JP2021008675A - Brilliant reversible light color changeable flat yarn, and product using the same - Google Patents

Abstract

To provide: a highly merchantable brilliant reversible light color changeable flat yarn having soft feeling, allowing brilliancy and color change by light irradiation to be recognized from both front and back sides, and having applicability to a variety of fields such as a toy field, a decorative field, a designing field, and the like; and a product using the same.SOLUTION: The brilliant reversible light color changeable flat yarn 1 is provided with a reversible light color changeable layer 3 containing a reversible light color changeable material on one broad width surface of a flat yarn composed of a transparent brilliant resin film 2 having an optical property selected from any of metal glossiness, pearlescence, hologram property, iris property, and light reflection property.SELECTED DRAWING: Figure 1

Description

The present invention relates to a bright reversible photochromic flat yarn and a product using the same. More specifically, the present invention relates to a brilliant reversible photochromic flat yarn which exhibits a color change when irradiated with light and whose brilliance and brilliance can be visually recognized from both the front and back surfaces, and a product using the same.

Conventionally, a reversible photochromic gold-silver thread having a resin layer (photochromic layer) dyed with a photochromic dye on the side where the metal vapor deposition layer can be seen is provided (see, for example, Patent Document 1).
The reversible photochromic gold and silver thread has a photochromic layer provided on a metal vapor deposition layer, and by irradiating light with a predetermined wavelength, a color change from a metallic luster color to another color tone can be reversibly visually recognized. However, the color change is visible only on the surface where the photochromic layer is provided on the metal vapor deposition layer, and by providing the metal vapor deposition layer and the photochromic layer on both sides of the base material in order, the color change at the time of light irradiation is front and back. Although it is visible on both sides, the gold and silver threads become thicker, which may impair the flexible texture of the threads.

Japanese Unexamined Patent Publication No. 60-139839

The present invention is to provide a brilliant reversible photo-discoloring flat yarn having a flexible texture and in which color change and brilliance due to light irradiation can be visually recognized from both the front and back surfaces, and a product using the same. ..

According to the present invention, reversible light is applied to one wide surface of a flat yarn made of a transparent bright resin film having an optical property selected from any of metallic luster, pearl luster, hologram property, iris property, and light reflectivity. A holographic reversible holographic plain yarn provided with a first reversible holographic layer containing a discoloring material is a requirement.
Further, a second reversible photocoloring layer containing a reversible photocoloring material is provided on the opposite wide surface of the plain yarn made of the transparent bright resin film on which the first reversible photocoloring layer is provided. Is a requirement.
Further, a first reversible photocoloring layer containing a reversible photocoloring material is provided on one wide surface of a flat yarn made of a transparent resin film, and the first reversible photocoloring layer is provided. A brilliant reversible photodiscolorable flat yarn provided with a transparent brilliant layer having an optical property selected from any of metallic luster, pearl luster, hologram property, iris property, and light reflectivity on the opposite wide surface. Is a requirement.
Further, on one wide surface of the flat yarn made of a transparent resin film, a first reversible photocoloring layer containing a reversible photocoloring material, and metallic luster, pearl luster, hologram property, iris property, A brilliant reversible photo-discoloring flat yarn provided with a transparent brilliant layer having an optical property selected from any of light reflectivity is required.
Further, a second reversible photocoloring material containing a reversible photocoloring material is provided on the opposite wide surface of the plain yarn made of the transparent resin film on which the first reversible photocoloring layer and the transparent bright layer are provided. The layers are provided, the reversible photocoloring materials contained in the first and second reversible photocoloring layers are materials that exhibit different colors at the time of color development, and the first and second reversible light The reversible photodiscoloring material contained in the discoloration layer is a material in which at least one of the color development time and the decolorization time is different from each other, and the visible light transmission rate of the brilliant reversible photodiscoloration plain yarn in the color-developed state is 5% or more. It is a requirement that the product contains the brilliant reversible photo-discoloring flat yarn.

According to the present invention, the color change and brilliance of a reversible photocoloring layer containing a reversible photocoloring material, which has a flexible texture, can be visually recognized from both the front and back sides, and the toy field, decoration field, design field, etc. , It is possible to provide a highly commercially available bright reversible photo-discoloring flat yarn having applicability to various fields and a product using the same.

It is a vertical cross-sectional view of an Example of the brilliant reversible photocoloring flat yarn of this invention. It is a vertical cross-sectional view of another Example of the bright reversible photocoloring flat yarn of this invention. It is a vertical cross-sectional view of another Example of the bright reversible photocoloring flat yarn of this invention. It is a vertical cross-sectional view of another Example of the bright reversible photocoloring flat yarn of this invention. It is a vertical cross-sectional view of another Example of the bright reversible photocoloring flat yarn of this invention. It is a vertical cross-sectional view of another Example of the bright reversible photocoloring flat yarn of this invention. It is a vertical cross-sectional view of another Example of the bright reversible photocoloring flat yarn of this invention. It is a vertical cross-sectional view of another Example of the bright reversible photocoloring flat yarn of this invention. It is a vertical cross-sectional view of another Example of the bright reversible photocoloring flat yarn of this invention. It is a vertical cross-sectional view of another Example of the bright reversible photocoloring flat yarn of this invention. It is a vertical cross-sectional view of another Example of the bright reversible photocoloring flat yarn of this invention. It is a vertical cross-sectional view of another Example of the bright reversible photocoloring flat yarn of this invention.

As shown in FIG. 1, the brilliant reversible photochromic flat yarn (1) of the present invention has transparency having an optical property selected from any of metallic luster, pearl luster, hologram property, iris property, and light reflectivity. A first reversible holographic layer (3) containing a reversible holographic material is provided on one wide surface of a flat yarn made of a brilliant resin film (2).
Further, as shown in FIG. 2, a second reversible photocoloring material containing a reversible photocoloring material is contained on the opposite wide surface of the plain yarn made of the transparent brilliant resin film on which the first reversible photocoloring layer is provided. It is also possible to have a structure in which the layer (4) is provided.

As a transparent brilliant resin film having metal luster, a transparent metal luster pigment is melt-blended in a transparent thermoplastic resin or a transparent thermosetting resin to form a resin such as pellets, powder, or paste. A single-layer transparent brilliant resin film obtained by preparing a composition and molding it into a flat form such as a sheet or a film by various molding means such as extrusion molding, calendar molding, and inflation molding can be used.
In addition, printing means such as screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer, etc., can be used to apply liquid compositions such as printing inks and paints prepared by dispersing transparent metallic glossy pigments in vehicles. A transparent bright layer (transparent metal gloss layer) is formed on a transparent support by a coating means such as brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, roller coating, and dip coating. A transparent glittering resin film having a structure can also be used.
As the flat thread made of the transparent bright resin film, a transparent bright resin film having a single layer or a laminated structure can be used.
The transparent bright layer is a layer formed by a compound other than the solvent volatilized in the liquid composition.

Specifically, the transparent metal bright pigment includes a transparent metal bright pigment 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 metal glossy pigment having color flop property and the like.

The transparent metal gloss pigment in which the surface of the core material such as the glass piece is coated with a metal oxide is a transparent metal in which a flake-shaped glass piece is used as the core material and the surface thereof is coated with a metal oxide such as titanium oxide. Examples thereof include a glossy pigment and a two-layer coating type transparent metal glossy pigment in which a glass piece of borosilicate is used as a core material, and the surface thereof is coated with silicon dioxide and further coated with titanium oxide.
The transparent metallic luster pigment in which the flake-shaped glass piece is used as the core material and the surface thereof is coated with a metal oxide such as titanium oxide has high metallic luster and transparency by using glass as the core material. Further, depending on the coverage of the metal oxide, it exhibits a metallic luster such as gold, silver, copper, or metallic. Specifically, as a transparent metal gloss pigment in which the surface of the flake-shaped glass piece is coated with titanium oxide, it is manufactured by Nippon Plate Glass Co., Ltd., trade name: Metashine 5090RS (average particle size: 90 μm, thickness: 5 μm, color tone). : Silver), 5090RY (average particle size: 90 μm, thickness: 5 μm, color: gold), 5090RR (average particle size: 90 μm, thickness: 5 μm, color: metallic red), 5090RB (average particle size: 90 μm, Thickness: 5 μm, Color: Metallic Blue), 5090RG (Average Particle Diameter: 90 μm, Thickness: 5 μm, Color: Metallic Green), 1080RS (Average Particle Diameter: 80 μm, Thickness: 1 μm, Color: Silver), 1080 RY (Average) Particle size: 80 μm, thickness: 1 μm, color tone: gold), 1080 RR (average particle size: 80 μm, thickness: 1 μm, color tone: metallic red), 1080 RB (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: gold), 1040RR (average particle size: 40 μm, thickness: 1 μm, color tone: metallic red), 1040RB (average particle size: 40 μm, thickness: 1 μm, color tone: metallic blue), 1040RG (average particle size) : 40 μm, Thickness: 1 μm, Color: Metallic Green), 1030RS (Average particle size: 30 μm, Thickness: 1 μm, Color: Silver), 1030RY (Average particle size: 30 μm, Thickness: 1 μm, Color: Gold), 1030RR (Average particle size: 30 μm, thickness: 1 μm, color tone: metallic red), 1030 RB (average particle size: 30 μm, thickness: 1 μm, color tone: metallic blue), 1030 RG (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: metallic green) etc. ..
The average particle diameter is the average particle diameter obtained by the laser diffraction method, and the volume-based median diameter is a particle diameter corresponding to 50% of the cumulative distribution.

In the two-layer coating type transparent metal gloss pigment in which the borosilicate glass piece is used as a core material, the surface thereof is coated with silicon dioxide, and the surface thereof is further coated with titanium oxide, the borosilicate glass used as the core material is more than ordinary glass. Since it has excellent impact resistance, heat resistance, and chemical resistance, it can maintain a state in which it is hard to crack even if the thickness of the core material is reduced. Therefore, the mass per reflection area can be reduced, and the light transmittance of the pigment can be improved. Further, depending on the coverage of the metal oxide, it exhibits a metallic luster such as gold, silver, copper, or metallic.
As a transparent metal gloss pigment in which the surface of the borosilicate glass piece is coated with silicon dioxide and further coated with titanium oxide, specifically, a product manufactured by Merck Co., Ltd., trade name: Miraval5311 Scientific White (average particle size: 10 to 10). 100 μm, color: silver), 5320 Scientific Gold (average particle size: 10-100 μm, color: gold), 5400 Luxury Twinkle (average particle size: 20-200 μm, color: gold), 5401 Royal Twinkle (average particle) Diameter: 20-200 μm, Color: Metallic Red), 5402 Pacific Twincle (Average Particle Size: 20-200 μm, Color: Metallic Blue), 5411 Magic White (Average Particle Diameter: 20-200 μm, Color: Silver), Same 5420 Magic Gold (average particle size: 20-200 μm, color tone: gold), 5421 Magic Copper (average particle size: 20-200 μm, color tone: copper color), 5422 Magic Red (average particle size: 20-200 μm, color tone) : Bronze), 5423 Magic Lilac (average particle size: 20-200 μm, color: metallic violet), 5424 Magic Blue (particle size: 20-200 μm, color: metallic blue), 5425 Magic Turquoise (average particle size) : 20 to 200 μm, color tone: metallic turquoise), 5426 Magic Green (average particle size: 20 to 200 μm, color tone: metallic green) and the like can be exemplified.
The average particle diameter is the average particle diameter obtained by the laser diffraction method, and the average thickness is 0.1 to 1.0 μm.

Examples of the transparent metallic luster pigment having a color flop property include a cholesteric liquid crystal type metallic luster pigment, a transparent metallic luster pigment 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 described. The liquid crystal polymer used as a cholesteric liquid crystal type metallic luster pigment has a property that only a part of the light incident on a wide spectral region is reflected due to the interference effect of light, and all the other regions transmit the light. The region of the reflection spectrum is determined by the pitch width of the spiral polymer and the refractive index of the material, and the region of the reflection spectrum is divided into left and right spirally polarized light components, depending on the direction of rotation of the helix. One can be reflected and the other can be transmitted. As a result, the cholesteric liquid crystal type metallic luster pigment has the property of transmitting and reflecting over the entire spectral region, that is, the excellent metallic luster and the color flop property in which the hue changes depending on the viewpoint. Further, the cholesteric liquid crystal type metallic luster pigment has not only metallic luster but also transparency.

Examples of the cholesteric liquid crystal type metallic gloss pigment include a material based on a siloxane skeleton having mesogene as a side chain. Specifically, 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: gold to dark green ), The same Maple (average particle size: 30 μm, thickness: 5 μm, color tone: bronze to dark green) and the like can be exemplified.
The average particle diameter is the average particle diameter obtained by the laser diffraction method, and the volume-based median diameter is a particle diameter corresponding to 50% of the cumulative distribution.

The transparent metallic luster pigment in which the silicon oxide is coated with one or more kinds of metal oxides has light transmission and expresses various colors by the visual angle and the angle of light hit by the interference effect of light. It has a possible color flop property and excellent metallic luster. Further, when silicon oxide is coated in multiple layers with two or more kinds of metal oxides, color flop properties and metallic luster can be more effectively imparted by using metal oxides having different light reflectances. Examples of the metal oxide include tin oxide, titanium oxide, iron oxide and the like.
Specifically, as a transparent metal gloss pigment in which the silicon oxide is coated with one or more kinds of metal oxides, specifically, manufactured by Merck Co., Ltd., trade name: Colorstream T10-01 Viola Fantasy (average particle size: 5 to 5). 50 μm, color tone: purple to green), T10-02 Arctic Field (average particle size: 5 to 50 μm, color tone: silver to purple), T10-03 Tropical Sunrise (average particle size: 5 to 50 μm, color tone: brown to brown Green), T10-04 Lapis Sunlight (average particle size: 5 to 50 μm, color: gold to bluish green), F10-51 Lava Red (average particle size 5 to 50 μm, color: copper to red), T20 -01 WNT Viola Fantasy (average particle size: 5-40 μm, color tone: purple to green), T20-02 WNT Arctic Field (average particle size: 5-40 μm, color tone: silver to purple), T20-03 WNT Tropical 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: golden to bluish green), F20-51 SW Lava Red (average) Particle size: 5 to 40 μm, color tone: copper to red) and the like can be exemplified.
The average particle diameter is the average particle diameter obtained by the laser diffraction method, and the average thickness is 0.01 to 1.0 μm.

As a transparent brilliant resin film having pearl luster, a transparent pearl luster pigment is melt-blended in a transparent thermoplastic resin or a transparent thermosetting resin to form a resin such as pellets, powder, or paste. A single-layer transparent brilliant resin film obtained by preparing a composition and molding it into a flat form such as a sheet or a film by various molding means such as extrusion molding, calendar molding, and inflation molding can be used.
In addition, printing means such as screen printing, offset printing, process printing, gravure printing, coaters, tampo printing, transfer, etc., can be used to apply liquid compositions such as printing inks and paints prepared by dispersing transparent pearl luster pigments in vehicles. A transparent bright layer (transparent pearl luster layer) is formed on a transparent support by a coating means such as brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, roller coating, and dip coating. A transparent glittering resin film having a structure can also be used.
As the flat thread made of the transparent bright resin film, a transparent bright resin film having a single layer or a laminated structure can be used.
The transparent bright layer is a layer formed by a compound other than the solvent volatilized in the liquid composition.

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

Transparent pearl luster pigments containing natural mica as a core material include those in which the surface of natural mica particles is coated with titanium oxide, those in which the upper layer of titanium oxide is further coated with iron oxide or a non-discoloring dye, and natural mica. Examples thereof include those in which the surface of particles is coated with iron oxide, a golden pearl luster pigment having a particle size of 5 to 50 μm in which the surface of natural mica is coated with 41 to 44% by mass of titanium oxide, and the surface of natural mica is 30 to 38. A golden pearl luster pigment with a particle size of 5 to 60 μm, which is coated with mass% titanium oxide and the upper layer is coated with 0.5 to 10 mass% of non-discoloring colored pigment, and the surface of natural mica is 16 to 39 mass%. Silver pearl luster pigment with a particle size of 5 to 100 μm coated with titanium oxide, metallic pearl luster pigment with the surface of natural mica coated with 45 to 58% by mass of titanium oxide, oxidation of the surface of natural mica by 45 to 58% by mass. Examples thereof include metallic pearl luster pigments coated with titanium and the upper layer thereof coated with 0.5 to 10% by mass of a non-color-changing colored dye pigment. Further, depending on the coverage of the metal oxide, it exhibits a pearl luster such as gold, silver, copper, or metallic.

Specific examples of the transparent pearl luster pigment in which the surface of the natural mica is coated with titanium oxide are manufactured by Merck Co., Ltd., trade name: Iriodin100 (average particle size: 10 to 60 μm, color tone: silver pearl), 103 ( Average particle size: 10 to 60 μm, color tone: rutile sterling silver), 103 WNT (average particle size: 10 to 60 μm, color tone: rutile sterling silver), 111 (average particle size: 1 to 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 raster satin), 153 (average particle size: 20 to 100 μm, color tone: flash pearl), 153 WII (average particle size: 20 to 100 μm, color tone: flash pearl), 163 (average particle size: 20 to 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) Particle size: 5 to 25 μm, color tone: rutile fine red), 215 (average particle size: 10 to 60 μm, color tone: rutile red pearl), 217 (average particle size: 10 to 60 μm, color tone: rutile copper) Pearl), 219 (average particle size: 10 to 60 μm, color tone: rutile lilac pearl), 221 (average particle size: 5 to 25 μm, color tone: 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 to 60 μm, color tone: rutile green pearl), 249 (average particle size: 10 to 125 μm, color tone: flash gold), 259 (average particle size: 10 to 125 μm, color tone: flash. 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 tone: Ultra Gold), 7215 (Average particle size: 10 to 60 μm, Color tone: Ultra Red), 7217 (Average particle size: 1) 0 to 60 μm, color tone: ultra copper), 7219 (average particle size: 10 to 60 μm, color tone: ultra lilac), 7215 (average particle size: 10 to 60 μm, color tone: ultra blue), 7235 (average particle size) : 10-60 μm, color tone: ultra green),
Made by BASF, trade name: Lumina Gold (average particle size: 8 to 48 μm, color tone: gold), Red (average particle size: 8 to 48 μm, color tone: metallic red), Red Blue (average particle size: 8 to 8 to 48 μm, color tone: metallic blue, Aqua Blue (average particle size: 8 to 48 μm, color tone: metallic blue), Green (average particle size: 8-48 μm, color tone: metallic green), Turquoise (average particle size: 8) ~ 48 μm, color tone: metallic blue) and the like can be exemplified.
The average particle diameter is the average particle diameter obtained by the laser diffraction method, and the average thickness is 0.1 to 1.0 μm.

Further, as a transparent pearl luster pigment in which the surface of the natural mica is coated with titanium oxide and the upper layer thereof is coated with iron oxide, specifically, it is manufactured by Merck Co., Ltd., trade name: Iriodin300 (average particle size: 10). ~ 60 μm, color tone: gold pearl), 302 (average particle size: 5 to 25 μm, color tone: gold satin), 303 (average particle size: 10 to 60 μm, 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 to 25 μm, color tone: royal gold satin), 325 (average particle size: 5 to 25 μm, color tone: solar gold satin), 326 (Average particle size: 5 to 25 μm, color: Olympic gold satin),
Examples thereof include BASF's product name: Lumina Brass (average particle size: 8 to 48 μm, color tone: gold).
The average particle diameter is the average particle diameter obtained by the laser diffraction method, and the average thickness is 0.1 to 1.0 μm.

Further, as a transparent pearl luster pigment in which the surface of the natural mica is coated with iron oxide, specifically, it is manufactured by Merck Co., Ltd., trade name: Iriodin500 (average particle size: 10 to 60 μm, color tone: copper color), the same. 502 (average particle size: 10-60 μm, color tone: red brown), 504 (average particle size: 10-60 μm, color tone: red), 505 (average particle size: 10-60 μm, color tone: red violet), same 520 (average particle size: 5 to 25 μm, color: bronze satin), 522 (average particle size: 5 to 25 μm, color: red brown satin), 524 (average particle size: 5 to 25 μm, color: red satin) ,
Examples thereof include BASF's product name: Lumina Copper (average particle size: 8 to 48 μm, color tone: copper color), Ruset (average particle size: 8 to 48 μm, color tone: metallic red) and the like.
The average particle diameter is the average particle diameter obtained by the laser diffraction method, and the average thickness is 0.1 to 1.0 μm.

A transparent pearl luster pigment whose core material is synthetic mica and whose surface is coated with a metal oxide has a higher content of metal ions such as impurities and iron, which are coloring factors, than a system using natural mica as the core material. It has a small amount, excellent brilliance, a glittering appearance, and high transparency. Further, depending on the coverage of the metal oxide, it exhibits a pearl luster such as gold, silver, copper, or metallic. Examples of the synthetic mica include KMg3 (AlSi3O10) F2.
The shape of the synthetic mica is not specified, but a flat shape or a scale shape can be exemplified.

Specifically, as a transparent pearl luster pigment in which the surface of the synthetic mica is coated with titanium oxide, manufactured by Nippon Koken Kogyo Co., Ltd., trade name: TWINCLE PEARL SXB (average particle size: 5 to 30 μm, color tone: silver) , YXB (average particle size: 5 to 30 μm, color tone: gold), RXB (average particle size: 5 to 30 μm, color tone: metallic red), VXB (average particle size: 5 to 30 μm, color tone: metallic violet) , BXB (average particle size: 5 to 30 μm, color tone: metallic blue), GXB (average particle size: 5 to 30 μm, color tone: metallic green), RYXB (average particle size: 5 to 30 μm, color tone: gold), Same SXD (average particle size: 5 to 60 μm, color tone: silver), same YXD (average particle size: 5 to 60 μm, color tone: gold), same RXD (average particle size: 5 to 60 μm, color tone: metallic red), same VXD (average particle size: 5 to 60 μm, color tone: metallic violet), BXD (average particle size: 5 to 60 μm, color tone: metallic blue), GXD (average particle size: 5 to 60 μm, color tone: metallic green), same RYXD (average particle size: 5 to 60 μm, color tone: gold), SXE (average particle size: 20 to 80 μm, color tone: silver), YXE (average particle size: 20 to 80 μm, color tone: gold color), RXE (average particle size: 20 to 80 μm, color tone: gold) Average particle size: 20-80 μm, color tone: metallic red), VXE (average particle size: 20-80 μm, color tone: metallic violet), BXE (average particle size: 20-80 μm, color tone: metallic blue), GXE (Average particle size: 20 to 80 μm, color tone: metallic green), RYXE (average particle size: 20 to 80 μm, color tone: gold), SX (average particle size: 40 to 200 μm, color tone: silver), YX (average particle size) Particle size: 40 to 200 μm, color tone: gold), RX (average particle size: 40 to 200 μm, color tone: metallic red), VX (average particle size: 40 to 200 μm, color tone: metallic violet), BX (average) Particle size: 40 to 200 μm, color tone: metallic blue), GX (average particle size: 40 to 200 μm, color tone: metallic green), RYX (average particle size: 40 to 200 μm, color tone: gold), SXC-SO (average particle size: 40 to 200 μm, color tone: gold) Average particle size: 10-40 μm, color tone: silver), YXC-SO (average particle size: 10-40 μm, color tone: gold), RXC-SO (average particle size: 10-40 μm, color tone: metallic red), Same VXC-SO (average grain Child diameter: 10-40 μm, color tone: metallic violet), BXC-SO (average particle diameter: 10-40 μm, color tone: metallic blue), GXC-SO (average particle size: 10-40 μm, color tone: metallic green), RYXC-SO (average particle size: 10-40 μm, color tone: gold), SXB-SO (average particle size: 5 to 30 μm, color tone: silver), SXD-SO (average particle size: 5 to 60 μm, color tone) : Silver),
Made by Nippon Koken Kogyo Co., Ltd., Product name: ULTIMICA SB-100 (average particle size: 5 to 30 μm, color tone: silver), SD-100 (average particle size: 10 to 60 μm, color tone: silver color), SE -100 (average particle size: 15 to 100 μm, color tone: silver), SF-100 (average particle size: 44 to 150 μm, color tone: silver), SH-100 (average particle size: 150 to 600 μm, color tone: silver color) ), YB-100 (average particle size: 5 to 30 μm, color tone: gold), YD-100 (average particle size: 10 to 60 μm, color tone: gold), YE-100 (average particle size: 15 to 100 μm, Color: YF-100 (average particle size: 44 to 150 μm, color: gold), RB-100 (average particle size: 5 to 300 μm, color: 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), same 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 to 150 μm, color tone: metallic purple), VB-100 (average particle size: 5 to 30 μm, color tone: metallic violet), VD-100 (average) Particle size: 10 to 60 μm, color tone: metallic violet), VE-100 (average particle size: 15 to 100 μm, color tone: metallic violet), VF-100 (average particle size: 44 to 150 μm, color tone: metallic violet) , BB-100 (average particle size: 5 to 30 μm, color tone: metallic blue), BD-100 (average particle size: 10 to 60 μm, color tone: metallic blue), BE-100 (average particle size: 15 to 15 100 μm, color tone: metallic blue, BF-100 (average particle size: 44 to 150 μm, color tone: metallic blue), GB-100 (average particle size: 5 to 30 μm, color tone: metallic green), GD-100 (average particle size: metallic green) Average particle size: 10 to 60 μm, color tone: metallic green), GE-100 (average particle size: 15 to 100 μm, color tone: metallic green), GF-100 (average particle size: 44 to 150) μm, color tone: metallic green) and the like can be exemplified.
The average particle diameter is the average particle diameter obtained by the laser diffraction method, and the average thickness is 0.01 to 1.0 μm.

A transparent pearl luster pigment whose core material is flaky aluminum oxide and whose surface is coated with a metal oxide such as titanium oxide is excellent because the surface of the core material aluminum oxide has high reflectance and a sharp particle size distribution. It exhibits high brilliance and high transparency. Further, depending on the coverage of the metal oxide, it exhibits a pearl luster such as gold, silver, copper, or metallic.

Specific examples of the pigment in which the surface of the flaky aluminum oxide is coated with titanium oxide are manufactured by Merck Co., Ltd., trade name: Xirallic T50-10 Crystal Silver (average particle size: 5 to 40 μm, color tone: silver), the same. T60-10 WNT Crystal Silver (average particle size: 5 to 30 μm, color: silver), T60-20 WNT Sunbeam Gold (average particle size: 5 to 30 μm, color: gold), T60-21 WNT Solaris Red (average) Particle size: 5 to 30 μm, color tone: metallic red, T60-23 WNT Galaxy Blue (average particle size: 5 to 30 μm, color tone: metallic blue), T60-24 WNT Stellar Green (average particle size: 5 to 30 μm) , Color: T60-25 WNT Cosmic Turquoise (Average particle size: 5-30 μm, Color: Metallic blue), F60-50 WNT Fireside Copper (Average particle size: 5-30 μm, Color: Copper), The same F60-51 WNT Radiant Red (average particle size: 5 to 30 μm, color tone: metallic red) and the like can be exemplified.
The average particle diameter is the average particle diameter obtained by the laser diffraction method, and the average thickness is 0.1 to 1.0 μm.

As the transparent thermoplastic resin or the transparent thermosetting resin into which the transparent metal gloss pigment or the transparent pearl gloss pigment is melt-blended, a colorless transparent or colored transparent resin can be used, and the reversible photocoloring layer The design, characters, and color change of the reversible photocoloring layer are not particularly limited as long as they 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 acid ester. Resin, methacrylic acid 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 resin, ethylene-methacrylic acid ester copolymer resin, acrylonitrile-styrene copolymer resin, cycloolefin copolymer, etc.
Examples thereof include thermosetting resins such as epoxy resins, epoxy acrylates, phenol resins, unsaturated polyester resins, urea resins, aryl resins, and silicone resins.
The transparent metallic luster pigment or the transparent pearl luster pigment is contained in a transparent thermoplastic resin or a transparent thermosetting resin in a proportion of 0.1 to 40% by mass, preferably 0.3 to 30% by mass. It is mixed. If the blending ratio of the pigment exceeds 40% by mass, the dispersion stability and processability tend to be poor when dispersed in the resin. On the other hand, if the ratio is less than 0.1% by mass, it becomes difficult to exhibit the desired brilliance.

The vehicle that disperses the transparent metallic luster pigment or the transparent pearl luster pigment is composed of a solvent, a binder resin, and various additives if necessary, and examples of the solvent include water and various organic solvents.
Specifically, the organic solvent includes 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 thereof include methyl-3-methoxybutanol, 3-methyl-1,3-butanediol, 1,3-butanediol, and hexylene glycol.

Specifically, the binder resin includes an ionomer resin, an isobutylene-maleic anhydride copolymer resin, an acrylonitrile-acrylics styrene copolymer resin, an acrylonitrile-styrene copolymer resin, an acrylonitrile-butadiene-styrene copolymer resin, and an 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 acid ester resin, polymethylmethacrylate resin, epoxy acrylate resin, alkylphenol resin, rosin-modified phenol resin, Login-modified alkyd resin, phenol resin-modified alkyd resin, styrene-modified alkyd resin, epoxy resin-modified alkyd resin, acrylic-modified alkyd resin, aminoalkide 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, silicon 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 Acids, polymethacrylates, acrylic acid ester emulsions, methacrylate ester emulsions, vinyl acetate-acrylic acid ester copolymer emulsions, ethylene-vinyl acetate copolymer emulsions, styrene-acrylic acid ester copolymer emulsions, Vinyl chloride-based Emma Lujon, 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, kumaron plastic , Polybutene, phenoxyplastic, liquid polybutadiene, liquid rubber, petroleum hydrocarbon resin, cyclopentadiene petroleum resin and other synthetic resins,
Examples thereof include natural or semi-synthetic resins such as cellulose derivatives, alginic acid derivatives, rosin derivatives, starches, polysaccharides, gums, natural rubbers, cellacs, agar, casein, glue, gelatin, and polyterpene.

Examples of the additive include a cross-linking agent, a curing agent, a desiccant, a plasticizer, a viscosity regulator, a dispersant, an ultraviolet absorber, an antioxidant, a light stabilizer, an antioxidant, a smoothing agent, a gelling agent, and a defoaming agent. Examples thereof include agents, matting agents, penetrants, pH adjusters, foaming agents, coupling agents, moisturizing agents, lubricants, fungicides, preservatives, rust preventives and the like.

As the transparent support, a colorless transparent or colored transparent one can be used, and is particularly limited as long as the design, characters, color change during light irradiation, etc. of the reversible photocoloring layer can be visually recognized. It's not a thing. Specifically, a sheet or film using a general-purpose resin such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polymethylmethacrylate, polyacrylate, polystyrene, polycarbonate, cellulose acetate, polyvinyl alcohol, and polyamide. Examples thereof include a thermoplastic resin molded body having a flat shape such as a shape. A transparent plastic sheet using a resin such as polyethylene, polypropylene, polyethylene terephthalate, or polyvinyl chloride is preferable because it is highly flexible and excellent in safety.

Further, as a transparent brilliant resin film having pearl luster, the multilayer film is a transparent multilayer film exhibiting a light interference phenomenon in which 10 or more layers made of polymers having different refractive indices are provided as intermediate layers. A transparent pearl glossy resin film containing a translucent dye can also be used. The transparent pearl glossy resin film is formed by laminating at least 10 layers or more of a film (thin film layer) made of an extremely thin translucent thermoplastic resin having a uniform thickness of about 30 to 500 nm and contacting the film. Adjacent layers are translucent resins of different materials, have different refractive indexes by a numerical value of at least 0.03, and contain a translucent dye in the layers. Therefore, the translucent dye enhances or changes at least one color tone of the reflected color and the transmitted color of the layer.
Examples of the thermoplastic resin include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as polymethylmethacrylate and polyacrylate, polyolefin resins such as polyethylene and polypropylene, polystyrene, and ethylene-vinyl acetate copolymer resins. .. Examples of the translucent dye include azo dyes, anthraquinone dyes, pyridone dyes, and pyrazolone derivative dyes. The translucent dye is contained in one layer or two or more layers, and may be contained in all layers. The amount of the dye added is sufficient to strengthen or change at least one of the transmitted colors of the thin film layer, at least one of the reflected light of the thin film layer, or both of them as compared with the non-added system. Is added in a large amount.
Specific examples of the transparent pearl glossy resin film include BASF, trade name: AURORA FILM and the like.

As the transparent holographic resin film having a hologram property, a transparent holographic resin film using a general-purpose hologram can be used as long as it has a light transmitting property.
As the hologram, for example, a transparent hologram forming layer (particularly made of a transparent resin) provided with a fine uneven pattern is provided with a transparent reflective layer (a thin film made of a metal, a metal compound, etc.) on the surface of the uneven pattern. Examples thereof include a relief hologram to be formed and a volumetric hologram (Lipman hologram). In particular, a relief hologram is preferably used because of its high convenience and high visual effect as a laminated body.

As a transparent brilliant resin film having iris properties, the outermost layers on the front and back are polypropylene layers, and 113 layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene are alternately formed inside, and a blue reflection A transparent multilayer film with a thickness of 15 μm having light and green interference light, the outermost layers on the front and back were polypropylene layers, and 113 layers of ethylene-vinyl acetate copolymer thin layers and polystyrene thin layers were alternately formed inside. , A transparent multilayer film with a thickness of 17 μm having green reflected light and red interference light, the outermost layers on the front and back are polypropylene layers, and thin layers of ethylene-vinyl acetate copolymer and thin layers of polystyrene are alternately 226 inside. A transparent multilayer film with a thickness of 28 μm having blue reflected light and green interference light formed in layers, the outermost layers on the front and back are polypropylene layers, and a thin layer of ethylene-vinyl acetate copolymer and a thin layer of polystyrene are formed inside. 226 layers of transparent multilayer film with red reflected light and green interference light with a thickness of 31 μm, the outermost layers on the front and back are polyester layers, and thin layers of polypropylene and thin layers of polyolefin are alternately formed inside. A transparent multilayer film with a thickness of 15 μm having blue reflected light and green interference light formed in 113 layers. The outermost layers on the front and back are polypropylene layers, and thin layers of polypropylene and thin layers of polyolefin are alternately 113. A transparent multilayer film with a thickness of 17 μm having red reflected light and green interfering light, with polypropylene layers on the front and back outermost layers, and 113 layers of polyolefin thin layers and polyester thin layers alternately formed inside. A transparent multilayer film with a thickness of 15 μm having blue reflected light and green interference light, the outermost layers on the front and back were polypropylene layers, and 113 layers of polyolefin thin layers and polyester thin layers were alternately formed inside. , A transparent multilayer film with a thickness of 17 μm having red reflected light and green interference light, the outermost layers on the front and back were acrylic resin layers, and 113 layers of polypropylene thin layers and acrylic resin thin layers were alternately formed inside. , A transparent multilayer film with a thickness of 15 μm having blue reflected light and green interference light, the outermost layers on the front and back were acrylic resin layers, and 113 layers of polypropylene thin layers and acrylic resin thin layers were alternately formed inside. , A transparent multilayer film with a thickness of 17 μm having red reflected light and green interference light, the outermost layers on the front and back were acrylic resin layers, and 113 layers of polypropylene thin layers and acrylic resin thin layers were alternately formed inside. , Blue reflected light and green interference A transparent multilayer film with a thickness of 30 μm that has light, the outermost layers on the front and back are acrylic resin layers, and 113 layers of polyester thin layers and acrylic resin thin layers are alternately formed inside, and red reflected light and green interference A 34 μm transparent multilayer film with light, the outermost layers on the front and back are acrylic resin layers, and 226 layers of polyester thin layers and acrylic resin thin layers are alternately formed inside, and blue reflected light and green interference light are formed. A transparent multilayer film with a thickness of 28 μm, the outermost layers on the front and back are acrylic resin layers, and 226 layers of polyester thin layers and acrylic resin thin layers are alternately formed inside, and red reflected light and green interference light are generated. It has a transparent multilayer film with a thickness of 31 μm, the outermost layers on the front and back are polyester layers, and 113 layers of polyester thin layers and acrylic resin thin layers are alternately formed inside, and it 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 polyester layers, and 113 layers of polyester thin layers and acrylic resin thin layers are alternately formed inside, and red reflected light and green interference with a thickness of 17 μm are formed. A transparent iris resin film such as a transparent multilayer film having light can be used.
Specifically, as the transparent iris resin film, ENGELHARD Co., Ltd., trade name: IRIDESCENT FILM and the like can be exemplified.

The transparent brilliant resin film having light reflectivity has, for example, a structure in which a plurality of polyester thin films are laminated while shifting the stretching axis, has a metallic luster like a mirror surface, and is described by the viewing angle. A transparent light-reflecting resin film that exhibits a metallic luster color change and is transparent depending on the viewing angle can be used.
Specific examples of the transparent light-reflecting resin film include Hologram Supply Co., Ltd., trade name: Magical Film (Mirage Film) and the like.

The transparency of the transparent brilliant resin film is a property of transmitting light having a wavelength in the visible light region (wavelength region of 380 to 780 nm defined by JIS B 7079), and the transparent brilliant property. The light transmittance (visible light transmittance) in the visible light region of the resin film is preferably 5% or more, more preferably 10% or more, still more preferably 20% or more. When the visible light transmittance of the transparent brilliant resin film is less than 5%, it is difficult to visually recognize the pattern, characters, or color change of the adjacent reversible photocoloring layer, and the brilliant reversible photocoloring flat yarn becomes It becomes difficult to visually recognize the various shades presented on both the front and back sides.
For the visible light transmittance, a transparent bright layer or a transparent bright resin film is provided on a transparent base material that transmits light having a wavelength in the visible light region, and a spectrophotometer [manufactured by Hitachi, Ltd., product. Name: U-3210] was used to measure in the wavelength region of 380 nm to 780 nm, and the value was taken as an intermediate value between the maximum value and the minimum value.

Examples of the reversible photocoloring material contained in the first and second reversible photocoloring layers include photochromic compounds such as a spirooxazine derivative, a spiropyran derivative, and a naphthopyran derivative.
The spirooxazine derivatives are shown below, but the present invention is not limited thereto.
Specifically, as an indolinospyrobenzoxazine-based 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'-Methyldispyro [cyclohexane-1,3'-[3H] indole-2'(1'H), 3 "- [3H] pyrido [4,3-f] [1,4] benzoxazine],
1'-Methyl-5'-Nitrodispyro [Cyclopentane-1,3'-[3H] -Indole-2'(1'H), 3 "- [3H] Pyrid [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'-methyldispyro [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-Iodine-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'-methyldispyro [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'-methyldispyro [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] Pyrid [2,3-f] [1,4] Benzoxazine ],
9 ″ -bromo-1'-methoxycarbonylmethyl-5'-trifluoromethyldispyro [cyclopentane-1,3'-[3H] -indole-2'[1'H], 3 "- [3H] pyridoes [2,3-f] [1,4] benzoxazine],
1-Benzyl-3,3-di-nbutyl-7'-ethyl-5-methoxyspiro [2H-indole-1,3'-[3H] pyrido [2,3-f] [1,4] benzoxazine ],
1'-n-Butyl-6'-iododispyro [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] pyridoes [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'-Methyldispyro [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 "-iododispyro [cyclopentane-1,3'-[3H] -indole-2'(1'H), 3"-[3H] pyrido [2,3-f] [1,4 ] Benzyloxazine],
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] Pyrid [2,3-f] [1" , 4] Benzoxazine],
1,3-diethyl-3-methylspiro [2H-indole-2,3'-[3H] pyrido [2,3-f] [1,4] benzoxazine],
1'-methoxycarbonylmethyl dispiro [cyclohexane-1,3'-[3H] -indole-2'(1'H)-[3H] pyrido [2,3-f] [1,4] benzoxazine], etc. , Indole ring of indole spirobenzoxazine and halogen, methyl, ethyl, methylene, ethylene, hydroxyl group and other substitutions of the benzene ring can be exemplified.

Specifically, as an indolinospironaftoxazine-based compound,
1,3,3-trimethyl-Indolinospironaftoxazine,
1,3,3-trimethyl-5-chloro-indolinospironaftoxazine,
1,3,3-trimethyl-5-bromo-indolinospironaftoxazine,
1,3,3,5-tetramethyl-indolinospyronaftoxazine,
1,3,3-trimethyl-5-n-propyl-indolinospyronaftoxazine,
1,3,3-trimethyl-5-isobutyl-indolinospironaftoxazine,
1,3,3-trimethyl-5-methoxy-indolinospironaftoxazine,
1,3,3-trimethyl-5-n-propoxy-indolinospironaftoxazine,
1,3,3-trimethyl-5-cyano-indolinospironaftoxazine,
1-n-propyl-3,3-dimethyl-indolinospironaftoxazine,
1-isobutyl-3,3-dimethyl-indolinospyronaftoxazine,
1-n-octyl-3,3-dimethyl-indolinospironaftoxazine,
1-n-octadecyl-3,3-dimethyl-indolinospironaftoxazine,
1,3,3-trimethyl-8'-Sodium Sulfonate-Indolinospironaftoxazine,
1,3,3-trimethyl-9'-methoxy-indolinospironaftoxazine,
1,3,3-trimethyl-8'-cyano-indolinospironaftoxazine,
1,3,3-trimethyl-5-trifluoro-indolinospironaftoxazine,
1- (4'-methylphenyl) -3,3-dimethyl-indolinospyronaftoxazine,
1,3,3-trimethyl-6'-(2,3-dihydro-1-indolino) -indolinospironaftoxazine,
1,3,3-trimethyl-6'-(1-piperidinyl) -indolinospironaftoxazine,
1,3,3-trimethyl-6'-(1-morpholino) -indolinospironaftoxazine,
1-Ethyl-3,3-dimethyl-6-trifluoromethyl-6'-(1-morpholino) -indolinospironaftoxazine,
1,3,3-trimethyl-6-trifluoromethyl-6'-(1-piperidinyl) -indolinospyronaftoxazine,
1-Benzyl-3,3-dimethyl-Indolinospironaftoxazine,
1- (4-Methoxybenzyl) -3,3-dimethyl-indolinospironaftoxazine,
1- (4-chlorobenzyl) -3,3-dimethyl-indolinospironaftoxazine,
1-Ethyl-3,3-Dimethyl-Indolinospironaftoxazine,
1-Isopropyl-3,3-dimethyl-Indolinospironaftoxazine,
1- (2-phenoxyethyl) -3,3-dimethyl-indolinospironaftoxazine,
1,3-Dimethyl-3-ethyl-Indolinospironaftoxazine,
1,3,3-trimethyl-9'-hydroxy-indolinospironaftoxazine,
1,3-Dimethyl-3-ethyl-8'-hydroxy-indolinospyronaftoxazine,
1,3,3,5-tetramethyl-9'-methoxy-indolinospyronaftoxazine,
1,3,3,5,6-pentamethyl-9'-methoxy-indolinospironaftoxazine,
1,3,3-trimethyl-4-trifluoromethyl-5'-methoxy-indolinospironaftoxazine,
1,3,3-trimethyl-5'-methoxy-6'-trifluoromethyl-indolinospironaftoxazine,
1,3,3-trimethyl-4-trifluoromethyl-9'-methoxy-indolinospironaftoxazine,
1,3,5,6-Tetramethyl-3-ethyl-Indolinospironaftoxazine,
1,3,3,5,6-pentamethyl-indolinospironaftoxazine,
1-Methyl-3,3-diphenyl-Indolinospironaftoxazine,
1- (4-Methoxybenzyl) -3,3-dimethyl-indolinospironaftoxazine,
1- (3,5-dimethylbenzyl) -3,3-dimethyl-indolinospironaftoxazine,
Substitutes of halogen, methyl, ethyl, methylene, ethylene, hydroxyl group, etc. of the indole ring and benzene ring of indolinospironaftoxazine, such as 1- (2-fluorobenzyl) -3,3-dimethyl-indolinospironaftoxazine Can be exemplified.

Specifically, as an indolinospirofenantrooxazine-based compound,
1,3,3-trimethyl-spiroindoline phenanthrooxazine,
1,3,3-trimethyl-5-Chloro-spirindoline phenanthrooxazine and other substituents of indole ring and benzene ring of indolinospirofenantrooxazine, methyl, ethyl, methylene, ethylene, hydroxyl group, etc. Can be exemplified.

Specifically, as an indolinospyroquinolinoxazine-based compound,
Examples of substitutions such as halogen, methyl, ethyl, methylene, ethylene, and hydroxyl groups of the indole ring and the benzene ring of indolinospirinolinoxazine such as 1,3,3-trimethyl-spirinodolin quinolinoxazine can be exemplified.

The spiropirane derivative is shown below, but the present invention is not limited thereto.
1,3,3-trimethyl-indolinobenzopyrrilospiran,
1,3,3-trimethylindolino-6'-bromobenzopyrrilospiran,
1,3,3-trimethylindolino-8'-methoxybenzopyrrilospiran,
1,3,3-trimethylindolino-β-naphthopyrillospirane,
Examples thereof include 1,3,3-trimethylindolino-6'-nitrobenzopyrrilospiran.

The naphthopirane derivative is shown below, but the present invention is not limited thereto.
3,3,9,9-Tetraphenyl-3H, 9H-Naft [2,1-b: 6,5-b'] dipyran,
3,3,10,10-Tetraphenyl-3H, 10H-Naft [2,1-b: 7,8-b'] Dipyran,
3,3,9,9-Tetraphenyl-3H, 10H-Naft [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 thereof include 3,3-diphenyl-8- (1H-benzotriazole-1-yl) carbonyl-3H-naphtho [4,3-b] pyran.

Further, examples of the photochromic compound having photomemory property (color memory property and photochromic property) include a flugide derivative and a diarylethene derivative.
The diarylethene derivatives are shown below, but the present invention is not limited thereto.
1- (1,2-dimethyl-3-indrill) -2- (2-methyl-3-benzothienyl) -3,3,4,5,5-hexafluorocyclopentene,
1- (2-Methyl-5-Phenyl-3-thienyl) -2- (5-Methyl-2-phenyl-4-thiazoyl) -3,3,4,5,4,5-hexafluorocyclopentene,
1,2-Bis (2-Methoxy-3-benzothienyl) -3,3,4,5,5-hexafluorocyclopentene,
1,2-bis (2-methoxy-5-methyl-3-thienyl) -3,3,4,5,5-hexafluorocyclopentene,
1,2-bis (2-methyl-6-nitro-3-benzothienyl) -3,3,4,5,5-hexafluorocyclopentene,
1,2-bis (6-amino-2-methyl-3-benzothienyl) -3,3,4,5,5-hexafluorocyclopentene,
1,2-Bis (6-amino-2-ethyl-3-benzothienyl) -3,3,4,5,5-hexafluorocyclopentene,
1,2-Bis [2-methyl-6- (1-pyrrolidino) -3-benzothienyl] -3,3,4,5,5-hexafluorocyclopentene,
1,2-bis (6-diethylamino-2-methyl-3-benzothienyl) -3,3,4,5,5-hexafluorocyclopentene,
1,2-bis (6-acetylamino-2-methyl-3-benzothienyl) -3,3,4,5,5-hexafluorocyclopentene,
1,2-Bis [2-methyl-6- (1-piperidino) -3-benzothienyl] -3,3,4,5,5-hexafluorocyclopentene,
1,2-bis (6-dibenzylamino-2-methyl-3-benzothienyl) -3,3,4,5,5-hexafluorocyclopentene,
1,2-bis [2-butyl-6- (1-piperidino) -3-benzofuranyl] -3,3,4,5,5-hexafluorocyclopentene,
1,2-Bis [2-methyl-6- (1-morpholino) -3-benzothienyl] -3,3,4,5,5-hexafluorocyclopentene,
1,2-Bis (3-methoxy-2-benzothienyl) -3,3,4,5,5-hexafluorocyclopentene,
1,2-bis (2-methyl-6-nitro-3-benzofuranyl) -3,3,4,5,5-hexafluorocyclopentene,
1,2-bis (3-methyl-2-thienyl) -3,3,4,5,5-hexafluorocyclopentene,
1,2-bis (3-methyl-2-benzothienyl) -3,3,4,5,5-hexafluorocyclopentene,
1- (2-Methyl-3-benzothienyl) -2- (3-Methyl-2-benzofuranyl) -3,3,4,5,5-hexafluorocyclopentene,
1- (2-Methyl-5-Phenyl-3-thienyl) -2- (3-Methyl-2-benzothienyl) -3,3,4,5,5-hexafluorocyclopentene,
1,2-bis (2-butyl-6-nitro-3-benzofuranyl) -3,3,4,5,5-hexafluorocyclopentene,
1,2-bis (2-methyl-5-phenyl-3-thienyl) -3,3,4,5,5-hexafluorocyclopentene,
1- (2-Methyl-5-Phenyl-3-thienyl) -2- (2,4-Dimethyl-5-Phenyl-3-thienyl) -3,3,4,5,4,5-hexafluorocyclopentene,
1,2-bis [2,4-dimethyl-5- (4-methoxyphenyl) -3-thienyl] -3,3,4,5,5-hexafluorocyclopentene,
1,2-bis [2-methyl-5- (4-dimethylaminophenyl) -3-thienyl] -3,3,4,5,5-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] -3,3,4,5,5-hexafluorocyclopentene,
1,2-Bis [2,4-dimethyl-5- (2-phenylethenyl) -3-thienyl] -3,3,4,5,5-hexafluorocyclopentene,
1,2-Bis [2,4-dimethyl-5- (4-aminophenyl) -3-thienyl] -3,3,4,5,5-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) -3,3,4,5,5-hexafluorocyclopentene,
1,2-Bis [2-ethyl-6- (5-methyl-2-thienyl) -3-benzothienyl] -3,3,4,5,5-hexafluorocyclopentene,
1,2-Bis [2-ethyl-6- (1-piperidino) -3-benzothienyl] -3,3,4,5,5-hexafluorocyclopentene,
1,2-Bis (6-dibenzylamino-2-ethyl-3-benzothienyl) -3,3,4,5,5-hexafluorocyclopentene,
Examples thereof include 1,2-bis [2-ethyl-6- (1-morpholino) -3-benzothienyl] -3,3,4,5,5-hexafluorocyclopentene.

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

As the styrene-based oligomer, one having a weight average molecular weight of 200 to 6000, preferably 200 to 4000 is used.
When the weight average molecular weight of the styrene-based oligomer exceeds 6000, color residue is likely to occur due to light irradiation, the color development density is likely to be low, and it is easy to adjust the discoloration sensitivity. On the other hand, when the weight average molecular weight is less than 200, the amount of the contained monomers increases and the stability is lacking, so that the light resistance is easily impaired.

The styrene-based oligomer is a compound having a styrene skeleton or a hydrogenated product thereof, and is a low molecular weight polystyrene, a styrene-α-methylstyrene copolymer, an α-methylstyrene polymer, and a common weight of α-methylstyrene and vinyltoluene. Coalescence and the like can be mentioned.
Specific examples of the low molecular weight polystyrene include Sanyo Kasei Kogyo Co., Ltd., trade name: Heimer SB-75 (weight average molecular weight: 2000), ST-95 (weight average molecular weight: 4000) and the like.
Specific examples of the styrene-α-methylstyrene copolymer include those manufactured by Eastman Chemical Co., Ltd., trade names: Picolastic A-5 (weight average molecular weight: 317), A-75 (weight average molecular weight: 917), and the like. It can be exemplified.
Specifically, as the α-methylstyrene polymer, manufactured by Eastman Chemical Co., Ltd., trade name: Crystallex 3085 (weight average molecular weight: 664), 3100 (weight average molecular weight: 1020), 1120 (weight average molecular weight: 2420). ) Etc. can be exemplified.
Specific examples of the copolymer of α-methylstyrene and vinyltoluene include those manufactured by Eastman Chemical Co., Ltd., trade names: Picotex LC (weight average molecular weight: 950), 100 (weight average molecular weight: 1740), and the like. ..

As the acrylic oligomer, one having a weight average molecular weight of 12000 or less, preferably 1000 to 8000, and more preferably 1500 to 6000 is used.
If the weight average molecular weight of the acrylic oligomer exceeds 12000, it tends to be difficult to adjust the discoloration sensitivity. On the other hand, when the weight average molecular weight is less than 1000, the amount of monomers contained is large and the stability is lacking, so that the color density tends to be low and the light resistance is easily impaired.

Examples of the acrylic oligomer include an acrylic acid ester copolymer and the like.
Specifically, as an acrylic acid ester copolymer, manufactured by Toa Synthetic Co., Ltd., trade name: ARUFON UP-1170 (weight average molecular weight: 8000), 1080 (weight average molecular weight: 6000), 1000 (weight average molecular weight) : 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 ( Weight average molecular weight: 2000) and the like can be exemplified.

As the terpene-based oligomer, one having a weight average molecular weight of 250 to 4000, preferably 300 to 4000 is used.
When the weight average molecular weight of the terpene-based oligomer exceeds 4000, color residue is likely to occur due to light irradiation, the color development density is likely to be low, and it is easy to adjust the discoloration sensitivity. On the other hand, when the weight average molecular weight is less than 250, the amount of the contained monomers increases and the stability is lacking, so that the light resistance is easily impaired.

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

As the terpene phenol-based oligomer, one having a weight average molecular weight of 200 to 2000, preferably 500 to 1200 is used.
If the weight average molecular weight of the terpene phenol-based 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 is large and the stability is lacking, so that the color density tends to be low.

The terpene phenol-based oligomer is a compound obtained by copolymerizing a cyclic terpene monomer and phenols or a hydrogenated product thereof, and examples thereof include an α-pinene-phenol copolymer.
Specifically, as an α-pinen-phenol copolymer, manufactured by Yasuhara Chemical Co., Ltd., trade names: YS Polystar T145 (weight average molecular weight: 1050), T130 (weight average molecular weight: 900), T500 (weight average molecular weight). : 500), S145 (weight average molecular weight: 1050) and the like can be exemplified.

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

The mass ratio of the photochromic compound to the styrene-based oligomer or acrylic-based oligomer is preferably 1: 1 to 1: 10000, and more preferably 1: 5 to 1: 500.
The mass ratio of the photochromic compound to the terpene-based oligomer is preferably 1: 1 to 1: 5000, and more preferably 1: 5 to 1: 500.
The mass ratio of the photochromic compound to the terpene phenol-based oligomer is preferably 1: 1 to 1:50, more preferably 1: 2 to 1:30.
When the mass ratio of the photochromic compound to the oligomer satisfies the above range, the photochromic compound satisfies the color-developing function and easily exhibits a sufficient color-developing density.

Further, as the reversible photochromic material, a reversible photochromic microcapsule pigment in which the reversible photochromic composition is encapsulated in microcapsules, or a reversible photochromic substance dispersed in a thermoplastic resin or a 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 includes 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 a dispersion cooling method, an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to the application. Further, a secondary resin film may be further provided on the surface of the microcapsules according to the purpose to impart durability, or the surface characteristics may be modified for practical use.
The reversible photochromic microcapsule pigment preferably has an inclusion / wall film in the range of 7/1 to 1/1 (mass ratio), and the wall film ratio is within the above range, so that when the color is developed. It is possible to prevent a decrease in color density and sharpness, and more preferably, inclusions / wall film = 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, and more preferably 0.5 to 1.5 μm.
When the average particle size of the reversible photocolorable microcapsule pigment or resin particles exceeds 10 μm, the transparency of the reversible photocoloring layer is likely to be impaired, and the brilliance of the reversible photocoloring plain yarn in the color-developed state and the decolorized state It becomes difficult to visually recognize the color change during light irradiation from both the front and back sides. Further, since the thickness of the reversible photocoloring layer becomes thick, the texture is liable to be impaired. On the other hand, if the average particle size is less than 0.5 μm, it becomes difficult to exhibit high-concentration color development.
To measure the average particle size, the particle area is determined using the image analysis type 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. It is a value calculated and measured as the average particle diameter of particles corresponding to equal volume spheres based on the value.
If the particle size of all or most of the particles exceeds 0.2 μm, use a particle size distribution measuring device [Beckman Coulter Co., Ltd., product name: Multisizer 4e] to equal volume by the Coulter method. It is also possible to measure as the average particle size of particles corresponding to a sphere.
Furthermore, a laser diffraction / scattering type particle size distribution measuring device calibrated based on the numerical values measured using the software or the measuring device by the Coulter method [manufactured by Horiba Seisakusho Co., Ltd., product name: LA-300. ] May be used to measure the volume-based particle size and average particle size.

As the first and second reversible photocoloring layers, liquid compositions such as printing inks and paints prepared by dispersing a reversible photocoloring material in a vehicle are used for screen printing, offset printing, process printing, and gravure printing. , Coater, tampo printing, transfer printing, etc., brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, roller coating, dipping coating, etc., directly made of transparent bright resin film. It can be formed on top as a coating layer.
The coating layer is a layer formed by a compound other than the solvent volatilized in the liquid composition.
Examples of the reversible discoloration layer include solid patterns, circles, ovals, squares, rectangles, various characters, symbols, figures, patterns, as well as people, animals, plants, fruits, foodstuffs, vehicles, buildings, celestial bodies, and the like. It may be a statue.

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

The vehicle that disperses the reversible photochromic material is composed of a solvent, a binder resin, and various additives if necessary, and must not affect the color-developing function, discoloration function, sensitivity, etc. of the reversible photo-color-changing material. However, it is not particularly limited. Examples of the solvent include water and various organic solvents.
Specifically, the organic solvent includes 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 thereof include methyl-3-methoxybutanol, 3-methyl-1,3-butanediol, 1,3-butanediol, and hexylene glycol.

Specifically, the binder resin includes an ionomer resin, an isobutylene-maleic anhydride copolymer resin, an acrylonitrile-acrylics styrene copolymer resin, an acrylonitrile-styrene copolymer resin, an acrylonitrile-butadiene-styrene copolymer resin, and an 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 acid ester resin, polymethylmethacrylate resin, epoxy acrylate resin, alkylphenol resin, rosin-modified phenol resin, Login-modified alkyd resin, phenol resin-modified alkyd resin, styrene-modified alkyd resin, epoxy resin-modified alkyd resin, acrylic-modified alkyd resin, aminoalkide 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, silicon 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 Acids, polymethacrylates, acrylic acid ester emulsions, methacrylate ester emulsions, vinyl acetate-acrylic acid ester copolymer emulsions, ethylene-vinyl acetate copolymer emulsions, styrene-acrylic acid ester copolymer emulsions, Vinyl chloride-based Emma Lujon, 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, kumaron plastic , Polybutene, phenoxyplastic, liquid polybutadiene, liquid rubber, petroleum hydrocarbon resin, cyclopentadiene petroleum resin and other synthetic resins,
Examples thereof include natural or semi-synthetic resins such as cellulose derivatives, alginic acid derivatives, rosin derivatives, starches, polysaccharides, gums, natural rubbers, cellacs, agar, casein, glue, gelatin, and polyterpene.
The reversible photochromic material is blended in the binder resin at a ratio of 0.1 to 40% by mass, preferably 0.5 to 20% by mass, and more preferably 1 to 10% by mass. If the blending ratio of the reversible photochromic material exceeds 40% by mass, dispersion stability and processability are likely to be lacking when dispersed in the binder resin, and remarkable improvement in color development density is hardly observed, and further decolorization is observed. Residual color is likely to occur in the state. On the other hand, if the ratio is less than 0.1% by mass, it becomes difficult to show a desired color development density, and it is difficult to sufficiently satisfy the discoloration function.

Examples of the additive include a cross-linking agent, a curing agent, a desiccant, a plasticizer, a viscosity regulator, a dispersant, an ultraviolet absorber, an antioxidant, a light stabilizer, an antioxidant, a smoothing agent, a gelling agent, and a defoaming agent. Examples thereof include agents, matting agents, penetrants, pH adjusters, foaming agents, coupling agents, moisturizing agents, lubricants, fungicides, preservatives, rust preventives and the like.

As the transparent thermoplastic resin or the transparent thermosetting resin for melt-blending the reversible photochromic material, a colorless transparent or colored transparent resin can be used, and the reversible photochromic material has a decolorizing function. It is not particularly limited as long as it does not affect the discoloration function, sensitivity, or the like. Specifically, polyethylene, polypropylene, polyisobutylene, polybutadiene, polymethylpentene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylene-dimethylene terephthalate, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, acrylic acid ester. Resin, methacrylic acid 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 resin, ethylene-methacrylic acid ester copolymer resin, acrylonitrile-styrene copolymer resin, cycloolefin copolymer, etc.
Examples thereof include thermosetting resins such as epoxy resins, epoxy acrylates, phenol 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, and more preferably 1 to 10% by mass. It is mixed in proportion. If the blending ratio of the reversible photocoloring material exceeds 30% by mass, dispersion stability and processability are likely to be lacking when dispersed in the resin, and a remarkable improvement in color development density is hardly observed. On the other hand, if the ratio is less than 0.1% by mass, it becomes difficult to show a desired color development density, and it is difficult to sufficiently satisfy the discoloration function.

As the transparent support, a colorless transparent or colored transparent one can be used, and is not particularly limited as long as the transparent bright layer or the transparent bright resin film can be visually recognized. Absent. Specifically, a sheet or film using a general-purpose resin such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polymethylmethacrylate, polyacrylate, polystyrene, polycarbonate, cellulose acetate, polyvinyl alcohol, and polyamide. Examples thereof include a thermoplastic resin molded body having a flat shape such as a shape. A transparent plastic sheet using a resin such as polyethylene, polypropylene, polyethylene terephthalate, or polyvinyl chloride is preferable because it is highly flexible and excellent in safety.

The reversible photocoloring layer has transparency in a color-developed state and a decolorized state, and the transparency means transmitting light having a wavelength in the visible light region (wavelength region of 380 to 780 nm defined by JIS B 7079). The light transmittance (visible light transmittance) in the visible light region of the reversible light discoloration layer in the color-developed state is preferably 5% or more, more preferably 10% or more, still more preferably 20% or more. is there. When the visible light transmittance of the reversible photocoloring layer is less than 5%, it is difficult to visually recognize the brilliance of the adjacent transparent brilliant layer or the transparent brilliant resin film, and the brilliant reversible photocoloring flat yarn is exhibited on both the front and back sides. It becomes difficult to see various shades.
The visible light transmittance is determined by providing a reversible light discoloration layer on a transparent substrate that transmits light having a wavelength in the visible light region, and in a color-developed state, a spectrophotometer [manufactured by Hitachi, Ltd., product name: U. -3210] was used to measure in the wavelength region of 380 nm to 780 nm, and the value was taken as an intermediate value between the maximum value and the minimum value.

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

As the reversible photocolorable resin film, a reversible photocolorable material is melt-blended with a transparent thermoplastic resin, a transparent thermosetting resin, or the like to prepare a molding resin composition such as pellets, powder, or paste. However, a single-layer reversible photochromic resin film formed into a flat form such as a sheet or a film by various molding means such as extrusion molding, calendar molding, and inflation molding can be used.
In addition, printing means such as screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer, etc. A laminated reversible photochromic resin film formed as a coating layer on a transparent support by coating means such as brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, roller coating, and dip coating. It can also be used.
As the flat thread made of the reversible photocolorable resin film, a single layer or laminated reversible photocolorable resin film can be used.
The coating layer is a layer formed by a compound other than the solvent volatilized in the liquid composition.

As the transparent bright layer, a liquid composition such as a printing ink or a paint prepared by dispersing a transparent metal gloss pigment or a transparent pearl gloss pigment in a vehicle is used for screen printing, offset printing, process printing, and gravure printing. , Coater, tampo printing, transfer printing, etc., brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, roller coating, dipping coating, etc. It can be formed on top as a coating layer.
The coating layer is a layer formed by a compound other than the solvent volatilized in the liquid composition.

Further, a transparent metal gloss pigment or a transparent pearl gloss pigment is melt-blended in a transparent thermoplastic resin or a transparent thermosetting resin to prepare a resin composition for molding such as pellets, powders, or pastes. It is also possible to use a single-layer transparent brilliant resin film formed into a flat form such as a sheet or a film by various molding means such as extrusion molding, calendar molding, and inflation molding.
Further, the liquid composition is coated with printing means such as screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, and roller coating. It is also possible to use a transparent brilliant resin film having a laminated structure formed as a coating layer on the transparent support by a coating means such as dip coating.
As the transparent bright layer, a transparent bright resin film having a single layer or a laminated structure can be used.
Further, as the transparent brilliant resin film, the transparent pearl gloss, hologram property, iris property, light reflective resin film and the like can also be used.
The transparent bright resin film and the plain thread made of the reversible photocoloring resin film can be bonded to each other with an adhesive or the like to form a transparent bright layer on the flat thread made of the reversible photocoloring resin film. it can.

The bright reversible photocoloring flat yarn (1) shown in FIG. 1 is formed by providing a first reversible photocoloring layer (3) on one wide surface of the flat yarn made of a transparent bright resin film (2). ..
The bright reversible photocoloring flat yarn has a flexible texture because the number of constituent layers is small, and further, the transparent bright resin film and the reversible photocoloring layer have transparency. In the brilliant reversible photochromic flat yarn, the transparent brilliant resin film and the reversible photocoloring layer are visually recognized from both the front and back sides, and the brilliance and the color change at the time of light irradiation are observed from the photochromic layer side or the transparent brilliant resin film side. It can be visually recognized.
Further, the same effect as described above is also exhibited in the configuration in which the transparent bright layer (6) is provided on one wide surface of the plain yarn made of the reversible photochromic resin film (5) shown in FIG.

In the bright reversible photocoloring flat yarn (1) shown in FIG. 2, a first reversible photocoloring layer (3) is provided on one wide surface of the flat yarn made of a transparent bright resin film (2), and further. The second reversible photocoloring layer (4) is provided on the opposite wide surface on which the first reversible photocoloring layer is provided. In the brilliant reversible photochromic flat yarn, since the transparent brilliant resin film and the first and second reversible photochromic layers are all transparent, the front and back surfaces of the above-mentioned brilliant reversible photochromic flat yarn In addition to the effect that the brilliance and the color change at the time of light irradiation can be visually recognized from both sides, the presence of two reversible photocoloring layers exhibits various changes at the time of light irradiation.
Even when the bright layer in the bright reversible photocoloring flat yarn is an opaque bright layer that does not transmit light, two reversible photocoloring layers are provided on both the front and back surfaces of the opaque bright layer to form the configuration of FIG. It is possible to obtain a bright reversible photo-discoloring flat yarn exhibiting the same effect as that of FIG. 2, but since the number of layers constituting the structure shown in FIG. 2 is large and the flexible texture is easily impaired, the bright structure shown in FIG. Sexually reversible photocolorable flat yarn is suitable.

When the reversible photocoloring materials contained in the first and second reversible photocoloring layers have the same color at the time of color development, the reversible photocoloring layer shown in FIG. 1 has only one layer. On the other hand, the color density at the time of light irradiation becomes high, and the color change at the time of light irradiation can be visually recognized more clearly.
Further, when the colors exhibited by the reversible photocoloring materials contained in the first and second reversible photocoloring layers are different from each other at the time of color development, the color exhibited by the brilliant reversible photocoloring flat yarn at the time of light irradiation is It is a color in which the color exhibited by the first reversible photocoloring layer and the color exhibited by the second reversible photocoloring layer are mixed, and is difficult to exhibit when the reversible photocoloring layer shown in FIG. 1 has only one layer. Is suitable because it is visible.
Further, when at least one of the color development time and the decolorization time of the first and second reversible photocoloring layers is different from each other, the brilliant reversible photocoloring plain yarn in the decolorized state is irradiated with light, or the color-developed state. When the irradiation of light to the bright reversible photocoloring flat yarn is stopped, the color changes stepwise, and this color change is visually recognized from both the front and back sides of the brightly reversible photocoloring flat yarn, and the changeability at the time of light irradiation is more diverse. Therefore, it is more preferable.

As shown in FIG. 4, the brilliant reversible photochromic flat yarn (1) of the present invention has metallic luster, pearl luster, hologram property, etc. on one wide surface of the flat yarn made of a transparent resin film (7). A transparent bright layer (6) having an optical property selected from either iridescent or light reflective is provided, and a reversible photochromic material is contained in the opposite wide surface on which the transparent bright layer is provided. The first reversible photocoloring layer (3) is provided.

Further, as shown in FIGS. 5 and 6, one of the wide surfaces of the flat yarn made of the transparent resin film (7) has metallic luster, pearl luster, hologram property, iris property, or light reflection property. It is also possible to provide a transparent bright layer (6) having a selected optical property and a first reversible holographic layer (3) containing a reversible holographic material.

Further, as shown in FIGS. 7 and 8, one of the wide surfaces of the flat yarn made of the transparent resin film (7) has a metallic luster, a pearl luster, a hologram property, an iris property, or a light reflection property. A transparent bright layer (6) having selected optical properties and a first reversible photocoloring layer (3) containing a reversible photocoloring material are provided, and the transparent bright layer and the first reversible light are provided. A second reversible photocoloring layer (4) containing a reversible photocoloring material may be provided on the opposite wide surface on which the discoloration layer is provided.

The transparent resin film is not particularly limited as long as the brilliance of the transparent brilliant layer and the design, characters, color change at the time of light irradiation, etc. of the light discoloration 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, and vinyl alcohol resins such as ethylene-vinyl alcohol copolymers. Examples thereof include films made of general-purpose resins such as polyvinyl chloride resin, polyvinylidene chloride resin, polyacrylic acid ester resin, polyacrylic acid resin, polyester resin, rayon, and cupra, and the thickness of the film ranges from 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 is a property of transmitting light having 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 resin film is visible. The light transmittance (visible light transmittance) in the light region is preferably 5% or more, more preferably 10% or more, still 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 light discoloration layer and the brilliance of the transparent brilliant layer, and the brilliance It becomes difficult to visually recognize the various shades of the reversible photochromic flat yarn on both the front and back sides.
For the visible light transmittance, a transparent resin film is provided on a transparent base material that transmits light having a wavelength in the visible light region, and a spectrophotometer [manufactured by Hitachi, Ltd., product name: U-3210] is used. It was measured in the wavelength region of 380 nm to 780 nm and used as an intermediate value between the maximum value and the minimum value.

As the transparent bright layer, a liquid composition such as a printing ink or a paint prepared by dispersing a transparent metal gloss pigment or a transparent pearl gloss pigment in a vehicle is used for screen printing, offset printing, process printing, and gravure printing. , Coater, tampo printing, transfer printing, etc., brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, roller coating, dipping coating, etc. It can be formed on top as a coating layer.
The coating layer is a layer formed by a compound other than the solvent volatilized in the liquid composition.

Further, a transparent metal gloss pigment or a transparent pearl gloss pigment is melt-blended in a transparent thermoplastic resin or a transparent thermosetting resin to prepare a resin composition for molding such as pellets, powders, or pastes. It is also possible to use a single-layer transparent brilliant resin film formed into a flat form such as a sheet or a film by various molding means such as extrusion molding, calendar molding, and inflation molding.
Further, the liquid composition is coated with printing means such as screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, and roller coating. It is also possible to use a transparent brilliant resin film having a laminated structure formed as a coating layer on the transparent support by a coating means such as dip coating.
As the transparent bright layer, a transparent bright resin film having a single layer or a laminated structure can be used.
Further, as the transparent brilliant resin film, the transparent pearl gloss, hologram property, iris property, light reflective resin film and the like can also be used.
The transparent brilliant resin film and the plain thread made of the transparent resin film can be bonded to each other with an adhesive or the like to form a transparent brilliant layer on the plain thread made of the transparent resin film.
Further, the transparent brilliant resin film and the first photocoloring layer provided on the flat thread made of the transparent resin film are bonded to each other with an adhesive or the like to form the flat thread made of the transparent resin film. A transparent bright layer can also be formed.

As the first and second reversible photocoloring layers, liquid compositions such as printing inks and paints prepared by dispersing a reversible photocoloring material in a vehicle are used for screen printing, offset printing, process printing, and gravure printing. , Coater, tampo printing, transfer printing, etc., brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, roller coating, dipping coating, etc., directly made of transparent bright resin film. Alternatively, it can be formed as a coating layer on the transparent bright layer.
The coating layer is a layer formed by a compound other than the solvent volatilized in the liquid composition.

Further, a reversible photochromic material is melt-blended with a transparent thermoplastic resin, a transparent thermosetting resin, or the like to prepare a resin composition for molding such as pellets, powder, or paste, and extrusion molding, calendar molding, etc. It is also possible to use a single-layer reversible photochromic resin film formed into a flat form such as a sheet or a film by various molding means such as inflation molding.
In addition, the liquid composition is subjected to screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer and other printing means, brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, roller coating, etc. It is also possible to use a reversible photochromic resin film having a laminated structure formed as a coating layer on a transparent support by a coating means such as dip coating.
As the first and second reversible photocoloring layers, a single layer or a laminated reversible photocoloring resin film can be used.
The reversible photocoloring resin film and the plain thread made of the transparent resin film are bonded together with an adhesive or the like to form first and second reversible photocoloring layers on the flat thread made of the transparent resin film. can do.
Further, the reversible photochromic resin film and the transparent bright layer provided on the flat thread made of the transparent resin film are bonded to each other with an adhesive or the like, and the first is formed on the plain thread made of the transparent resin film. It is possible to form a reversible photocoloring layer.
The first and second reversible discoloration layers include solid patterns, circles, ovals, squares, rectangles, various characters, symbols, figures, patterns, as well as people, animals, plants, fruits, foodstuffs, and vehicles. , Buildings, celestial bodies, etc.

The bright reversible photocolorable flat yarn having the configuration shown in FIGS. 4 to 8 using a flat yarn made of a transparent resin film can be visually recognized from both the front and back sides and the color change at the time of light irradiation, and the flexibility is impaired. It is suitable because heat resistance and durability can be imparted without any problem.

Since all the layers constituting the bright reversible photocoloring flat yarn of the present invention have transparency, the bright reversible photocoloring flat yarn itself also has transparency, and all the layers can be visually recognized from both the front and back sides. be able to. The light transmittance (visible light transmittance) in the visible light region of the brilliant reversible photocoloring flat yarn is preferably 5% or more, more preferably 10% or more, still more preferably 20% or more. When the visible light transmittance of the brilliant reversible photocoloring flat yarn is less than 5%, it is difficult to visually recognize the design, characters, or color change of the reversible photocoloring layer during light irradiation, and the brilliant reversible photodiscoloration. It becomes difficult to visually recognize the various shades of the plain yarn on both the front and back sides.
For the visible light transmittance, a spectrophotometer [manufactured by Hitachi, Ltd., a product in which a bright reversible photochromic flat thread is provided on a transparent base material that transmits light having a wavelength in the visible light region and is in a colored state. Name: U-3210] was used to measure in the wavelength region of 380 nm to 780 nm, and the value was taken as an intermediate value between the maximum value and the minimum value.

All the layers constituting the brilliant reversible photochromic flat yarn of the present invention are preferably layers that transmit light having a wavelength of 500 nm or less, and can sufficiently exhibit the decolorizing function of the reversible photocoloring layer. Therefore, the color change of the brilliant reversible photo-discoloring plain yarn at the time of light irradiation can be clearly visually recognized from both the front and back sides. If the brilliant reversible photochromic flat yarn contains a layer that does not transmit light having a wavelength of 500 nm or less, it becomes a factor that impairs the decolorizing function of the reversible photocoloring material contained in the reversible photocoloring layer, and the light It becomes difficult to visually recognize the color change during irradiation from both the front and back sides.

Further, as shown in FIG. 9, a non-color-changing layer (8) containing a non-color-changing colorant such as a general dyeing pigment, a fluorescent dyeing pigment, and a phosphorescent pigment is provided between each layer to irradiate light. It is possible to exhibit a reciprocal color change from colored (1) to colored (2), and to make the color change of the brilliant reversible photocoloring flat yarn more diverse.

The non-color-changing layer is a liquid composition such as printing ink or paint prepared by dispersing a non-color-changing colorant in a vehicle, and screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer, etc. It can be formed as a coating layer between each layer by a coating means such as printing means, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, and dip coating.
The coating layer is a layer formed by a compound other than the solvent volatilized in the liquid composition.
Examples of the non-discoloring layer include solid patterns, circles, ovals, squares, rectangles, various characters, symbols, figures, patterns, people, animals, plants, fruits, foodstuffs, vehicles, buildings, celestial bodies, and the like. It may be a statue.
The non-color-changing colorant is preferably contained within a range that does not impair the transparency of the bright reversible photo-coloring flat yarn.

Further, the non-discoloring colorant is blended with the transparent thermoplastic or thermosetting resin to prepare a molding resin composition such as pellets, powders, or pastes, and extrusion molding, calendar molding, inflation molding or the like is prepared. It is also possible to use a single-layer non-discoloring resin film formed into a flat form such as a sheet or a film by various molding means such as.
Further, the liquid composition is coated with printing means such as screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, and roller coating. It is also possible to use a non-discoloring resin film having a laminated structure formed as a coating layer on a transparent support by a coating means 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.
Further, by applying a transparent bright layer or a transparent resin film containing a non-color-changing colorant, or a reversible photo-coloring layer obtained by using a non-color-changing colorant and a reversible photo-coloring material in combination. It is possible to bring about a reciprocal color change from colored (1) to colored (2).

Further, as shown in FIG. 10, a transparency protective layer (9) can be provided on the reversible photocoloring layer to improve durability. The transparency of the transparent protective layer is a property of transmitting light having 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 is visible. The light transmittance (visible light transmittance) in the light region is preferably 5% or more, more preferably 10% or more, 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 design, characters, or color change of the adjacent reversible photocoloring layer when irradiated with light, and the bright reversible photocoloring warp yarns are on both sides. It becomes difficult to visually recognize the various shades presented by.
For the visible light transmittance, a transparent layer is provided on a transparent base material that transmits light having a wavelength in the visible light region, and a spectrophotometer [manufactured by Hitachi, Ltd., product name: U-3210] is used. The measurement was performed in the wavelength region of 380 nm to 780 nm, and the value was taken as an 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, can sufficiently exhibit the color-developing function of the reversible photocoloring layer, and can exhibit the brilliance at the time of light irradiation. The color change of the backlit discoloration flat yarn can be clearly visually recognized from both the front and back sides. If the transparent protective layer is a layer that does not transmit light having a wavelength of 500 nm or less, it becomes a factor that impairs the decolorizing function of the reversible photocoloring material contained in the reversible photocoloring layer, and the color changes during light irradiation. It becomes difficult to see from both sides.

The brilliant reversible photochromic flat yarn of the present invention is a laminate in which a reversible photochromic layer is provided on a transparent brilliant resin film, or a laminate in which a transparent brilliant layer and a reversible photochromic layer are provided on a transparent resin film. It can also be obtained by cutting the body to a suitable width with a slitter.

The width (W) of the brilliant reversible photocolorable 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 at the time of light irradiation. At the same time, the strength of the plain yarn can be satisfied.
The thickness (T) of the brilliant reversible photo-discoloring 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 has a flexible texture. It can satisfy the applicability to products and the strength of flat yarn.

Further, if an adhesive layer is provided between each layer when producing the laminate constituting the bright reversible photocolorable flat yarn of the present invention, the flat yarn can be obtained without going through a complicated manufacturing process.
For example, a first reversible photocoloring layer is provided on a transparent resin film, and an adhesive layer is provided on the opposite surface to which the first reversible photocoloring layer is provided, via an adhesive layer. On both the front and back sides of a laminate with a transparent glitter resin film attached, or a transparent resin film with an adhesive layer on one side, and a transparent glitter resin film attached via an adhesive layer. By cutting the laminate provided with the first and second reversible photocoloring layers with a slitter, a brilliant reversible photocoloring flat yarn can be obtained.

The adhesive used for the adhesive layer has no effect on the decolorizing function, discoloring function, sensitivity, etc. of the reversible photocoloring material contained in the reversible photocoloring layer, and has a transparent brilliance adjacent to the adhesive layer. It is not particularly limited as long as the brilliance of the resin film or the transparent brilliant layer, the design of the reversible photocoloring layer, the characters, the color change at the time of light irradiation, and the like are visible.
Examples of the adhesive used for the adhesive layer include acrylic resin, polyurethane resin, ethylene-vinyl acetate copolymer resin, rubber resin, silicone resin, epoxy resin and the like.

Specifically, the following can be exemplified as a product using the brilliant reversible photo-discoloring flat yarn.
(1) Toys For dolls or animal elephant toys, dolls or animal elephant toys Hair, doll houses and furniture, clothing, hats, bags, shoes and other doll accessories, accessory toys, stuffed animals, drawing toys, toys Picture books, stacking toys, block toys, clay toys, fluid toys, frames, kites, musical instrument toys, cooking toys, gun toys, capture toys, background toys, and toys that imitate vehicles, animals, plants, buildings, and food. etc,
(2) Clothing T-shirts, sweatshirts, blouses, dresses, swimwear, raincoats, ski wear and other clothing, shoes and shoe cords and other footwear, handkerchiefs, towels, bath mats and other cloth personal belongings, gloves, ties, hats , Scarves, and mufflers, etc.
(3) Indoor decorations Carpets, curtains, curtain strings, table hangings, rugs, cushions, carpets, rugs, chair upholstery, sheets, mats, picture frames, artificial flowers, photo stands, etc.
(4) Furniture Duvets, pillows, mattresses, bedding such as beds, chairs, sofas, etc.
(5) Accessories Rings, bracelets, tiaras, earrings, hair clips, artificial nails, ribbons, scarves, watches, eyeglasses, etc.
(6) Others Bags, packaging containers, embroidery threads, exercise equipment, fishing equipment, coasters, musical instruments, purses and other bags, umbrellas, training equipment, etc.

Further, the bright reversible photo-discoloring flat yarn of the present invention can be twisted by a method such as round twisting, bellows twisting, sash twisting, hagoromo twisting, and empty twisting, and can be used in the above products.

Examples are shown below, but the present invention is not limited thereto. In addition, the part in an Example shows a mass part.

Example 1 (see FIG. 1)
Preparation of Brilliant Reversible Photochromic Flat Thread 1,3,3-trimethyl Indolino-spironaftoxazine 2 parts, 100 parts of 50% acrylic resin xylene solution, 1 part of defoaming agent, 40 parts of xylene, and methyl isobutyl The first reversible photochromic screen ink was prepared by uniformly mixing in a vehicle consisting of 40 parts of ketone.
Next, the reversible photodiscoloration was performed on a transparent pearl glossy resin film (2) (manufactured by BASF, trade name: AURORA 8181RG) (visible light transmittance: 70%) having a thickness of 18 μm as a transparent brilliant resin film. A first reversible photocoloring 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 for solid printing on a 120-mesh screen plate using a sex screen ink (color development state). (Visible light transmittance: 90%) was formed in the above to obtain a brilliant reversible photochromic laminate.
Next, the brilliant reversible photochromic laminate was cut with a microslitter so as to form a thread having a width of 250 μm, and a 33 μm-thick brilliant reversible photochromic flat thread (1) (visible light transmittance in a colored state). : 60%) was obtained.
The brilliant reversible photochromic flat yarn has a flexible texture, and before exposure to sunlight, the pearl luster of the transparent pearl luster resin film is visible from both the front and back sides, and the first possibility is when exposed to sunlight. The backlit discoloration layer developed blue, and blue with pearl luster was visually recognized from both the front and back sides. After that, when it was left indoors for a while, the first reversible photocoloring layer was decolorized and returned to its original state. This change in aspect could be repeated.

Example 2 (see FIG. 1)
Preparation of Brilliant Reversible Photodiscolorable Flat Thread 1,3,3-trimethyl Indolino-spironaftoxazine 1 part, styrene-α-methylstyrene copolymer (manufactured by Eastman Chemical Co., Ltd., trade name: picorastic A-5) ) 30 parts of a reversible photocoloring microcapsule pigment (average particle size: 1.5 μm) containing a reversible photocoloring composition uniformly heated and dissolved in 100 parts, 62 parts of a urethane emulsion, and a thickener. A reversible photochromic screen ink was prepared by uniformly mixing 2 parts, 0.5 part of a leveling agent, 0.5 part of a defoaming agent, and 5 parts of a cross-linking agent in a vehicle.
Next, the reversible photodiscoloration was performed on a transparent pearl glossy resin film (2) (manufactured by BASF, trade name: AURORA 8181RG) (visible light transmittance: 70%) having a thickness of 18 μm as a transparent brilliant resin film. A first reversible photocoloring 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 for solid printing on a 120-mesh screen plate using a sex screen ink (color development state) (Visible light transmittance: 85%) was formed in (1) to obtain a brilliant reversible photochromic laminate.
Next, the brilliant reversible photochromic laminate was cut with a microslitter so as to form a thread having a width of 250 μm, and a 33 μm-thick brilliant reversible photochromic flat thread (1) (visible light transmittance in a colored state). : 56%) was obtained.
The brilliant reversible photochromic flat yarn has a flexible texture, and before exposure to sunlight, the pearl luster of the transparent pearl luster resin film is visible from both the front and back sides, and the first possibility is when exposed to sunlight. The backlit discoloration layer developed blue, and blue with pearl luster was visually recognized from both the front and back sides. After that, when it was left indoors for a while, the first reversible photocoloring layer was decolorized and returned to its original state. This change in aspect could be repeated.

Example 3
Fabrication of Bright Reversible Photo-Discoloring Plying Using a twisting machine, the brightness of Example 2 is possible so that the transparent pearl glossy resin film is on the surface around the transparent polyester fiber as the core material. Backlight discoloring plain yarn was twisted in a hagoromo to obtain a bright reversible photochromic twisted yarn.
In the brilliant reversible photochromic twisted yarn, the plain yarn is loosely wound around the core material, so that the pearl luster due to the transparent pearl glossy resin film can be visually recognized at the place where the plain yarn is wound, and between the plain yarns. The core material is visually recognized, but since the core material is transparent, the pearl luster due to the transparent pearl luster resin film is visually recognized through the core material. Before exposure to sunlight, the pearl luster is uniformly visible from the entire surface of the twisted yarn, and when exposed to sunlight, the first reversible photochromic layer develops blue, and the blue color with pearl luster is from the entire surface of the twisted yarn. It was visually recognized uniformly, and the changeability at the time of light irradiation was clear. After that, when it was left indoors for a while, the first reversible photocoloring layer was decolorized and returned to its original state. This change in aspect could be repeated.

Example 4 (see FIG. 2)
Preparation of Brilliant Reversible Photochromic Flat Thread 1,3,3-trimethyl-Indolinospironaftoxazine 1 part, styrene-α-methylstyrene copolymer (manufactured by Eastman Chemical Co., Ltd., trade name: picorastic A-5) ) 30 parts of a reversible photocoloring microcapsule pigment (average particle size: 1.5 μm) containing a reversible photocoloring composition uniformly heated and dissolved in 100 parts, 62 parts of a urethane emulsion, and a thickener. The first reversible photochromic screen ink was prepared by uniformly mixing 2 parts, 0.5 part of a leveling agent, 0.5 part of a defoaming agent, and 5 parts of a cross-linking agent in a vehicle.
Next, on the transparent pearl glossy resin film (2) (manufactured by BASF, trade name: AURORA 8181RG) (visible light transmittance: 70%) having a thickness of 18 μm as the transparent brilliant resin film, the first A first reversible photochromic layer with a film thickness of 15 μm that changes from a colorless transparent state to a blue transparent state when exposed to sunlight after solid printing on a 120-mesh screen plate using reversible photochromic screen ink (3). (Visible light transmittance in the colored state: 85%) was formed.
Next, 1,3,3-trimethyl-6-trifluoromethyl-indolino-6'-(1-piperidinyl) -spironaftoxazine 1 part was added to an acrylic acid ester copolymer [manufactured by Toa Synthetic Co., Ltd., trade name. : ARUFON UP-1070] 30 parts of a reversible photocolorable microcapsule pigment (average particle size 1.5 μm) containing a reversible photocoloring composition uniformly heated and dissolved in 100 parts was combined with 62 parts of a urethane emulsion. , 2 parts of thickener, 0.5 parts of leveling agent, 0.5 parts of defoaming agent, and 5 parts of cross-linking agent are uniformly mixed in the vehicle to form a second reversible photochromic screen ink. Was prepared.
Next, solid printing is performed on the opposite surface of the transparent pearl glossy resin film on which the first reversible photochromic layer is provided, using the second reversible photochromic screen ink on a 120-mesh screen plate. Then, when exposed to sunlight, a second reversible light-changing layer (4) (visible light transmittance in the colored state: 85%) having a thickness of 15 μm, which changes from a colorless transparent state to a pink transparent state, is formed to be brilliant. A reversible photochromic laminate was obtained.
Next, the brilliant reversible photochromic laminate was cut with a microslitter so as to form a thread having a width of 250 μm, and a 48 μm-thick brilliant reversible photochromic flat thread (1) (visible light transmittance in a colored state) : 51%) was obtained.
The brilliant reversible photochromic flat yarn has a flexible texture, and before exposure to sunlight, the pearl luster of the transparent pearl luster resin film is visible from both the front and back sides, and when exposed to sunlight, the first and first The two reversible photochromic layers were each colored, and purple with pearl luster was visually recognized from both the front and back sides. After that, when it was left indoors for a while, the second photocoloring layer was decolorized and blue with pearl luster was visually recognized, and when it was left unattended, the first reversible photocoloring layer was decolorized and returned to the original state. .. This change in aspect could be repeated. The bright reversible photocolorable flat yarn has different colors and decoloring sensitivities of the reversible photocoloring materials contained in the first and second reversible photocoloring layers, so that the exposure to sunlight is gradually stopped. It changed to a different color, and the changeability was more satisfied.

Example 5 (see FIG. 4)
Preparation of Brilliant Reversible Photochromic Flat Thread 1,3,3-trimethyl Indolino-spironaftoxazine 2 parts, 100 parts of 50% acrylic resin xylene solution, 1 part of defoaming agent, 40 parts of xylene, and methyl isobutyl The 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 transparent PET film (visible light transmittance: 99%) (7) having a thickness of 12 μm as a transparent resin film using the reversible photochromic screen ink on a 120-mesh screen plate. A first reversible photocoloring layer (3) having a film thickness of 15 μm (visible light transmittance in the colored state: 90%) was formed, which changed from a colorless transparent state to a blue transparent state when exposed to sunlight.
In addition, 10 parts of a transparent metallic luster pigment [manufactured by Nippon Plate Glass Co., Ltd., trade name: Metashine 5090RS] in which the surface of a flake-shaped glass piece is coated with titanium oxide, 100 parts of a 50% acrylic resin xylene solution, and an eraser. 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, the metallic luster ink is applied to the entire surface of the transparent PET film on the opposite surface where the first reversible photochromic layer is provided with a doctor coater, and a transparent bright layer (transparency) having a film thickness of 5 μm is applied. A metallic luster layer) (6) (visible light transmittance: 60%) was formed to obtain a brilliant reversible photochromic laminate.
Next, the brilliant reversible photochromic laminate was cut with a microslitter so as to form a thread having a width of 250 μm, and a brilliant reversible photochromic flat thread (1) having a thickness of 32 μm (visible light transmittance in a colored state). : 54%) was obtained.
The brilliant reversible photochromic flat yarn has a flexible texture, and the metallic luster due to the transparent metallic luster layer is visible from both the front and back sides before exposure to sunlight, and the first reversible photodiscoloration when exposed to sunlight. The layer developed a blue color, and a blue color having a metallic luster was visually recognized from both the front and back sides. After that, when it was left indoors for a while, the first reversible photocoloring layer was decolorized and returned to its original state. This change in aspect could be repeated. Further, the brilliant reversible photocolorable flat yarn was excellent in heat resistance and strength by providing a transparent PET film.

Example 6
Preparation of Bright Reversible Photo-Discoloring Plying The bright reversible photo-changing plain yarn of Example 5 was air-twisted using a twisting machine to obtain a bright reversible photo-changing twisted yarn.
Before exposure to sunlight, the metallic luster of the transparent metallic luster layer of the brilliant reversible photochromic twisted yarn is uniformly visible from the entire surface of the twisted yarn, and when exposed to sunlight, the first reversible photochromic layer becomes blue. The blue color with metallic luster was uniformly visible from the entire surface of the twisted yarn, and the changeability at the time of light irradiation was clear. After that, when it was left indoors for a while, the first reversible photocoloring layer was decolorized and returned to its original state. This change in aspect could be repeated. Further, the brilliant reversible photochromic twisted yarn was excellent in heat resistance and strength by providing a transparent PET film.

Example 7 (see FIG. 5)
Preparation of Brilliant Reversible Photochromic Flat Thread 1,3,3-trimethyl-6-trifluoromethyl-Indolino-6'-(1-piperidinyl) -spironaftoxazine 1 part, acrylic acid ester copolymer [Toa Synthesis] Made by Co., Ltd., Trade name: ARUFON UP-1070] 30 parts of reversible photochromic microcapsule pigment (average particle size: 1.2 μm) containing a reversible photochromic composition uniformly heated and dissolved in 100 parts. Is uniformly mixed in a vehicle consisting of 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a cross-linking agent. Backlight discoloration screen ink was prepared.
Next, solid printing was performed on a transparent PET film (7) (visible light transmittance: 99%) having a thickness of 12 μm as a transparent resin film using the reversible photochromic screen ink on a 180-mesh screen plate. A first reversible photocoloring layer (3) (visible light transmittance in the colored state: 87%) having a film thickness of 10 μm, which changes from a colorless transparent state to a pink transparent state when exposed to sunlight, was formed.
In addition, 10 parts of a transparent pearl gloss pigment [manufactured by Nippon Koken Kogyo Co., Ltd., trade name: ULTIMICA YD-100] in which the surface of synthetic mica is coated with titanium oxide, 100 parts of a 50% acrylic resin xylene solution, and a defoamer. A pearly glossy 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, the pearl glossy ink is applied to the entire surface of the first reversible photochromic layer with a doctor coater to obtain a transparent bright layer (transparent metallic luster layer) (6) (visible light) having a film thickness of 5 μm. (Transmittance: 60%) was formed to obtain a brilliant reversible photochromic laminate.
Next, the brilliant reversible photochromic laminate was cut with a microslitter into a thread having a width of 200 μm to form a thread having a thickness of 27 μm. : 52%) was obtained.
The brilliant reversible photochromic flat yarn has a flexible texture, and before exposure to sunlight, the pearl luster due to the transparent pearl luster layer is visible from both the front and back sides, and when exposed to sunlight, the first reversible photodiscoloration occurs. The layer developed a pink color, and a pink color with pearl luster was visually recognized from both the front and back sides. After that, when it was left indoors for a while, the first reversible photocoloring layer was decolorized and returned to its original state. This change in aspect could be repeated. Further, the brilliant reversible photocolorable flat yarn was excellent in heat resistance and strength by providing a transparent PET film.

Example 8 (see FIG. 9)
Preparation of Bright Reversible Photochromic Flat Thread 1,3,3-trimethyl-6-Trifluoromethyl-Indolino-6'-(1-piperidinyl) -Spironaftoxazine 1 part, acrylic acid ester copolymer [Toa Synthetic Made by Co., Ltd., trade name: ARUFON UP-1070] 30 parts of reversible photochromic microcapsule pigment (average particle size: 1.5 μm) containing a reversible photochromic composition uniformly heated and dissolved in 100 parts. Is uniformly mixed in a vehicle consisting of 62 parts of a urethane emulsion, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a cross-linking agent. Backlight discoloration screen ink was prepared. In addition, 0.5 parts of yellow general pigment, 91.8 parts of urethane emulsion, 2 parts of thickener, 0.2 parts of leveling agent, 0.5 part of defoaming agent, and 5 parts of cross-linking agent. A non-discoloring screen ink was prepared by uniformly mixing in a vehicle consisting of.
Next, solid printing was performed on a transparent PET film (7) (visible light transmittance: 99%) having a thickness of 12 μm as a transparent resin film using the non-color-changing screen ink on a 225 mesh screen plate, and the film was yellow. A transparent non-discoloring layer (8) (visible light transmittance: 90%) having a film thickness of 5 μm was formed. Further, solid printing is performed on the non-color-changing layer with a 180-mesh screen plate using a reversible photocolor-changing screen ink, and when exposed to sunlight, the film has a thickness of 10 μm and changes from a colorless transparent state to a blue transparent state. One reversible photocoloring layer (3) (visible light transmittance in the colored state: 85%) was formed.
In addition, 10 parts of a transparent pearl gloss pigment [manufactured by Nippon Koken Kogyo Co., Ltd., trade name: ULTIMICA YD-100] in which the surface of synthetic mica is coated with titanium oxide, 100 parts of a 50% acrylic resin xylene solution, and a defoamer. A pearly glossy 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, the pearl glossy ink is applied to the entire surface of the first reversible photocoloring layer with a doctor coater, and a transparent bright layer (transparent pearl glossy layer) (6) (visible light) having a film thickness of 5 μm is applied. (Transmittance: 60%) was formed to obtain a brilliant reversible photochromic laminate.
Next, the brilliant reversible photocoloring laminate was cut with a microslitter so as to form a thread having a width of 200 μm to obtain a reversible photocoloring flat thread (1) (visible light transmittance: 45%) having a thickness of 32 μm. It was.
The brilliant reversible photochromic flat yarn has a flexible texture, and before exposure to sunlight, yellow with pearl luster is visible from both the front and back sides, and when exposed to sunlight, the first reversible photochromic layer becomes pink. The orange color with pearl luster was visually recognized from both the front and back sides. After that, when it was left indoors for a while, the first reversible photocoloring layer was decolorized and returned to its original state. This change in aspect could be repeated. Further, the brilliant reversible photocolorable flat yarn was excellent in heat resistance and strength by providing a transparent PET film.

Example 9 (see FIG. 11)
Preparation of Bright Reversible Photo-Discoloring Flat Thread 1,3,3-trimethyl-Indolinospironaftoxazine 1 part, 100 parts of acrylic acid ester copolymer [manufactured by Toa Synthetic Co., Ltd., trade name: ARUFON UP-1070] A urethane emulsion containing 30 parts of a reversible photocoloring microcapsule pigment (average particle size: 1.5 μm) and 0.1 part of a pink general pigment containing a reversible photocoloring composition uniformly heated and dissolved therein. 62 parts, 2 parts of thickener, 0.5 parts of leveling agent, 0.5 parts of defoaming agent, and 5 parts of cross-linking agent are uniformly mixed in a vehicle to make a reversible photochromic screen ink. Was prepared.
Next, solid printing was performed on a transparent PET film (7) (visible light transmittance: 99%) having a thickness of 12 μm as a transparent resin film with a 180-mesh screen plate using the reversible photochromic screen ink. , A photocoloring layer (first reversible photochromic layer) (first reversible photochromic layer) containing a reversible photocoloring material and a non-coloring agent having a thickness of 10 μm that changes from a pink transparent state to a purple transparent state when exposed to sunlight. ) (Visible light transmittance in the colored state: 80%) was formed.
Next, an adhesive composed of a urethane resin and ethyl acetate was applied by gravure printing on the opposite surface of the transparent PET film on which the first reversible photocoloring layer was provided, and the ethyl acetate was evaporated to a thickness of 2 μm. A transparent pearl glossy resin film (2) having a thickness of 18 μm as a transparent brilliant resin film (manufactured by BASF: trade name: AURORA 8181RG) (visible light transmission: 70). %) Was pressure-welded with a roll and bonded to obtain a brilliant reversible photochromic laminate.
Next, the brilliant reversible photochromic laminate was cut with a microslitter into a thread having a width of 300 μm to form a thread having a thickness of 42 μm (1) (visible light transmittance: 55%). Got
The brilliant reversible photochromic flat yarn has a flexible texture, and before exposure to sunlight, a pearly pink color is visible from both the front and back sides, and when exposed to sunlight, the first reversible photochromic layer is blue. The color was developed and purple with pearl luster was visually recognized from both the front and back sides. After that, when it was left indoors for a while, the first reversible photocoloring layer was decolorized and returned to its original state. This change in aspect could be repeated. Further, the brilliant reversible photocolorable flat yarn was excellent in heat resistance and strength by providing a transparent PET film.

Example 10
Preparation of a zoomorphic toy with hair using a brilliant reversible photochromic flat thread The zoomorphic flat thread of Example 9 is transplanted to the tail of a zoomorphic toy in the shape of a horse by a conventional method and brilliant. A zoomorphic toy with hair using reversible photocolorable flat yarn was produced. Before exposure to sunlight, the brilliant reversible photochromic flat yarn has a pearly pink color that is visible from both the front and back sides, and when exposed to sunlight, the first reversible photochromic layer develops a blue color and has pearl luster. Purple with sex was visually recognized from both the front and back sides. After that, when it was left indoors for a while, the first reversible photocoloring layer was decolorized and returned to its original state. This change in aspect could be repeated. Further, the brilliant reversible photocolorable flat yarn was excellent in heat resistance and strength by providing a transparent PET film.

Example 11 (see FIG. 12)
Fabrication of Bright Reversible Photo-Discoloring Flat Thread A transparent hologram resin film (2) (visible light transmittance: 80%) having a thickness of 18 μm and having an adhesive layer (11) on the back surface is adhered as a transparent bright resin film. A transparent PET film (7) (visible light transmission: 99%) having a thickness of 12 μm was pressure-bonded with a roll as a transparent resin film via a layer.
Next, 1 part of 1,3,3-trimethyl-indolinospironaftoxazine was uniformly heated and dissolved in 100 parts of an acrylic acid ester copolymer [manufactured by Toa Synthetic Co., Ltd., trade name: ARUFON UP-1070]. 30 parts of a reversible photocolorable microcapsule pigment (average particle size: 1.2 μm) containing the reversible photocolorable composition, 62 parts of a urethane emulsion, 2 parts of a thickener, and 0.5 part of a leveling agent. And 0.5 parts of the defoaming agent and 5 parts of the cross-linking agent were uniformly mixed in the vehicle to prepare the first reversible photochromic screen ink. In addition, 1,3,3-trimethyl-6-trifluoromethyl-indolino-6'-(1-piperidinyl) -spironaftoxazine 1 part was added to an acrylic acid ester copolymer [manufactured by Toa Synthetic Co., Ltd., trade name. : ARUFON UP-1070] 30 parts of a reversible photocolorable microcapsule pigment (average particle size: 1.2 μm) containing a reversible photocoloring composition uniformly heated and dissolved in 100 parts, 62 parts of a urethane emulsion , 2 parts of thickener, 0.5 part of leveling agent, 0.5 part of defoaming agent, and 5 parts of cross-linking agent are uniformly mixed in the vehicle to form a second reversible photochromic screen. Ink was prepared.
Next, solid printing is performed on the transparent hologram resin film with a 180-mesh screen plate using the first reversible photochromic screen ink, and when exposed to sunlight, the colorless transparent state changes to a blue transparent state. A first reversible photocoloring layer (3) (visible light transmittance in a colored state: 87%) having a changing film thickness of 10 μm was formed. Further, on the transparent PET film, solid printing is performed on a 180-mesh screen plate using the second reversible photochromic screen ink, and when exposed to sunlight, a film that changes from a colorless transparent state to a pink transparent state. A second photochromic layer (4) having a thickness of 10 μm (visible light transmittance in the colored state: 87%) was formed to obtain a brilliant reversible photochromic laminate.
Next, the brilliant reversible photochromic laminate was cut with a microslitter so as to form a thread having a width of 350 μm, and a brilliant reversible photochromic flat thread (1) having a thickness of 50 μm (visible light transmittance in a colored state). : 60%) was obtained.
The brilliant reversible photochromic flat yarn has a flexible texture, and before exposure to sunlight, the holographic properties of the transparent holographic resin film are visible from both the front and back sides, and when exposed to sunlight, the first and second Each of the reversible photocoloring layers developed a color, and holographic purple was visually recognized from both the front and back sides. After that, when it was left indoors for a while, the first and second reversible photocoloring layers were decolorized and returned to their original state. This change in aspect could be repeated. Further, the brilliant reversible photocolorable flat yarn was excellent in heat resistance and strength by providing a transparent PET film.

Comparative Example 1
Preparation of Brilliant Reversible Photodiscolorable Flat Thread 1,3,3-trimethyl Indolino-spironaftoxazine 1 part, styrene-α-methylstyrene copolymer (manufactured by Eastman Chemical Co., Ltd., trade name: picorastic A-5) ) 30 parts of a reversible photocoloring microcapsule pigment (average particle size: 1.5 μm) containing a reversible photocoloring composition uniformly heated and dissolved in 100 parts, 62 parts of a urethane emulsion, and a thickener. A reversible photochromic screen ink was prepared by uniformly mixing 2 parts, 0.5 part of a leveling agent, 0.5 part of a defoaming agent, and 5 parts of a cross-linking agent in a vehicle.
Next, on an opaque pearl glossy resin film (visible light transmittance: 0%) having a thickness of 18 μm, solid printing is performed on a 120-mesh screen plate using the reversible photochromic screen ink, and the film is exposed to sunlight. A first reversible photocoloring 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 the colored state: 85%) is formed to form a brilliant reversible photocoloring laminate. Got
Next, the brilliant reversible photochromic laminate was cut into a thread having a width of 250 μm with a microslitter, and a 33 μm-thick brilliant reversible photochromic flat yarn (visible light transmittance in the colored state: 0%). ) Was obtained.
The brilliant reversible photochromic flat yarn has a flexible texture, and before exposure to sunlight, the pearl luster of the opaque pearl luster resin film is visible from both the front and back sides, and when exposed to sunlight, the first reversible light. The discolored layer developed a blue color, and a blue color having pearl luster was visually recognized from the first reversible photochromic layer side of the brilliant reversible photochromic flat yarn. However, the pearl glossiness is only visible from the opaque pearl glossy resin film side, the color change of the first reversible photocoloring layer is not visually recognized, and the brilliant reversible photocoloring flat yarn shines from both the front and back sides. It was not possible to visually recognize the sex and the color change during light irradiation. After that, when it was left indoors for a while, the first reversible photocoloring layer was decolorized and returned to its original state. This change in aspect could be repeated.

Comparative Example 2
Fabrication of Bright Reversible Photo-Discoloring Plying Using a twisting machine, the bright reversible light of Comparative Example 1 is used so that an opaque pearl glossy resin film is surfaced around the transparent polyester fiber as the core material. The discolorable flat yarn was twisted in a hagoromo to obtain a bright reversible photocolorable twisted yarn.
In the brilliant reversible photochromic twisted yarn, the plain yarn is loosely wound around the core material, so that the pearl luster due to the opaque pearl glossy resin film can be visually recognized at the place where the plain yarn is wound, and between the plain yarns. The core material is visible, but since the core material is transparent, the pearl luster due to the opaque pearl luster resin film is visually recognized through the core material. Before exposure to sunlight, the pearl luster is uniformly visible from 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 blue color with pearl luster was visually recognized, and there was little changeability during light irradiation. After that, when it was left indoors for a while, the first reversible photocoloring layer was decolorized and returned to its original state. This change in aspect could be repeated.

Comparative Example 3
Preparation of Brilliant Reversible Photochromic Flat Thread 1,3,3-trimethyl Indolino-spironaftoxazine 2 parts, 100 parts of 50% acrylic resin xylene solution, 1 part of defoaming agent, 40 parts of xylene, and methyl isobutyl The 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 transparent PET film (visible light transmittance: 99%) (7) having a thickness of 12 μm as a transparent resin film using the reversible photochromic screen ink on a 120-mesh screen plate. A first reversible photocoloring layer (3) having a film thickness of 15 μm (visible light transmittance in the colored state: 90%) was formed, which changed from a colorless transparent state to a blue transparent state when exposed to sunlight.
Further, 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 are uniformly mixed in a vehicle to form a metal. A glossy ink was prepared.
Next, the metallic luster ink is applied to the front surface of the transparent PET film with a doctor coat on the opposite surface where the first reversible photochromic layer is provided, and an opaque bright layer (opaque metallic luster) having a film thickness of 5 μm is applied. A layer) (visible light transmittance: 0%) was formed to obtain a brilliant reversible photochromic laminate.
Next, the brilliant reversible photochromic laminate was cut with a microslitter so as to form a thread having a width of 250 μm, and a brilliant reversible photocolorable flat thread having a thickness of 32 μm (visible light transmittance in the colored state: 0%). ) Was obtained.
The brilliant reversible photocolorable flat yarn has a flexible texture, and the metallic luster due to the opaque metallic luster layer is visible from both the front and back sides before exposure to sunlight, and the first reversible photocoloring layer is exposed to sunlight. Colored to blue, and blue with metallic luster was visually recognized from the first reversible photocoloring layer side of the bright reversible photocoloring flat yarn. However, the metallic luster is only visible from the opaque metallic luster layer side, the color change of the first reversible photocoloring layer is not visually recognized, and the brilliant reversible photocoloring plain yarn is brilliant from both the front and back sides. The color change during light irradiation could not be visually recognized. After that, when it was left indoors for a while, the first reversible photocoloring layer was decolorized and returned to its original state. This change in aspect could be repeated. Further, the brilliant reversible photocolorable flat yarn was excellent in heat resistance and strength by providing a transparent PET film.

Comparative Example 4
Preparation of Bright Reversible Photo-Discoloring Plying The bright reversible photo-changing flat yarn of Comparative Example 3 was air-twisted using a twisting machine to obtain a bright reversible photo-changing twisted yarn.
In the bright reversible photochromic twisted yarn, the metallic luster due to the opaque metallic luster layer is uniformly visible from the entire surface of the twisted yarn before being exposed to sunlight, and when exposed to sunlight, the first reversible photochromic layer turns blue. The color was developed and a blue color having a metallic luster was partially visible, and the changeability at the time of light irradiation was poor. After that, when it was left indoors for a while, the first reversible photocoloring layer was decolorized and returned to its original state. This change in aspect could be repeated. Further, the brilliant reversible photocolorable flat yarn was excellent in heat resistance and strength by providing a transparent PET film.

1 Bright reversible photo-discoloring flat thread 2 Transparent bright resin film 3 1st reversible photo-coloring layer 4 2nd reversible photo-coloring layer 5 Reversible photo-coloring resin film 6 Transparent bright layer 7 Transparent resin film 8 Non Discoloration layer 9 Transparent protective layer 10 Reversible photocoloring layer containing reversible photocoloring material and non-coloring agent 11 Adhesive layer

Claims (9)

A reversible photochromic material is applied to one wide surface of a flat yarn made of a transparent bright resin film having an optical property selected from metallic luster, pearl luster, hologram property, iris property, and light reflectivity. A brilliant reversible holographic plain yarn provided with a first holographic layer containing it. Claim 1 in which a second photocoloring layer containing a reversible photocoloring material is provided on the opposite wide surface of the plain yarn made of the transparent bright resin film on which the first photocoloring layer is provided. The brilliant reversible photochromic flat yarn described. A first photochromic layer containing a reversible photochromic material is provided on one wide surface of a flat yarn made of a transparent resin film, and the opposite wide surface is provided with the first photochromic layer. A brilliant reversible photochromic flat yarn provided with a transparent brilliant layer having an optical property selected from any of metallic luster, pearl luster, hologram property, iris property, and light reflection property on a surface. On one wide surface of a flat yarn made of a transparent resin film, a first photochromic layer containing a reversible photochromic material, and metallic luster, pearl luster, hologram property, iris property, and light reflection property. A brilliant reversible photochromic flat yarn provided with a transparent brilliant layer having an optical property selected from any of them. A second photocoloring layer containing a reversible photocoloring material is provided on the opposite wide surface of the plain yarn made of the transparent resin film on which the first photocoloring layer and the transparent bright layer are provided. The bright reversible photocolorable flat yarn according to claim 4. The bright reversible photocoloring flat yarn according to claim 2 or 5, wherein the reversible photocoloring material contained in the first and second photocoloring layers is a material that exhibits different colors at the time of color development. The bright reversible photocoloring according to claim 2, 5 or 6, wherein the reversible photocoloring material contained in the first and second photocoloring layers is a material in which at least one of the color development time and the decolorization time is different from each other. Sex flat thread. The bright reversible photocoloring flat yarn according to any one of claims 1 to 7, wherein the brightly reversible photocoloring flat yarn in a colored state has a visible light transmittance of 5% or more. A product containing the brilliant reversible photo-discoloring flat yarn according to any one of claims 1 to 8.

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