JP2014132127A - Synthetic leather - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a synthetic leather used as a portable miscellaneous goods fabric, a furniture fabric, a flooring fabric, an ornament part fabric or the like, and having unexpectedness where the design stands out from the darkness especially by preventing the design from being conspicuous in bright place and performing light storage light emission in dark place.SOLUTION: There is provided a flexible laminate including: a fiber fabric as a base material; a colored resin layer arranged on either surface of the fiber fabric; and a light accumulating and light emitting resin layer covering the colored resin layer. The light accumulating and light emitting resin layer contains light accumulating and light emitting particles, has translucency in which a visible light transmittance (JISZ8722) is 20-60%; and further has a recessed part and a non-recessed part, the difference in height of the recessed part and the non-recessed part is set to 0.3 mm to 3.0 mm.

Description

  The present invention relates to a synthetic leather having phosphorescent light emitting properties, such as a bag, a handbag, a pouch, a wallet, a regular case, a business card case, a fabric for portable goods such as a bag, a furniture for a chair or a sofa, a door mat, a rug mat. Can be used for flooring fabrics such as clothes, fabrics for decorative parts such as clothing and shoes, and fabrics for decorative parts for pets such as collars and reeds. The present invention relates to a synthetic leather having an unexpected property in which the design emerges in the dark.

  Arrangement of phosphorescent pigment applied products is effective as a marker for blackouts and darkness and as guidance display means. In particular, on emergency exit guide plates, symbol marks that run into doors opened by people are drawn in two-tone sections, which emerge from phosphorescence so that the figure of a person becomes a silhouette in the dark. As described above, most of the phosphorescent light-emitting products are mainly displayed by a shadowed light emitting portion (light) and a non-light-accumulating light emitting portion (darkness) in the dark. As such a shadow display, the background is composed of phosphorescent light so that the message is composed of non-luminescent luminous darkness, and the background is composed of non-luminescent luminous darkness. To do. In any configuration, it is necessary to secure a certain amount of luminous emission while increasing the display amount of messages, symbol marks, and the like. For this purpose, the balance between the luminous luminous part (light) and the non-luminous luminous part (darkness) 1: 1 is ideal. That is, in the message plate using such phosphorescent light emission, about half of the message plate needs to be constituted by a non-luminous phosphorescent portion (darkness). However, these message plates are also highly expected as illumination means in power outages and darkness, and securing more phosphorescent light emitting parts (light) has become an issue.

  On the other hand, a sheet in which a phosphorescent pigment is kneaded in a thermoplastic resin film is used for many purposes. These include, for example, a sheet containing a phosphorescent substance in a specific aggregation state in a thermoplastic resin (Patent Document 1), and a phosphorescent polyolefin foam (Patent Document 1) characterized in that a phosphorescent pigment is mixed in a polyolefin resin. Document 2) and the like are disclosed. Each of these sheets and foams can be easily formed into a long length by kneading a phosphorescent substance or phosphorescent pigment into the resin, and has high emission luminance because the entire surface of the sheet or foam emits phosphorescent light. However, if these sheets are given a design by printing pattern or marking film sticking, the luminous and luminous properties of the design part are concealed, resulting in shadows in the dark, reducing the emission brightness of the entire sheet and foam. In addition, the presence of a phosphorescent substance or phosphorescent pigment concealed under the design portion has been wasted. For this reason, attempts have been made to promote phosphorescent emission from below the design part by using light-transmitting ink or light-transmitting marking film. However, if the ink or marking film has a red or black hue, the phosphorescent emission is offset. For example, the design expression in the dark and dark places is limited and the appearance of the design in the darkness is not surprising. Therefore, in the bright place, the design is not conspicuous, and it is a sheet that has the unexpectedness that the design emerges in the dark by phosphorescent light emission in the dark, especially for fabrics such as bags, handbags, pouches, wallets, chairs and There was no synthetic leather that could be used for furniture fabrics such as sofas, flooring fabrics such as doormats and rug mats, and decorative part fabrics such as clothing and shoes.

JP 2004-263114 A JP 2000-336201 A

  The present invention is applied to fabrics for portable goods such as bags, handbags, pouches, wallets, periodic holders, business card holders, furniture fabrics such as chairs and sofas, flooring fabrics such as entrance mats and rug mats, clothing and shoes, etc. Can be used for decorative parts fabrics, collars, reeds and other pet parts decorative parts. Especially, the design is not conspicuous in the bright place, and the design is unexpectedly exposed in the dark by phosphorescent emission in the dark place. Synthetic leather is provided.

  In the present invention, in a flexible laminate in which a fiber fabric is used as a base material, a colored resin layer is provided on one surface of the fiber fabric, and a phosphorescent light-emitting resin layer covering the colored resin layer is provided. The phosphorescent resin layer contains phosphorescent particles and has a light transmittance of 20 to 60% (JIS Z8722). Further, the phosphorescent resin layer has a depressed portion and a non-depressed portion, It has been found that by setting the depression height difference to be 0.3 mm to 3.0 mm, a synthetic leather having an effect that the design stands out in the darkness can be obtained by phosphorescent light emission in the dark place without making the design stand out in the light place. The above problems have been solved.

  That is, the synthetic leather of the present invention can be obtained by using a fiber cloth as a base material and having a colored resin layer provided on one surface of the fiber cloth and a phosphorescent light emitting resin layer covering the colored resin layer. A flexible laminate, wherein the phosphorescent resin layer includes phosphorescent particles and has a light transmittance of 20 to 60% (JIS Z8722), and the phosphorescent resin layer is depressed. It is preferable that it has a part and a non-depression part, and the depression height difference is 0.3 mm-3.0 mm. As a result, the design expressed by the depressed portion is not conspicuous in the bright place, and it is possible to obtain an unexpected effect that brings out the design by the depressed portion in the dark by phosphorescent light emission in the dark place.

  In the synthetic leather of the present invention, it is preferable that the non-depressed portion of the phosphorescent resin layer is made of a foam, and the depressed portion of the phosphorescent resin layer is made of a non-foam. As a result, the design expressed by the depressed portion is not conspicuous in the bright place, and it is possible to obtain an unexpected effect that brings out the design by the depressed portion in the dark by phosphorescent light emission in the dark place.

  The synthetic leather of the present invention has the Munsell lightness of 7 to 9.5 and the Munsell saturation of 0 to 3 of the colored resin layer, and the depressed portion of the phosphorescent light-emitting resin layer has a higher luminous intensity than the non-depressed portion. It is preferable to do. By doing this, the design expressed by the depression is not conspicuous in the light place, and the unexpected effect that the design by the depression appears brighter than the other parts in the dark by phosphorescent light emission in the dark place. Make it possible.

  The synthetic leather of the present invention preferably has a Munsell lightness of 4 or less and a Munsell saturation of 6 or more of the colored resin layer, and the non-depressed portion of the phosphorescent light-emitting resin layer stores and emits light with higher brightness than the depressed portion. . As a result, the design expressed by the depressed part is not conspicuous in the bright place, and the design by the depressed part is made darker than the other parts by phosphorescent light emission in the dark place, and the design is darkened by brightening the design background part. It is possible to obtain an unexpected effect that appears on the screen.

  In the synthetic leather of the present invention, it is preferable that a transparent protective layer made of a film or a coating film is provided on the entire surface of the phosphorescent resin layer. As a result, antifouling properties, abrasion resistance, and scratch resistance can be imparted.

  The synthetic leather of the present invention preferably has a thermoplastic resin coating layer on the back surface of the flexible laminate. Thereby, the heat weldability of the synthetic leather of the present invention is enabled.

  According to the present invention, the synthetic leather having the effect of making the design stand out in the dark is obtained by phosphorescent light emission in the dark place without making the design stand out in the light place, so that these can be used for bags, handbags, pouches, wallets, , Fabric for portable goods such as business card holders, furniture for chairs and sofas, fabric for doors and floors such as rug mats, fabric for decorative parts such as clothes and shoes, decorative parts for pets such as collars and leads It can be used for applications such as fabrics, and it is possible to display an unexpected design in the dark.

The figure showing an example of the cross section of the synthetic leather of this invention The figure showing an example of the cross section of the synthetic leather of this invention The figure showing an example of the cross section of the synthetic leather of this invention The figure showing an example of the cross section of the synthetic leather of this invention The figure showing an example of the design light emission of the synthetic leather of this invention The figure showing an example of the design light emission of the synthetic leather of this invention

  The synthetic leather of the present invention is a flexible laminate in which a fiber cloth is used as a base material, a colored resin layer is provided on one surface of the fiber cloth, and a phosphorescent light emitting resin layer covering the colored resin layer is provided. The phosphorescent resin layer contains phosphorescent particles and has a light transmittance of 20 to 60% (JIS Z8722), and the phosphorescent resin layer has a recessed portion and a non-recessed portion. And the depression height difference is 0.3 mm to 3.0 mm, preferably the non-depressed portion of the phosphorescent resin layer is made of foam and the phosphorescent resin layer is depressed. The part is made of non-foamed material. Furthermore, it is preferable that the Munsell lightness of the colored resin layer is 7 to 9.5 and the Munsell saturation is 0 to 3, or the Munsell lightness of the colored resin layer is 4 or less and the Munsell saturation is 6 or more.

  The fiber fabric constituting the base material used for the synthetic leather of the present invention may be any of woven fabric, knitted fabric and non-woven fabric. Examples of the woven fabric include known woven fabrics such as plain weave, twill weave, satin weave and imitation weave. Of these, plain weave fabric is preferred because the weft strength and stretch balance of the resulting synthetic leather are equivalent. The woven fabric is woven with warps and wefts, and is composed of warps and warps in which the gaps between the yarns are evenly arranged in parallel. 35 / inch), or a non-openly woven fabric having a porosity of less than 5% (number of yarns to be driven is 30 to 100 / inch), and the thickness and mass are not particularly limited. The open-mesh fabric is suitable for a base laminate fabric for heat laminating or bonding a colored resin layer film, and the non-open-woven fabric is impregnated with a solution of a thermoplastic resin composition forming a colored resin layer, and coated or hot-melt coated. Suitable for industrial fabrics. In addition, these fiber fabrics have water-repellent treatment to prevent water penetration from the fiber cross section, flame-proof treatment to give self-extinguishing properties when flaming, and adhesion to the colored resin layer. An adhesion treatment for imparting can also be performed.

  Examples of the warp and weft forming the fiber fabric include monofilaments, multifilaments, short fiber spun yarns, and the types of fibers are specifically kenaf, cotton, polypropylene, polyethylene, polyester (polyethylene terephthalate, polyethylene). Naphthalate, polybutylene terephthalate), nylon, vinylon, acrylic, aromatic polyester, aromatic polyamide, aromatic heterocyclic polymer (polyimidazole, polyoxazole, etc.), glass, silica, basalt, alumina, boron, Examples thereof include fibers such as carbon and stainless steel, mixed fibers thereof, and core-sheath fibers. Polyester (polyethylene terephthalate), polypropylene, and nylon fibers are preferable for general use. In particular, synthetic leather obtained by using fiber yarns of aromatic polyesters, aromatic polyamides, aromatic heterocyclic polymers, etc. can be given heat resistance and blade-proofing properties, and glass, silica, basalt Fire resistance can be imparted to synthetic leather obtained by using fiber yarns made of alumina, carbon or the like.

  The warp and weft yarns forming the fiber fabric are preferably multifilament yarns or short fiber spun yarns. In the case of multifilament yarns, the number of filaments is 30 to 300, and the fineness is 138 to 2223 dtex (decitex), preferably 277 to 1112 dtex multifilament yarn fibers are preferred because they are excellent in the handleability of synthetic leather from which a woven fabric can be obtained that is woven with 10 to 50 threads per inch. Further, in the case of short fiber spun yarn, those in the range of 10th (591 dtex), 20th (295 dtex), 30th (197 dtex), 40th (148 dtex), 60th (97 dtex), especially 10th (591 dtex), It is excellent in handling of synthetic leather from which short fiber spun yarns in the range of 14th (422 dtex), 16th (370 dtex), 20th (295 dtex), 24th (246 dtex), 30th (197 dtex) and the like can be obtained.

  The resin as a component for forming the colored resin layer in the synthetic leather of the present invention is a vinyl chloride resin (containing a plasticizer), a vinyl chloride copolymer resin, an olefin resin, an olefin copolymer resin, a urethane resin, or a urethane resin. Copolymer resin, acrylic resin, acrylic copolymer resin, vinyl acetate resin, vinyl acetate copolymer resin, styrene resin, styrene copolymer resin, polyester resin, polyester copolymer resin, fluorine-containing copolymer Polymer resins, silicone resins, polycarbonates, polyamides, polyethers, polyester amides, polyphenylene sulfides, polyether esters and other thermoplastic resins, and cross-linked products of these thermoplastic resins, especially vinyl chloride resins (plasticizers) Containing), olefin resin, urethane resin, etc., texture, printability, The preferred is excellent, such as the 耗性. The colored resin layer is a colored film or colored sheet formed by a calendar method, a T-die extrusion method, or a coating method, and particularly has a thickness of 0.1 mm to 2.0 mm, preferably 0.2 mm to 1.0 mm. In the present invention, the most preferable example is a polyester (polyethylene terephthalate) fiber fabric as a base material, and a colored soft polyvinyl chloride resin film or sheet having a thickness of 0.2 mm to 0.5 mm on one side is used as an adhesive or means for thermal lamination. A colored resin layer is formed by laminating the layers.

  In the colored resin layer, known organic pigments and inorganic pigments may be used alone or in combination in any amount. Examples of organic pigments include azo pigments (insoluble monoazo pigments, insoluble disazo pigments, azo lake pigments, condensed azo pigments, metal complex azo pigments), phthalocyanine pigments (phthalocyanine blue, phthalocyanine green), dyed lake pigments (acid dye lakes). Pigments, basic dye lake pigments), condensed polycyclic pigments (anthraquinone pigments, thioindigo pigments, perinone pigments, perylene pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, iso Indoline pigments), other nitroso pigments, alizarin lake pigments, metal complex azomethine pigments, aniline pigments, etc. are used alone or in combination. Examples of inorganic pigments include metal oxides, metal sulfides, metal sulfates, metal carbonates, metal hydroxides, chromic acid metal salts, spinel structure oxides, rutile structure oxides, or the like. It is a combination. In particular, the white pigment is used alone or in combination, such as titanium dioxide and zinc oxide, and other calcium carbonate, magnesium carbonate, barium sulfate, silica, aluminum hydroxide, magnesium hydroxide, magnesium oxide and the like. As the black pigment, carbon black, acetylene black, aniline black, titanium black, graphite or the like can be used alone or in combination.

  The hue of the colored resin layer is not limited, but it is preferable that the colored resin layer has Munsell lightness 7 to 9.5 and Munsell saturation 0 to 3, particularly white or white (slightly colored white). . The design display in the dark in the synthetic leather obtained by having such a colored resin layer can be clarified. This is because the thickness of the depressed portion of the phosphorescent resin layer becomes thinner than that of the non-depressed portion, and the colored resin layer becomes a reflection layer of the phosphorescent light emission to increase the brightness, and stands out from the phosphorescent light emission of the non-depressed portion several times. Because it becomes like this. In contrast, the colored resin layer may have a Munsell lightness of 4 or less and a Munsell saturation of 6 or more, and may be particularly black or dark (dark gray, dark green, dark brown, etc.). The design display in the dark in the synthetic leather obtained by having such a colored resin layer can be clarified. This is because the thickness of the depressed portion of the phosphorescent resin layer is thinner than that of the non-depressed portion, so that the colored resin layer becomes an absorption layer of phosphorescent light emission to reduce the luminance, and the phosphorescent light emission of the non-depressed portion is conspicuous in several stages. Because it becomes.

  In the synthetic leather of the present invention, the resin as the component that forms the phosphorescent resin layer is vinyl chloride resin (containing plasticizer), vinyl chloride copolymer resin, olefin resin, olefin copolymer resin, urethane resin, Urethane copolymer resin, acrylic resin, acrylic copolymer resin, vinyl acetate resin, vinyl acetate copolymer resin, styrene resin, styrene copolymer resin, polyester resin, polyester copolymer resin, fluorine Containing copolymer resins, silicone resins, polycarbonates, polyamides, polyethers, polyester amides, polyphenylene sulfides, polyether esters and the like, and crosslinked products of these thermoplastic resins, especially vinyl chloride resins ( Plasticizer), olefin resin, urethane resin, etc. Preferably excellent in such wear resistance. The phosphorescent light-emitting resin layer is a sheet containing phosphorescent pigment particles by a calendar method, a T-die extrusion method, or a coating method, and particularly has a thickness of 0.5 mm to 5.0 mm, preferably 1.0 mm to 3.0 mm. . In the present invention, the most preferable example is that a polyester (polyethylene terephthalate) fiber fabric is used as a base material, and a colored soft polyvinyl chloride resin film or sheet having a thickness of 0.2 to 0.5 mm is laminated on one side. A phosphorescent light-emitting resin layer is formed by laminating a phosphorescent light-emitting soft polyvinyl chloride resin layer of 0.0 mm to 3.0 mm by means of coating or heat lamination. The visible light transmittance (JIS Z8722) of the phosphorescent light-emitting resin layer is preferably 20 to 60%, particularly preferably 25 to 50%. The higher the visible light transmittance of the phosphorescent light-emitting resin layer, the greater the contribution to the phosphorescent light-emitting effect or the silhouette effect due to the better influence of the Munsell lightness and Munsell saturation of the colored resin layer as the base.

The phosphorescent resin layer contains phosphorescent pigment particles in the above resin alone or in combination with 10 to 100 mass%, preferably 25 to 75 mass%, based on the phosphorescent resin layer. As the phosphorescent pigment particles, known phosphorescent phosphor particles, mainly green phosphorescent color type particles, blue phosphorescent color type particles and the like can be used. As a blue phosphorescent color type, 0.001 to 10 mol% of a divalent metal aluminate (for example, strontium aluminate) base crystal was added to a divalent metal using a rare earth element as an activator. Particles. Divalent metals include magnesium, calcium, strontium, barium, zinc, and rare earth elements include cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, etc. Specifically, MoAl ₂ O ₃ : Eu, Mo · xAl ₂ O ₃ : y · SiO ₂ Eu, MoSi ₂ O ₃ Eu, SrAl ₂ O ₄ : Eu, Dy, Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy, CaAl ₂ O ₄ : Eu, Nd, SrAl ₁₄ B ₁₄ O ₂₅ : Eu, Dy and the like can be exemplified, but in particular, alumina molybdenum oxide (MoAl ₂ O ₃ : Eu) and alumina strontium oxide (SrAl ₂ O) _4: Eu, Dy) system of the blue to blue Preferred phosphorescent luminous body particles phosphorescent in the. In addition, yttrium oxide / sulfur system [Y ₂ O ₂ : S: Eu, Ln (orange light emission)], calcium sulfide / bismuth system [CaS: Bi (purple blue light emission)], calcium sulfide / strontium / bismuth system [CaSrS: Bi (blue light emission)], zinc sulfide / copper system [ZnS: Cu (green light emission)], zinc sulfide / cadmium / copper system [ZnCdS: Cu (yellow to orange light emission)] and other sulfide-based phosphorescent phosphors, Eu-activated alkaline earth silicon nitride phosphor containing Al that emits red light such as CaAlSiN ₃ : Eu, (Sr, Ca) AlSiN ₃ : Eu, Eu that emits red light such as Ca ₂ Si ₅ N ₈ : Eu, Tm , Tm activated alkaline earth silicon nitride phosphors and the like can also be used.

  In the synthetic leather of the present invention, the phosphorescent resin layer has a depressed portion and a non-depressed portion to form a visually unnoticeable design base, and the depressed height difference is 0.3 mm to 3.0 mm, preferably 0.5 mm. -1.0 mm. If the depression height difference is less than 0.3 mm, the resultant synthetic leather may make it difficult to display a clear design in the dark. Moreover, when the depression height difference exceeds 3.0 mm, not only the feeling of the obtained synthetic leather is deteriorated, but also foreign matter may be caught in the depression depending on the design. The depressed portion and the non-depressed portion of the phosphorescent resin layer are, for example, a mold in which a design pattern is engraved on the phosphorescent resin layer (unevenness difference of 0.5 mm to 5.0 mm), and the softening temperature of the phosphorescent resin layer. After pressing at the above temperature, the concave mold can be performed by removing the mold and cooling. Such an indented design pattern stamp can be formed by continuously forming a large number of design stamps by using a convex embossing roll. In particular, the depressed portion and the non-depressed portion of the phosphorescent light-emitting resin layer are preferably configured such that the non-depressed portion is made of a foam and the depressed portion is made of a non-foamed body. In such a configuration, the entire phosphorescent light-emitting resin layer is first formed of a foam having a thickness of 0.5 mm to 5.0 mm, and a mold having a design pattern engraved (difference in height of unevenness of 0.5 mm to 5.0 mm) is phosphorescent. After pressing above the softening temperature of the luminescent resin layer, the mold can be removed to remove the mold. In such a concave mold, the boundary between the depressed portion and the non-depressed portion does not necessarily have to be a cliff shape with a right angle as in the shape image of “concave”, but a mortar shape, or a boundary between the depressed portion and the non-depressed portion. May be rounded steps. In addition, such a design pattern stamp can be continuously formed with a large number of concave stamps by a relief embossing roll. In this way, the appearance of the design pattern is a character composed of multiple concavities such as designs, symbol marks, pictograms, logo marks composed of concavities as outlines (Hiragana, Katakana, Alphabet, Kanji, Foreign characters, Ancient characters) , And their design characters), monograms, numbers, symbols, geometric patterns, combinations of emoticons, and the like.

  The total volume of the bubble cells occupying the phosphorescent resin layer by the foam is 20 to 50% by volume with respect to the total volume of the phosphorescent resin layer. By containing 20 to 50% by volume of the bubble cell, the hue of the colored resin layer is prevented from interfering with the phosphorescent resin layer as a bulky irregular reflection structure that lowers the phosphorescent emission density. By embossing the phosphorescent light-emitting resin layer using this foam with a metal stamp or relief embossing roll, the cell is completely crushed in the recess, and the depression (non-foam) of any depth is foamed. Form a part of. Examples of the foam cell include a trace caused by the generation of a pyrolysis gas of the chemical foaming agent, an air entrainment caused by stirring of the viscous resin, and an addition of balloon particles obtained by expanding the gas-encapsulated microcapsules. As the chemical blowing agent, a thermal decomposition type chemical blowing agent such as azodicarboxamide, oxybisbenzenesulfonyl hydrazide, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, diazoaminobenzene, azobisisobutyronitrile and the like can be used. The bubble cell may be an open cell that partially shares a space with an adjacent bubble cell or a closed cell. When the bubble cell content is less than 20% by volume, the resultant synthetic leather may make it difficult to display a clear design in the dark. On the other hand, if the foamed cell content exceeds 50% by volume, the wear strength of the phosphorescent resin layer may be lowered and the handleability of the synthetic leather may be deteriorated. As a means for applying a concave mold other than the method of thermally pressing the relief embossing on the foam as described above, a benzotriazole-based compound, trimellitic anhydride, or the like is used on the surface of the foam precursor. It is possible to use chemical embossing that performs foaming by heating after printing with a transparent ink contained as a suppressor and foams only the portion other than the printing portion. The concave embossing by chemical embossing is generally formed in a gentle mortar shape.

  It is preferable to provide a transparent protective layer made of a film or a coating film on the entire surface of the phosphorescent resin layer from the viewpoint of imparting antifouling properties, abrasion resistance, and scratch resistance. The resin that forms the film and the coating film is vinyl chloride resin (containing plasticizer), vinyl chloride copolymer resin, olefin resin (polyethylene resin, polypropylene resin), olefin copolymer resin (ethylene-vinyl acetate copolymer) Coalesce resin), urethane resin, urethane copolymer resin (acryl-urethane copolymer resin), acrylic resin, acrylic copolymer resin (acryl-silicon copolymer resin, acrylic-fluorine copolymer resin), In thermoplastic resins such as vinyl acetate resin, vinyl acetate copolymer resin, polyester resin, polyester copolymer resin, vinylidene fluoride resin, fluorine-containing copolymer resin, and cross-linked products of these thermoplastic resins However, vinyl chloride resin (containing plasticizer), urethane resin, fluorine-containing copolymer resin, etc. The preferred is excellent, such as the 耗性. The transparent protective layer is a film and a multilayer film by a calendar method or a T-die extrusion method, or a coating film by a coating method casting method, and particularly has a thickness of 0.005 mm to 0.5 mm, preferably 0.01 mm to 0.2 mm. . In order to improve the light resistance of the phosphorescent pigment particles of the phosphorescent resin layer, these transparent protective layers are coated with known ultraviolet absorbers such as benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers. It contains at least a known hindered amine light stabilizer, and a known antioxidant can be used if necessary. The total amount of these added is 0.05 to 5% by mass based on the weathering protective layer. Is preferred. Further, on the surface of these transparent protective layers, a thin film made of one or more selected from fine particle silica (particularly colloidal silica), photocatalytic substance (particularly titanium dioxide), and organic silicate compound (hydrolyzed condensate of methyl or ethyl silicate). By forming the synthetic leather, it is possible to obtain a synthetic leather having further excellent antifouling properties.

  The synthetic leather of the present invention can be provided with a thermoplastic resin coating layer on the back surface as necessary. This enables a heat welding process (hot air fusion, thermal iron fusion, high frequency fusion, etc.) by overlaying the synthetic leathers of the present invention. The resin for forming the thermoplastic resin coating layer can be selected from one or more of the above-described colored resin layer and the resin for forming the phosphorescent resin layer. The layer may contain any amount of known organic pigments and inorganic pigments, either alone or in combination.

Hereinafter, the synthetic leather of the present invention will be specifically described.
1-4 is a figure showing an example of the cross section of the synthetic leather of this invention. The synthetic leather (1) in FIG. 1 is provided with a colored resin layer (3-1) having Munsell lightness of 7 to 9.5 and Munsell saturation of 0 to 3 on one surface of the fiber fabric (2). A flexible laminate (1) provided with a phosphorescent resin layer (4) on (3-1) and further provided with a transparent protective layer (5) on the surface of the phosphorescent resin layer (4). ), And in particular, the phosphorescent resin layer (4) is composed of a non-foamed depression (4-1-1) and a non-foaming non-depression (4-2-1), and (4-3) is It represents the height difference of the depression.

  The synthetic leather (1) of FIG. 2 is provided with a colored resin layer (3-1) having Munsell lightness of 7 to 9.5 and Munsell saturation of 0 to 3 on one surface of the fiber fabric (2). A flexible laminate (1) provided with a phosphorescent resin layer (4) on (3-1) and further provided with a transparent protective layer (5) on the surface of the phosphorescent resin layer (4). In particular, the phosphorescent resin layer (4) is composed of a non-foamed depression (4-1-1) and a foaming non-depression (4-2-2), and (4-3) is a depression height. It represents the difference.

  The synthetic leather (1) in FIG. 3 is obtained by replacing the colored resin layer (3-1) in FIG. 2 with a colored resin layer (3-2) having Munsell lightness of 4 or less and Munsell saturation of 6 or more.

  The synthetic leather (1) in FIG. 4 is obtained by providing a thermoplastic resin coating layer (6) on the back surface of the flexible laminate (1) in FIG. 1-4, the depiction of the cliff-like depression height difference (4-3) having a right angle is an explanatory concept, and the depression (4-1) and the non-depression (4-2) according to the present invention. The boundary may be a mortar shape or a rounded step.

[Example 1]
<Fiber fabric>
Plain woven spun cloth made of polyester (PET) short fiber spun yarn [Yarn density: 44 warp 20th yarn (590dtex) /2.54cm x 40 weft 20th yarn (590dtex) /2.54cm: porosity 4.2%: mass 228 g / m ² ] was used.
<Colored resin layer>
A white soft vinyl chloride resin film of the following composition 1 having a thickness of 0.15 mm by calendering is laminated on one surface of the plain woven spun cloth by heat fusion using a laminator under hot roll conditions at 160 ° C. to give a colored resin layer Formed. The white colored resin layer had Munsell lightness of 9.5 and Munsell saturation of 0.5.
[Composition 1]
White soft vinyl chloride resin composition
100 parts by mass of vinyl chloride resin (degree of polymerization 1050)
DOP (plasticizer) 55 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn (stabilizer) 2 parts by mass
Titanium oxide (white pigment) 10 parts by mass <phosphorescent resin layer>
On the surface of the colored resin layer, a soft vinyl chloride resin film containing phosphorescent pigment particles by calendering with a thickness of 0.35 mm composed of the following formulation 2 is heat-sealed using a laminator under a heat roll condition of 160 ° C. Laminated and formed a phosphorescent resin layer. The visible light transmittance of the phosphorescent resin layer was 24% translucency.
[Composition 2]
Composition containing soft vinyl chloride resin containing phosphorescent pigment particles
100 parts by mass of vinyl chloride resin (degree of polymerization 1050)
DOP (plasticizer) 55 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn (stabilizer) 2 parts by mass
Blue phosphorescent phosphorescent pigment particles (MoAl ₂ O ₃ : Eu) 35 parts by mass
Benzotriazole-based compound (ultraviolet absorber) 0.2 parts by mass <transparent protective layer>
On the surface of the phosphorescent light emitting resin layer, a transparent acrylic resin coating film having a thickness of 0.005 mm composed of the following formulation 3 was provided by gravure coating to form a transparent protective layer.
[Composition 3]
Composition containing transparent acrylic resin
100 parts by mass of acrylic resin (PMMA)
Benzotriazole-based compound (ultraviolet absorber) 0.2 parts by mass
Solvent (methyl ethyl ketone) 800 parts by mass A synthetic leather having a thickness of 0.92 mm and a mass of 1187 g / m ² was obtained by the above steps.
<design>
A high-frequency wave in which a metal mold (4 cm × 22.5 cm) in which the letters “HIRAOKA” (character size 2.5 cm × 2.5 cm × 7 characters) are engraved in a convex shape on the phosphorescent light-emitting resin layer surface of the synthetic leather Using a welding device, a stamping press was performed under the conditions of an anode current of 1.0 A, a fusion time of 5 seconds, and a cooling time of 5 seconds, and the letter “HIRAOKA” was shaped into a concave shape, and the depression and non-depression portions A synthetic leather (Fig. 1) having a depressed height difference of 0.3 mm was obtained, but the letters "HIRAOKA" were not noticeable. Further, the visible light transmittance of this non-depressed portion was 24%, and the visible light transmittance of the depressed portion was 43%.
<Design recognition in the dark>
When the above synthetic leather was irradiated with two 36-watt 40-type straight-tube three-wavelength daylight white fluorescent lamps at a distance of 2 m for 1 hour, the fluorescent lamp was extinguished and the interior of the room was made into a completely dark room, "HIRAOKA" The characters "" were observed with high luminance and blue phosphorescence, and were clearly more conspicuous than the blue phosphorescence around the characters.

[Example 2]
<Fiber fabric>
Plain woven spun cloth made of polyester (PET) short fiber spun yarn [Yarn density: 44 warp 20th yarn (590dtex) /2.54cm x 40 weft 20th yarn (590dtex) /2.54cm: porosity 4.2%: mass 228 g / m ² ] was used.
<Colored resin layer>
A white soft vinyl chloride resin film of the following composition 1 having a thickness of 0.15 mm by calendering is laminated on one surface of the plain woven spun cloth by heat fusion using a laminator under hot roll conditions at 160 ° C. to give a colored resin layer Formed. The white colored resin layer had Munsell lightness of 9.5 and Munsell saturation of 0.5.
[Composition 1]
White soft vinyl chloride resin composition
100 parts by mass of vinyl chloride resin (degree of polymerization 1050)
DOP (plasticizer) 55 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn (stabilizer) 2 parts by mass
Titanium oxide (white pigment) 10 parts by mass <phosphorescent resin layer>
On the surface of the colored resin layer, a soft vinyl chloride resin film containing phosphorescent pigment particles by calendering having a thickness of 0.35 mm composed of the following composition 4 is heat-sealed using a laminator under a heat roll condition of 160 ° C. The precursor of the luminous phosphorescent resin foam layer was formed by laminating. The visible light transmittance of this precursor was 24% translucency.
[Composition 2]
Composition containing soft vinyl chloride resin containing phosphorescent pigment particles
100 parts by mass of vinyl chloride resin (degree of polymerization 1050)
DOP (plasticizer) 55 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn (stabilizer) 2 parts by mass
Azodicarboxamide (Pyrolytic chemical foaming agent) 10 parts by mass
Blue phosphorescent phosphorescent pigment particles (MoAl ₂ O ₃ : Eu) 35 parts by mass
Benzotriazole-based compound (ultraviolet absorber) 0.2 parts by mass <transparent protective layer>
On the surface of the phosphorescent light emitting resin layer, a transparent acrylic resin coating film having a thickness of 0.005 mm composed of the following formulation 3 was provided by gravure coating to form a transparent protective layer.
[Composition 3]
Composition containing transparent acrylic resin
100 parts by mass of acrylic resin (PMMA)
Benzotriazole-based compound (ultraviolet absorber) 0.2 parts by mass
Solvent (methyl ethyl ketone) 800 parts by mass A synthetic leather having a thickness of 0.92 mm and a mass of 1185 g / m ² was obtained by the above process, and this was left in a hot air oven at 200 ° C. for 1 minute to form a phosphorescent resin layer. The resultant was foamed to a thickness of 3 times to obtain a synthetic leather having a thickness of 1.65 mm and a mass of 1080 g / m ² .
<design>
A high-frequency wave in which a metal mold (4 cm × 22.5 cm) in which the letters “HIRAOKA” (character size 2.5 cm × 2.5 cm × 7 characters) are engraved in a convex shape on the phosphorescent light-emitting resin layer surface of the synthetic leather Using a welding device, a stamping press was performed under the conditions of an anode current of 1.0 A, a fusion time of 5 seconds, and a cooling time of 5 seconds, and the letter “HIRAOKA” was shaped into a concave shape, and the depression and non-depression portions Synthetic leather (Fig. 2) with a depressed height difference of 0.85 mm was obtained, but the letters "HIRAOKA" were inconspicuous. Further, the visible light transmittance of this non-depressed portion was 21%, and the visible light transmittance of the depressed portion was 40%.
<Design recognition in the dark>
As a result of performing the same fluorescent lamp irradiation to dark-out dark room test as in Example 1 on the synthetic leather, the characters “HIRAOKA” were observed with high-intensity blue phosphorescence emission, which was more clearly than the blue phosphorescence emission around the characters. It was conspicuous.

[Example 3]
A synthetic leather having a thickness of 1.65 mm and a mass of 1180 g / m ² was obtained in the same manner as in Example 2 except that the colored resin layer of Example 2 (white coloring) was changed to a black colored resin layer of Formulation 4 below. This synthetic leather is a synthetic leather (FIG. 3) in which the letter “HIRAOKA” is shaped into a concave shape as in Example 2, and the height difference between the depressed portion and the non-depressed portion is 0.85 mm. The visible light transmittance of the portion was 21%, and the visible light transmittance of the depressed portion was 40%.
<Colored resin layer>
A 0.15 mm thick black soft vinyl chloride resin film composed of the following formulation 4 was laminated by heat fusion using a laminator under hot roll conditions at 160 ° C. to form a colored resin layer. The black colored resin layer had Munsell lightness of 1 and Munsell saturation of 9.
[Composition 4]
Black soft vinyl chloride resin composition
100 parts by mass of vinyl chloride resin (degree of polymerization 1050)
DOP (plasticizer) 55 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn (stabilizer) 2 parts by mass
Carbon black (black pigment) 5 parts by mass <Design recognition in the dark>
The above synthetic leather (the letters “HIRAOKA” are inconspicuous in a bright place) were subjected to the same fluorescent lamp irradiation to unlit dark room test as in Example 1. As a result, the low phosphorescence emission brightness of the character portion of “HIRAOKA” was enhanced, and the silhouette effect was thereby enhanced, whereby the character portion of “HIRAOKA” was observed well.

[Example 4]
The same procedure as in Example 2 was conducted except that a thermoplastic resin coating layer of a calendered film having a thickness of 0.15 mm according to the following formulation 5 was provided on the back surface of the synthetic leather of Example 2, and had a thickness of 1.80 mm and a mass of 1360 g / A synthetic leather of m ² was obtained. This synthetic leather is a synthetic leather (FIG. 4) in which the letter “HIRAOKA” is shaped in a concave shape as in Example 2, and the depression height difference between the depression and the non-depression is 0.85 mm. The visible light transmittance of the portion was 21%, and the visible light transmittance of the depressed portion was 40%.
[Formulation 5]
Formulation composition for thermoplastic resin coating layer
100 parts by mass of vinyl chloride resin (degree of polymerization 1050)
DOP (plasticizer) 55 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn (stabilizer) 2 parts by mass
Titanium oxide (white pigment) 10 parts by mass <Design recognition in the dark>
The above-mentioned synthetic leather (characters “HIRAOKA” are not conspicuous in a bright place) were subjected to the same fluorescent lamp irradiation to extinction dark room test as in Example 1. As a result, the characters “HIRAOKA” were as high as the synthetic leather in Example 2. It was observed by emitting blue phosphorescence at a luminance level, and was clearly conspicuous than the blue phosphorescence around the character.

[Example 5]
The thickness is 1.65 mm and the mass is 1180 g / mass as in Example 2 except that the composition 2 (blue phosphorescent phosphorescent pigment particles) of the phosphorescent resin layer of Example 2 is changed to the composition 6 (green phosphorescent phosphorescent pigment particles). A synthetic leather of m ² was obtained. This synthetic leather is a synthetic leather (FIG. 2) in which the letter “HIRAOKA” is shaped in a concave shape as in Example 2, and the height difference between the depressed portion and the non-depressed portion is 0.85 mm. The visible light transmittance of the portion was 23%, and the visible light transmittance of the depressed portion was 45%.
[Composition 6]
Composition containing soft vinyl chloride resin containing phosphorescent pigment particles
100 parts by mass of vinyl chloride resin (degree of polymerization 1050)
DOP (plasticizer) 55 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn (stabilizer) 2 parts by mass
Green phosphorescent pigment particles (Mo · xAl ₂ O ₃ : y · SiO ₂ Eu)
35 parts by mass
Benzotriazole compound (ultraviolet absorber) 0.2 parts by mass <Design recognition in the dark>
The above-mentioned synthetic leather (characters “HIRAOKA” are not conspicuous in a bright place) were subjected to the same fluorescent lamp irradiation to extinction dark room test as in Example 1. As a result, the characters “HIRAOKA” were as high as the synthetic leather in Example 2. It was observed by emitting blue phosphorescence at a luminance level, and was clearly conspicuous than the blue phosphorescence around the character.

[Example 6]
The thickness is 1.65 mm and the mass is 1180 g / mass as in Example 2 except that the formulation 2 (blue phosphorescent phosphorescent pigment particles) of the phosphorescent resin layer of Example 2 is changed to formulation 7 (orange phosphorescent phosphorescent pigment particles). A synthetic leather of m ² was obtained. This synthetic leather is a synthetic leather (FIG. 2) in which the letter “HIRAOKA” is shaped in a concave shape as in Example 2, and the height difference between the depressed portion and the non-depressed portion is 0.85 mm. The visible light transmittance of the portion was 21%, and the visible light transmittance of the depressed portion was 38%.
[Composition 7]
Composition containing soft vinyl chloride resin containing phosphorescent pigment particles
100 parts by mass of vinyl chloride resin (degree of polymerization 1050)
DOP (plasticizer) 55 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn (stabilizer) 2 parts by mass
Orange phosphorescent phosphorescent pigment particles (Y ₂ O ₂ : S: Eu, Ln) 35 parts by mass
Benzotriazole compound (ultraviolet absorber) 0.2 parts by mass <Design recognition in the dark>
The above-mentioned synthetic leather (characters “HIRAOKA” are not conspicuous in a bright place) were subjected to the same fluorescent lamp irradiation to extinction dark room test as in Example 1. As a result, the characters “HIRAOKA” were as high as the synthetic leather in Example 2. It was observed by emitting blue phosphorescence at a luminance level, and was clearly conspicuous than the blue phosphorescence around the character.

[Comparative Example 1]
In the synthetic leather of Example 1, a synthetic leather having a thickness of 0.77 mm and a mass of 982 g / m ² was obtained in the same manner as in Example 1 except that the colored resin layer was omitted. As in Example 1, a synthetic leather with the letters “HIRAOKA” shaped was subjected to a dark room test of fluorescent light irradiation to extinction similar to that in Examples 1 to 6. As a result, the colored resin layer that affected the phosphorescent resin layer was omitted. Thus, the blue phosphorescence emission of the character “HIRAOKA” was assimilated with the blue phosphorescence emission of the character peripheral portion, and the character design of “HIRAOKA” was difficult to recognize.

[Comparative Example 2]
In the synthetic leather of Example 2, a synthetic leather having a thickness of 1.50 mm and a mass of 982 g / m ² was obtained in the same manner as in Example 2 except that the colored resin layer was omitted. As in Example 1, a synthetic leather with the letters “HIRAOKA” shaped was subjected to a dark room test of fluorescent light irradiation to extinction similar to that in Examples 1 to 6. As a result, the colored resin layer that affected the phosphorescent resin layer was omitted. Thus, the blue phosphorescence emission of the character “HIRAOKA” was assimilated with the blue phosphorescence emission of the character peripheral portion, and the character design of “HIRAOKA” was difficult to recognize.

[Comparative Example 3]
Example 1 except that the synthetic leather with the letters “HIRAOKA” in Example 1 was recessed so that the difference in the height of the depression of the phosphorescent resin layer and the non-depression was 0.1 mm. It was the same. When this synthetic leather is irradiated with 2 36W / 40 straight tube 3 wavelength day white fluorescent lamps at a distance of 2m for 1 hour, the fluorescent lamp is turned off and the interior is completely darkened. Due to the small difference, the blue phosphorescence emission of the character “HIRAOKA” was assimilated with the blue phosphorescence emission of the peripheral portion of the character, and the character design of “HIRAOKA” was extremely difficult to recognize.

[Comparative Example 4]
Example 2 except that the synthetic leather in which the character “HIRAOKA” of Example 2 was molded was concavely molded such that the difference in level of the depressed part of the phosphorescent resin layer and the non-depressed part was 0.2 mm. It was the same. This synthetic leather was subjected to the same fluorescent lamp irradiation to extinguishing dark room test as in Examples 1 to 6. As a result, the blue phosphorescence emission of the characters “HIRAOKA” was the same as the blue phosphorescence emission of the character peripheral portion due to the small difference in the height of the depression. The character design of “HIRAOKA” was extremely difficult to recognize.

[Comparative Example 5]
In the synthetic leather of Example 1, the phosphorescent resin layer was changed to the composition of Formula 8 below, and the visible light transmittance of the phosphorescent resin layer was changed to 10%. A synthetic leather having a thickness of 0.92 mm and a mass of 1187 g / m ² was obtained. As in Example 1, a synthetic leather with the letters “HIRAOKA” shaped was subjected to a dark room test in the same manner as in Examples 1 to 6, except that the phosphorescent resin layer had a hue of the underlying colored resin layer. Since it became difficult to be influenced, the blue phosphorescence emission of the character “HIRAOKA” and the blue phosphorescence emission of the portion around the character became extremely low in luminance, and the character design of “HIRAOKA” was difficult to recognize.
[Composition 8]
Composition containing soft vinyl chloride resin containing phosphorescent pigment particles
100 parts by mass of vinyl chloride resin (degree of polymerization 1050)
DOP (plasticizer) 55 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn (stabilizer) 2 parts by mass
Blue phosphorescent phosphorescent pigment particles (MoAl ₂ O ₃ : Eu) 35 parts by mass
Titanium oxide (white pigment) 10 parts by mass
Benzotriazole-based compound (ultraviolet absorber) 0.2 parts by mass

[Comparative Example 6]
In the synthetic leather of Example 2, the phosphorescent resin layer was changed to the composition of Formula 9 below, and the visible light transmittance of the phosphorescent resin layer was changed to 10%. A synthetic leather having a thickness of 1.65 mm and a mass of 1187 g / m ² was obtained. As in Example 1, a synthetic leather with the letters “HIRAOKA” shaped was subjected to a dark room test in the same manner as in Examples 1 to 6, except that the phosphorescent resin layer had a hue of the underlying colored resin layer. Since it became difficult to be influenced, the blue phosphorescence emission of the character “HIRAOKA” and the blue phosphorescence emission of the portion around the character became extremely low in luminance, and the character design of “HIRAOKA” was difficult to recognize.
[Composition 9]
Composition containing soft vinyl chloride resin containing phosphorescent pigment particles
100 parts by mass of vinyl chloride resin (degree of polymerization 1050)
DOP (plasticizer) 55 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn (stabilizer) 2 parts by mass
Azodicarboxamide (Pyrolytic chemical foaming agent) 10 parts by mass
Blue phosphorescent phosphorescent pigment particles (MoAl ₂ O ₃ : Eu) 35 parts by mass
Titanium oxide (white pigment) 10 parts by mass
Benzotriazole-based compound (ultraviolet absorber) 0.2 parts by mass

[Comparative Example 7]
In the synthetic leather of Example 1, the phosphorescent resin layer was changed to a composition having the following formulation 10 and the visible light transmittance of the phosphorescent resin layer was changed to 70%. A synthetic leather having a thickness of 0.92 mm and a mass of 1023 g / m ² was obtained. As in Example 1, a synthetic leather with the letters “HIRAOKA” shaped was subjected to a dark room test in the same manner as in Examples 1 to 6, except that the phosphorescent resin layer had a hue of the underlying colored resin layer. Despite being easily affected, by reducing the content of phosphorescent pigment particles, the blue phosphorescence emission of the characters “HIRAOKA” and the blue phosphorescence emission of the peripheral portions of the characters become extremely low in luminance, and “HIRAOKA” The letter design was difficult to recognize.
[Composition 10]
Composition containing soft vinyl chloride resin containing phosphorescent pigment particles
100 parts by mass of vinyl chloride resin (degree of polymerization 1050)
DOP (plasticizer) 55 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn (stabilizer) 2 parts by mass
Blue phosphorescent phosphorescent pigment particles (MoAl ₂ O ₃ : Eu) 5 parts by mass
Benzotriazole-based compound (ultraviolet absorber) 0.2 parts by mass

[Comparative Example 8]
In the synthetic leather of Example 2, the thickness of the phosphorescent resin layer was changed to the composition of Formula 11 below, and the visible light transmittance of the phosphorescent resin layer was changed to 70%. A synthetic leather having a thickness of 1.65 mm and a mass of 1023 g / m ² was obtained. As in Example 1, a synthetic leather with the letters “HIRAOKA” shaped was subjected to a dark room test in the same manner as in Examples 1 to 6, except that the phosphorescent resin layer had a hue of the underlying colored resin layer. Despite being easily affected, by reducing the content of phosphorescent pigment particles, the blue phosphorescence emission of the characters “HIRAOKA” and the blue phosphorescence emission of the peripheral portions of the characters become extremely low in luminance, and “HIRAOKA” The letter design was difficult to recognize.
[Composition 11]
Composition containing soft vinyl chloride resin containing phosphorescent pigment particles
100 parts by mass of vinyl chloride resin (degree of polymerization 1050)
DOP (plasticizer) 55 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn (stabilizer) 2 parts by mass
Azodicarboxamide (Pyrolytic chemical foaming agent) 10 parts by mass
Blue phosphorescent phosphorescent pigment particles (MoAl ₂ O ₃ : Eu) 5 parts by mass
Benzotriazole-based compound (ultraviolet absorber) 0.2 parts by mass

[Reference Comparative Example 1]
In the synthetic leather of Example 1, the thickness of the colored resin layer is 0 as in Example 1 except that the colored resin layer is a composition of the following formulation 12 and the Munsell brightness of the colored resin layer is 5 and Munsell saturation 8 A synthetic leather having a weight of .92 mm and a mass of 1187 g / m ² was obtained. As in Example 1, a synthetic leather with the letter “HIRAOKA” shaped was subjected to the same fluorescent lamp irradiation to unlit dark room test as in Examples 1 to 6. As a result, the hue of the colored resin layer was not bright or dark. Because of the hue, the blue phosphorescence emission of the character “HIRAOKA” was assimilated with the blue phosphorescence emission of the peripheral portion of the character, and the character design of “HIRAOKA” was difficult to recognize.
[Composition 12]
Composition containing soft vinyl chloride resin
100 parts by mass of vinyl chloride resin (degree of polymerization 1050)
DOP (plasticizer) 55 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn (stabilizer) 2 parts by mass
Titanium oxide (white pigment) 10 parts by mass
Carbon black (black pigment) 5 parts by mass

[Reference Comparative Example 2]
In the synthetic leather of Example 2, the thickness is 1 as in Example 2 except that the colored resin layer is a composition of the following formulation 13 and the Munsell lightness of the colored resin layer is 5 and Munsell saturation 8 A synthetic leather having a thickness of .65 mm and a mass of 1187 g / m ² was obtained. As in Example 1, a synthetic leather with the letter “HIRAOKA” shaped was subjected to the same fluorescent lamp irradiation to unlit dark room test as in Examples 1 to 6. As a result, the hue of the colored resin layer was not bright or dark. Because of the hue, the blue phosphorescence emission of the character “HIRAOKA” was assimilated with the blue phosphorescence emission of the peripheral portion of the character, and the character design of “HIRAOKA” was difficult to recognize.
[Formulation 13]
Composition containing soft vinyl chloride resin
100 parts by mass of vinyl chloride resin (degree of polymerization 1050)
DOP (plasticizer) 55 parts by mass
Epoxidized soybean oil (stabilizer) 4 parts by mass
Ba-Zn (stabilizer) 2 parts by mass
Titanium oxide (white pigment) 10 parts by mass
Carbon black (black pigment) 5 parts by mass

  As is clear from Examples 1 to 6 and Comparative Examples 1 to 8, the synthetic leather of the present invention has an effect that the design does not stand out in the bright place, and the design stands out in the dark by phosphorescent light emission in the dark place. Because it is possible to obtain synthetic leather with these, these are fabrics for portable goods such as bags, handbags, pouches, wallets, periodic pockets, business card holders, furniture fabrics such as chairs and sofas, flooring fabrics such as doormats and rug mats It can be used for fabrics for decorative parts such as clothes and shoes, and fabrics for decorative parts for pets such as collars and leads, and it is possible to display unexpected designs in the dark.

1 Synthetic leather (flexible laminate)
2 Fiber fabric 3 Colored resin layer 3-1 Munsell lightness 7 to 9.5, Munsell saturation 0 to 3
3-2 Munsell lightness 4 or less, Munsell chroma 6 or more 4 Photoluminescent resin layer 4-1 Depressed part 4-1-1 Non-foamed depressed part 4-1-2 Foamed depressed part 4-2 Non-depressed part 4-2 -1 Non-foamed non-recessed portion 4-2-2 Foamed non-recessed portion 4-3 Recessed height difference 4-4 Bubble 5 Transparent protective layer 6 Thermoplastic resin coating layer

Claims (6)

A flexible laminate in which a colored resin layer is provided on one surface of the fiber fabric, and a phosphorescent light emitting resin layer covering the colored resin layer is provided on the surface of the fiber fabric, The phosphorescent resin layer contains phosphorescent particles and has a visible light transmittance (JIS).
Z8722) is 20 to 60% translucent, and the phosphorescent resin layer has a depressed portion and a non-depressed portion, and the depressed height difference is 0.3 mm to 3.0 mm. Synthetic leather to do.   2. The synthetic leather according to claim 1, wherein a non-depressed portion of the phosphorescent resin layer is made of a foam, and a depressed portion of the phosphorescent resin layer is made of a non-foam.   The colored resin layer has Munsell lightness of 7 to 9.5 and Munsell saturation of 0 to 3, and the depressed portion of the phosphorescent light emitting resin layer stores and emits light with higher luminance than the non-depressed portion. Synthetic leather as described.   The synthetic leather according to claim 1 or 2, wherein the colored resin layer has a Munsell lightness of 4 or less and a Munsell saturation of 6 or more, and a non-depressed portion of the phosphorescent resin layer emits and emits light with higher brightness than the depressed portion. .   The synthetic leather of any one of Claims 1-4 by which the transparent protective layer which consists of a film or a coating film is provided in the whole surface of the said luminous luminous resin layer.   The synthetic leather according to any one of claims 1 to 5, further comprising a thermoplastic resin coating layer on a back surface of the flexible laminate.