layers of polyester thin layers and acrylic resin thin layers, red reflected light and green interference light. A transparent multilayer film with a thickness of 31 μm, the outermost layers on the front and back are polyester layers, and the inside is made up of 113 thin layers of polyester and thin layers of acrylic resin , which emit blue reflected light and green interference light. A transparent multilayer film with a thickness of 15 μm , the outermost layer on the front and back is a polyester layer, and 113 thin layers of polyester and thin layers of acrylic resin are alternately formed inside, and the film has a thickness of 17 μm. Either by a transparent multilayer film with interference light ,
The light reflection property is due to a transparent light reflection film having a structure in which a plurality of polyester thin films are laminated with their stretching axes shifted,
The transparency is a requirement for the glittering, reversible photochromic flat thread having the property of transmitting light in the wavelength range of 380 to 780 nm as defined by JIS B 7079.
Furthermore, a second reversible photochromic layer containing a reversible photochromic material is provided on the opposite wide side of the flat yarn made of the transparent glitter resin film on which the first reversible photochromic layer is provided. The requirement is that the
Furthermore, a first reversible photochromic layer containing a reversible photochromic material is provided on one wide surface of a flat thread made of a transparent resin film, and the first reversible photochromic layer is provided. A glittering reversible photochromic flat yarn comprising a transparent glittering layer having an optical property selected from metallic luster, pearlescent properties, holographic properties, iris properties, and light reflectivity on the opposite wide side. And,
The metallic luster is a transparent metallic luster pigment obtained by coating the surface of a glass piece with a metal oxide, a cholesteric liquid crystal type metallic luster pigment, or a transparent metallic luster obtained by coating silicon oxide with one or more kinds of metal oxides. It is due to any of the pigments,
The pearlescent property is achieved by a transparent pearlescent pigment obtained by coating the surface of natural mica, synthetic mica, or flaky aluminum oxide with a metal oxide, or by using 10 or more layers of polymers with different refractive indexes. A transparent multilayer film exhibiting a light interference phenomenon provided in an intermediate layer is a transparent pearlescent resin film containing a translucent dye in the multilayer film,
The hologram property is based on a relief hologram in which a transparent reflective layer is formed on the surface of the uneven pattern on a transparent hologram forming layer provided with a fine uneven pattern, or a volume hologram,
The iris has a polypropylene layer on the front and back outermost layers, and 113 thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene are alternately formed inside , and has blue reflected light and green interference light. A transparent multilayer film with a thickness of 15 μm , the outermost layers on the front and back are polypropylene layers, and the inside has 113 alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layers on the front and back are polypropylene layers, and the inside is made up of 226 alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene , blue reflection. A transparent multilayer film with a thickness of 28 μm that emits light and green interference light , the outermost layer on the front and back is a polypropylene layer, and the inside has 226 layers of alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene. , a transparent multilayer film with a thickness of 31 μm that has red reflected light and green interference light, the outermost layer on the front and back is a polyester layer, and the inside has 113 alternating thin layers of polyester and thin layers of polyolefin , a blue film. A transparent multilayer film with a thickness of 15 μm that has reflected light of A transparent multilayer film with a thickness of 17 μm that has light and green interference light, the outermost layer on the front and back is a polypropylene layer , and the inside has 113 alternating thin layers of polyolefin and thin layers of polyester. A transparent multilayer film with a thickness of 15 μm that has green interference light , the outermost layer on the front and back is a polypropylene layer, and the inside has 113 alternating thin layers of polyolefin and thin layers of polyester. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 alternating thin layers of polyester and thin layers of acrylic resin , and has blue reflected light and green light. A transparent multilayer film with a thickness of 15 μm that has interference light , the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 layers of alternating polyester thin layers and acrylic resin thin layers, red reflected light and green reflected light. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 alternating thin layers of polyester and thin layers of acrylic resin, and has blue reflected light and green light. A transparent multilayer film with a thickness of 30 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 layers of alternating polyester thin layers and acrylic resin thin layers, red reflected light and green reflected light. A 34 μm transparent multilayer film with interference light, the outermost layers on the front and back are acrylic resin layers, and the inside is made up of 226 alternating thin layers of polyester and thin layers of acrylic resin , blue reflected light and green interference light. A transparent multilayer film with a thickness of 28 μm , the front and back outermost layers are acrylic resin layers, and the inside is made up of 226 alternating layers of polyester thin layers and acrylic resin thin layers, red reflected light and green interference light. A transparent multilayer film with a thickness of 31 μm, the outermost layers on the front and back are polyester layers, and the inside is made up of 113 thin layers of polyester and thin layers of acrylic resin , which emit blue reflected light and green interference light. A transparent multilayer film with a thickness of 15 μm , the outermost layer on the front and back is a polyester layer, and 113 thin layers of polyester and thin layers of acrylic resin are alternately formed inside, and the film has a thickness of 17 μm. Either by a transparent multilayer film with interference light ,
The light reflection property is due to a transparent light reflection film having a structure in which a plurality of polyester thin films are laminated with their stretching axes shifted,
The transparency is a requirement for the glittering, reversible photochromic flat thread having the property of transmitting light in the wavelength range of 380 to 780 nm as defined by JIS B 7079.
Furthermore, a first reversible photochromic layer containing a reversible photochromic material is provided on one wide side of the flat thread made of a transparent resin film, and metallic luster, pearlescent luster, hologram luster, iris luster, A glittering reversible photochromic flat yarn comprising a transparent glittering layer having optical properties selected from light reflecting properties,
The metallic luster is a transparent metallic luster pigment obtained by coating the surface of a glass piece with a metal oxide, a cholesteric liquid crystal type metallic luster pigment, or a transparent metallic luster obtained by coating silicon oxide with one or more kinds of metal oxides. It is due to any of the pigments,
The pearlescent property is achieved by a transparent pearlescent pigment obtained by coating the surface of natural mica, synthetic mica, or flaky aluminum oxide with a metal oxide, or by using 10 or more layers of polymers with different refractive indexes. A transparent multilayer film exhibiting a light interference phenomenon provided in an intermediate layer is a transparent pearlescent resin film containing a translucent dye in the multilayer film,
The hologram property is based on a relief hologram in which a transparent reflective layer is formed on the surface of the uneven pattern on a transparent hologram forming layer provided with a fine uneven pattern, or a volume hologram,
The iris has a polypropylene layer on the front and back outermost layers, and 113 thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene are alternately formed inside , and has blue reflected light and green interference light. A transparent multilayer film with a thickness of 15 μm , the outermost layers on the front and back are polypropylene layers, and the inside has 113 alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layers on the front and back are polypropylene layers, and the inside is made up of 226 alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene , blue reflection. A transparent multilayer film with a thickness of 28 μm that emits light and green interference light , the outermost layer on the front and back is a polypropylene layer, and the inside has 226 layers of alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene. , a transparent multilayer film with a thickness of 31 μm that has red reflected light and green interference light, the outermost layer on the front and back is a polyester layer, and the inside has 113 alternating thin layers of polyester and thin layers of polyolefin , a blue film. A transparent multilayer film with a thickness of 15 μm that has reflected light of A transparent multilayer film with a thickness of 17 μm that has light and green interference light, the outermost layer on the front and back is a polypropylene layer , and the inside has 113 alternating thin layers of polyolefin and thin layers of polyester. A transparent multilayer film with a thickness of 15 μm that has green interference light , the outermost layer on the front and back is a polypropylene layer, and the inside has 113 alternating thin layers of polyolefin and thin layers of polyester. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 alternating thin layers of polyester and thin layers of acrylic resin , and has blue reflected light and green light. A transparent multilayer film with a thickness of 15 μm that has interference light , the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 layers of alternating polyester thin layers and acrylic resin thin layers, red reflected light and green reflected light. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 alternating thin layers of polyester and thin layers of acrylic resin, and has blue reflected light and green light. A transparent multilayer film with a thickness of 30 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 layers of alternating polyester thin layers and acrylic resin thin layers, red reflected light and green reflected light. A 34 μm transparent multilayer film with interference light, the outermost layers on the front and back are acrylic resin layers, and the inside is made up of 226 alternating thin layers of polyester and thin layers of acrylic resin , blue reflected light and green interference light. A transparent multilayer film with a thickness of 28 μm , the front and back outermost layers are acrylic resin layers, and the inside is made up of 226 alternating layers of polyester thin layers and acrylic resin thin layers, red reflected light and green interference light. A transparent multilayer film with a thickness of 31 μm, the outermost layers on the front and back are polyester layers, and the inside is made up of 113 thin layers of polyester and thin layers of acrylic resin , which emit blue reflected light and green interference light. A transparent multilayer film with a thickness of 15 μm , the outermost layer on the front and back is a polyester layer, and 113 thin layers of polyester and thin layers of acrylic resin are alternately formed inside, and the film has a thickness of 17 μm. Either by a transparent multilayer film with interference light ,
The light reflection property is due to a transparent light reflection film having a structure in which a plurality of polyester thin films are laminated with their stretching axes shifted,
The transparency is a requirement for the glittering, reversible photochromic flat thread having the property of transmitting light in the wavelength range of 380 to 780 nm as defined by JIS B 7079.
Furthermore, a second photochromic layer containing a reversible photochromic material is provided on the opposite wide side of the flat thread made of the transparent resin film on which the first photochromic layer and the transparent glitter layer are provided. The reversible photochromic material contained in the first and second photochromic layers is a material that exhibits different colors when colored, and the reversible photochromic material contained in the first and second photochromic layer The reversible photochromic material to be used is one in which at least one of the color development time and the color erasure time is different from each other, and the photoluminescent reversible photochromic flat thread in the color development state has a wavelength of 380 nm to 780 nm using a spectrophotometer. The requirements are that the median value between the maximum value and the minimum value of visible light transmittance measured in the area is 5% or more, and that the product contains the glittering reversible photochromic flat yarn.

The present invention provides a reversible photochromic layer that has a flexible texture and contains a reversible photochromic material, and the color change and glitter due to light irradiation are visible from both the front and back sides, and is used in the toy field, decoration field, design field, etc. , it is possible to provide a glittering reversible photochromic flat thread with high commerciality and applicability to a variety of fields, and products using the same.

FIG. 1 is a longitudinal cross-sectional view of an embodiment of the glittering reversible photochromic flat yarn of the present invention. FIG. 3 is a longitudinal cross-sectional view of another example of the glittering reversible photochromic flat thread of the present invention. FIG. 3 is a longitudinal cross-sectional view of another example of the glittering reversible photochromic flat thread of the present invention. FIG. 3 is a longitudinal cross-sectional view of another example of the glittering reversible photochromic flat thread of the present invention. FIG. 3 is a longitudinal cross-sectional view of another example of the glittering reversible photochromic flat thread of the present invention. FIG. 3 is a longitudinal cross-sectional view of another example of the glittering reversible photochromic flat thread of the present invention. FIG. 3 is a longitudinal cross-sectional view of another example of the glittering reversible photochromic flat thread of the present invention. FIG. 3 is a longitudinal cross-sectional view of another example of the glittering reversible photochromic flat thread of the present invention. FIG. 3 is a longitudinal cross-sectional view of another example of the glittering reversible photochromic flat thread of the present invention. FIG. 3 is a longitudinal cross-sectional view of another example of the glittering reversible photochromic flat thread of the present invention. FIG. 3 is a longitudinal cross-sectional view of another example of the glittering reversible photochromic flat thread of the present invention. FIG. 3 is a longitudinal cross-sectional view of another example of the glittering reversible photochromic flat thread of the present invention.

As shown in FIG. 1, the glittering reversible photochromic flat yarn (1) of the present invention is transparent and has optical properties selected from metallic luster, pearlescent luster, holographic nature, iris luster, and light reflective nature. A first reversible photochromic layer (3) containing a reversible photochromic material is provided on one wide surface of a flat thread made of a glittering resin film (2).
Further, as shown in FIG. 2, a second reversible photochromic material containing a reversible photochromic material is provided on the opposite wide side of the flat yarn made of the transparent glitter resin film on which the first reversible photochromic layer is provided. A structure including a layer (4) can also be provided.

A transparent glittering resin film having metallic luster can be prepared by melt-blending a transparent metallic luster pigment into a transparent thermoplastic resin or a transparent thermosetting resin to form a molding resin such as pellets, powder, or paste. A single-layer transparent glittering resin film can be used, which is obtained by preparing a composition and molding it into a planar form such as a sheet or film by various molding methods such as extrusion molding, calendar molding, and inflation molding.
In addition, liquid compositions such as printing inks and paints prepared by dispersing transparent metallic luster pigments in a vehicle can be applied to printing methods such as screen printing, offset printing, process printing, gravure printing, coaters, pad printing, and transfer. A laminate in which a transparent glitter layer (transparent metallic luster layer) is formed on a transparent support by coating methods such as brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, and dip coating. It is also possible to use a transparent glittering resin film having the following structure.
As the flat thread made of the transparent glitter resin film, a transparent glitter resin film having a single layer or a laminated structure can be used.
The transparent glitter layer is a layer formed by evaporation of the solvent in the liquid composition and other compounds.

Specifically, the transparent metallic luster pigments include transparent metallic luster pigments in which the surface of a core material such as a glass piece is coated with a metal oxide such as titanium oxide, zirconium oxide, chromium oxide, vanadium oxide, or iron oxide. , transparent metallic luster pigments having color flop properties, and the like.

The transparent metallic luster pigment in which the surface of a core substance such as a glass piece is coated with a metal oxide is a transparent metallic pigment in which the core substance is a flake-shaped glass piece and the surface thereof is coated with a metal oxide such as titanium oxide. Examples include glossy pigments and two-layer coated transparent metallic luster pigments in which a borosilicate glass piece is used as a core material, the surface of which is coated with silicon dioxide, and further coated with titanium oxide.
A transparent metallic luster pigment in which the flake-shaped glass piece is used as a core material and the surface thereof is coated with a metal oxide such as titanium oxide has high metallic luster and transparency due to the use of glass as the core material. Furthermore, depending on the coverage of the metal oxide, it exhibits metallic luster such as gold, silver, copper, or metallic color. Specifically, the transparent metallic luster pigment in which the surface of the flake-shaped glass piece is coated with titanium oxide is manufactured by Nippon Sheet Glass Co., Ltd., trade name: Metashine 5090RS (average particle size: 90 μm, thickness: 5 μm, color tone). : silver color), 5090RY (average particle size: 90 μm, thickness: 5 μm, color tone: gold), 5090RR (average particle size: 90 μm, thickness: 5 μm, color tone: metallic red), 5090RB (average particle size: 90 μm, Thickness: 5 μm, color tone: metallic blue), 5090RG (average particle size: 90 μm, thickness: 5 μm, color tone: metallic green), 1080RS (average particle size: 80 μm, thickness: 1 μm, color tone: silver), 1080RY (average Particle size: 80 μm, thickness: 1 μm, color tone: golden), 1080RR (average particle size: 80 μm, thickness: 1 μm, color tone: metallic red), 1080RB (average particle size: 80 μm, thickness: 1 μm, color tone: metallic blue) ), 1080RG (average particle size: 80 μm, thickness: 1 μm, color tone: metallic green), 1040RS (average particle size: 40 μm, thickness: 1 μm, color tone: silver), 1040RY (average particle size: 40 μm, thickness: 1 μm) , color tone: golden), same 1040RR (average particle size: 40 μm, thickness: 1 μm, color tone: metallic red), same 1040RB (average particle size: 40 μm, thickness: 1 μm, color tone: metallic blue), same 1040RG (average particle size : 40 μm, thickness: 1 μm, color tone: metallic green), 1030RS (average particle size: 30 μm, thickness: 1 μm, color tone: silver), 1030RY (average particle size: 30 μm, thickness: 1 μm, color tone: gold), 1030RR (average particle size: 30 μm, thickness: 1 μm, color tone: metallic red), 1030RB (average particle size: 30 μm, thickness: 1 μm, color tone: metallic blue), 1030RG (average particle size: 30 μm, thickness: 1 μm, color tone) : metallic green), E025RS (average particle size: 25 μm, thickness: 0.5 μm, color tone: silver), E025RY (average particle size: 25 μm, thickness: 0.5 μm, color tone: gold), E025RR (average particle size) : 25 μm, thickness: 0.5 μm, color tone: metallic red), E025RB (average particle size: 25 μm, thickness: 0.5 μm, color tone: metallic blue), E025RG (average particle size: 25 μm, thickness: 0.5 μm) , color tone: metallic green).
Note that the average particle diameter is an average particle diameter determined by a laser diffraction method, and is a particle diameter whose volume-based median diameter corresponds to 50% of the cumulative distribution.

The two-layer coated transparent metallic luster pigment is made by using the borosilicate glass piece as a core material, the surface of which is coated with silicon dioxide, and further coated with titanium oxide. Because it has excellent impact resistance, heat resistance, and chemical resistance, it can maintain a state of being difficult to break even if the thickness of the core material is reduced. Therefore, it is possible to reduce the mass per reflective area and to improve the light transmittance of the pigment. Furthermore, depending on the coverage of the metal oxide, it exhibits metallic luster such as gold, silver, copper, or metallic color.
Specifically, the transparent metallic luster pigment in which the surface of the borosilicate glass piece is coated with silicon dioxide and further coated with titanium oxide is Miraval 5311 Scenic White (product name: Miraval 5311 Scenic White, manufactured by Merck Co., Ltd., average particle size: 10~ 100 μm, color tone: silver), 5320 Scenic Gold (average particle size: 10 to 100 μm, color tone: golden), 5400 Luxury Twinkle (average particle size: 20 to 200 μm, color tone: golden), 5401 Royal Twinkle (average particle size Size: 20-200 μm, color tone: metallic red), 5402 Pacific Twincle (average particle size: 20-200 μm, color tone: metallic blue), 5411 Magic White (average particle size: 20-200 μm, color tone: silver), 5420 Magic Gold (average particle size: 20 to 200 μm, color tone: golden), 5421 Magic Copper (average particle size: 20 to 200 μm, color tone: copper color), 5422 Magic Red (average particle size: 20 to 200 μm, color tone : red copper color), 5423 Magic Lilac (average particle size: 20 to 200 μm, color tone: metallic violet), 5424 Magic Blue (particle size: 20 to 200 μm, color tone: metallic blue), 5425 Magic Turquoise (average particle size 5426 Magic Green (average particle size: 20 to 200 μm, color tone: metallic green).
Note that the average particle diameter is the average particle diameter determined by laser diffraction, and the average thickness is 0.1 to 1.0 μm.

Examples of the transparent metallic luster pigments having color flop properties include cholesteric liquid crystal type metallic luster pigments, transparent metallic luster pigments in which silicon oxide is coated with one or more kinds of metal oxides, and the like.
The cholesteric liquid crystal type metallic luster pigment will be explained. Liquid crystal polymers used as cholesteric liquid crystal metallic luster pigments have the property of reflecting only a part of incident light in a wide spectral range due to the light interference effect, and transmitting light in all other areas. The area of the reflection spectrum is determined by the pitch width of the helical polymer and the refractive index of the material, and the reflection spectral area is divided into left- and right-handed helically polarized light components, depending on the direction of rotation of the helix. This makes it possible for one side to be reflected and the other side to be transmitted. As a result, the cholesteric liquid crystal type metallic luster pigment has the property of transmitting and reflecting over the entire spectral range, that is, it has excellent metallic luster and a color flop property in which the hue changes depending on the viewpoint. Further, the cholesteric liquid crystal type metallic luster pigment has transparency as well as metallic luster.

Examples of the cholesteric liquid crystal type metallic luster pigment include materials based on a siloxane skeleton having mesogen in the side chain, and specifically, manufactured by Wacker Chemie Co., Ltd., trade name: HELICONE HC Sapphire (average particle size: 30 μm, Thickness: 5 μm, color tone: blue to black), Scarabeus (average particle size: 30 μm, thickness: 5 μm, color tone: green to blue), Jade (average particle size: 30 μm, thickness: 5 μm, color tone: golden to dark green) ), Maple (average particle diameter: 30 μm, thickness: 5 μm, color tone: copper red to deep green), etc.
Note that the average particle diameter is an average particle diameter determined by a laser diffraction method, and is a particle diameter whose volume-based median diameter corresponds to 50% of the cumulative distribution.

The transparent metallic luster pigment, which is made by coating silicon oxide with one or more metal oxides, has light transmittance and expresses various colors depending on the viewing angle and the angle at which the light hits due to the interference effect of light. It has good color flop properties and excellent metallic luster. Furthermore, when silicon oxide is coated in multiple layers with two or more types of metal oxides, color flop properties and metallic luster can be more effectively imparted by using metal oxides with different light reflectances. Examples of the metal oxide include tin oxide, titanium oxide, iron oxide, and the like.
Specifically, the transparent metallic luster pigment in which silicon oxide is coated with one or more metal oxides is Colorstream T10-01 Viola Fantasy (average particle size: 5 to 50 μm, color tone: purple to green), T10-02 Arctic Fire (average particle size: 5 to 50 μm, color tone: silver to purple), T10-03 Tropic Sunrise (average particle size: 5 to 50 μm, color tone: brown to brown) green), T10-04 Lapis Sunlight (average particle size: 5-50 μm, color tone: golden to blue-green), F10-51 Lava Red (average particle size: 5-50 μm, color tone: copper-colored to red), T20 -01 WNT Viola Fantasy (average particle size: 5 to 40 μm, color tone: purple to green), T20-02 WNT Arctic Fire (average particle size: 5 to 40 μm, color tone: silver to purple), T20-03 WNT Tropic Sunrise (average particle size: 5-40 μm, color tone: brown to green), T20-04 WNT Lapis Sunlight (average particle size: 5-40 μm, color tone: gold to blue-green), F20-51 SW Lava Red (average Particle size: 5 to 40 μm, color tone: copper-colored to red), etc.
Note that the average particle diameter is the average particle diameter determined by laser diffraction, and the average thickness is 0.01 to 1.0 μm.

A transparent glittering resin film having pearlescent properties can be prepared by melt-blending a transparent pearlescent pigment into a transparent thermoplastic resin or a transparent thermosetting resin to form a molding resin such as pellets, powder, or paste. A single-layer transparent glittering resin film can be used, which is obtained by preparing a composition and molding it into a planar form such as a sheet or film by various molding methods such as extrusion molding, calendar molding, and inflation molding.
In addition, liquid compositions such as printing inks and paints prepared by dispersing transparent pearlescent pigments in a vehicle can be applied to printing methods such as screen printing, offset printing, process printing, gravure printing, coaters, pad printing, and transfer. A laminate in which a transparent glitter layer (transparent pearlescent layer) is formed on a transparent support by coating methods such as brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, and dip coating. It is also possible to use a transparent glittering resin film having the following structure.
As the flat thread made of the transparent glitter resin film, a transparent glitter resin film having a single layer or a laminated structure can be used.
The transparent glitter layer is a layer formed by evaporation of the solvent in the liquid composition and other compounds.

The transparent pearlescent pigment is a transparent pigment in which the surface of a core material such as natural mica, synthetic mica, or flaky aluminum oxide is coated with a metal oxide such as titanium oxide, zirconium oxide, chromium oxide, vanadium oxide, or iron oxide. A pearlescent pigment is used.

Transparent pearlescent pigments containing natural mica as a core material include natural mica particles whose surfaces are coated with titanium oxide, those whose upper layer of titanium oxide is further coated with iron oxide or non-discoloring dyes and pigments, and natural mica. The surface of the particles is coated with iron oxide, etc., and the surface of natural mica is coated with 41 to 44 mass% titanium oxide, which is a golden pearlescent pigment with a particle size of 5 to 50 μm, and the surface of natural mica is coated with 30 to 38 μm. A golden pearlescent pigment with a particle size of 5 to 60 μm coated with 0.5 to 10 mass % of a non-discoloring colored pigment coated with 16 to 39 mass % of a natural mica surface. A silvery pearlescent pigment with a particle size of 5 to 100 μm coated with titanium oxide, a metallic pearlescent pigment whose surface of natural mica is coated with 45 to 58% by mass of titanium oxide, a surface of natural mica coated with 45 to 58% by mass of oxidation Examples include metallic pearlescent pigments coated with titanium and the upper layer coated with 0.5 to 10% by mass of non-discoloring colored dyes and pigments. Furthermore, depending on the coverage of the metal oxide, it exhibits a pearlescent color such as gold, silver, copper, or metallic color.

Specific examples of the transparent pearlescent pigment in which the surface of natural mica is coated with titanium oxide include Iriodin 100 (product name: Iriodin 100 (average particle size: 10 to 60 μm, color tone: silver pearl), manufactured by Merck Co., Ltd., Iriodin 103 (average particle size: 10 to 60 μm, color tone: silver pearl)). Average particle size: 10-60 μm, color tone: rutile sterling silver), 103 WNT (average particle size: 10-60 μm, color tone: rutile sterling silver), 111 (average particle size: 1-15 μm, color tone: rutile fine satin) ), 111 WNT (average particle size: 1 to 15 μm, color tone: rutile fine satin), 120 (average particle size: 5 to 25 μm, color tone: raster satin), 123 (average particle size: 5 to 25 μm, color tone) : Bright Luster Satin), 153 (average particle size: 20-100 μm, color tone: flash pearl), 153 WII (average particle size: 20-100 μm, color tone: flash pearl), 163 (average particle size: 20-100 μm, color tone: flash pearl) 180 μm, color tone: shimmer pearl), 201 (average particle size: 5 to 25 μm, color tone: rutile fine gold), 205 (average particle size: 10 to 60 μm, color tone: rutile platinum gold), 211 (average Particle size: 5-25 μm, color tone: rutile fine red), 215 (average particle size: 10-60 μm, color tone: rutile red pearl), 217 (average particle size: 10-60 μm, color tone: rutile copper) Pearl), 219 (average particle size: 10 to 60 μm, color: rutile/lilac pearl), 221 (average particle size: 5 to 25 μm, color: rutile, fine blue), 223 (average particle size: 5 to 5) 25 μm, color tone: rutile fine lilac), 225 (average particle size: 10 to 60 μm, color tone: rutile blue pearl), 231 (average particle size: 5 to 25 μm, color tone: rutile fine green), 235 (Average particle size: 10-60μm, color tone: rutile green pearl), 249 (average particle size: 10-125μm, color tone: flash gold), 259 (average particle size: 10-125μm, color tone: flash gold) red), 289 (average particle size: 10-125 μm, color tone: flash blue), 299 (average particle size: 10-125 μm, color tone: flash green), 7205 (average particle size: 10-60 μm, Color: Ultra Gold), 7215 (Average Particle Size: 10-60 μm, Color: Ultra Red), 7217 (Average Particle Size: 10-60 μm, Color: Ultra Copper), 7219 (Average Particle Size: 10-60 μm) , color tone: ultra lilac), same 7215 (average particle size: 10 to 60 μm, color tone: ultra blue), same 7235 (average particle size: 10 to 60 μm, color tone: ultra green),
Manufactured by BASF, product name: Lumina Gold (average particle size: 8-48 μm, color tone: golden), Lumina Red (average particle size: 8-48 μm, color tone: metallic red), Lumina Red Blue (average particle size: 8-48 μm, color tone: metallic red). 48 μm, color tone: metallic blue), Aqua Blue (average particle size: 8 to 48 μm, color tone: metallic blue), Green (average particle size: 8 to 48 μm, color tone: metallic green), Turquoise (average particle size: 8 ~48 μm, color tone: metallic blue).
Note that the average particle diameter is the average particle diameter determined by laser diffraction, and the average thickness is 0.1 to 1.0 μm.

Further, as a transparent pearlescent pigment in which the surface of the natural mica is coated with titanium oxide and the upper layer is further coated with iron oxide, a specific example of the transparent pearlescent pigment is manufactured by Merck Co., Ltd., trade name: Iriodin 300 (average particle size: 10 -60μm, color tone: gold pearl), 302 (average particle size: 5-25μm, color tone: gold satin), 303 (average particle size: 10-60μm, color tone: royal gold), 305 (average particle size: 10-60 μm, color tone: Solar Gold), 306 (average particle size: 10-60 μm, color tone: Olympic Gold), 309 (average particle size: 10-60 μm, color tone: Medallion Gold), 320 (average particle size) : 10-60 μm, color tone: bright gold pearl), 323 (average particle size: 5-25 μm, color tone: royal gold satin), 325 (average particle size: 5-25 μm, color tone: solar gold satin), 326 (Average particle size: 5 to 25 μm, color tone: Olympic gold satin),
For example, Lumina Brass (product name: Lumina Brass, manufactured by BASF) (average particle size: 8 to 48 μm, color tone: golden).
Note that the average particle diameter is the average particle diameter determined by laser diffraction, and the average thickness is 0.1 to 1.0 μm.

Specific examples of the transparent pearlescent pigment in which the surface of natural mica is coated with iron oxide include Iriodin 500 (trade name: average particle size: 10 to 60 μm, color tone: copper color) manufactured by Merck Co., Ltd. 502 (average particle size: 10 to 60 μm, color tone: red brown), 504 (average particle size: 10 to 60 μm, color tone: red), 505 (average particle size: 10 to 60 μm, color tone: red violet), 520 (average particle size: 5 to 25 μm, color tone: bronze satin), 522 (average particle size: 5 to 25 μm, color tone: red brown satin), 524 (average particle size: 5 to 25 μm, color tone: red satin) ,
Examples include Lumina Copper (average particle size: 8 to 48 μm, color tone: copper color) manufactured by BASF, and Russet (average particle size: 8 to 48 μm, color tone: metallic red).
Note that the average particle diameter is the average particle diameter determined by laser diffraction, and the average thickness is 0.1 to 1.0 μm.

Transparent pearlescent pigments that use synthetic mica as a core material and whose surface is coated with metal oxides have a lower content of impurities and metal ions that become coloring factors, such as iron, than systems that use natural mica as the core material. It has excellent glitter, a glittering appearance, and high transparency. Furthermore, depending on the coverage of the metal oxide, it exhibits a pearlescent color such as gold, silver, copper, or metallic color. Examples of synthetic mica include KMg3(AlSi3O10)F2.
Although the shape of the synthetic mica is not specified, examples include a flattened mica and a scaly shape.

Specifically, the transparent pearlescent pigment in which the surface of the synthetic mica is coated with titanium oxide is manufactured by Nihon Koken Kogyo Co., Ltd., trade name: TWINCLE PEARL SXB (average particle size: 5 to 30 μm, color tone: silver). , the same YXB (average particle size: 5-30 μm, color tone: golden), the same RXB (average particle size: 5-30 μm, color tone: metallic red), the same VXB (average particle size: 5-30 μm, color tone: metallic violet) , the same BXB (average particle size: 5 to 30 μm, color tone: metallic blue), the same GXB (average particle size: 5 to 30 μm, color tone: metallic green), the same RYXB (average particle size: 5 to 30 μm, color tone: golden), The same SXD (average particle size: 5 to 60 μm, color tone: silver), the same YXD (average particle size: 5 to 60 μm, color tone: golden), the same RXD (average particle size: 5 to 60 μm, color tone: metallic red), the same YXD (average particle size: 5 to 60 μm, color tone: metallic red) VXD (average particle size: 5 to 60 μm, color: metallic violet), BXD (average particle size: 5 to 60 μm, color: metallic blue), GXD (average particle size: 5 to 60 μm, color: metallic green), RYXD (average particle size: 5-60 μm, color tone: golden), SXE (average particle size: 20-80 μm, color tone: silver), YXE (average particle size: 20-80 μm, color tone: golden), RXE (average particle size: 20-80 μm, color tone: golden). Average particle size: 20-80μm, color: metallic red), VXE (average particle size: 20-80μm, color: metallic violet), BXE (average particle size: 20-80μm, color: metallic blue), GXE (Average particle size: 20-80μm, color tone: metallic green), RYXE (average particle size: 20-80μm, color tone: golden), SX (average particle size: 40-200μm, color tone: silver), YX (average Particle size: 40-200 μm, color tone: golden), same RX (average particle size: 40-200 μm, color tone: metallic red), same VX (average particle size: 40-200 μm, color tone: metallic violet), same BX (average Particle size: 40-200 μm, color tone: metallic blue), same GX (average particle size: 40-200 μm, color tone: metallic green), same RYX (average particle size: 40-200 μm, color tone: gold), same SXC-SO ( Average particle size: 10-40 μm, color tone: silver), YXC-SO (average particle size: 10-40 μm, color tone: golden), RXC-SO (average particle size: 10-40 μm, color tone: metallic red), The same VXC-SO (average particle size: 10-40 μm, color tone: metallic violet), the same BXC-SO (average particle size: 10-40 μm, color tone: metallic blue), the same GXC-SO (average particle size: 10-40 μm) , color tone: metallic green), the same RYXC-SO (average particle size: 10 to 40 μm, color tone: golden), the same SXB-SO (average particle size: 5 to 30 μm, color tone: silver), the same SXD-SO (average particle size :5-60μm, color tone: silver),
Manufactured by Nihon Koken Kogyo Co., Ltd., product name: ULTIMICA SB-100 (average particle size: 5 to 30 μm, color tone: silver), ULTIMICA SD-100 (average particle size: 10 to 60 μm, color tone: silver), ULTIMICA SE -100 (average particle size: 15-100 μm, color tone: silver), SF-100 (average particle size: 44-150 μm, color tone: silver), SH-100 (average particle size: 150-600 μm, color tone: silver) ), YB-100 (average particle size: 5-30 μm, color tone: golden), YD-100 (average particle size: 10-60 μm, color tone: golden), YE-100 (average particle size: 15-100 μm, Color tone: golden), YF-100 (average particle size: 44-150 μm, color tone: golden), RB-100 (average particle size: 5-300 μm, color tone: metallic red), RD-100 (average particle size) : 10-60 μm, color tone: metallic red), RE-100 (average particle size: 15-100 μm, color tone: metallic red), RF-100 (average particle size: 44-150 μm, color tone: metallic red), RBB-100 (average particle size: 5 to 30 μm, color tone: metallic purple), RBD-100 (average particle size: 10 to 60 μm, color tone: metallic purple), RBE-100 (average particle size: 15 to 100 μm, Color tone: metallic purple), RBF-100 (average particle size: 44-150 μm, color tone: metallic purple), VB-100 (average particle size: 5-30 μm, color tone: metallic violet), VD-100 (average Particle size: 10-60 μm, color tone: metallic violet), VE-100 (average particle size: 15-100 μm, color tone: metallic violet), VF-100 (average particle size: 44-150 μm, color tone: metallic violet) , BB-100 (average particle size: 5-30 μm, color tone: metallic blue), BD-100 (average particle size: 10-60 μm, color tone: metallic blue), BE-100 (average particle size: 15-30 μm), 100 μm, color tone: metallic blue), BF-100 (average particle size: 44-150 μm, color tone: metallic blue), GB-100 (average particle size: 5-30 μm, color tone: metallic green), GD-100 (average particle size: 5-30 μm, color tone: metallic green). Average particle size: 10-60 μm, color tone: metallic green), GE-100 (average particle size: 15-100 μm, color tone: metallic green), GF-100 (average particle size: 44-150 μm, color tone: metallic green), etc. I can give an example.
Note that the average particle diameter is the average particle diameter determined by laser diffraction method, and the average thickness is 0.01 to 1.0 μm.

Transparent pearlescent pigments, which have flaky aluminum oxide as a core material and whose surface is coated with a metal oxide such as titanium oxide, are excellent because the aluminum oxide core surface has a high reflectance and a sharp particle size distribution. It exhibits brightness and high transparency. Furthermore, depending on the coverage of the metal oxide, it exhibits a pearlescent color such as gold, silver, copper, or metallic color.

Specifically, the pigment in which the surface of the flaky aluminum oxide is coated with titanium oxide includes Xirallic T50-10 Crystal Silver (average particle size: 5 to 40 μm, color tone: silver) manufactured by Merck Co., Ltd. T60-10 WNT Crystal Silver (average particle size: 5-30 μm, color tone: silver), T60-20 WNT Sunbeam Gold (average particle size: 5-30 μm, color tone: gold), T60-21 WNT Solaris Red (average Particle size: 5-30 μm, color tone: metallic red), T60-23 WNT Galaxy Blue (average particle size: 5-30 μm, color tone: metallic blue), T60-24 WNT Stellar Green (average particle size: 5-30 μm) , color tone: metallic green), same T60-25 WNT Cosmic Turquise (average particle size: 5 to 30 μm, color tone: metallic blue), same F60-50 WNT Fireside Copper (average particle size: 5 to 30 μm, color tone: copper color), Examples include F60-51 WNT Radiant Red (average particle size: 5 to 30 μm, color tone: metallic red).
Note that the average particle diameter is the average particle diameter determined by laser diffraction, and the average thickness is 0.1 to 1.0 μm.

The transparent thermoplastic resin or transparent thermosetting resin with which the transparent metallic luster pigment or the transparent pearlescent pigment is melt-blended may be colorless and transparent or colored and transparent. There is no particular limitation as long as the design, characters, color change of the reversible photochromic layer, etc. can be visually recognized. Specifically, polyethylene, polypropylene, polyisobutylene, polybutadiene, polymethylpentene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylene-dimethylene terephthalate, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, acrylic ester. Resin, methacrylate ester resin, polyvinyl butyral, polyarylate, polyetherimide, polycarbonate, polysulfone, ionomer resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, ethylene-acrylic Thermoplastic resins such as acid ester copolymer resins, ethylene-methacrylic acid ester copolymer resins, acrylonitrile-styrene copolymer resins, cycloolefin copolymers,
Examples include thermosetting resins such as epoxy resins, epoxy acrylates, phenolic resins, unsaturated polyester resins, urea resins, aryl resins, and silicone resins.
The transparent metallic luster pigment or transparent pearlescent pigment is contained in the transparent thermoplastic resin or transparent thermosetting resin in a proportion of 0.1 to 40% by mass, preferably 0.3 to 30% by mass. It is blended. When the blending ratio of the pigment exceeds 40% by mass, dispersion stability and processing suitability are likely to be poor during dispersion into a resin. On the other hand, if the proportion is less than 0.1% by mass, it becomes difficult to exhibit desired glitter.

The vehicle in which the transparent metallic luster pigment or the transparent pearlescent pigment is dispersed is composed of a solvent, a binder resin, and, if necessary, various additives. Examples of the solvent include water and various organic solvents.
Specifically, the organic solvents include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, and ethylene glycol monomethyl ether. , ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, n-octane, isooctane, n-heptane, methylcyclohexane, ethylcyclohexane, toluene, xylene, 3-methoxybutanol, 3- Examples include methyl-3-methoxybutanol, 3-methyl-1,3-butanediol, 1,3-butanediol, and hexylene glycol.

Specifically, the binder resin includes ionomer resin, isobutylene-maleic anhydride copolymer resin, acrylonitrile-acrylic styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, and acrylonitrile-chlorinated resin. Polyethylene-styrene copolymer resin, ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinyl acetate resin, vinyl chloride resin , vinylidene chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, polycarbonate resin, polybutadiene, polyethylene terephthalate resin, polybutylene terephthalate resin, polystyrene resin, High impact polystyrene resin, styrene-maleic acid copolymer resin, acrylic-styrene copolymer resin, polypropylene resin, polymethylstyrene resin, acrylic ester resin, polymethyl methacrylate resin, epoxy acrylate resin, alkylphenol resin, rosin-modified phenolic resin, Rosin modified alkyd resin, phenolic resin modified alkyd resin, styrene modified alkyd resin, epoxy resin modified alkyd resin, acrylic modified alkyd resin, amino alkyd resin, butyral resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, epoxy resin, alkyd Resin, styrene-butadiene copolymer resin, unsaturated polyester resin, saturated polyester resin, vinyl chloride-acrylic copolymer resin, polyisobutylene, butyl rubber, cyclized rubber, chlorinated rubber, polyvinyl alkyl ether, fluororesin, silicone resin, phenol Resin, petroleum hydrocarbon resin, ketone resin, toluene resin, xylene resin, melamine resin, urea resin, benzoguanamine resin, polyethylene oxide, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer resin, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylic acid ester, polymethacrylate, acrylic ester emulsion, methacrylic ester emulsion, vinyl acetate-acrylic ester copolymer emulsion, ethylene-vinyl acetate copolymer emulsion, styrene-acrylic ester copolymer emulsion, Vinyl chloride emulsion, vinylidene chloride emulsion, polyvinyl acetate emulsion, polyolefin emulsion, rosin ester emulsion, epoxy resin emulsion, polyurethane emulsion, synthetic rubber latex, low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polystyrene, Synthetic resins such as Kumaron plastic, polybutene, phenoxy plastic, liquid polybutadiene, liquid rubber, petroleum hydrocarbon resin, cyclopentadiene petroleum resin,
Examples include natural or semi-synthetic resins such as cellulose derivatives, alginic acid derivatives, rosin derivatives, starches, polysaccharides, gums, natural rubber, shellac, agar, casein, glue, gelatin, and polyterpene.

The additives include crosslinking agents, curing agents, desiccants, plasticizers, viscosity modifiers, dispersants, ultraviolet absorbers, antioxidants, light stabilizers, antisettling agents, smoothing agents, gelling agents, and antifoaming agents. agents, matting agents, penetrants, pH adjusters, foaming agents, coupling agents, humectants, lubricants, fungicides, preservatives, rust preventives, and the like.

The transparent support may be colorless or transparent, and is particularly limited as long as the design, text, or color change upon irradiation of the reversible photochromic layer can be visually recognized. It's not a thing. Specifically, sheets and films made of general-purpose resins such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyacrylate, polystyrene, polycarbonate, cellulose acetate, polyvinyl alcohol, polyamide, etc. Examples include thermoplastic resin molded bodies in planar shapes such as shapes. Transparent plastic sheets using resins such as polyethylene, polypropylene, polyethylene terephthalate, and polyvinyl chloride are preferred because they are highly flexible and safe.

In addition, as a transparent glittering resin film having pearlescent properties, a transparent multilayer film exhibiting a light interference phenomenon in which ten or more layers made of polymers having different refractive indexes are provided as an intermediate layer is used. A transparent pearlescent resin film containing a translucent dye can also be used. The transparent pearlescent resin film is formed by laminating at least 10 or more films (thin film layers) made of extremely thin translucent thermoplastic resin having a uniform thickness of about 30 to 500 nm, and having a uniform thickness of about 30 to 500 nm. Adjacent layers are made of different materials of light-transmitting resin, have different refractive indexes by at least 0.03, and contain a light-transmitting dye in the layers. Therefore, the light-transmitting dye enhances or changes at least one of the reflected and transmitted colors of the layer.
Examples of the thermoplastic resin include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as polymethyl methacrylate and polyacrylate, polyolefin resins such as polyethylene and polypropylene, polystyrene, and ethylene-vinyl acetate copolymer resins. . Examples of the light-transmitting dye include azo dyes, anthraquinone dyes, pyridone dyes, and pyrazolone derivative dyes. The light-transmitting dye may be contained in one layer, two or more layers, or may be contained in all layers. The amount of dye added is sufficient to intensify or change at least one of the transmitted colors of the thin film layer, or at least one of the reflected light of the thin film layer, or both, compared to the undoped system. amount is added.
Specific examples of the transparent pearlescent resin film include AURORA FILM, manufactured by BASF, Inc., and the like.

As the transparent glittering resin film having holographic properties, a transparent holographic resin film using a general-purpose hologram can be used as long as it has light transmittance.
For the hologram, for example, a transparent hologram forming layer (particularly made of transparent resin) provided with a fine uneven pattern, and a transparent reflective layer (a thin film made of metal, metal compound, etc.) on the surface of the uneven pattern are used. Examples include a relief hologram formed, a volume hologram (Lippmann hologram), and the like. In particular, relief holograms are preferably used because they are convenient and have a high visual effect as a laminate.

The transparent glittering resin film with iris properties is a blue reflective film whose outermost layers on the front and back are polypropylene layers and 113 thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene are alternately formed inside. A transparent multilayer film with a thickness of 15 μm that emits light and green interference light, the front and back outermost layers are polypropylene layers, and the inside is made up of 113 alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene. , a transparent multilayer film with a thickness of 17 μm having a green reflected light and a red interference light, the front and back outermost layers are polypropylene layers, and the inside is made up of alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene. A transparent multilayer film with a thickness of 28 μm having blue reflected light and green interference light, the outermost layer on the front and back is a polypropylene layer, and the inside has a thin layer of ethylene-vinyl acetate copolymer and a thin layer of polystyrene. A transparent multilayer film with a thickness of 31 μm that has 226 layers of alternating red reflected light and green interference light, the outermost layer on the front and back is a polyester layer, and the inside has alternating thin layers of polyester and thin layers of polyolefin. A transparent multilayer film with a thickness of 15 μm that has 113 layers formed on it and has blue reflected light and green interference light, the outermost layer on the front and back is a polyester layer, and the inside has 113 thin layers of polyester and thin layers of polyolefin alternately. A transparent multilayer film with a thickness of 17 μm that has red reflected light and green interference light, the outermost layer on the front and back is a polypropylene layer, and the inside has 113 layers of alternating thin layers of polyolefin and thin layers of polyester. A transparent multilayer film with a thickness of 15 μm having blue reflected light and green interference light, the front and back outermost layers were polypropylene layers, and the inside was formed with 113 alternating thin layers of polyolefin and thin layers of polyester. , a transparent multilayer film with a thickness of 17 μm that has red reflected light and green interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 thin layers of polyester and thin layers of acrylic resin alternately formed. , a transparent multilayer film with a thickness of 15 μm that has blue reflected light and green interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 thin layers of polyester and thin layers of acrylic resin alternately formed. , a transparent multilayer film with a thickness of 17 μm that has red reflected light and green interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 thin layers of polyester and thin layers of acrylic resin alternately formed. , a transparent multilayer film with a thickness of 30 μm that has blue reflected light and green interference light, the front and back outermost layers are acrylic resin layers, and the inside has 113 thin layers of polyester and thin layers of acrylic resin formed alternately. , 34 μm transparent multilayer film with red reflected light and green interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside is made of 226 alternating thin layers of polyester and thin layers of acrylic resin, blue. A transparent multilayer film with a thickness of 28 μm that has reflected light of A transparent multilayer film with a thickness of 31 μm that has reflected light of A transparent multilayer film with a thickness of 15 μm that has reflected light and green interference light, the outermost layer on the front and back is a polyester layer, and the inside has 113 thin layers of polyester and thin layers of acrylic resin formed alternately, and has a thickness of 17 μm. A transparent iris resin film such as a transparent multilayer film having red reflected light and green interference light can be used.
A specific example of the transparent iris resin film is IRIDESCENT FILM manufactured by ENGELHARD.

A transparent glittering resin film having light reflection properties may have, for example, a structure in which a plurality of polyester thin films are laminated with their stretching axes shifted, and have mirror-like metallic luster, and the film may have a mirror-like metallic luster, and the film may have a mirror-like metallic luster depending on the viewing angle. A transparent light-reflecting resin film that exhibits a color change with metallic luster and is also transparent depending on the viewing angle can be used.
Specific examples of the transparent light-reflective resin film include Magical Film (Mirage Film) manufactured by Hologram Supply Co., Ltd.

The transparency that the transparent glitter resin film has refers to the property of transmitting light with a wavelength in the visible light region (wavelength region of 380 to 780 nm as defined by JIS B 7079). The light transmittance of the resin film in the visible light region (visible light transmittance) is preferably 5% or more, more preferably 10% or more, and still more preferably 20% or more. When the visible light transmittance of the transparent photochromic resin film is less than 5%, it is difficult to visually recognize the patterns, characters, or color change upon irradiation of the adjacent reversible photochromic layer, and the photochromic flat threads are difficult to see. It becomes difficult to visually recognize the various hues that appear on both the front and back sides.
The above visible light transmittance is measured by using a spectrophotometer [manufactured by Hitachi, Ltd., product: U-3210] was measured in the wavelength range from 380 nm to 780 nm, and the value was set as the intermediate value between the maximum value and the minimum value.

Examples of the reversible photochromic material contained in the first and second reversible photochromic layers include photochromic compounds such as spirooxazine derivatives, spiropyran derivatives, and naphthopyran derivatives.
The spirooxazine derivatives are shown below, but the present invention is not limited thereto.
Specifically, as an indolinospirobenzoxazine compound,
1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
6'-chloro-5-fluoro-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
3,3-dimethyl-1-ethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine],
5,7-difluoro-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine],
5-cyano-3,3-dimethyl-1-(methoxycarbonyl)methylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
1'-methyldispiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]pyrido[4,3-f][1,4]benzoxazine],
1'-Methyl-5'-nitrodispiro[cyclopentane-1,3'-[3H]-indole-2'(1'H),3''-[3H]pyrido[4,3-f][1,4 ]Benzoxazine],
1,3,3,5'-tetramethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
6'-Fluoro-1'-methyldispiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]pyrido[4,3-f][1,4]benzo Oxazine],
1-benzyl-6'-chloro-3,3-dimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
6'-methoxy-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
5-chloro-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
5-bromo-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
5-iodo-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
5-trifluoromethyl-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
3,3-diethyl-1-methylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
1,3,3,6'-tetramethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
6-chloro-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
5'-Fluoro-1'-methyldispiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]pyrido[4,3-f][1,4]benzo Oxazine],
5-cyano-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
5-ethoxycarbonyl-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
4',6'-difluoro-1'-methyldispiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]pyrido[4,3-f][1, 4] Benzoxazine],
3,3-dimethyl-1-(methoxycarbonyl)methylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
3,3-dimethyl-1-phenylspiro[2H-indole-2,3′-[3H]pyrido[4,3-f][1,4]benzoxazine],
5-methoxy-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
1,3,3,5-tetramethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
7'-chloro-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
1,3,3,7'-tetramethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
7'-methoxy-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
1,3,3-trimethylspiro[2H-indole-2,3′-[3H]pyrido[2,3-f][1,4]benzoxazine],
6'-chloro-5-fluoro-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[2,3-f][1,4]benzoxazine],
5-chloro-1,3-dimethyl-3-ethyl-5'-methoxyspiro[2H-indole-2,3'-[3H]pyrido[2,3-f][1,4]benzoxazine],
3,3-diethyl-1-methyl-5-nitrospiro[2H-indole-2,3′-[3H]pyrido[2,3-f][1,4]benzoxazine],
1',6'-dimethylspiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]pyrido[2,3-f][1,4]benzoxazine ],
9″-Bromo-1′-methoxycarbonylmethyl-5′-trifluoromethyldispiro[cyclopentane-1,3′-[3H]-indole-2′[1′H],3″-[3H]pyrido [2,3-f][1,4]benzoxazine],
1-Benzyl-3,3-di-n-butyl-7'-ethyl-5-methoxyspiro[2H-indole-1,3'-[3H]pyrido[2,3-f][1,4]benzoxazine ],
1′-n-butyl-6′-iododispiro[cycloheptane-1,3′-[3H]-indole-2′(1′H),3″-[3H]pyrido[2,3-f][1 ,4]benzoxazine],
3,3-dimethyl-9'-iodo-1-naphthylspiro[2H-indole-2,3'-[3H]pyrido[2,3-f][1,4]benzoxazine],
4'-cyano-1'-[2-(methoxycarbonyl)ethyl]dispiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]pyrido[2,3 -f][1,4]benzoxazine],
7-methoxycarbonyl-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[2,3-f][1,4]benzoxazine],
4-bromo-3,3-diethyl-9'-ethoxy-1-(2-phenyl)ethylspiro[2H-indole-2,3'-[2,3-f][1,4]benzoxazine],
1'-methyldispiro[cyclohexane-1,3'-[3H]-indole-2'(1'H),3''-[3H]pyrido[2,3-f][1,4]benzoxazine],
6-fluoro-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[2,3-f][1,4]benzoxazine],
5-ethyl-9-fluoro-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[2,3-f][1,4]benzoxazine],
1'-benzyl-6''-iododispiro[cyclopentane-1,3'-[3H]-indole-2'(1'H),3''-[3H]pyrido[2,3-f][1,4 ]Benzoxazine],
5-ethoxy-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[2,3-f][1,4]benzoxazine],
1'-Methyl-5'-trichloromethyldispiro[cyclohexane-1,3'-[3H]-indole-2'(1'H),3''-[3H]pyrido[2,3-f][1 ,4]benzoxazine],
1,3-diethyl-3-methylspiro[2H-indole-2,3'-[3H]pyrido[2,3-f][1,4]benzoxazine],
1'-methoxycarbonylmethyldispiro[cyclohexane-1,3'-[3H]-indole-2'(1'H)-[3H]pyrido[2,3-f][1,4]benzoxazine], etc. , halogen, methyl, ethyl, methylene, ethylene, and hydroxyl groups on the indole ring and benzene ring of indolinospirobenzoxazine can be exemplified.

Specifically, indolinospironaphthoxazine compounds include:
1,3,3-trimethyl-indolinospironaphthoxazine,
1,3,3-trimethyl-5-chloro-indolinospironaphthoxazine,
1,3,3-trimethyl-5-bromo-indolinospironaphthoxazine,
1,3,3,5-tetramethyl-indolinospironaphthoxazine,
1,3,3-trimethyl-5-n-propyl-indolinospironaphthoxazine,
1,3,3-trimethyl-5-isobutyl-indolinospironaphthoxazine,
1,3,3-trimethyl-5-methoxy-indolinospironaphthoxazine,
1,3,3-trimethyl-5-n-propoxy-indolinospironaphthoxazine,
1,3,3-trimethyl-5-cyano-indolinospironaphthoxazine,
1-n-propyl-3,3-dimethyl-indolinospironaphthoxazine,
1-isobutyl-3,3-dimethyl-indorinospironaphthoxazine,
1-n-octyl-3,3-dimethyl-indolinospironaphthoxazine,
1-n-octadecyl-3,3-dimethyl-indolinospironaphthoxazine,
Sodium 1,3,3-trimethyl-8'-sulfonate-indorinospironaphthoxazine,
1,3,3-trimethyl-9'-methoxy-indolinospironaphthoxazine,
1,3,3-trimethyl-8'-cyano-indolinospironaphthoxazine,
1,3,3-trimethyl-5-trifluoro-indolinospironaphthoxazine,
1-(4'-methylphenyl)-3,3-dimethyl-indorinospironaphthoxazine,
1,3,3-trimethyl-6'-(2,3-dihydro-1-indolino)-indorinospironaphthoxazine,
1,3,3-trimethyl-6'-(1-piperidinyl)-indorinospironaphthoxazine,
1,3,3-trimethyl-6'-(1-morpholino)-indorinospironaphthoxazine,
1-ethyl-3,3-dimethyl-6-trifluoromethyl-6'-(1-morpholino)-indolinospironaphthoxazine,
1,3,3-trimethyl-6-trifluoromethyl-6'-(1-piperidinyl)-indolinospironaphthoxazine,
1-benzyl-3,3-dimethyl-indolinospironaphthoxazine,
1-(4-methoxybenzyl)-3,3-dimethyl-indorinospironaphthoxazine,
1-(4-chlorobenzyl)-3,3-dimethyl-indorinospironaphthoxazine,
1-ethyl-3,3-dimethyl-indolinospironaphthoxazine,
1-isopropyl-3,3-dimethyl-indorinospironaphthoxazine,
1-(2-phenoxyethyl)-3,3-dimethyl-indorinospironaphthoxazine,
1,3-dimethyl-3-ethyl-indolinospironaphthoxazine,
1,3,3-trimethyl-9'-hydroxy-indolinospironaphthoxazine,
1,3-dimethyl-3-ethyl-8'-hydroxy-indorinospironaphthoxazine,
1,3,3,5-tetramethyl-9'-methoxy-indorinospironaphthoxazine,
1,3,3,5,6-pentamethyl-9'-methoxy-indorinospironaphthoxazine,
1,3,3-trimethyl-4-trifluoromethyl-5'-methoxy-indorinospironaphthoxazine,
1,3,3-trimethyl-5'-methoxy-6'-trifluoromethyl-indorinospironaphthoxazine,
1,3,3-trimethyl-4-trifluoromethyl-9'-methoxy-indorinospironaphthoxazine,
1,3,5,6-tetramethyl-3-ethyl-indolinospironaphthoxazine,
1,3,3,5,6-pentamethyl-indolinospironaphthoxazine,
1-methyl-3,3-diphenyl-indolinospironaphthoxazine,
1-(4-methoxybenzyl)-3,3-dimethyl-indorinospironaphthoxazine,
1-(3,5-dimethylbenzyl)-3,3-dimethyl-indorinospironaphthoxazine,
1-(2-fluorobenzyl)-3,3-dimethyl-indolinospironaphthoxazine, etc., substituted products of indole ring and benzene ring of indolinospironaphthoxazine with halogen, methyl, ethyl, methylene, ethylene, hydroxyl group, etc. can be exemplified.

Specifically, indolinospirophenanthrooxazine compounds include:
1,3,3-trimethyl-spiroindoline phenanthrooxazine,
1,3,3-trimethyl-5-chloro-spiroindolinephenanthrooxazine, etc., substituted products of indole ring and benzene ring of indolinospirophenanthrooxazine with halogen, methyl, ethyl, methylene, ethylene, hydroxyl group, etc. can be exemplified.

Specifically, indolinospiruquinolinooxazine compounds include:
Examples include substituted substances such as halogen, methyl, ethyl, methylene, ethylene, and hydroxyl groups on the indole ring and benzene ring of indolinospiroquinolinooxazine, such as 1,3,3-trimethyl-spiroindolinequinolinooxazine.

The spiropyran derivatives are shown below, but the present invention is not limited thereto.
1,3,3-trimethyl-indolinobenzopyrillospiran,
1,3,3-trimethylindolino-6'-bromobenzopyrrillospiran,
1,3,3-trimethylindolino-8'-methoxybenzopyrylospirane,
1,3,3-trimethylindolino-β-naphtopyrillospiran,
Examples include 1,3,3-trimethylindolino-6'-nitrobenzopyrillospiran.

The naphthopyran derivatives are shown below, but the present invention is not limited thereto.
3,3,9,9-tetraphenyl-3H,9H-naphtho[2,1-b:6,5-b']dipyran,
3,3,10,10-tetraphenyl-3H,10H-naphtho[2,1-b:7,8-b']dipyran,
3,3,9,9-tetraphenyl-3H,10H-naphtho[4,3-b:8,7-b]dipyran,
3,3-diphenyl-9-methoxy-3H-naphtho[4,3-b]pyran,
3,3-diphenyl-10-methyl-3H-naphtho[2,1-b:5,6-b']dipyran-8-one,
3,3,9,9-tetra(4'-methoxy-phenyl)-3H,9H-naphtho[2,1-b:6,5-b']dipyran,
3,3-diphenyl-8-[2-(4-dimethylamino)phenyl]ethene-3H-naphtho[4,3-b']pyran,
3,3-diphenyl-5-acetoxy-3H-naphtho[4,3-b]pyran,
Examples include 3,3-diphenyl-8-(1H-benzotriazol-1-yl)carbonyl-3H-naphtho[4,3-b]pyran.

Furthermore, examples of photochromic compounds having photomemory properties (color memory and photochromic properties) include fulgide derivatives, diarylethene derivatives, and the like.
The diarylethene derivatives are shown below, but the present invention is not limited thereto.
1-(1,2-dimethyl-3-indolyl)-2-(2-methyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1-(2-methyl-5-phenyl-3-thienyl)-2-(5-methyl-2-phenyl-4-thiazoyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(2-methoxy-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(2-methoxy-5-methyl-3-thienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(2-methyl-6-nitro-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(6-amino-2-methyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(6-amino-2-ethyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis[2-methyl-6-(1-pyrrolidino)-3-benzothienyl]-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(6-diethylamino-2-methyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(6-acetylamino-2-methyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis[2-methyl-6-(1-piperidino)-3-benzothienyl]-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(6-dibenzylamino-2-methyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis[2-butyl-6-(1-piperidino)-3-benzofuranyl]-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis[2-methyl-6-(1-morpholino)-3-benzothienyl]-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(3-methoxy-2-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(2-methyl-6-nitro-3-benzofuranyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(3-methyl-2-thienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(3-methyl-2-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1-(2-methyl-3-benzothienyl)-2-(3-methyl-2-benzofuranyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1-(2-methyl-5-phenyl-3-thienyl)-2-(3-methyl-2-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(2-butyl-6-nitro-3-benzofuranyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(2-methyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1-(2-methyl-5-phenyl-3-thienyl)-2-(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis[2,4-dimethyl-5-(4-methoxyphenyl)-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis[2-methyl-5-(4-dimethylaminophenyl)-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene,
1-[2-methyl-5-(4-methylphenyl)-3-thienyl]-2-[2,4-dimethyl-5-(4-methylphenyl)-3-thienyl]-3,3,4, 4,5,5-hexafluorocyclopentene,
1-[2-methyl-5-(4-methoxyphenyl)-3-thienyl]-2-[2,4-dimethyl-5-(4-methoxyphenyl)-3-thienyl]-3,3,4, 4,5,5-hexafluorocyclopentene,
1-[2-methyl-5-(4-methylphenyl)-3-thienyl]-2-[2,4-dimethyl-5-(4-methoxyphenyl)-3-thienyl]-3,3,4, 4,5,5-hexafluorocyclopentene,
1,2-bis[2,4-dimethyl-5-(4-dimethylaminophenyl)-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis[2,4-dimethyl-5-(2-phenylethenyl)-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis[2,4-dimethyl-5-(4-aminophenyl)-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene,
1-(2,4-dimethyl-5-phenyl-3-thienyl)-2-[2,4-dimethyl-5-(2-phenylethenyl)-3-thienyl]-3,3,4,4, 5,5-hexafluorocyclopentene,
1,2-bis(2-ethyl-6-nitro-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis[2-ethyl-6-(5-methyl-2-thienyl)-3-benzothienyl]-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis[2-ethyl-6-(1-piperidino)-3-benzothienyl]-3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis(6-dibenzylamino-2-ethyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene,
Examples include 1,2-bis[2-ethyl-6-(1-morpholino)-3-benzothienyl]-3,3,4,4,5,5-hexafluorocyclopentene.

Further, as the reversible photochromic material, a reversible photochromic composition in which a photochromic compound is dissolved in various oligomers can also be used. Examples of the oligomers include styrene oligomers, acrylic oligomers, terpene oligomers, and terpene phenol oligomers. By using the reversible photochromic composition, it is possible to improve light resistance, improve color density, and adjust color change sensitivity.

The styrene oligomer used has a weight average molecular weight of 200 to 6,000, preferably 200 to 4,000.
When the weight average molecular weight of the styrene oligomer exceeds 6000, color remains when exposed to light, the color density tends to be low, and it tends to be difficult to adjust the color change sensitivity. On the other hand, when the weight average molecular weight is less than 200, the amount of monomers contained increases, resulting in lack of stability, which tends to impair light resistance.

The styrenic oligomer is a compound having a styrene skeleton or a hydrogenated product thereof, and includes low molecular weight polystyrene, styrene-α-methylstyrene copolymer, α-methylstyrene polymer, and copolymer of α-methylstyrene and vinyltoluene. Examples include merging.
Specific examples of the low molecular weight polystyrene include Hymer SB-75 (weight average molecular weight: 2000) and Hymer ST-95 (weight average molecular weight: 4000) manufactured by Sanyo Chemical Industries, Ltd.
Specifically, as the styrene-α-methylstyrene copolymer, Eastman Chemical Co., Ltd., trade name: Picolastic A-5 (weight average molecular weight: 317), Picolastic A-75 (weight average molecular weight: 917), etc. I can give an example.
Specifically, the α-methylstyrene polymers are manufactured by Eastman Chemical Company and have trade names: Crystallex 3085 (weight average molecular weight: 664), Crystallex 3100 (weight average molecular weight: 1020), and Crystallex 1120 (weight average molecular weight: 2420). ) etc. can be exemplified.
Specific examples of copolymers of α-methylstyrene and vinyltoluene include Eastman Chemical Co., trade names: Picotex LC (weight average molecular weight: 950), Picotex LC 100 (weight average molecular weight: 1740), etc. .

The acrylic oligomer used has a weight average molecular weight of 12,000 or less, preferably 1,000 to 8,000, more preferably 1,500 to 6,000.
When the weight average molecular weight of the acrylic oligomer exceeds 12,000, it tends to be difficult to adjust the discoloration sensitivity. On the other hand, if the weight average molecular weight is less than 1000, the amount of monomers contained increases and stability is lacking, so that the color density tends to be low and the light resistance tends to be impaired.

Examples of the acrylic oligomer include acrylic ester copolymers.
Specifically, the acrylic acid ester copolymers include ARUFON UP-1170 (weight average molecular weight: 8000), ARUFON UP-1170 (weight average molecular weight: 8000), ARUFON UP-1170 (weight average molecular weight: 6000), ARUFON UP-1000 (weight average molecular weight) manufactured by Toagosei Co., Ltd. :3000), 1020 (weight average molecular weight: 2000), 1010 (weight average molecular weight: 1700), UH-2000 (weight average molecular weight: 11000), US-6100 (weight average molecular weight: 2500), UC-3510 ( Examples include weight average molecular weight: 2000).

The terpene oligomer used has a weight average molecular weight of 250 to 4,000, preferably 300 to 4,000.
When the weight average molecular weight of the terpene oligomer exceeds 4,000, color remains after light irradiation, the color density tends to be low, and it tends to be difficult to adjust the color change sensitivity. On the other hand, if the weight average molecular weight is less than 250, the amount of monomers contained increases, resulting in lack of stability, which tends to impair light resistance.

The terpene-based oligomer is a compound having a terpene skeleton, and includes α-pinene polymer, β-pinene polymer, d-limonene polymer, and the like.
A specific example of the α-pinene polymer is Picolite A115 (trade name: weight average molecular weight: 833) manufactured by Eastman Chemical Company.
A specific example of the β-pinene polymer is Picolite S115 (trade name: weight average molecular weight: 1710) manufactured by Eastman Chemical Company.
A specific example of the d-limonene polymer is Picolite C115 (trade name: weight average molecular weight: 902) manufactured by Eastman Chemical Company.

The terpene phenol oligomer used has a weight average molecular weight of 200 to 2,000, preferably 500 to 1,200.
When the weight average molecular weight of the terpene phenol oligomer exceeds 2000, it tends to be difficult to adjust the discoloration sensitivity. On the other hand, when the weight average molecular weight is less than 200, the amount of monomers contained increases, resulting in a lack of stability, which tends to result in a low color density.

The terpene phenol oligomer is a compound obtained by copolymerizing a cyclic terpene monomer and a phenol, or a hydrogenated product thereof, and examples include α-pinene-phenol copolymer.
Specifically, α-pinene-phenol copolymers are manufactured by Yasuhara Chemical Co., Ltd. and have trade names: YS Polystar T145 (weight average molecular weight: 1050), YS Polystar T130 (weight average molecular weight: 900), and YS Polystar T500 (weight average molecular weight :500) and S145 (weight average molecular weight: 1050).

The weight average molecular weight of the styrene oligomer, acrylic oligomer, terpene oligomer, and terpene phenol oligomer is measured by GPC method (gel permeation chromatography).
The oligomers may be used alone or in combination of two or more.

The mass ratio of the photochromic compound to the styrene oligomer or acrylic oligomer is preferably 1:1 to 1:10,000, more preferably 1:5 to 1:500.
The mass ratio of the photochromic compound to the terpene oligomer is preferably 1:1 to 1:5000, more preferably 1:5 to 1:500.
The mass ratio of the photochromic compound to the terpene phenol oligomer is preferably 1:1 to 1:50, more preferably 1:2 to 1:30.
When the mass ratio of the photochromic compound and the oligomer satisfies the above range, the photochromic compound satisfies the color developing and erasing function and tends to exhibit sufficient color density.

In addition, the reversible photochromic material may include a reversible photochromic microcapsule pigment in which the reversible photochromic composition is encapsulated in microcapsules, or a reversible photochromic pigment dispersed in a thermoplastic resin or thermosetting resin. Resin particles can also be used.
By encapsulating the reversible photochromic composition in microcapsules, a chemically and physically stable pigment can be formed. The microencapsulation can be carried out by conventionally known isocyanate-based interfacial polymerization methods, melamine-formalin-based in-situ polymerization methods, in-liquid curing coating methods, phase separation methods from aqueous solutions, phase separation methods from organic solvents, and melting. There are dispersion cooling methods, air suspension coating methods, spray drying methods, etc., which are appropriately selected depending on the application. Furthermore, depending on the purpose, a secondary resin film can be further provided on the surface of the microcapsules to impart durability or to modify the surface characteristics for practical use.
Preferably, the reversible photochromic microcapsule pigment has an inclusion/wall film ratio in the range of 7/1 to 1/1 (mass ratio), and when the ratio of the wall film is within the above range, it is possible to More preferably, the ratio of inclusions/wall film is 6/1 to 1/1 (mass ratio).

The reversible photochromic microcapsule pigment or resin particles have an average particle diameter of 0.5 to 10 μm, preferably 0.5 to 3 μm, more preferably 0.5 to 1.5 μm, which satisfies practical use.
When the average particle diameter of the reversible photochromic microcapsule pigment or resin particles exceeds 10 μm, the transparency of the reversible photochromic layer is likely to be impaired, and the glittering property of the reversible photochromic flat thread in the colored state and decolored state is reduced. The color change upon irradiation with light becomes difficult to see from both the front and back sides. Moreover, since the thickness of the reversible photochromic layer increases, the texture is likely to be impaired. On the other hand, if the average particle diameter is less than 0.5 μm, it becomes difficult to exhibit high-density color development.
In addition, to measure the average particle diameter, the area of the particle is determined using the image analysis particle size distribution measurement software "Macview" manufactured by Mountech, and the projected area circle equivalent diameter (Heywood diameter) is calculated from the area of the particle area. This value is calculated and measured as the average particle diameter of particles equivalent to a sphere with equal volume.
In addition, if the particle diameter of all or most of the particles exceeds 0.2 μm, use a particle size distribution analyzer [manufactured by Beckman Coulter, Inc., product name: Multisizer 4e] to measure the particle size using the Coulter method. It is also possible to measure as the average particle diameter of particles equivalent to spheres.
Furthermore, a laser diffraction/scattering particle size distribution measuring device [manufactured by Horiba, Ltd., product name: LA-300] was calibrated based on the numerical values measured using the software or the Coulter method measuring device. ] may be used to measure the volume-based particle size and average particle size.

For the first and second reversible photochromic layers, a liquid composition such as a printing ink or paint prepared by dispersing a reversible photochromic material in a vehicle is used by screen printing, offset printing, process printing, or gravure printing. A flat thread made of a transparent glittering resin film can be directly coated with a printing method such as a coater, tampo printing, or transfer, or by a coating method such as brush coating, spray coating, electrostatic coating, electrocoating, flow coating, roller coating, or dip coating. It can be formed as a coating layer thereon.
Note that the coating layer is a layer formed of other compounds after the solvent in the liquid composition evaporates.
The reversible discoloration layer includes solid patterns, circles, ovals, squares, rectangles, various characters, symbols, figures, patterns, as well as shapes of people, animals, plants, fruits, foodstuffs, vehicles, buildings, celestial bodies, etc. It may be a statue.

In addition, a resin composition for molding such as pellets, powder, or paste is prepared by melt-blending a reversible photochromic material with a transparent thermoplastic resin or a transparent thermosetting resin, and then extrusion molding, calendar molding, etc. A single-layer reversible photochromic resin film formed into a planar form such as a sheet or film by various forming means such as inflation molding can be used.
In addition, the liquid composition may be applied to printing methods such as screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer, etc., brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, etc. It is also possible to use a reversible photochromic resin film with a laminated structure formed as a coating layer on a transparent support by coating means such as dip coating.
As the first and second reversible photochromic layers, reversible photochromic resin films having a single layer or a laminated structure can be used.
The reversible photochromic resin film and the flat thread made of the transparent glitter resin film are bonded together with an adhesive or the like, and first and second photochromic layers are formed on the flat thread made of the transparent glitter resin film. can be formed.

The vehicle in which the reversible photochromic material is dispersed is composed of a solvent, a binder resin, and, if necessary, various additives, and must not affect the coloring/fading function, color changing function, sensitivity, etc. of the reversible photochromic material. However, it is not particularly limited. Examples of the solvent include water and various organic solvents.
Specifically, the organic solvents include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, and ethylene glycol monomethyl ether. , ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, n-octane, isooctane, n-heptane, methylcyclohexane, ethylcyclohexane, toluene, xylene, 3-methoxybutanol, 3- Examples include methyl-3-methoxybutanol, 3-methyl-1,3-butanediol, 1,3-butanediol, and hexylene glycol.

Specifically, the binder resin includes ionomer resin, isobutylene-maleic anhydride copolymer resin, acrylonitrile-acrylic styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, and acrylonitrile-chlorinated resin. Polyethylene-styrene copolymer resin, ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinyl acetate resin, vinyl chloride resin , vinylidene chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, polycarbonate resin, polybutadiene, polyethylene terephthalate resin, polybutylene terephthalate resin, polystyrene resin, High impact polystyrene resin, styrene-maleic acid copolymer resin, acrylic-styrene copolymer resin, polypropylene resin, polymethylstyrene resin, acrylic ester resin, polymethyl methacrylate resin, epoxy acrylate resin, alkylphenol resin, rosin-modified phenolic resin, Rosin modified alkyd resin, phenolic resin modified alkyd resin, styrene modified alkyd resin, epoxy resin modified alkyd resin, acrylic modified alkyd resin, amino alkyd resin, butyral resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, epoxy resin, alkyd Resin, styrene-butadiene copolymer resin, unsaturated polyester resin, saturated polyester resin, vinyl chloride-acrylic copolymer resin, polyisobutylene, butyl rubber, cyclized rubber, chlorinated rubber, polyvinyl alkyl ether, fluororesin, silicone resin, phenol Resin, petroleum hydrocarbon resin, ketone resin, toluene resin, xylene resin, melamine resin, urea resin, benzoguanamine resin, polyethylene oxide, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer resin, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylic acid ester, polymethacrylate, acrylic ester emulsion, methacrylic ester emulsion, vinyl acetate-acrylic ester copolymer emulsion, ethylene-vinyl acetate copolymer emulsion, styrene-acrylic ester copolymer emulsion, Vinyl chloride emulsion, vinylidene chloride emulsion, polyvinyl acetate emulsion, polyolefin emulsion, rosin ester emulsion, epoxy resin emulsion, polyurethane emulsion, synthetic rubber latex, low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polystyrene, Synthetic resins such as Kumaron plastic, polybutene, phenoxy plastic, liquid polybutadiene, liquid rubber, petroleum hydrocarbon resin, cyclopentadiene petroleum resin,
Examples include natural or semi-synthetic resins such as cellulose derivatives, alginic acid derivatives, rosin derivatives, starches, polysaccharides, gums, natural rubber, shellac, agar, casein, glue, gelatin, and polyterpene.
The reversible photochromic material is blended into the binder resin in an amount of 0.1 to 40% by weight, preferably 0.5 to 20% by weight, and more preferably 1 to 10% by weight. If the blending ratio of the reversible photochromic material exceeds 40% by mass, dispersion stability and processing suitability will tend to be lacking when dispersing into the binder resin, and it will be difficult to notice a significant improvement in the coloring density, and furthermore, it will be difficult to decolorize the material. Residual color is likely to occur under certain conditions. On the other hand, if the ratio is less than 0.1% by mass, it will be difficult to exhibit the desired color density and it will be difficult to fully satisfy the color changing function.

The additives include crosslinking agents, curing agents, desiccants, plasticizers, viscosity modifiers, dispersants, ultraviolet absorbers, antioxidants, light stabilizers, antisettling agents, smoothing agents, gelling agents, and antifoaming agents. agents, matting agents, penetrants, pH adjusters, foaming agents, coupling agents, humectants, lubricants, fungicides, preservatives, rust preventives, and the like.

As the transparent thermoplastic resin or transparent thermosetting resin with which the reversible photochromic material is melt-blended, colorless and transparent resins or colored transparent resins can be used. There is no particular limitation as long as it does not affect the color change function or sensitivity. Specifically, polyethylene, polypropylene, polyisobutylene, polybutadiene, polymethylpentene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylene-dimethylene terephthalate, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, acrylic ester. Resin, methacrylate ester resin, polyvinyl butyral, polyarylate, polyetherimide, polycarbonate, polysulfone, ionomer resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, ethylene-acrylic Thermoplastic resins such as acid ester copolymer resins, ethylene-methacrylic acid ester copolymer resins, acrylonitrile-styrene copolymer resins, cycloolefin copolymers,
Examples include thermosetting resins such as epoxy resins, epoxy acrylates, phenolic resins, unsaturated polyester resins, urea resins, aryl resins, and silicone resins.
The reversible photochromic material is contained in a transparent thermoplastic resin or a transparent thermosetting resin in an amount of 0.1 to 30% by mass, preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass. Mixed in proportions. When the blending ratio of the reversible photochromic material exceeds 30% by mass, dispersion stability and processing suitability tend to be lacking during dispersion into a resin, and it is difficult to notice a significant improvement in color density. On the other hand, if the ratio is less than 0.1% by mass, it will be difficult to exhibit the desired color density and it will be difficult to fully satisfy the color changing function.

The transparent support may be colorless or transparent, and is not particularly limited as long as the brightness of the transparent glitter layer or the transparent glitter resin film can be visually recognized. do not have. Specifically, sheets and films made of general-purpose resins such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyacrylate, polystyrene, polycarbonate, cellulose acetate, polyvinyl alcohol, polyamide, etc. Examples include thermoplastic resin molded bodies in planar shapes such as shapes. Transparent plastic sheets using resins such as polyethylene, polypropylene, polyethylene terephthalate, and polyvinyl chloride are preferred because they are highly flexible and safe.

The reversible photochromic layer has transparency in a colored state and a decolored state, and the transparency means that light having a wavelength in the visible light region (wavelength region of 380 to 780 nm defined by JIS B 7079) is transmitted. The light transmittance (visible light transmittance) in the visible light region of the reversible photochromic layer in a colored state is preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more. be. When the visible light transmittance of the reversible photochromic layer is less than 5%, it is difficult to visually recognize the glitter of the adjacent transparent glitter layer or transparent glitter resin film, and the glitter reversible photochromic flat yarn is exhibited on both the front and back surfaces. It becomes difficult to visually recognize various colors.
The above visible light transmittance is measured using a spectrophotometer [manufactured by Hitachi, Ltd., product name: U], in which a reversible photochromic layer is provided on a transparent substrate that transmits light with wavelengths in the visible light range, and in a colored state. -3210] in the wavelength range from 380 nm to 780 nm, and the value was taken as the intermediate value between the maximum value and the minimum value.

As shown in FIG. 3, the glittering reversible photochromic flat yarn (1) of the present invention is provided with a transparent glittering layer (6) on one wide surface of the flat yarn made of a reversible photochromic resin film (5). It can also be configured.

As the reversible photochromic resin film, a resin composition for molding such as pellets, powder, or paste is prepared by melt-blending a reversible photochromic material with a transparent thermoplastic resin, a transparent thermosetting resin, or the like. However, a single-layer reversible photochromic resin film formed into a planar form such as a sheet or film by various molding methods such as extrusion molding, calendar molding, and inflation molding can be used.
In addition, a liquid composition such as a printing ink or paint prepared by dispersing a reversible photochromic material in a vehicle can be applied to printing methods such as screen printing, offset printing, process printing, gravure printing, coater, pad printing, and transfer. A reversible photochromic resin film with a laminated structure is formed as a coating layer on a transparent support by coating methods such as brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, and dip coating. It can also be used.
As the flat thread made of the reversible photochromic resin film, a reversible photochromic resin film having a single layer or a laminated structure can be used.
Note that the coating layer is a layer formed of other compounds after the solvent in the liquid composition evaporates.

As the transparent glitter layer, a liquid composition such as a printing ink or paint prepared by dispersing a transparent metallic luster pigment or a transparent pearlescent pigment in a vehicle is used by screen printing, offset printing, process printing, or gravure printing. A flat thread made of a directly reversible photochromic resin film can be applied by printing methods such as coater, tampo printing, transfer, etc., and application methods such as brush coating, spray coating, electrostatic coating, electrocoating, flow coating, roller coating, and dip coating. It can be formed as a coating layer thereon.
Note that the coating layer is a layer formed of other compounds after the solvent in the liquid composition evaporates.

In addition, a transparent metallic luster pigment or a transparent pearlescent pigment is melt-blended in a transparent thermoplastic resin or a transparent thermosetting resin to prepare a molding resin composition such as pellets, powder, or paste, It is also possible to use a single-layer transparent glitter resin film formed into a planar form such as a sheet or film by various molding methods such as extrusion molding, calendar molding, and inflation molding.
In addition, the liquid composition may be applied by printing means such as screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer, etc., brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, and roller coating. It is also possible to use a transparent glitter resin film having a laminated structure, which is formed as a coating layer on a transparent support by coating means such as dip coating.
As the transparent glitter layer, a transparent glitter resin film having a single layer or a laminated structure can be used.
Furthermore, the transparent pearlescent, holographic, iris, light-reflective resin films, etc. can also be used as the transparent glitter resin film.
The transparent glittering resin film and the flat thread made of the reversible photochromic resin film may be bonded together with an adhesive or the like to form a transparent glittering layer on the flat thread made of the reversible photochromic resin film. can.

The glittering reversible photochromic flat yarn (1) shown in FIG. 1 is formed by providing a first reversible photochromic layer (3) on one wide surface of a flat yarn made of a transparent glittering resin film (2). .
The glittering reversible photochromic flat yarn has a flexible texture due to the small number of constituent layers, and furthermore, since the transparent glittering resin film and the reversible photochromic layer have transparency, The photochromic reversible photochromic flat yarn has a transparent photochromic resin film and a reversible photochromic layer that are visible from both the front and back sides, and the photochromic layer side or the transparent photochromic resin film side allows the photochromic property and color change upon irradiation to be observed from the photochromic layer side or the transparent photochromic resin film side. Can be visually recognized.
Furthermore, the same effect as described above is also obtained in the structure shown in FIG. 3, in which a transparent glitter layer (6) is provided on one wide surface of the flat thread made of the reversible photochromic resin film (5).

The glittering reversible photochromic flat yarn (1) shown in FIG. 2 has a first reversible photochromic layer (3) provided on one wide surface of the flat yarn made of a transparent glittering resin film (2), and further , a second reversible photochromic layer (4) is provided on the wide surface opposite to where the first reversible photochromic layer is provided. In the glittering reversible photochromic flat yarn, since the transparent glittering resin film and the first and second reversible photochromic layers are all transparent, the front and back sides of the glittering reversible photochromic flat yarn described above are transparent. In addition to the effect of being able to see glitter and color change when irradiated with light from both sides, it exhibits a wide variety of changes when irradiated with light because it has two reversible photochromic layers.
Even when the glittering layer in the glittering reversible photochromic flat yarn is an opaque glittering layer that does not transmit light, the structure shown in FIG. However, compared to the structure shown in FIG. 2, the number of layers is large and the soft texture is likely to be lost. Reversible photochromic flat threads are preferred.

When the reversible photochromic materials respectively contained in the first and second reversible photochromic layers exhibit the same color when colored, the reversible photochromic layer shown in FIG. 1 has a configuration of only one layer. On the other hand, the color density upon irradiation with light is higher, and the color change upon irradiation with light is more clearly visible.
Further, when the reversible photochromic materials respectively contained in the first and second reversible photochromic layers exhibit different colors when colored, the color exhibited by the glittering reversible photochromic flat thread upon irradiation with light is: The color is a mixture of the color exhibited by the first reversible photochromic layer and the color exhibited by the second reversible photochromic layer, and is a color that is difficult to exhibit with the configuration of only one reversible photochromic layer shown in FIG. 1. This is suitable because it is visible.
Furthermore, when at least one of the coloring time or decoloring time of the first and second reversible photochromic layers is different from each other, the photoluminescent reversible photochromic flat yarn in the decolored state is irradiated with light, or the coloring state is When the irradiation of light to the photoluminescent reversible photochromic flat thread is stopped, the color changes stepwise, and this color change is visible from both the front and back sides of the photoluminescent reversible photochromic flat thread, making the change upon irradiation with light more diverse. Therefore, it is more suitable.

As shown in FIG. 4, the glittering reversible photochromic flat yarn (1) of the present invention has metallic luster, pearlescent luster, hologram luster, A transparent glitter layer (6) having an optical property selected from either iris properties or light reflection properties is provided, and a reversible photochromic material is contained on the wide surface opposite to where the transparent glitter layer is provided. A first reversible photochromic layer (3) is provided.

In addition, as shown in FIGS. 5 and 6, one wide surface of the flat thread made of the transparent resin film (7) is coated with metallic luster, pearlescent luster, holographic luster, iris luster, or light reflective nature. It is also possible to have a structure in which a transparent glitter layer (6) having selected optical properties and a first reversible photochromic layer (3) containing a reversible photochromic material are provided.

In addition, as shown in FIGS. 7 and 8, one wide surface of the flat thread made of the transparent resin film (7) is coated with metallic luster, pearlescent luster, holographic luster, iris luster, or light reflective nature. a transparent glitter layer (6) having selected optical properties and a first reversible photochromic layer (3) containing a reversible photochromic material; It is also possible to provide a second reversible photochromic layer (4) containing a reversible photochromic material on the wide side opposite to where the color changing layer is provided.

The transparent resin film is not particularly limited as long as the glitter of the transparent glitter layer and the pattern, characters, or color change upon irradiation of light of the photochromic layer can be visually recognized. Specifically, polyolefin resins such as polyethylene and polypropylene, cellulose derivatives such as cellulose acetate, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyvinyl alcohol, vinyl alcohol resins such as ethylene-vinyl alcohol copolymers, Examples include films made of general-purpose resins such as polyvinyl chloride resin, polyvinylidene chloride resin, polyacrylic ester resin, polyacrylic acid resin, polyester resin, rayon, cupra, etc., and the thickness of the film is in the range of 1 to 25 μm. It is effective, preferably 5 to 20 μm, more preferably 10 to 15 μm.

The transparency of the transparent resin film refers to the property of transmitting light with a wavelength in the visible light range (wavelength range of 380 to 780 nm defined by JIS B 7079), and the transparency of the transparent resin film The light transmittance in the optical region (visible light transmittance) is preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more. When the visible light transmittance of the transparent resin film is less than 5%, it is difficult to visually recognize the design, characters, or color change of the adjacent reversible photochromic layer when irradiated with light, or the glitter of the transparent glitter layer, and the glitter is less than 5%. It becomes difficult to visually recognize the various hues that the flat yarn exhibits on both the front and back sides.
The above visible light transmittance was measured using a spectrophotometer [manufactured by Hitachi, Ltd., product name: U-3210] by providing a transparent resin film on a transparent base material that transmits light with wavelengths in the visible light range. The measurement was carried out in the wavelength range from 380 nm to 780 nm, and the intermediate value between the maximum value and the minimum value was taken as the value.

As the transparent glitter layer, a liquid composition such as a printing ink or paint prepared by dispersing a transparent metallic luster pigment or a transparent pearlescent pigment in a vehicle is used by screen printing, offset printing, process printing, or gravure printing. A flat thread made of a directly reversible photochromic resin film can be applied by printing methods such as coater, tampo printing, transfer, etc., and application methods such as brush coating, spray coating, electrostatic coating, electrocoating, flow coating, roller coating, and dip coating. It can be formed as a coating layer thereon.
Note that the coating layer is a layer formed of other compounds after the solvent in the liquid composition evaporates.

In addition, a transparent metallic luster pigment or a transparent pearlescent pigment is melt-blended in a transparent thermoplastic resin or a transparent thermosetting resin to prepare a molding resin composition such as pellets, powder, or paste, It is also possible to use a single-layer transparent glitter resin film formed into a planar form such as a sheet or film by various molding methods such as extrusion molding, calendar molding, and inflation molding.
In addition, the liquid composition may be applied by printing means such as screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer, etc., brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, and roller coating. It is also possible to use a transparent glitter resin film having a laminated structure, which is formed as a coating layer on a transparent support by coating means such as dip coating.
As the transparent glitter layer, a transparent glitter resin film having a single layer or a laminated structure can be used.
Furthermore, the transparent pearlescent, holographic, iris, light-reflective resin films, etc. can also be used as the transparent glitter resin film.
The transparent glittering resin film and the flat thread made of the transparent resin film can be bonded together with an adhesive or the like to form a transparent glittering layer on the flat thread made of the transparent resin film.
Further, the transparent glitter resin film and the first photochromic layer provided on the flat thread made of the transparent resin film are bonded together with an adhesive or the like, and A transparent glitter layer can also be formed.

For the first and second reversible photochromic layers, a liquid composition such as a printing ink or paint prepared by dispersing a reversible photochromic material in a vehicle is used by screen printing, offset printing, process printing, or gravure printing. A flat thread made of a transparent glittering resin film can be directly coated with a printing method such as a coater, tampo printing, or transfer, or by a coating method such as brush coating, spray coating, electrostatic coating, electrocoating, flow coating, roller coating, or dip coating. Alternatively, it can be formed as a coating layer on a transparent glitter layer.
Note that the coating layer is a layer formed of other compounds after the solvent in the liquid composition evaporates.

In addition, a resin composition for molding such as pellets, powder, or paste is prepared by melt-blending a reversible photochromic material with a transparent thermoplastic resin or a transparent thermosetting resin, and then extrusion molding, calendar molding, etc. It is also possible to use a single-layer reversible photochromic resin film formed into a planar form such as a sheet or film by various forming means such as inflation molding.
In addition, the liquid composition may be applied to printing methods such as screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer, etc., brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, etc. It is also possible to use a reversible photochromic resin film with a laminated structure formed as a coating layer on a transparent support by coating means such as dip coating.
As the first and second reversible photochromic layers, reversible photochromic resin films having a single layer or a laminated structure can be used.
The reversible photochromic resin film and the flat thread made of the transparent resin film are bonded together with an adhesive or the like to form first and second reversible photochromic layers on the flat thread made of the transparent resin film. can do.
Further, the reversible photochromic resin film and the transparent glitter layer provided on the flat thread made of the transparent resin film are bonded together with an adhesive or the like, and the first layer is placed on the flat thread made of the transparent resin film. A reversible photochromic layer can be formed.
The first and second reversible color changing layers include solid patterns, circles, ovals, squares, rectangles, various characters, symbols, figures, and patterns, as well as people, animals, plants, fruits, foods, and vehicles. , a building, a celestial body, etc.

The glittering reversible photochromic flat threads having the configurations shown in FIGS. 4 to 8 using flat threads made of a transparent resin film have glitter properties and color changes upon light irradiation that are visible from both the front and back surfaces, and impair flexibility. This is preferable because heat resistance and durability can be imparted without any damage.

Since all the layers constituting the glittering reversible photochromic flat yarn of the present invention have transparency, the glittering reversible photochromic flat yarn itself also has transparency, and all layers are visible from both the front and back sides. be able to. The light transmittance (visible light transmittance) of the glittering reversible photochromic flat yarn in the visible light region is preferably 5% or more, more preferably 10% or more, and still more preferably 20% or more. When the visible light transmittance of the photoluminescent reversible photochromic flat yarn is less than 5%, it is difficult to visually recognize the patterns, characters, or color changes upon irradiation of the photoluminescent and reversible photochromic layer, and the photoluminescent reversible photochromic flat thread is less than 5%. It becomes difficult to visually recognize the various hues that the flat yarn exhibits on both the front and back sides.
The above visible light transmittance was measured using a spectrophotometer [manufactured by Hitachi, Ltd., product: U-3210] was measured in the wavelength range from 380 nm to 780 nm, and the value was set as the intermediate value between the maximum value and the minimum value.

It is preferable that all the layers constituting the glittering reversible photochromic flat yarn of the present invention are layers that transmit light with a wavelength of 500 nm or less, so that the coloring and fading function of the reversible photochromic layer can be fully expressed. The color change of the glittering reversible photochromic flat thread upon irradiation with light can be clearly seen from both the front and back sides. If the photoluminescent reversible photochromic flat yarn contains a layer that does not transmit light with a wavelength of 500 nm or less, it will be a factor that inhibits the coloring and decoloring function of the reversible photochromic material contained in the reversible photochromic layer, and the light It becomes difficult to visually recognize the color change during irradiation from both the front and back sides.

In addition, as shown in FIG. 9, by providing a non-color-changing layer (8) containing a non-color-changing colorant such as general dyes and pigments, fluorescent dyes and pigments, and phosphorescent pigments between each layer, light irradiation is possible. This exhibits a tautochromic color change from colored (1) to colored (2), thereby making the color change of the glittering reversible photochromic flat thread more diverse.

The non-color-changing layer is formed by applying a liquid composition such as a printing ink or paint prepared by dispersing a non-color-changing colorant in a vehicle to screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer, etc. A coating layer can be formed between each layer by printing means, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, or other coating means.
Note that the coating layer is a layer formed of other compounds after the solvent in the liquid composition evaporates.
The non-discolored layer includes solid patterns, circles, ovals, squares, rectangles, various characters, symbols, figures, patterns, as well as shapes of people, animals, plants, fruits, foodstuffs, vehicles, buildings, celestial bodies, etc. It may be a statue.
The non-chromic coloring agent is preferably contained within a range that does not impair the transparency of the glittering, reversible photochromic flat yarn.

In addition, a resin composition for molding such as pellets, powder, or paste is prepared by blending the non-discoloring coloring agent with the transparent thermoplastic or thermosetting resin, and the resin composition is then subjected to extrusion molding, calendar molding, or inflation molding. It is also possible to use a single-layer non-color-changing resin film formed into a planar form such as a sheet or film by various forming methods such as the above.
In addition, the liquid composition may be applied by printing means such as screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer, etc., brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, and roller coating. It is also possible to use a non-discoloring resin film with a laminated structure, which is formed as a coating layer on a transparent support by a coating method such as dip coating.
As the non-color-changing layer, a non-color-changing resin film having a single layer or a laminated structure can be used.
Furthermore, by applying a transparent glitter layer or a transparent resin film containing a non-chromatic coloring agent, or a reversible photochromic layer comprising a combination of a non-chromatic coloring agent and a reversible photochromic material, A tautochromic color change from colored (1) to colored (2) can be produced.

Further, as shown in FIG. 10, a transparent protective layer (9) can be provided on the reversible photochromic layer to improve durability. The transparency of the transparent protective layer refers to the property of transmitting light with a wavelength in the visible light region (wavelength region of 380 to 780 nm defined by JIS B 7079), and the transparency of the transparent protective layer The light transmittance in the optical region (visible light transmittance) is preferably 5% or more, more preferably 10% or more, and still more preferably 20% or more. When the visible light transmittance of the transparent protective layer is less than 5%, it is difficult to visually recognize the patterns, characters, or color change upon irradiation of the adjacent reversible photochromic layer, and the glittering reversible photochromic flat threads are visible on both surfaces. It becomes difficult to visually recognize the various hues that appear on the screen.
Note that the visible light transmittance was measured using a spectrophotometer [manufactured by Hitachi, Ltd., product name: U-3210] by providing a transparent layer on a transparent base material that transmits light with wavelengths in the visible light range. The measurement was performed in the wavelength range from 380 nm to 780 nm, and the value was taken as the intermediate value between the maximum value and the minimum value.

Further, the transparent protective layer is preferably a layer that transmits light having a wavelength of 500 nm or less, so that the coloring/decoloring function of the reversible photochromic layer can be fully expressed, and the glittering property when irradiated with light can be improved. The color change of the backlight-changing flat yarn can be clearly seen from both the front and back sides. If the transparent protective layer is a layer that does not transmit light with a wavelength of 500 nm or less, it will be a factor that inhibits the coloring and fading function of the reversible photochromic material contained in the reversible photochromic layer, resulting in color change upon irradiation with light. becomes difficult to visually recognize from both the front and back sides.

The glittering reversible photochromic flat thread of the present invention can be a laminate in which a reversible photochromic layer is provided on a transparent glittering resin film, or a laminate in which a transparent glittering layer and a reversible photochromic layer are provided on a transparent resin film. It can also be obtained by cutting the body into appropriate widths using a slitter.

The width (W) of the glittering reversible photochromic flat yarn is 100 to 5000 μm, preferably 150 to 2000 μm, more preferably 200 to 1000 μm, and by satisfying the above range, a clear color change can be visually recognized when irradiated with light. At the same time, the strength of the flat yarn can be satisfied.
Further, the thickness (T) of the glittering reversible photochromic flat yarn is 5 to 50 μm, preferably 5 to 45 μm, more preferably 5 to 40 μm, and by satisfying the above range, it has a flexible texture and It can satisfy the applicability to products and the strength of flat yarn.

Moreover, if an adhesive layer is provided between each layer when producing the laminate constituting the glittering, reversible photochromic flat yarn of the present invention, the flat yarn can be obtained without going through a complicated manufacturing process.
For example, a laminate in which a first reversible photochromic layer is provided on a transparent resin film, and an adhesive layer is provided on the opposite side to which the first reversible photochromic layer is provided, is coated with the adhesive layer. A laminate with a transparent glitter resin film pasted, or a laminate with a transparent resin film pasted with an adhesive layer on one side, and a transparent glitter resin film pasted through the adhesive layer on both sides of the laminate. A glittering reversible photochromic flat thread can be obtained by cutting the laminate provided with the first and second reversible photochromic layers using a slitter.

The adhesive used in the adhesive layer has no effect on the coloring/decoloring function, color changing function, sensitivity, etc. of the reversible photochromic material contained in the reversible photochromic layer, and has transparency and brightness adjacent to the adhesive layer. There are no particular limitations as long as the glitter of the resin film or the transparent glitter layer, the designs, letters, or color changes upon irradiation of light of the reversible photochromic layer are visible.
Examples of the adhesive used in the adhesive layer include acrylic resins, polyurethane resins, ethylene-vinyl acetate copolymer resins, rubber resins, silicone resins, and epoxy resins.

Specifically, the following products can be exemplified as products using the glittering reversible photochromic flat yarn.
(1) Toys Dolls or animal-shaped toys, hair for dolls or animal-shaped toys, accessories for dolls such as doll houses and furniture, clothing, hats, bags, and shoes, accessory toys, stuffed animals, drawing toys, toys for toys Picture books, building blocks toys, block toys, clay toys, fluid toys, spinning tops, kites, musical instrument toys, cooking toys, gun toys, catching toys, background toys, and toys imitating vehicles, animals, plants, buildings, food, etc. etc,
(2) Clothing Clothes such as T-shirts, sweatshirts, blouses, dresses, swimsuits, raincoats, and ski wear, footwear such as shoes and shoelaces, cloth personal items such as handkerchiefs, towels, and wrapping cloths, gloves, ties, and hats. , scarves, mufflers, etc.
(3) Indoor decorations: carpets, curtains, curtain strings, table hangers, rugs, cushions, carpets, rugs, upholstery, sheets, mats, picture frames, artificial flowers, photo frames, etc.
(4) Furniture Futons, pillows, mattresses, bedding such as beds, chairs, sofas, etc.
(5) Accessories Rings, bangles, tiaras, earrings, hair clips, artificial nails, ribbons, scarves, watches, glasses, etc.
(6) Others Bags, packaging containers, embroidery threads, athletic equipment, fishing gear, coasters, musical instruments, bags such as wallets, umbrellas, and teaching materials, etc.

Furthermore, the photoluminescent and reversible photochromic flat yarn of the present invention can be twisted into yarn by methods such as round twisting, bellows twisting, sash twisting, hagoromo twisting, and dry twisting, and can also be used in the above-mentioned products.

Examples are shown below, but the present invention is not limited thereto. In addition, parts in Examples indicate parts by mass.

Example 1 (see Figure 1)
Preparation of bright reversible photochromic flat yarn 2 parts of 1,3,3-trimethylindolino-spironaphthoxazine, 100 parts of 50% acrylic resin xylene solution, 1 part of antifoaming agent, 40 parts of xylene, and methyl isobutyl A first reversible photochromic screen ink was prepared by uniformly mixing in a vehicle consisting of 40 parts of ketone.
Next, the above-mentioned reversible light discoloration was applied onto a transparent pearlescent resin film (2) (manufactured by BASF, trade name: AURORA 8181RG) (visible light transmittance: 70%) with a thickness of 18 μm as a transparent glittering resin film. The first reversible photochromic layer (3) with a film thickness of 15 μm changes from a colorless transparent state to a blue transparent state when exposed to sunlight (coloring state). Visible light transmittance: 90%) was formed to obtain a glittering, reversible photochromic laminate.
Next, the photoluminescent reversible photochromic laminate was cut into threads with a width of 250 μm using a microslitter to obtain a photoluminescent reversible photochromic flat yarn (1) with a thickness of 33 μm (visible light transmittance in a colored state). :60%).
The photoluminescent reversible photochromic flat thread has a flexible texture, and before being exposed to sunlight, the pearlescent property due to the transparent pearlescent resin film is visible from both the front and back sides, and when exposed to sunlight, it becomes the first pearlescent. The backlight color change layer developed a blue color, and the pearlescent blue color was visible from both the front and back surfaces. After that, when it was left indoors for a while, the first reversible photochromic layer disappeared and returned to its original state. This change in aspect could be repeated.

Example 2 (see Figure 1)
Preparation of photoluminescent and reversible photochromic flat yarn 1 part of 1,3,3-trimethylindolino-spironaphthoxazine was mixed with styrene-α-methylstyrene copolymer (manufactured by Eastman Chemical Co., trade name: Picolastic A-5). ), 30 parts of a reversible photochromic microcapsule pigment (average particle size: 1.5 μm) containing a reversible photochromic composition uniformly dissolved by heating, 62 parts of a urethane emulsion, and a thickener. A reversible photochromic screen ink was prepared by uniformly mixing the following components in a vehicle consisting of 2 parts of a leveling agent, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent.
Next, the above-mentioned reversible photochromic resin film was placed on a transparent pearlescent resin film (2) (manufactured by BASF, trade name: AURORA 8181RG) (visible light transmittance: 70%) with a thickness of 18 μm as a transparent glitter resin film. The first reversible photochromic layer (3) with a film thickness of 15 μm changes from a colorless transparent state to a blue transparent state when exposed to sunlight (coloring state). Visible light transmittance: 85%) was formed to obtain a glittering, reversible photochromic laminate.
Next, the photoluminescent reversible photochromic laminate was cut into threads with a width of 250 μm using a micro slitter to obtain a photoluminescent reversible photochromic flat yarn (1) with a thickness of 33 μm (visible light transmittance in a colored state). :56%).
The glittering, reversible photochromic flat thread has a flexible texture, and before being exposed to sunlight, the pearlescent property due to the transparent pearlescent resin film is visible from both the front and back sides, and when exposed to sunlight, it becomes the first pearlescent. The backlight color change layer developed a blue color, and the pearlescent blue color was visible from both the front and back surfaces. After that, when it was left indoors for a while, the first reversible photochromic layer disappeared and returned to its original state. This change in aspect could be repeated.

Example 3
Preparation of glittering reversible photochromic twisted yarn Using a twisting machine, the glittering yarn of Example 2 was placed around the transparent polyester fiber as the core material so that the transparent pearlescent resin film was on the surface of the core material. The reverse photochromic flat yarn was twisted to give a glittering reversible photochromic twisted yarn.
In the photoluminescent reversible photochromic twisted yarn, the flat threads are loosely wound around the core material, so the pearlescent properties due to the transparent pearlescent resin film can be seen where the flat threads are wound, and the areas between the flat threads are visible. The core material is visible, but since the core material is transparent, the pearlescent properties of the transparent pearlescent resin film are visible through the core material. Before exposure to sunlight, pearlescent properties are visible uniformly from the entire surface of the twisted yarn, and when exposed to sunlight, the first reversible photochromic layer develops a blue color, and the pearlescent blue color appears from the entire surface of the twisted yarn. It was visually recognized uniformly, and the change upon irradiation with light was clear. After that, when it was left indoors for a while, the first reversible photochromic layer disappeared and returned to its original state. This change in aspect could be repeated.

Example 4 (see Figure 2)
Preparation of photoluminescent, reversible photochromic flat thread 1 part of 1,3,3-trimethyl-indolinospironaphthoxazine was mixed with styrene-α-methylstyrene copolymer (manufactured by Eastman Chemical Co., trade name: Picolastic A-5). ), 30 parts of a reversible photochromic microcapsule pigment (average particle size: 1.5 μm) containing a reversible photochromic composition uniformly dissolved by heating, 62 parts of a urethane emulsion, and a thickener. A first reversible photochromic screen ink was prepared by uniformly mixing in a vehicle consisting of 2 parts of a leveling agent, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent.
Next, the first transparent resin film (2) (manufactured by BASF, trade name: AURORA 8181RG) (visible light transmittance: 70%) with a thickness of 18 μm was applied as a transparent glitter resin film. A first reversible photochromic layer (3) with a film thickness of 15 μm that is printed solidly on a 120 mesh screen plate using reversible photochromic screen ink and changes from a colorless transparent state to a blue transparent state when exposed to sunlight. (Visible light transmittance in colored state: 85%) was formed.
Next, 1 part of 1,3,3-trimethyl-6-trifluoromethyl-indolino-6'-(1-piperidinyl)-spironaphthoxazine was added to an acrylic acid ester copolymer [manufactured by Toagosei Co., Ltd., trade name :ARUFON UP-1070] 30 parts of a reversible photochromic microcapsule pigment (average particle size 1.5 μm) containing a reversible photochromic composition uniformly dissolved by heating in 100 parts, and 62 parts of a urethane emulsion. , 2 parts of a thickening agent, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent are mixed uniformly into a vehicle to prepare a second reversible photochromic screen ink. was prepared.
Next, on the opposite side of the transparent pearlescent resin film on which the first reversible photochromic layer is provided, solid printing is performed using a 120 mesh screen plate using the second reversible photochromic screen ink. A second reversible photochromic layer (4) with a film thickness of 15 μm that changes from a colorless transparent state to a pink transparent state when exposed to sunlight (visible light transmittance in a colored state: 85%) is formed to create a glittering effect. A reversible photochromic laminate was obtained.
Next, the photoluminescent reversible photochromic laminate was cut into threads with a width of 250 μm using a micro slitter to obtain the photoluminescent reversible photochromic flat yarn (1) with a thickness of 48 μm (visible light transmittance in a colored state). :51%).
The glittering reversible photochromic flat thread has a flexible texture, and before being exposed to sunlight, the pearlescent properties due to the transparent pearlescent resin film are visible from both the front and back sides, and when exposed to sunlight, the first and second layers are visible. The two reversible photochromic layers each developed a color, and a pearlescent purple color was visible from both the front and back surfaces. After that, when it was left indoors for a while, the second photochromic layer disappeared and a pearlescent blue color was visible, and when left for a while, the first reversible photochromic layer disappeared and returned to its original state. . This change in aspect could be repeated. The photoluminescent reversible photochromic flat yarn has different colors and decoloring sensitivities of the reversible photochromic materials contained in the first and second reversible photochromic layers. It changed to a different color over time, making the changeability more satisfying.

Example 5 (see Figure 4)
Preparation of bright reversible photochromic flat yarn 2 parts of 1,3,3-trimethylindolino-spironaphthoxazine, 100 parts of 50% acrylic resin xylene solution, 1 part of antifoaming agent, 40 parts of xylene, and methyl isobutyl A first reversible photochromic screen ink was prepared by uniformly mixing in a vehicle consisting of 40 parts of ketone.
Next, solid printing was performed on a 12 μm thick transparent PET film (visible light transmittance: 99%) (7) as a transparent resin film using a 120 mesh screen plate using the reversible photochromic screen ink. A first reversible photochromic layer (3) with a film thickness of 15 μm that changes from a colorless transparent state to a blue transparent state when exposed to sunlight (visible light transmittance in a colored state: 90%) was formed.
In addition, 10 parts of a transparent metallic luster pigment [manufactured by Nippon Sheet Glass Co., Ltd., trade name: Metashine 5090RS] whose surface was coated with titanium oxide on the surface of a flake-shaped glass piece, 100 parts of a 50% acrylic resin xylene solution, and A metallic luster ink was prepared by uniformly mixing 1 part of a foaming agent, 40 parts of xylene, and 40 parts of methyl isobutyl ketone in a vehicle.
Next, on the opposite side of the transparent PET film on which the first reversible photochromic layer is provided, the metallic luster ink is applied to the entire surface using a doctor coater to form a transparent glitter layer (transparent glitter layer) with a film thickness of 5 μm. A metallic luster layer) (6) (visible light transmittance: 60%) was formed to obtain a glittering reversible photochromic laminate.
Next, the photoluminescent reversible photochromic laminate was cut into threads with a width of 250 μm using a micro slitter to obtain a photoluminescent reversible photochromic flat thread (1) with a thickness of 32 μm (visible light transmittance in a colored state). :54%).
The glittering reversible photochromic flat yarn has a flexible texture, and before being exposed to sunlight, the metallic luster due to the transparent metallic luster layer is visible from both the front and back surfaces, and when exposed to sunlight, the first reversible photochromic flat thread is visible. The layer developed a blue color, and the blue color with metallic luster was visible from both the front and back surfaces. After that, when it was left indoors for a while, the first reversible photochromic layer disappeared and returned to its original state. This change in aspect could be repeated. Moreover, the glittering reversible photochromic flat yarn had excellent heat resistance and strength by providing a transparent PET film.

Example 6
Preparation of glittering reversible photochromic twisted yarn The glittering reversible photochromic flat yarn of Example 5 was dry-twisted using a twisting machine to obtain a glittering reversible photochromic twisted yarn.
Before the glittering reversible photochromic twisted yarn is exposed to sunlight, the metallic luster due to the transparent metallic luster layer is uniformly visible from the entire surface of the twisted yarn, and when exposed to sunlight, the first reversible photochromic layer turns blue. A blue color with metallic luster was uniformly visible from the entire surface of the twisted yarn, and its change upon irradiation with light was clear. After that, when it was left indoors for a while, the first reversible photochromic layer disappeared and returned to its original state. This change in aspect could be repeated. Further, the glittering reversible photochromic twisted yarn had excellent heat resistance and strength by providing a transparent PET film.

Example 7 (see Figure 5)
Preparation of photoluminescent, reversible photochromic flat yarn One part of 1,3,3-trimethyl-6-trifluoromethyl-indolino-6'-(1-piperidinyl)-spironaphthoxazine was mixed with acrylic ester copolymer [Toagosei Co., Ltd. Co., Ltd., product name: ARUFON UP-1070] 30 parts of a reversible photochromic microcapsule pigment (average particle size: 1.2 μm) containing a reversible photochromic composition uniformly dissolved by heating in 100 parts. was uniformly mixed in a vehicle consisting of 62 parts of urethane emulsion, 2 parts of thickener, 0.5 part of leveling agent, 0.5 part of antifoaming agent, and 5 parts of crosslinking agent. A reverse photochromic screen ink was prepared.
Next, solid printing was performed on a 12 μm thick transparent PET film (7) (visible light transmittance: 99%) as a transparent resin film using a 180 mesh screen plate using the reversible light-changing screen ink. A first reversible photochromic layer (3) with a film thickness of 10 μm that changes from a colorless transparent state to a pink transparent state when exposed to sunlight (visible light transmittance in a colored state: 87%) was formed.
In addition, 10 parts of a transparent pearlescent pigment made of synthetic mica coated with titanium oxide [manufactured by Nihon Koken Kogyo Co., Ltd., trade name: ULTIMICA YD-100], 100 parts of a 50% acrylic resin xylene solution, and A pearlescent ink was prepared by uniformly mixing in a vehicle consisting of 1 part foaming agent, 40 parts xylene, and 40 parts methyl isobutyl ketone.
Next, the pearlescent ink is applied to the entire surface of the first reversible photochromic layer using a doctor coater to form a transparent glitter layer (transparent metallic luster layer) (6) (visible light) with a film thickness of 5 μm. Transmittance: 60%) to obtain a glittering, reversible photochromic laminate.
Next, the photoluminescent reversible photochromic laminate was cut into threads with a width of 200 μm using a micro slitter to obtain a photoluminescent reversible photochromic flat yarn (1) with a thickness of 27 μm (visible light transmittance in a colored state). :52%).
The glittering reversible photochromic flat yarn has a flexible texture, and before being exposed to sunlight, the pearlescent property due to the transparent pearlescent layer is visible from both the front and back surfaces, and when exposed to sunlight, the first reversible photochromic color changes. The layer developed a pink color, and the pink color with pearlescent properties was visible from both the front and back sides. After that, when it was left indoors for a while, the first reversible photochromic layer disappeared and returned to its original state. This change in aspect could be repeated. Moreover, the glittering reversible photochromic flat yarn had excellent heat resistance and strength by providing a transparent PET film.

Example 8 (see Figure 9)
Preparation of photoluminescent, reversible photochromic flat yarn One part of 1,3,3-trimethyl-6-trifluoromethyl-indolino-6'-(1-piperidinyl)-spironaphthoxazine was mixed with acrylic ester copolymer [Toagosei Co., Ltd. Co., Ltd., product name: ARUFON UP-1070] 30 parts of a reversible photochromic microcapsule pigment (average particle size: 1.5 μm) containing a reversible photochromic composition uniformly dissolved by heating in 100 parts. was uniformly mixed in a vehicle consisting of 62 parts of urethane emulsion, 2 parts of thickener, 0.5 part of leveling agent, 0.5 part of antifoaming agent, and 5 parts of crosslinking agent. A reverse photochromic screen ink was prepared. Additionally, 0.5 parts of a general yellow pigment was mixed with 91.8 parts of a urethane emulsion, 2 parts of a thickener, 0.2 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent. A non-color-changing screen ink was prepared by uniformly mixing in a vehicle consisting of:
Next, solid printing was performed on a 12 μm thick transparent PET film (7) (visible light transmittance: 99%) as a transparent resin film using a 225-mesh screen plate using the non-color-changing screen ink, and a yellow color was applied. A transparent non-discoloring layer (8) with a thickness of 5 μm (visible light transmittance: 90%) was formed. Furthermore, solid printing was performed on the non-color-changing layer using a 180-mesh screen plate using a reversible photochromic screen ink, and a 10-μm-thick layer was printed on the non-color-changing layer, which changed from a colorless transparent state to a blue transparent state when exposed to sunlight. A reversible photochromic layer (3) (visible light transmittance in a colored state: 85%) was formed.
In addition, 10 parts of a transparent pearlescent pigment made of synthetic mica coated with titanium oxide [manufactured by Nihon Koken Kogyo Co., Ltd., trade name: ULTIMICA YD-100], 100 parts of a 50% acrylic resin xylene solution, and A pearlescent ink was prepared by uniformly mixing in a vehicle consisting of 1 part foaming agent, 40 parts xylene, and 40 parts methyl isobutyl ketone.
Next, the pearlescent ink is applied to the entire surface of the first reversible photochromic layer using a doctor coater to form a transparent luster layer (transparent pearlescent layer) (6) (visible light) with a film thickness of 5 μm. Transmittance: 60%) to obtain a glittering, reversible photochromic laminate.
Next, the glittering reversible photochromic laminate was cut into threads with a width of 200 μm using a microslitter to obtain a reversible photochromic flat thread (1) with a thickness of 32 μm (visible light transmittance: 45%). Ta.
The glittering reversible photochromic flat thread has a flexible texture, and before being exposed to sunlight, a pearlescent yellow color is visible from both the front and back surfaces, and when exposed to sunlight, the first reversible photochromic layer becomes pink. The color developed, and a pearlescent orange color was visible from both the front and back sides. After that, when it was left indoors for a while, the first reversible photochromic layer disappeared and returned to its original state. This change in aspect could be repeated. Moreover, the glittering reversible photochromic flat yarn had excellent heat resistance and strength by providing a transparent PET film.

Example 9 (see Figure 11)
Preparation of photoluminescent and reversible photochromic flat yarn 1 part of 1,3,3-trimethyl-indolinospironaphthoxazine was mixed with 100 parts of acrylic acid ester copolymer [manufactured by Toagosei Co., Ltd., trade name: ARUFON UP-1070]. 30 parts of a reversible photochromic microcapsule pigment (average particle size: 1.5 μm) containing a reversible photochromic composition uniformly dissolved by heating and 0.1 part of a pink general pigment were mixed into a urethane emulsion. A reversible photochromic screen ink is prepared by uniformly mixing 62 parts of a thickening agent, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent into a vehicle. was prepared.
Next, solid printing was performed on a 12 μm thick transparent PET film (7) (visible light transmittance: 99%) as a transparent resin film using a 180 mesh screen plate using the reversible light-changing screen ink. , a photochromic layer (first reversible photochromic layer) (10 ) (visible light transmittance in colored state: 80%) was formed.
Next, an adhesive made of urethane resin and ethyl acetate is applied by gravure printing to the opposite side of the transparent PET film on which the first reversible photochromic layer is provided, and the ethyl acetate is evaporated to give a thickness of 2 μm. A transparent pearlescent resin film (2) with a thickness of 18 μm (manufactured by BASF, trade name: AURORA 8181RG) (visible light transmittance: 70 %) were pressed together with a roll to obtain a glittering reversible photochromic laminate.
Next, the glittering reversible photochromic laminate was cut into threads with a width of 300 μm using a micro slitter to obtain glittering reversible photochromic flat threads (1) with a thickness of 42 μm (visible light transmittance: 55%). I got it.
The glittering reversible photochromic flat yarn has a flexible texture, and before being exposed to sunlight, a pink color with pearlescent properties is visible from both the front and back sides, and when exposed to sunlight, the first reversible photochromic layer turns blue. The color developed and a pearlescent purple color was visible from both the front and back sides. After that, when it was left indoors for a while, the first reversible photochromic layer disappeared and returned to its original state. This change in aspect could be repeated. Moreover, the glittering reversible photochromic flat yarn had excellent heat resistance and strength by providing a transparent PET film.

Example 10
Production of an animal-shaped toy with hair using photoluminescent reversible photochromic flat yarn The photoluminescent reversible photochromic flat yarn of Example 9 was flocked to the tail of an animal-shaped toy in the shape of a horse by a conventional method. An animal-shaped toy with hair made of reversible photochromic flat yarn was fabricated. The glittering reversible photochromic flat yarn has a pearlescent pink color that is visible from both the front and back sides before being exposed to sunlight, and when exposed to sunlight, the first reversible photochromic layer develops a blue color and becomes pearlescent. A characteristic purple color was visible from both the front and back sides. After that, when it was left indoors for a while, the first reversible photochromic layer disappeared and returned to its original state. This change in aspect could be repeated. Moreover, the glittering reversible photochromic flat yarn had excellent heat resistance and strength by providing a transparent PET film.

Example 11 (see Figure 12)
Preparation of photoluminescent reversible photochromic flat yarn A transparent holographic resin film (2) with a thickness of 18 μm (visible light transmittance: 80%) having an adhesive layer (11) on the back surface as a transparent photoluminescent resin film was bonded. The layer was bonded to a 12 μm thick transparent PET film (7) (visible light transmittance: 99%) as a transparent resin film by pressure bonding with a roll.
Next, 1 part of 1,3,3-trimethyl-indolinospironaphthoxazine was uniformly dissolved in 100 parts of acrylic acid ester copolymer [manufactured by Toagosei Co., Ltd., trade name: ARUFON UP-1070] by heating. 30 parts of reversible photochromic microcapsule pigment (average particle size: 1.2 μm) containing the reversible photochromic composition prepared above, 62 parts of urethane emulsion, 2 parts of thickener, and 0.5 part of leveling agent. A first reversible photochromic screen ink was prepared by uniformly mixing 0.5 parts of an antifoaming agent and 5 parts of a crosslinking agent in a vehicle. In addition, 1 part of 1,3,3-trimethyl-6-trifluoromethyl-indolino-6'-(1-piperidinyl)-spironaphthoxazine was added to an acrylic acid ester copolymer [manufactured by Toagosei Co., Ltd., trade name :ARUFON UP-1070] 30 parts of a reversible photochromic microcapsule pigment (average particle diameter: 1.2 μm) containing a reversible photochromic composition uniformly dissolved by heating in 100 parts, and 62 parts of a urethane emulsion. and 2 parts of a thickening agent, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent to form a second reversible photochromic screen. An ink was prepared.
Next, solid printing is performed on the transparent holographic resin film using a 180 mesh screen plate using the first reversible photochromic screen ink, and when exposed to sunlight, the colorless state changes from a colorless transparent state to a blue transparent state. A first reversible photochromic layer (3) having a varying thickness of 10 μm (visible light transmittance in a colored state: 87%) was formed. Further, solid printing is performed on the transparent PET film using a 180 mesh screen plate using the second reversible photochromic screen ink, and a film that changes from a colorless transparent state to a pink transparent state when exposed to sunlight. A second photochromic layer (4) having a thickness of 10 μm (visible light transmittance in a colored state: 87%) was formed to obtain a glittering reversible photochromic laminate.
Next, the photoluminescent reversible photochromic laminate was cut into threads with a width of 350 μm using a micro slitter to obtain a photoluminescent reversible photochromic flat thread (1) with a thickness of 50 μm (visible light transmittance in a colored state). :60%).
The photoluminescent, reversible photochromic flat yarn has a flexible texture, and before being exposed to sunlight, the hologram properties due to the transparent holographic resin film are visible from both the front and back surfaces, and when exposed to sunlight, the first and second layers are visible. Each of the reversible photochromic layers developed a color, and a holographic purple color was visible from both the front and back sides. After that, when it was left indoors for a while, the first and second reversible photochromic layers disappeared and returned to their original state. This change in aspect could be repeated. Moreover, the glittering reversible photochromic flat yarn had excellent heat resistance and strength by providing a transparent PET film.

Comparative example 1
Preparation of photoluminescent and reversible photochromic flat yarn 1 part of 1,3,3-trimethylindolino-spironaphthoxazine was mixed with styrene-α-methylstyrene copolymer (manufactured by Eastman Chemical Co., trade name: Picolastic A-5). ), 30 parts of a reversible photochromic microcapsule pigment (average particle size: 1.5 μm) containing a reversible photochromic composition uniformly dissolved by heating, 62 parts of a urethane emulsion, and a thickener. A reversible photochromic screen ink was prepared by uniformly mixing the following components in a vehicle consisting of 2 parts of a leveling agent, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent.
Next, solid printing was performed on a 18 μm thick opaque pearlescent resin film (visible light transmittance: 0%) using a 120 mesh screen plate using the reversible photochromic screen ink and exposed to sunlight. and a first reversible photochromic layer (3) with a film thickness of 15 μm that changes from a colorless transparent state to a blue transparent state (visible light transmittance in a colored state: 85%) to form a glittering reversible photochromic laminate. I got it.
Next, the photoluminescent reversible photochromic laminate was cut into threads with a width of 250 μm using a micro slitter to obtain photoluminescent reversible photochromic flat threads with a thickness of 33 μm (visible light transmittance in colored state: 0%). ) was obtained.
The glittering reversible photochromic flat yarn has a flexible texture, and before being exposed to sunlight, the pearlescent property due to the opaque pearlescent resin film is visible from both the front and back sides, and when exposed to sunlight, the first reversible light The color changing layer developed a blue color, and a pearlescent blue color was visually recognized from the first reversible photochromic layer side of the glittering reversible photochromic flat yarn. However, only the pearl luster is visible from the side of the opaque pearlescent resin film, and no color change in the first reversible photochromic layer is visible, and the glitter shines from both the front and back sides of the glittering reversible photochromic flat yarn. It was not possible to visually recognize the color change during light irradiation. After that, when it was left indoors for a while, the first reversible photochromic layer disappeared and returned to its original state. This change in aspect could be repeated.

Comparative example 2
Preparation of glittering reversible photochromic twisted yarn Using a twisting machine, the glittering reversible light of Comparative Example 1 was placed around the transparent polyester fiber as the core material so that the opaque pearlescent resin film was on the surface of the core material. The color-changing flat threads were twisted to give a glittering, reversible photochromic twisted thread.
In the photoluminescent reversible photochromic twisted yarn, the flat yarns are loosely wound around the core material, so that the area where the flat yarns are wound has a visible pearlescent property due to the opaque pearlescent resin film. The core material is visible, but since the core material is transparent, the pearlescent properties of the opaque pearlescent resin film are visible through the core material. Before exposure to sunlight, pearlescent properties are visible uniformly over the entire surface of the twisted yarn, but when exposed to sunlight, the first reversible photochromic layer develops a blue color and is only visible through the core material. A pearlescent blue color was visible, and the changeability upon irradiation with light was poor. After that, when it was left indoors for a while, the first reversible photochromic layer disappeared and returned to its original state. This change in aspect could be repeated.

Comparative example 3
Preparation of bright reversible photochromic flat yarn 2 parts of 1,3,3-trimethylindolino-spironaphthoxazine, 100 parts of 50% acrylic resin xylene solution, 1 part of antifoaming agent, 40 parts of xylene, and methyl isobutyl A first reversible photochromic screen ink was prepared by uniformly mixing in a vehicle consisting of 40 parts of ketone.
Next, solid printing was performed on a 12 μm thick transparent PET film (visible light transmittance: 99%) (7) as a transparent resin film using a 120 mesh screen plate using the reversible photochromic screen ink. A first reversible photochromic layer (3) with a film thickness of 15 μm that changes from a colorless transparent state to a blue transparent state when exposed to sunlight (visible light transmittance in a colored state: 90%) was formed.
In addition, 10 parts of an opaque metallic luster pigment, 100 parts of a 50% acrylic resin xylene solution, 1 part of an antifoaming agent, 40 parts of xylene, and 40 parts of methyl isobutyl ketone were uniformly mixed in a vehicle containing 10 parts of a 50% acrylic resin xylene solution. A glossy ink was prepared.
Next, on the opposite side of the transparent PET film on which the first reversible photochromic layer is provided, the metallic luster ink is applied to the front surface using a doctor coat to form an opaque luster layer (opaque metallic luster) with a film thickness of 5 μm. layer) (visible light transmittance: 0%) to obtain a glittering, reversible photochromic laminate.
Next, the photoluminescent reversible photochromic laminate was cut into threads with a width of 250 μm using a micro slitter to obtain photoluminescent reversible photochromic flat threads with a thickness of 32 μm (visible light transmittance in colored state: 0%). ) was obtained.
The glittering reversible photochromic flat thread has a flexible texture, and before being exposed to sunlight, the metallic luster due to the opaque metallic luster layer is visible from both the front and back surfaces, and when exposed to sunlight, the first reversible photochromic layer is visible. was colored blue, and a blue color with metallic luster was visually recognized from the first reversible photochromic layer side of the glittering reversible photochromic flat yarn. However, only the metallic luster is visible from the side of the opaque metallic luster layer, and no color change in the first reversible photochromic layer is visible, and the luster and luster are visible from both the front and back sides of the glittering reversible photochromic flat yarn. It was not possible to visually recognize the color change upon irradiation with light. After that, when it was left indoors for a while, the first reversible photochromic layer disappeared and returned to its original state. This change in aspect could be repeated. Moreover, the glittering reversible photochromic flat yarn had excellent heat resistance and strength by providing a transparent PET film.

Comparative example 4
Preparation of Glittering Reversible Photochromic Twisted Yarn Using a twisting machine, the glistening reversible photochromic flat yarn of Comparative Example 3 was dry-twisted to obtain a glittering reversible photochromic twisted yarn.
Before the glittering reversible photochromic twisted yarn is exposed to sunlight, the metallic luster due to the opaque metallic luster layer is uniformly visible from the entire surface of the twisted yarn, and when exposed to sunlight, the first reversible photochromic layer turns blue. The color was developed, and a blue color with metallic luster was partially visible, and the changeability upon irradiation with light was poor. After that, when it was left indoors for a while, the first reversible photochromic layer disappeared and returned to its original state. This change in aspect could be repeated. Moreover, the glittering reversible photochromic flat yarn had excellent heat resistance and strength by providing a transparent PET film.

1 Glittering reversible photochromic flat yarn 2 Transparent glittering resin film 3 First reversible photochromic layer 4 Second reversible photochromic layer 5 Reversible photochromic resin film 6 Transparent glittering layer 7 Transparent resin film 8 Non-reversible photochromic layer Color changing layer 9 Transparent protective layer 10 Reversible photochromic layer comprising a reversible photochromic material and a non-chromic coloring agent 11 Adhesive layer

Claims (9)

A reversible photochromic material is applied to one wide surface of a flat thread made of a transparent glittering resin film having optical properties selected from metallic luster, pearl luster, hologram, iris, and light reflectivity. A glittering reversible photochromic flat yarn provided with a first photochromic layer containing,
The metallic luster is a transparent metallic luster pigment obtained by coating the surface of a glass piece with a metal oxide, a cholesteric liquid crystal type metallic luster pigment, or a transparent metallic luster obtained by coating silicon oxide with one or more kinds of metal oxides. It is due to any of the pigments,
The pearlescent property is achieved by a transparent pearlescent pigment obtained by coating the surface of natural mica, synthetic mica, or flaky aluminum oxide with a metal oxide, or by using 10 or more layers of polymers with different refractive indexes. A transparent multilayer film exhibiting a light interference phenomenon provided in an intermediate layer is a transparent pearlescent resin film containing a translucent dye in the multilayer film,
The hologram property is based on a relief hologram in which a transparent reflective layer is formed on the surface of the uneven pattern on a transparent hologram forming layer provided with a fine uneven pattern, or a volume hologram,
The iris has a polypropylene layer on the front and back outermost layers, and 113 thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene are alternately formed inside , and has blue reflected light and green interference light. A transparent multilayer film with a thickness of 15 μm , the outermost layers on the front and back are polypropylene layers, and the inside has 113 alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layers on the front and back are polypropylene layers, and the inside is made up of 226 alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene , blue reflection. A transparent multilayer film with a thickness of 28 μm that emits light and green interference light , the outermost layer on the front and back is a polypropylene layer, and the inside has 226 layers of alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene. , a transparent multilayer film with a thickness of 31 μm that has red reflected light and green interference light, the outermost layer on the front and back is a polyester layer, and the inside has 113 alternating thin layers of polyester and thin layers of polyolefin , a blue film. A transparent multilayer film with a thickness of 15 μm that has reflected light of A transparent multilayer film with a thickness of 17 μm that has light and green interference light, the outermost layer on the front and back is a polypropylene layer , and the inside has 113 alternating thin layers of polyolefin and thin layers of polyester. A transparent multilayer film with a thickness of 15 μm that has green interference light , the outermost layer on the front and back is a polypropylene layer, and the inside has 113 alternating thin layers of polyolefin and thin layers of polyester. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 alternating thin layers of polyester and thin layers of acrylic resin , and has blue reflected light and green light. A transparent multilayer film with a thickness of 15 μm that has interference light , the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 layers of alternating polyester thin layers and acrylic resin thin layers, red reflected light and green reflected light. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 alternating thin layers of polyester and thin layers of acrylic resin, and has blue reflected light and green light. A transparent multilayer film with a thickness of 30 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 layers of alternating polyester thin layers and acrylic resin thin layers, red reflected light and green reflected light. A 34 μm transparent multilayer film with interference light, the outermost layers on the front and back are acrylic resin layers, and the inside is made up of 226 alternating thin layers of polyester and thin layers of acrylic resin , blue reflected light and green interference light. A transparent multilayer film with a thickness of 28 μm , the front and back outermost layers are acrylic resin layers, and the inside is made up of 226 alternating layers of polyester thin layers and acrylic resin thin layers, red reflected light and green interference light. A transparent multilayer film with a thickness of 31 μm, the outermost layers on the front and back are polyester layers, and the inside is made up of 113 thin layers of polyester and thin layers of acrylic resin , which emit blue reflected light and green interference light. A transparent multilayer film with a thickness of 15 μm , the outermost layer on the front and back is a polyester layer, and 113 thin layers of polyester and thin layers of acrylic resin are alternately formed inside, and the film has a thickness of 17 μm. Either by a transparent multilayer film with interference light ,
The light reflection property is due to a transparent light reflection film having a structure in which a plurality of polyester thin films are laminated with their stretching axes shifted,
The transparency is a property of transmitting light in a wavelength range of 380 to 780 nm as defined by JIS B 7079, and is a glittering reversible photochromic flat thread. Claim 1, wherein a second photochromic layer containing a reversible photochromic material is provided on a wide surface of the flat thread made of the transparent glitter resin film opposite to where the first photochromic layer is provided. The photoluminescent, reversible photochromic flat yarn described above. A first photochromic layer containing a reversible photochromic material is provided on one wide surface of a flat thread made of a transparent resin film, and the opposite wide surface on which the first photochromic layer is provided is provided. A glittering reversible photochromic flat yarn comprising a transparent glittering layer having an optical property selected from metallic luster, pearlescent property, holographic property, iris property, and light reflective property on its surface,
The metallic luster is a transparent metallic luster pigment obtained by coating the surface of a glass piece with a metal oxide, a cholesteric liquid crystal type metallic luster pigment, or a transparent metallic luster obtained by coating silicon oxide with one or more kinds of metal oxides. It is due to any of the pigments,
The pearlescent property is achieved by a transparent pearlescent pigment obtained by coating the surface of natural mica, synthetic mica, or flaky aluminum oxide with a metal oxide, or by using 10 or more layers of polymers with different refractive indexes. A transparent multilayer film exhibiting a light interference phenomenon provided in an intermediate layer is a transparent pearlescent resin film containing a translucent dye in the multilayer film,
The hologram property is based on a relief hologram in which a transparent reflective layer is formed on the surface of the uneven pattern on a transparent hologram forming layer provided with a fine uneven pattern, or a volume hologram,
The iris has a polypropylene layer on the front and back outermost layers, and 113 thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene are alternately formed inside , and has blue reflected light and green interference light. A transparent multilayer film with a thickness of 15 μm , the outermost layers on the front and back are polypropylene layers, and the inside has 113 alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layers on the front and back are polypropylene layers, and the inside is made up of 226 alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene , blue reflection. A transparent multilayer film with a thickness of 28 μm that emits light and green interference light , the outermost layer on the front and back is a polypropylene layer, and the inside has 226 layers of alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene. , a transparent multilayer film with a thickness of 31 μm that has red reflected light and green interference light, the outermost layer on the front and back is a polyester layer, and the inside has 113 alternating thin layers of polyester and thin layers of polyolefin , a blue film. A transparent multilayer film with a thickness of 15 μm that has reflected light of A transparent multilayer film with a thickness of 17 μm that has light and green interference light, the outermost layer on the front and back is a polypropylene layer , and the inside has 113 alternating thin layers of polyolefin and thin layers of polyester. A transparent multilayer film with a thickness of 15 μm that has green interference light , the outermost layer on the front and back is a polypropylene layer, and the inside has 113 alternating thin layers of polyolefin and thin layers of polyester. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 alternating thin layers of polyester and thin layers of acrylic resin , and has blue reflected light and green light. A transparent multilayer film with a thickness of 15 μm that has interference light , the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 layers of alternating polyester thin layers and acrylic resin thin layers, red reflected light and green reflected light. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 alternating thin layers of polyester and thin layers of acrylic resin, and has blue reflected light and green light. A transparent multilayer film with a thickness of 30 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 layers of alternating polyester thin layers and acrylic resin thin layers, red reflected light and green reflected light. A 34 μm transparent multilayer film with interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 226 alternating thin layers of polyester and thin layers of acrylic resin , blue reflected light and green interference light. A transparent multilayer film with a thickness of 28 μm , the outermost layer on the front and back is an acrylic resin layer, and the inside has 226 alternating thin layers of polyester and thin layers of acrylic resin, red reflected light and green interference light. A transparent multilayer film with a thickness of 31 μm, the outermost layers on the front and back are polyester layers, and the inside is made up of 113 thin layers of polyester and thin layers of acrylic resin , which emit blue reflected light and green interference light. A transparent multilayer film with a thickness of 15 μm , the outermost layer on the front and back is a polyester layer, and 113 thin layers of polyester and thin layers of acrylic resin are alternately formed inside, and the film has a thickness of 17 μm. Either by a transparent multilayer film with interference light ,
The light reflection property is due to a transparent light reflection film having a structure in which a plurality of polyester thin films are laminated with their stretching axes shifted,
The transparency is a property of transmitting light in a wavelength range of 380 to 780 nm as defined by JIS B 7079, and is a glittering reversible photochromic flat thread. A first photochromic layer containing a reversible photochromic material is formed on one wide side of a flat thread made of a transparent resin film, and a layer having metallic luster, pearl luster, hologram, iris, and light reflectivity. A glittering reversible photochromic flat yarn provided with a transparent glittering layer having optical properties selected from any of the above,
The metallic luster is a transparent metallic luster pigment obtained by coating the surface of a glass piece with a metal oxide, a cholesteric liquid crystal type metallic luster pigment, or a transparent metallic luster obtained by coating silicon oxide with one or more kinds of metal oxides. It is due to any of the pigments,
The pearlescent property is achieved by a transparent pearlescent pigment obtained by coating the surface of natural mica, synthetic mica, or flaky aluminum oxide with a metal oxide, or by using 10 or more layers of polymers with different refractive indexes. A transparent multilayer film exhibiting a light interference phenomenon provided in an intermediate layer is a transparent pearlescent resin film containing a translucent dye in the multilayer film,
The hologram property is based on a relief hologram in which a transparent reflective layer is formed on the surface of the uneven pattern on a transparent hologram forming layer provided with a fine uneven pattern, or a volume hologram,
The iris has a polypropylene layer on the front and back outermost layers, and 113 thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene are alternately formed inside , and has blue reflected light and green interference light. A transparent multilayer film with a thickness of 15 μm , the outermost layers on the front and back are polypropylene layers, and the inside has 113 alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layers on the front and back are polypropylene layers, and the inside is made up of 226 alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene , blue reflection. A transparent multilayer film with a thickness of 28 μm that emits light and green interference light , the outermost layer on the front and back is a polypropylene layer, and the inside has 226 layers of alternating thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene. , a transparent multilayer film with a thickness of 31 μm that has red reflected light and green interference light, the outermost layer on the front and back is a polyester layer, and the inside has 113 alternating thin layers of polyester and thin layers of polyolefin , a blue film. A transparent multilayer film with a thickness of 15 μm that has reflected light of A transparent multilayer film with a thickness of 17 μm that has light and green interference light, the outermost layer on the front and back is a polypropylene layer , and the inside has 113 alternating thin layers of polyolefin and thin layers of polyester. A transparent multilayer film with a thickness of 15 μm that has green interference light , the outermost layer on the front and back is a polypropylene layer, and the inside has 113 alternating thin layers of polyolefin and thin layers of polyester. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 alternating thin layers of polyester and thin layers of acrylic resin , and has blue reflected light and green light. A transparent multilayer film with a thickness of 15 μm that has interference light , the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 layers of alternating polyester thin layers and acrylic resin thin layers, red reflected light and green reflected light. A transparent multilayer film with a thickness of 17 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 alternating thin layers of polyester and thin layers of acrylic resin, and has blue reflected light and green light. A transparent multilayer film with a thickness of 30 μm that has interference light, the outermost layer on the front and back is an acrylic resin layer, and the inside has 113 layers of alternating polyester thin layers and acrylic resin thin layers, red reflected light and green reflected light. A 34 μm transparent multilayer film with interference light, the outermost layers on the front and back are acrylic resin layers, and the inside is made up of 226 alternating thin layers of polyester and thin layers of acrylic resin , blue reflected light and green interference light. A transparent multilayer film with a thickness of 28 μm , the front and back outermost layers are acrylic resin layers, and the inside is made up of 226 alternating layers of polyester thin layers and acrylic resin thin layers, red reflected light and green interference light. A transparent multilayer film with a thickness of 31 μm, the outermost layers on the front and back are polyester layers, and the inside is made up of 113 thin layers of polyester and thin layers of acrylic resin , which emit blue reflected light and green interference light. A transparent multilayer film with a thickness of 15 μm , the outermost layer on the front and back is a polyester layer, and 113 thin layers of polyester and thin layers of acrylic resin are alternately formed inside, and the film has a thickness of 17 μm. Either by a transparent multilayer film with interference light ,
The light reflection property is due to a transparent light reflection film having a structure in which a plurality of polyester thin films are laminated with their stretching axes shifted,
The transparency is a property of transmitting light in a wavelength range of 380 to 780 nm as defined by JIS B 7079, and is a glittering reversible photochromic flat thread. A second photochromic layer containing a reversible photochromic material is provided on the wide side of the flat thread made of the transparent resin film opposite to where the first photochromic layer and transparent glitter layer are provided. The glittering reversible photochromic flat yarn according to claim 4. The glittering reversible photochromic flat yarn according to claim 2 or 5, wherein the reversible photochromic materials contained in the first and second photochromic layers are materials that exhibit different colors when colored. The glittering reversible photochromic material according to claim 2, 5 or 6, wherein the reversible photochromic materials contained in the first and second photochromic layers are materials in which at least one of coloring time and color erasing time is different from each other. Gender flat thread. Claim: The intermediate value between the maximum and minimum visible light transmittance of the photoluminescent reversible photochromic flat yarn in a colored state measured in a wavelength range from 380 nm to 780 nm using a spectrophotometer is 5% or more. 8. The glittering reversible photochromic flat thread according to any one of 1 to 7. A product comprising the glittering reversible photochromic flat yarn according to any one of claims 1 to 8.

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