KR101800126B1 - Printing sheet and the method for manufacturing thereof - Google Patents

Abstract

The present invention relates to a printing sheet comprising a support layer, a binder layer, a white phosphorescent pigment layer, a bead type reflector and a transparent protective layer, and a method for producing the same, wherein the printing sheet of the present invention, And can emit white light even when emitting light.

Description

[0001] PRINTING SHEET AND THE METHOD FOR MANUFACTURING THEREOF [0002]

The present invention relates to a printed sheet and a method of manufacturing the same.

The phosphorescent sheet is used for various purposes such as identification or safety. For example, the luminous sheet is attached to induction signs, fire safety suits, road signs, and the like in the event of a fire. The luminescent sheet is very effective for the protection and safety of the wearer because it can confirm the position of the wearer when it is attached to the clothes of people working on roads or dangerous places, such as an environmentalist, a firefighter, and a construction worker.

However, the conventional phosphorescent sheet is mostly used for green light emission and limited for identification of safe evacuation in case of fire. Further, the conventional luminous sheet is not white which is required for clear printing, and since the luminous sheet is not white, there is a problem that it is difficult to be used in advertisement or fashion.

An object of the present invention is to provide a printing sheet comprising a support layer, a binder layer, a white phosphorescent pigment layer, a bead-shaped reflector and a transparent protective layer, and a method for producing the same.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

According to a first aspect of the present invention, A binder layer formed on the support layer; A first white phosphorescent pigment layer formed on the binder layer; A second white phosphorescent pigment layer formed on the first white phosphorescent pigment layer; A bead shaped reflector formed on the second white phosphorescent pigment layer; And a transparent protective layer formed on a protruded surface of the bead-shaped reflector, wherein the first white phosphorescent pigment layer, the second white phosphorescent pigment layer, and the bead-shaped reflector are embedded in a structure protruding from the binder layer And a printed sheet.

According to an aspect of the present invention, an ink fixing layer and a printing layer are further provided between the bead shaped reflector and the transparent protective layer, and the ink fixing layer and the printing layer may be formed on the protruded surface of the beaded reflector.

According to a second aspect of the present invention, A binder layer formed on the support layer; A first white phosphorescent pigment layer formed on the binder layer; A second white phosphorescent pigment layer formed on the first white phosphorescent pigment layer; A bead shaped reflector formed on the second white phosphorescent pigment layer; A coating layer forming an upper part of the plane while filling up the protruded structure of the bead-shaped reflector not buried in the binder layer; And a surface layer formed on the application layer.

According to one aspect, the printing sheet may further include a printing layer formed on the surface layer.

According to one aspect, on the surface layer, a printing layer and a transparent protective layer may be further included.

According to one aspect, the printing sheet may further include an adhesive layer and a release film layer below the support layer.

According to one aspect, the first white phosphorescent pigment layer comprises polyurethane, a phosphorescent pigment of uniaxial light and an opaque white pigment, and the second white phosphorescent pigment layer comprises at least one of a polyurethane, a phosphorescent pigment of long- , Nano pearles and transparent white pigments.

According to one aspect, the first white phosphorescent pigment layer comprises 2 to 5 parts by weight of the uniaxial light phosphorescent pigment and 5 to 8 parts by weight of the opaque white pigment, based on 100 parts by weight of the polyurethane, Wherein the phosphorescent pigment layer contains 2 to 5 parts by weight of the phosphorescent pigment of the intestinal luminescence, 5 to 8 parts by weight of the phosphorescent pigment of the uniaxial light, 3 to 5 parts by weight of the nanoparcle, 7 to 12 parts by weight of pigment.

According to one aspect of the present invention, the phosphorescent pigment of the long-axis light includes at least one selected from the group consisting of aluminum oxide, calcium oxide, strontium oxide, and Europium oxide, and the phosphorescent pigment of the short axis is zinc sulfide: And at least one selected from the group consisting of Zinc Sulfide Copper Doped (ZnS: Cu)), boron oxide, alkaline earth aluminate, and alkaline earth silicate.

According to one aspect, the ink fixing layer may include a base resin, a wetting agent, and a surfactant.

According to one aspect, the printing sheet may further include an adhesive binder layer and a fibrous layer on the printing layer.

A third aspect of the present invention provides a method of manufacturing a semiconductor device, comprising: attaching a bead shaped reflector on a carrier film; Forming a second white phosphorescent pigment layer on a protruded surface of the bead shaped reflector; Forming a first white phosphorescent pigment layer on the second white phosphorescent pigment layer; Forming a binder layer on the first white phosphorescent pigment layer; Attaching a support layer on the binder layer; And removing the carrier film attached to the bead-shaped reflector.

According to one aspect, after the step of removing the carrier film, a step of forming a printing fixation layer on the protruded surface of the bead-shaped reflector on the side where the carrier film is removed is formed; Forming a print layer on the print fixing layer; And forming a transparent protective layer on the print layer.

A fourth aspect of the present invention is a method for manufacturing a semiconductor device, comprising: attaching a bead shaped reflector on a carrier film; Forming a second white phosphorescent pigment layer on a protruded surface of the bead shaped reflector; Forming a first white phosphorescent pigment layer on the second white phosphorescent pigment layer; Forming a binder layer on the first white phosphorescent pigment layer; Attaching a support layer on the binder layer; Removing the carrier film attached to the bead-shaped reflector; Forming a coating layer on a side where the carrier film is removed; And forming a surface layer on the application layer, wherein the application layer forms a plane while filling up the protruded structure of the bead-shaped reflector.

According to one aspect, the method of manufacturing a print sheet may further include forming a print layer on the surface layer.

According to one aspect, the method of manufacturing a print sheet includes: forming a print layer on the surface layer; And forming a transparent protective layer on the print layer.

According to one aspect, the method for manufacturing a print sheet includes forming an adhesive layer below the support layer; And forming a release film layer below the adhesive layer.

According to one aspect, the first white phosphorescent pigment layer comprises polyurethane, a phosphorescent pigment of uniaxial light and an opaque white pigment, and the second white phosphorescent pigment layer comprises at least one of a polyurethane, a phosphorescent pigment of long- , Nano pearles and transparent white pigments.

According to one aspect, the first white phosphorescent pigment layer comprises 2 to 5 parts by weight of the uniaxial light phosphorescent pigment and 5 to 8 parts by weight of the opaque white pigment, based on 100 parts by weight of the polyurethane, Wherein the phosphorescent pigment layer contains 2 to 5 parts by weight of the phosphorescent pigment of the intestinal luminescence, 5 to 8 parts by weight of the phosphorescent pigment of the uniaxial light, 3 to 5 parts by weight of the nanoparcle, 7 to 12 parts by weight of pigment.

According to one aspect of the present invention, the phosphorescent pigment of the long-axis light includes at least one selected from the group consisting of aluminum oxide, calcium oxide, strontium oxide, and Europium oxide, and the phosphorescent pigment of the short axis is zinc sulfide: And at least one selected from the group consisting of Zinc Sulfide Copper Doped (ZnS: Cu)), boron oxide, alkaline earth aluminate, and alkaline earth silicate.

The printed sheet of the present invention has a white background color both before and after the light emission, and even if a pattern or the like is printed on the print layer, the texture of a clear and rich color can be expressed intact. Particularly, the printing sheet of the present invention simultaneously includes long-axis light and a phosphorescent pigment of uniaxial light to emit light temporarily with intense light of strong brightness, while the afterglow can be sustained for long time with long-axis light. Accordingly, the printed sheet of the present invention can be applied to clothes, bags, accessories, various subsidiary materials related to fashion, posters related to advertisements, stickers, packages, and the like, but is not limited thereto.

1 is a cross-sectional view of a printing sheet according to an embodiment of the present invention.
2 is a cross-sectional view of a printing sheet including an ink fixing layer and a printing layer, according to an embodiment of the present invention.
3 is a cross-sectional view of a printed sheet comprising an adhesive layer and a release film layer, according to one embodiment of the present invention.
4 is a cross-sectional view of a printed sheet comprising an adhesive layer and a release film layer, according to one embodiment of the present invention.
5 is a cross-sectional view of a printing sheet including a coating layer according to an embodiment of the present invention.
6 is a cross-sectional view of a printed sheet including a print layer formed on a surface layer, according to an embodiment of the present invention.
7 is a cross-sectional view of a printed sheet comprising an adhesive layer and a release film layer, according to an embodiment of the present invention.
Figs. 8 and 9 are cross-sectional views of a printing sheet including a binder layer for bonding and a fibrous layer according to an embodiment of the present invention. Fig.

In the following, embodiments will be described in detail with reference to the accompanying drawings. Like reference symbols in the drawings denote like elements.

Various modifications may be made to the embodiments described below. It is to be understood that the embodiments described below are not intended to limit the embodiments, but include all modifications, equivalents, and alternatives to them.

The terms used in the examples are used only to illustrate specific embodiments and are not intended to limit the embodiments. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises" or "having" and the like refer to the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this embodiment belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

In the following description of the present invention with reference to the accompanying drawings, the same components are denoted by the same reference numerals regardless of the reference numerals, and redundant explanations thereof will be omitted. In the following description of the embodiments, a detailed description of related arts will be omitted if it is determined that the gist of the embodiments may be unnecessarily blurred.

1 is a cross-sectional view of a printing sheet according to an embodiment of the present invention.

A first aspect of the present invention is a semiconductor device comprising: a support layer (10); A binder layer (20) formed on the support layer (10); A first white phosphorescent pigment layer 32 formed on the binder layer 20; A second white phosphorescent pigment layer (34) formed on the first white phosphorescent pigment layer; A bead shaped reflector 40 formed on the second white phosphorescent pigment layer 34; And a transparent protective layer (50) formed on the protruding surface of the bead shaped reflector (40), wherein the first white phosphorescent pigment layer (32), the second white phosphorescent pigment layer (34) (40) is embedded in a structure protruding from the binder layer (20).

According to one aspect, the support layer 10 includes a binder layer 20, a first white phosphorescent pigment layer 32, a second white phosphorescent pigment layer 34, a bead shaped reflector 40, and a transparent protective layer 50 . The support layer 10 that can be used in the present invention may be a transparent, translucent or opaque material. For example, the support layer 10 may be at least one kind selected from the group consisting of fibers, paper, leather, synthetic resin, As shown in FIG.

More specifically, the support layer 10 is selected from the group consisting of cotton, polyester, wool, rayon, lyocell, acetate, nylon, acrylic, spandex, polypropylene, vinylon and combinations thereof Woven or non-woven fabric, such as, but not limited to, woven or non-woven fabric. The blend fibers may be selected from the group consisting of T / C (polyester-cotton), T / R (polyester-rayon), A / T (acrylic- ), But is not limited thereto. The leather may be synthetic leather or natural leather. In addition, the film on which the support layer 110 can be formed may include at least one resin selected from the group consisting of polyester, polyolefin, polyurethane, polyvinyl chloride, polyimide, polycarbonate, . More specifically, as the films constituting the support layer 110, polyvinyl chloride (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate ), Polyurethane (PU), acrylic resin, polymethacrylate (PMMA), polyethylene (PE), polypropylene (PP), polycarbonate (PC), polyimide But are not limited to, at least one selected from the group consisting of resins, copolymers thereof, and the like.

According to one aspect, the binder layer 20 is a layer in which a part of the white phosphorescent pigment layer 30 and the bead shaped reflector 40 are embedded, and may include a binder resin having a binding force capable of fixing and supporting them. The binder resin that can be used in the present invention may be a natural resin and / or a synthetic resin and may be at least one selected from the group consisting of acrylic, urethane, silicone, epoxy, polyvinyl chloride, polyethylene, But it is not limited thereto. Depending on the composition of the bead type reflector and the phosphorescent pigment layer to be used, a suitable binder resin may be used. For example, an acrylic binder resin or a polyurethane resin may be preferably used.

Optionally, the binder layer 20 may comprise a white pigment, a yellow pigment, a red pigment, a blue pigment, a green pigment, a purple pigment, a black pigment and / or a fluorescent pigment. In addition, various background colors can be realized through proper mixing of pigments, and colors of four-sided continuous pattern can be realized. It is preferable that these color pigments and / or fluorescent pigments have non-yellowing properties.

The binder layer 20 may further include non-yellowing polyurethane so as to prevent separation of the bead-like reflector 40 adhered to one surface thereof and to maintain a stable color and improve visibility. Since the non-yellowing polyurethane has high elasticity, it is excellent in impact resistance, abrasion resistance and chemical resistance. In particular, since it has excellent resistance to moisture and salt even after curing, it is possible to reduce luminance or durability It is possible to prevent a problem such as reduction

The non-yellowing polyurethane can be synthesized from a compound having a polyol and an isocyanate. According to one embodiment, the polyol that can be used for synthesizing the non-yellowing polyurethane may include a polyester-based polyol, a hydrocarbon-based polyol, a polycarbonate-based polyol, and a lactone-based polyester polyol. According to one embodiment, the polyester-based polyol is selected from the group consisting of aliphatic acids such as adipic acid, glutaric acid, and acelic acid; Dicarboxylic acids selected from aromatic acids such as phthalic acid, terephthalic acid and naphthenic acid, and glycols such as ethylene glycol, diethylene glycol and 1,6-hexaethylene glycol; Polyester polyols obtained by the synthesis of diols such as polyhydric alcohols such as glycerol, trimethylol propane and pentaerythritol can be used. According to one embodiment, the isocyanate compound may be an aromatic, aliphatic or saturated or unsaturated isocyanate compound. More specifically, the isocyanate compound includes at least one selected from the group consisting of 4,4'-diphenylmethane diisocyanate (MDI), xylene diisocyanate, isophorone diisocyanate, and cyclohexyl diisocyanate (CHDI) But is not limited thereto.

When the non-yellowing polyurethane is synthesized, the ratio of the hard segment and the soft segment can be adjusted by appropriately adjusting the molar ratio (NCO / OH) of the isocyanate group (-NCO) of the isocyanate compound and the hydroxyl group (-OH) of the polyol. According to one embodiment of the present invention, the ratio of the hard segment in the synthesized non-yellowing polyurethane may be 5 to 40 wt%, and the NCO / OH ratio may be in the range of approximately 1.3 to 3.5. If the ratio of the hard segment is less than 5 wt%, the effect of preventing the bead-shaped reflector buried in the binder layer 20 may be insignificant. If the hard segment ratio exceeds 40 wt%, the viscoelasticity The contact area may be lowered and the adhesion property may be deteriorated.

The polyurethane can be synthesized through the reaction of a polyol with an isocyanate compound using a catalyst such as a metal and / or an amine. Optionally, suitable chain extenders may be used if necessary, such as low molecular weight amines such as diethanolamine, 1,4-butyleneamine and 1,6-hexamethylene diamine; A crosslinkable low molecular weight compound such as ethylene glycol, butanediol, 1,6-hexanediol, 1,4-cyclohexanediol and the like, which is a hydroxy compound, can be used for the synthesis. Generally, the chain extender may be added in an amount of 1.5 to 20 parts by weight based on 100 parts by weight of the polyol. The non-yellowing polyurethane may be of an aqueous or oily type and may include, but is not limited to, approximately 20 to 50% by weight of solids.

The binder layer 20 according to the present invention may be blended in a relative proportion of 80 to 120 parts by weight of binder resin, 5 to 20 parts by weight of pigment and 40 to 80 parts by weight of non-yellowing polyurethane, but is not limited thereto.

The printed sheet of the present invention comprises a white phosphorescent pigment layer 30 consisting of a first white phosphorescent pigment layer 32 and a second white phosphorescent pigment layer 34. Since the white phosphorescent pigment layer 30 is formed in a thin layer along a part of the curved surface of the bead shaped reflector 40, the white phosphorescent pigment layer 30 is embedded in the binder layer 20 together with the bead shaped reflector 40, .

According to an embodiment of the present invention, the first white phosphorescent pigment layer 32 may include polyurethane, a phosphorescent pigment of uniaxial light, and an opaque white pigment. According to an embodiment of the present invention, The two white phosphorescent pigment layers 34 may comprise polyurethane, phosphorescent pigments in long-axis phosphorescence, phosphorescent pigments in uniaxial light, nano pearles and transparent white pigments.

In addition, according to an embodiment of the present invention, the second white phosphorescent pigment layer 34 may include polyurethane, phosphorescent pigment of long-axis light, phosphorescent pigment of uniaxial light, nano pearl and transparent white pigment. Luminescent pigment refers to a substance that absorbs and accumulates energy sources of natural and artificial light used in everyday life such as sunlight, mercury lamp, fluorescent lamp, incandescent lamp and LED car headlight to emit fluorescent light in dark places. Since the more light containing a lot of white light absorbs and accumulates the light, it is efficient in order of solar light, mercury lamp, and fluorescent lamp. That is, the light having a higher energy in the visible light region, for example, a light having a wavelength of about 400 mm, has a higher efficiency in absorbing energy from the phosphorescent pigment.

According to one aspect of the present invention, the phosphorescent pigment is selected from the group consisting of zinc sulfide: copper doped (ZnS: Cu), aluminum oxide, calcium oxide, strontium oxide, And may include at least one selected from the group consisting of Europium Oxide, Boron Oxide, Alkaline earth aluminate and Alkali earth silicate, preferably ZnS: Cu. The phosphorescent pigment may be CaSrS, ZnCdS, ZnS or CaS activated by Bi; (Sr1-xMx) Al2O4: R wherein x is 0.1 to 0.9, M is at least one material selected from the group consisting of calcium, zinc, barium and magnesium, and R is at least one material selected from the group consisting of europium, lanthanum, cerium, praseodymium and neodymium (Wherein M is at least one substance selected from the group consisting of calcium, strontium and barium, or magnesium is added to the at least one substance), and in addition, Europium, Lanthanum , Cerium, praseodymium, neodymium, samarium, terdium, dysprosium, holmium, or combinations thereof. Preferably, strontium alumite (SrAl2O4: Eu, Dy) activated with Zns: Cu, Cl or europium ions having a size of 15 to 25 microns may be used. They are able to emit bright light for a long time in the dark because the afterglow luminance and afterglow time are about 10 times higher than the zinc sulfide pigment.

The phosphorescent pigment of the long-axis light may include at least one selected from the group consisting of aluminum oxide, calcium oxide, strontium oxide, and Europium oxide, and the phosphorescent pigment of the single axis may be zinc sulfide (Al2O3), Al2O3 (Al2O3), Copper Doped (ZnS: Cu), Boron Oxide, Alkaline Aluminate and Alkali earth silicate.

"White pigment" as referred to in the present invention refers to a pigment that is perceived as white in our eyes by the absorption of light being very small and reflecting or refracting most of the light.

According to one aspect, the white pigment may be at least one selected from the group consisting of titanium dioxide (TiO 2), zinc oxides, zinc sulfide (ZnS), lithopon mixed with zinc sulfide and BaO 4, lead white, antimony oxide (Sb2O3), and the like. Among them, the titanium-based white pigment is preferably selected from the group consisting of hydrates of Al ₂ O ₃ , SiO ₂ and ZnO and titanium dioxide (TiO 2) treated with phosphates such as Ti, Al, Zr and Zn to improve dispersibility, hiding power, ₂ ) may be used. On the other hand, fine powder of zinc oxide absorbs the ultraviolet rays of the white pigment well, but the hiding power is about 1/3 to 1/4 of the titanium white pigment. The lithopone-based white pigment may be a mixture of zinc oxide (ZnS) and barium sulfate (BaSO4).

Among the white pigments, transparent white pigments are excellent in reflecting light and can be used for raising the reflection effect of light. Opaque white pigments can be used for absorbing light and blocking the color of the back surface . For example, the opaque white pigment may be a titanium-based white pigment or a zinc oxide-based white pigment, and may include a hydrate such as Al ₂ O ₃ , SiO ₂ , ZnO, and titanium dioxide treated with a phosphate such as Ti, Al, Zr, It may include (TiO _2). Also, for example, the transparent white pigment may comprise a white pigment based on lithopon, lead white, or antimony oxide (Sb ₂ O ₃ ).

The polyurethane may be included in both the first white phosphorescent pigment layer and the second white phosphorescent pigment layer. Particularly, a non-yellowing polyurethane can be used for the first white phosphorescent pigment layer. Since the non-yellowing polyurethane can play a role of retarding the yellowing of the white pigment, it is preferably used together with the opaque white pigment. On the other hand, in order to increase the transparency of the second white phosphorescent pigment layer, the second white phosphorescent pigment layer preferably contains general polyurethane.

According to one aspect, the second white phosphorescent pigment layer may comprise a nano-pearl. For example, the nanopulp may be natural pearl essence such as mixed crystals of guanine / hypoxanthine; Or metal oxide mica, basic lead carbonate, bismuth oxychloride, and the like. More specifically, the nano-pearl may be Titanium dioxide-Coated mica coated with titanium oxide, mica iron coated with iron oxide, bismuth oxychloride, or mica coated with colored pigment. Preferably, nano-pearles with non-yellowing properties can be used.

According to one aspect, the first white phosphorescent pigment layer 32 may comprise 2 to 5 parts by weight of the uniaxial light phosphorescent pigment and 5 to 8 parts by weight of the opaque white pigment, based on 100 parts by weight of the polyurethane have. Since the first white phosphorescent pigment layer contains opaque white pigment together with a phosphorescent pigment of uniaxial light exhibiting a high luminous effect for a short period of time, it can play a role of temporarily emitting strong white light. Therefore, when the luminous pigment of the uniaxial light is less than 2 parts by weight, it is difficult to obtain sufficient light emission. When the amount of the luminous pigment is more than 5 parts by weight, it may be difficult to obtain white color due to inherent color. When the opaque white pigment is contained in an amount of less than 5 parts by weight, it is difficult to exhibit an opaque white background. If the opaque white pigment is contained in an amount exceeding 8 parts by weight, there is a fear of hindering the emission of the phosphorescent pigment. Since the printed sheet of the present invention can be used for advertising or fashion clothes, it is possible to temporarily and strongly express the strong brightness of the phosphorescent light that appears after the light reflection, in order to achieve more effective visual production.

According to one aspect of the present invention, the second white phosphorescent pigment layer (34) comprises, based on 100 parts by weight of the polyurethane, 2 to 5 parts by weight of the phosphorescent pigment in the long axis light, 5 to 8 parts by weight of the phosphorescent pigment in the short axis, 3 to 5 parts by weight of pearl, and 7 to 12 parts by weight of the transparent white pigment. Since the second white phosphorescent pigment layer contains a transparent white pigment and a light-emitting pigment of uniaxial light together with a long-luminescent luminous pigment having a long luminescence time, the white afterglow is continuously emitted for a predetermined period of time . Therefore, if the phosphorescent pigment of the long-axis light is less than 2 parts by weight, it is difficult to obtain a sufficient afterglow effect. If the amount of the phosphorescent pigment is more than 5 parts by weight, it may be difficult to obtain white color due to inherent phosphorescent color. Similarly, when the luminous pigment of the uniaxial light is less than 5 parts by weight, it is difficult to obtain a sufficient luminous effect. When the luminous effect is more than 8 parts by weight, it may be difficult to obtain white due to the inherent luminous color. When the transparent white pigment is contained in an amount of less than 7 parts by weight, light emission due to phosphorescence is unlikely to have a white color. If the transparent white pigment is contained in an amount exceeding 12 parts by weight, there is a fear of hindering light emission of the phosphorescent pigment. Since the printed sheet of the present invention can be used for advertising or fashion clothes, etc., it is possible to make the afterglow to last for a predetermined period of time by the long-term phosphorescent light emitted after reflection of light for more effective visual production.

The nano-pearl may serve to enhance the light reflecting action of the bead-shaped reflector, but when combined with a phosphorescent pigment, the luminescent action of the phosphorescent light can be inhibited. Therefore, the nano-pearl is preferably contained in an amount of 3 to 5 parts by weight based on 100 parts by weight of the polyurethane. When the content of the nano-pearl is less than 3 parts by weight, the light reflection effect of the reflective bead can not be enhanced. When the content of the nano-pearl is more than 5 parts by weight,

According to one aspect, the bead shaped reflector 40 is disposed on the white phosphorescent pigment layer 30. The white phosphorescent pigment layer 30 has a structure to surround a part of the bead shaped reflector 40 and has a structure in which the white phosphorescent pigment layer 30 and the bead shaped reflector 40 are partially embedded in the binder layer 20 . A plurality of the bead-shaped reflectors 40 may be used, and they may be closely arranged on one surface.

The bead shaped reflector 40 may include any bead having an appropriate refractive index capable of retroreflecting the light incident on the print sheet. For example, the bead-shaped reflector 40 may be appropriately selected from a transparent bead, a glass bead, a non-vitreous ceramic bead, or a transparent synthetic resin bead such as acrylic. Preferably, the bead shaped reflector 40 may be a glass bead having a high refractive index. The bead-shaped reflector 40 may have a spherical or elliptical cross-sectional shape, and may be spherical for uniform reflection efficiency. The size of the bead-shaped reflector 40 is not particularly limited, and may vary depending on the purpose and purpose of the adherend to which the printing sheet according to the present embodiment is applied. For example, the bead shape reflector 40 has a diameter D of 1.0 탆 to 2.0 탆, preferably 10 탆 to 1.0 탆, more preferably 20 탆 to 50 탆, particularly preferably 28 탆 to 40 탆, But is not limited thereto.

The bead-shaped reflector 40 according to an embodiment of the present invention may be embedded in the binder layer 20 with a structure protruding toward one surface of the binder layer 20, that is, a surface on which light is incident. According to one embodiment, only a part of the bead shaped reflector 40 is embedded in the binder layer 20, and the remainder may protrude to one surface of the binder layer 20, that is, a surface on which the light is incident. In another embodiment, the bead shaped reflector 40 may protrude 1/3 to 2/3 of the total diameter. Specifically, the height H of the bead-like reflector 40 protruding to the surface of the binder layer 40, that is, the 'protruding height' is 1/3 to 2/3 of the total diameter D of the bead- . When the projection height H of the bead shaped reflector 40 is within this range, it can be firmly coupled to and supported by the binder layer 20 with good reflection brightness.

When the projection height H of the bead-shaped reflector 40 is less than 1/3 of the diameter D, since the bead-shaped reflector 40 is buried excessively in the binder layer 120, the refractive index of the bead- It is difficult to ensure a good reflection luminance. If the protruding height H of the bead-shaped reflector 40 exceeds 2/3 of the diameter D, the bonding force of the bead-shaped reflector 40 to the binder layer 20 is weakened, Can not be firmly embedded in the binder layer 20 but can be released. That is, preferably, about half of the diameter of the bead shaped reflector 40 is embedded in the binder layer 20, and the other half can protrude to the surface of the binder layer 20.

According to one aspect, the transparent protective layer 50 may be made of a transparent resin. A thermally-decomposable resin or a UV-curable resin may be used as the resin constituting the transparent protective layer 50, and after a long time, it is preferable that there is no yellowing phenomenon. According to one aspect, the transparent protective layer 50 may comprise at least one transparent resin selected from the group consisting of a silicone resin, a polyurethane (PU), an acrylic resin, an epoxy resin, a polyvinyl chloride (PVC) have.

The transparent protective layer 50 may preferably include a silicone resin or a non-hydrophilic resin such as polyurethane (PU) in terms of water resistance. Alternatively, the transparent protective layer 50 may be formed by coating the transparent resin with a base resin and further including a waterproofing agent. The waterproofing agent may be a bentonite, a silicone (organopolysiloxane, etc.) or a urethane (Such as polyurethane)

2 is a cross-sectional view of a printing sheet including an ink fixing layer and a printing layer, according to an embodiment of the present invention.

According to one aspect, the printing sheet may further include an ink fixing layer 60 and a printing layer 70 between the bead shaped reflector 40 and the transparent protective layer 50.

The ink fixing layer 60 is for forming (printing) the printing layer 70, which is formed on top of the bead-shaped reflector 40. The ink fixing layer 60 is specifically formed by coating on the protruded surface of the bead shaped reflector 40. [ Since the printing layer 70 is formed on the surface of the ink fixing layer 60, it is preferable that printing can be performed on the surface of the ink fixing layer 60. [ Therefore, it is preferable that the ink fixing layer 60 has a good binding force with the bead-shaped reflector 40 and can fix the ink in an optimum state.

The composition of the ink fixing layer 60 may include an adhesive resin and may be, for example, a silicone resin, a polyurethane (PU) resin, a melamine resin, a polyvinyl chloride (PVC) resin, a polyvinyl alcohol PVA) resin, and an acrylic resin. In addition, the composition of the ink fixing layer 60 may further include an ink primer. The ink primer is for a good fixation of the ink, which can be preferably selected from the components contained in the ink for forming the printing layer (70). The ink primer is not particularly limited, but may be at least one selected from a wetting agent and a surfactant, which is included in a common ink composition.

According to one aspect, the ink fixing layer 60 may include a base resin, a wetting agent, and a surfactant. The ink fixing layer 60 may be formed of the above fixing resin such as silicone resin, polyurethane (PU) resin, melamine resin, polyvinyl chloride (PVC) resin, polyvinyl alcohol (PVA) resin and acrylic resin At least one base resin; Ink primers; And a solvent. In addition, 0.1 to 50 parts by weight of an ink primer and 30 to 150 parts by weight of a solvent may be included relative to 100 parts by weight of the base resin. The ink primer includes a wetting agent and a surfactant. The wetting agent may be included in an amount of 0.05 to 30 parts by weight based on 100 parts by weight of the base resin, and the surfactant may be included in an amount of 0.05 to 20 parts by weight. When the ink fixing layer 60 is formed with such a composition and content of the composition, it is possible to fix the ink in the optimum state without interfering with the reflection luminance.

According to one aspect, the wetting agent is selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-butanediol, , 2-butene-1,4-diol, 2-methyl-2-pentanediol, and the like.

According to one aspect, the surfactant may be at least one selected from the group consisting of polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyglycerin fatty acid ester and sorbitan fatty acid ester.

According to one aspect, the solvent may be at least one selected from the group consisting of water, ethanol, isopropanol, butanol, and pentanol.

In addition, the ink primer may further include an inorganic filler in addition to the wetting agent and the surfactant, and the inorganic filler may include silica, clay, talc, diatomaceous earth, zeolite, calcium carbonate, alumina, zinc oxide, . ≪ / RTI > The inorganic filler may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the base resin. The inorganic filler preferably has a fine size of 2.0 탆, and may have a diameter of, for example, 0.01 탆 to 2.0 탆.

The method of forming the ink fixing layer 60 is not limited, and it can be formed by various coating (or printing) methods. The ink fixing layer 60 can be formed by a method such as spray coating, CommaKnife coating, gravure coating and slot die coating, May be formed by coating one or more times with one or more methods selected from the UV coating methods used. Preferably, after coating the composition for ink fixation, curing and drying for 20 to 30 hours in an aging room where 40 to 50 ° C is maintained is good for stable deposition of ink.

The printing layer 70 is formed on the ink fixing layer 60 by a printing method, and the composition of the ink constituting the printing layer 70 is not limited. The ink may have a composition including at least four primary colors of C (Cyon), M (Magenta), Y (Yellow) and K (Black) as usual, for example, and may further contain other colorants (dyes and pigments) can do. The ink may include, for example, the four primary coloring matters, a fixing resin or an ink primer. At this time, the kind of the ink primer may be the same as that described in the ink fixing layer 60. The fixing resin may be selected from, for example, polyurethane (PU), silicone resin, melamine resin, polyvinyl chloride (PVC), and polyvinyl alcohol (PVA).

More specifically, the printing layer 70 is obtained by preparing a composition obtained by mixing conventional four primary coloring matters (C, M, Y and K), a fixing resin (for example, PU) and an ink primer, At a weight ratio of 100: 8, and then diluting the mixture in a diluting solvent mixed with toluene and methyl ethyl ketone (MEK) in a weight ratio of 5: 5. At this time, the ink may be formed by mixing 60 to 70% by weight of the mixture and 30 to 40% by weight of a diluting solvent. The ink may further contain, for example, carboxyl cellulose or the like as a viscosity control agent in addition to the above components. In the present invention, the composition of the ink is not limited, and it may conform to a composition commonly used in the printing field.

Figures 3 and 4 are cross-sectional views of a printed sheet comprising an adhesive layer and a release film layer, according to one embodiment of the present invention.

According to one aspect, it may further comprise an adhesive layer 80 and a release film layer 90 below the support layer 10. According to one aspect of the present invention, the printing sheet of the present invention can be adhered to an adherend such as clothing through a high-frequency system or a high-temperature press system. At this time, the adhesive layer 80 can be adhered to the adherend P by thermal fusion.

According to one aspect, the adhesive layer 80 may include an adhesive selected from a natural resin or a synthetic resin. Examples of the adhesive include a polyvinyl chloride (PVC), a polyolefin, a polyurethane, an acrylic, an ethylene vinyl acetate And an epoxy system, and the like.

The adhesive layer 80 may preferably be a polyurethane hot melt adhesive having good elasticity (stretchability) in consideration of characteristics of a textile product such as clothes and circularity after washing. The adhesive layer 80 may be thermally fused to the adherend P as described above, and it may be preferable to use a low melting point resin adhesive in consideration of the heat-sealability. For example, a low melting point resin adhesive such as a polyolefin type such as polyethylene (PE) and polypropylene (PP) or ethylene vinyl acetate (EVA) may be used.

According to one aspect, the release film layer 90 may be peeled off or removed from the adhesive layer 80 for adhesion between the adhesive layer 80 and the adherend. Accordingly, the release film layer 90 may be formed of paper, synthetic resin, or fiber material so that the release film layer 90 can be subjected to a release process.

According to one aspect, the release film layer 90 may be selected from synthetic resins comprising a polyester, polyolefin, polyurethane, polyimide, acrylic, and combinations thereof, and more specifically polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene terephthalate (PEN), polybutylene naphthalate (PBN), polyethylene (PE), polypropylene (PP), polyurethane (PU) ), Polyimide (PI), polycarbonate (PC), polyacrylic (PA), ethylene vinyl acetate (EVA) and copolymers thereof may be used, but the present invention is not limited thereto . On the other hand, non-limiting examples of the fibers constituting the release film layer 90 include woven or nonwoven fabrics composed of cotton fibers, polyester fibers, nylon fibers, rayon fibers, and blend fibers thereof.

5 is a cross-sectional view of a printing sheet including a coating layer according to an embodiment of the present invention.

The second aspect of the present invention provides a semiconductor device comprising: a binder layer (20) formed on the support layer (10); A first white phosphorescent pigment layer 32 formed on the binder layer 20; A second white phosphorescent pigment layer (34) formed on the first white phosphorescent pigment layer (32); A bead shaped reflector 40 formed on the second white phosphorescent pigment layer 34; A coating layer (100) forming an upper part of the plane while filling up the protruded structure of the bead shaped reflector (40) not embedded in the binder layer (20); And a surface layer (110) formed on the coating layer (100).

According to one aspect, the coating layer 100 is formed on a bead-shaped reflector 40 protruding in a direction opposite to the binder layer 20, and the space between the bead-shaped reflectors 40 is filled, Make it flat without bending.

According to one aspect, the coating layer 100 may contain at least one selected from the group consisting of an acrylic resin, an ester resin, a vinyl chloride resin, an olefin resin, a urethane resin, a fluorine resin, have. According to one aspect, durability can be enhanced by blending an appropriate amount of a crosslinking agent such as a compound, a melamine compound, an epoxy compound, or a silane compound, and crosslinking and curing.

According to one aspect, the coating layer 100 may be made of a thermosetting resin or a UV curable resin, and preferably does not have yellowing after a long period of time.

According to one aspect, a surface layer 110 is formed on the application layer 100. The surface layer 110 may be composed of polyvinyl chloride (PVC) or polyethylene terephthalate (PET). The surface layer 110 not only protects the surface but also adsorbs the printing ink to improve printing. For example, the surface layer 110 may be formed from a sol composition comprising polyvinyl chloride (PVC) and a plasticizer. The plasticizer may be at least one selected from, for example, dioctyl phthalate (DOP), dioctyl adipate (DOA), polyester plasticizer and the like, and a polyester plasticizer is preferable. The plasticizer is preferably blended in an amount of 20 to 50 parts by weight based on 100 parts by weight of polyvinyl chloride. Further, the surface layer 110 may further include a stabilizer and a diluent. The stabilizer may be a mixture of a light stabilizer and a heat stabilizer, and the diluent may be toluene, ethyl acetate, xylene, or butylene glycol.

6 is a cross-sectional view of a printed sheet including a print layer formed on a surface layer, according to an embodiment of the present invention.

According to one aspect, the printing sheet may further include a printing layer (70) formed on the surface layer. Alternatively, according to one aspect, the printing sheet may further include a printing layer 70 formed on the surface layer and a transparent protective layer 50 formed on the printing layer. A detailed description of the print layer and the transparent protective layer can be found in the above description.

7 is a cross-sectional view of a printed sheet comprising an adhesive layer and a release film layer, according to an embodiment of the present invention.

According to one aspect, the printed sheet comprises: a support layer (10); A binder layer (20) formed on the support layer (10); A first white phosphorescent pigment layer 32 formed on the binder layer 20; A second white phosphorescent pigment layer (34) formed on the first white phosphorescent pigment layer; A bead shaped reflector 40 formed on the second white phosphorescent pigment layer 34; A coating layer (100) forming an upper part of the plane while filling up the protruded structure of the bead shaped reflector (40) not embedded in the binder layer (20); And a surface layer (110) formed on the coating layer (100), wherein an adhesive layer (80) is formed under the support layer (10); A release film layer 90 may be included under the adhesive layer 80.

A printing sheet of the type as shown in Fig. 6 may also sequentially include the adhesive layer 80 and the release film layer 90 below the support layer 10. [0053] Fig.

In the case of the printing sheet of the second aspect of the present invention, the content of each constituent element can be referred to the above regarding the printing sheet of the first aspect of the present invention.

Figs. 8 and 9 are cross-sectional views of a printing sheet including a binder layer for bonding and a fibrous layer according to an embodiment of the present invention. Fig.

8 includes an ink fixing layer 60 formed on the surface of the bead shaped reflector 40 and a printing layer 70. The printing sheet 70 includes an adhesive binder layer 120 and a fiber layer 130).

9 includes a surface layer 110 and a printing layer 70 formed on a coating layer 100 filling the space between the bead shaped reflectors 40. The printing sheet 70 includes a binder layer Layer 120 and a fibrous layer 130. In one embodiment,

According to one aspect, the binder layer 120 for bonding may include a binder for bonding selected from natural resins or synthetic resins, and examples thereof include polyvinyl chloride (PVC), polyolefin, polyurethane, acrylic, ethylene vinyl acetate (EVA) based, epoxy based, and the like. The adhesive binder layer 120 is preferably a polyurethane based hot melt or a binder for bonding a low melting point resin such as polyolefin or ethylene vinyl acetate (EVA) such as polyethylene (PE) and polypropylene (PP) And a binder for bonding a transparent material may be more preferable.

According to one aspect, the fibrous layer 130 may be a perforated fibrous layer or a meshed fibrous layer. Due to the fibrous layer, the design of the printed sheet can be expressed with higher quality, and in particular, a hologram effect can be obtained with respect to the printed layer seen between the perforations or meshes.

A third aspect of the present invention is a method of manufacturing a semiconductor device, comprising: attaching a bead shaped reflector (40) on a carrier film; Forming a second white phosphorescent pigment layer (34) on the protruded surface of the bead shaped reflector (40); Forming a first white phosphorescent pigment layer (32) on the second white phosphorescent pigment layer (34); Forming a binder layer (20) on the first white phosphorescent pigment layer (32); Attaching a support layer (10) on the binder layer (20); And removing the carrier film attached to the bead-shaped reflector (40). For a more detailed description of each component, see above.

The method for producing a printing sheet of the present invention includes the step of adhering a bead shaped reflector (40) on a carrier film. According to one aspect, the carrier film may be a layer formed by applying a releasable resin capable of releasable to a peelable film such as PET. A bead-shaped reflector is attached to the carrier film to form a white phosphorescent pigment layer on the surface of the bead-shaped reflector. Thereafter, the bead-shaped reflector and the white phosphorescent pigment layer can be buried in the binder layer at one time. That is, a carrier film may be used to embed the white phosphorescent pigment layer 30 and the bead-shaped reflector 40 formed along the outer surface of the bead-shaped reflector all at once in the binder layer. The intervals of the bead-shaped reflectors 40 adhered on the carrier film may be very close or may be in contact with each other.

The method for producing a printing sheet of the present invention includes forming a second white phosphorescent pigment layer on the projected surface of a bead shaped reflector 40 adhered on a carrier film. The step of forming the second white phosphorescent pigment layer includes the steps of applying a solution containing a polyurethane, a phosphorescent pigment of long-axis light, a phosphorescent pigment of uniaxial light, a nano pearl and a transparent white pigment to the projected surface of the bead- This may include drying at 60 to 120 < 0 > C. According to one aspect of the present invention, the second white phosphorescent pigment layer comprises, based on 100 parts by weight of the polyurethane, 2 to 5 parts by weight of the phosphorescent pigment of the intense light, 5 to 8 parts by weight of the phosphorescent pigment of the uniaxial light, 5 parts by weight of the transparent white pigment, and 7 to 12 parts by weight of the transparent white pigment.

The method for producing a printing sheet of the present invention comprises forming a first white phosphorescent pigment layer (32) on the second white phosphorescent pigment layer (34). The step of forming the first white phosphorescent pigment layer comprises applying a solution comprising a polyurethane, a single-axis phosphorescent pigment and an opaque white pigment onto the second white phosphorescent pigment layer and drying it at 60 to 120 < 0 & . ≪ / RTI > According to one aspect, the first white phosphorescent pigment layer may comprise 2 to 5 parts by weight of the phosphorescent pigment of the uniaxial light, and 5 to 8 parts by weight of the opaque white pigment, based on 100 parts by weight of the polyurethane.

The method for producing a printing sheet of the present invention includes the step of forming a binder layer (20) on the first white phosphorescent pigment layer (32). The step of forming the binder layer may include the step of applying the binder solution onto the first white phosphorescent pigment layer and drying it at 60 to 120 캜.

The method for producing a printing sheet of the present invention comprises the step of adhering a supporting layer (10) on the binder layer (20). The support layer 10 may be made of a transparent, semitransparent or opaque material. According to one aspect, the support layer 10 may include at least one selected from the group consisting of fibers, paper, leather, and synthetic resins, or films made from quantum dot barriers. The thickness of the support layer 10 can be appropriately selected depending on the material to be selected.

According to one aspect, the method for manufacturing a printing sheet of the present invention is characterized in that after the step of removing the carrier film attached to the bead-shaped reflector (40), the beaded reflector (40) Forming a print fixing layer (60) on the surface; Forming a printing layer (70) on the printing fixation layer (60); And forming a transparent protective layer (50) on the print layer (70). That is, the print fixing layer 60, the print layer 70, and the transparent protective layer 50 may be sequentially formed on the protruded surface of the bead shaped reflector 40 from which the carrier film has been removed. A more detailed description of each component can be found in the above description.

A fourth aspect of the present invention is a method for manufacturing a semiconductor device, comprising: attaching a bead shaped reflector on a carrier film; Forming a second white phosphorescent pigment layer on a protruded surface of the bead shaped reflector; Forming a first white phosphorescent pigment layer on the second white phosphorescent pigment layer; Forming a binder layer on the first white phosphorescent pigment layer; Attaching a support layer on the binder layer; Removing the carrier film attached to the bead-shaped reflector; Forming a coating layer on a side where the carrier film is removed; And forming a surface layer on the application layer, wherein the application layer forms a plane while filling up the protruded structure of the bead-shaped reflector.

According to one aspect, the method of manufacturing a print sheet of the present invention may further include forming a print layer on the surface layer. Alternatively, the method for producing a printing sheet of the present invention comprises the steps of: forming a printing layer on the surface layer; And forming a transparent protective layer on the print layer.

The method for manufacturing a printing sheet according to the third and fourth aspects of the present invention includes the steps of: forming an adhesive layer below the supporting layer; And forming a release film layer below the adhesive layer. The adhesive layer may be formed by applying a pressure-sensitive adhesive having an appropriate adhesive force to the other surface (bottom surface) of the support layer 10. Usable adhesives may be, for example, a removable type, a permanent type, or a hot-melt type. The thickness of the adhesive layer 80 may be approximately 1 to 100 탆, preferably 5 to 80 탆, and more preferably 10 to 50 탆, but is not limited thereto. A release film layer 90 that can be detachably attached to the other surface (bottom surface) of the adhesive layer 80 can be formed. It is necessary to peel and remove the adhesive layer 80 from the adhesive layer 80 for adhesion between the adhesive layer 80 and the adherend when the print sheet of the present invention is adhered to the adherend. Can be formed. The material of the release film layer 90 may be a paper material, a synthetic resin material, a fiber material, or the like, and the thickness thereof may be appropriately adjusted depending on the material.

In an exemplary embodiment, the printing sheet according to the present invention can be applied in the form attached to an adherend. The adherend is not particularly limited and may be selected from clothing, fashion garments, shoes, bags, printed matter, safety signs, advertisements of workers working in dangerous places, and the like. For example, the adherend may be a plate-like object or printed matter, an advertising panel, clothing, or a bag. According to one aspect, the printing sheet according to the present invention can be adhered to an adherend through a method such as sewing or adhesion, or can be attached by sewing the edge of a printed sheet to a surface of the adherend. For example, the printing sheet of the present invention can be attached by heat welding by high-frequency or high-temperature press. Thermal fusion may be achieved through the adhesive layer 80 applied to the bottom surface of the support layer 10.

In the method for producing a printing sheet according to the third and fourth aspects of the present invention, the content of each constituent element can be referred to the above description regarding the printing sheet of the third and fourth aspects of the present invention.

The method for producing a printing sheet according to the third or fourth aspect of the present invention comprises the steps of: forming a binder layer for bonding 120; And forming a fiber layer 130 on the substrate. The adhesive binder layer 120 and the fiber layer 130 are preferably formed on the uppermost layer.

According to one aspect, the binder layer 120 for bonding may include a binder for bonding selected from natural resins or synthetic resins, and examples thereof include polyvinyl chloride (PVC), polyolefin, polyurethane, acrylic, ethylene vinyl acetate (EVA) based, epoxy based, and the like. The adhesive binder layer 120 is preferably a polyurethane based hot melt or a binder for bonding a low melting point resin such as polyolefin or ethylene vinyl acetate (EVA) such as polyethylene (PE) and polypropylene (PP) And a binder for bonding a transparent material may be more preferable.

According to one aspect, the fibrous layer 130 may be a perforated fibrous layer or a meshed fibrous layer. Due to the fibrous layer, the design of the printed sheet can be expressed more luxuriously, and in particular, a hologram effect can be obtained.

≪ Example 1 >

The glass beads were applied on the PET film coated with the pressure-sensitive adhesive at uniform intervals and attached. The second white phosphorescent pigment solution was coated on the surface of the glass beads and then dried at 100 DEG C for 48 hours.

Composition of the second white phosphorescent pigment solution: 100 parts by weight of polyurethane resin (solid content: 40%) / MEK (Methyl Ethyl Ketone) 70 parts by weight / DMF (Dimethylformamide) 20 parts by weight / TOL (Toluene) 3 parts by weight of luminous pigment (Aluminum Oxide), 6.5 parts by weight of ZnS (Cu), Nano Pearl, 4 parts by weight of ACCEL (Accelerator), 8 parts by weight of transparent white pigment (Sb ₂ O ₃ ) 10 parts by weight.

The first white phosphorescent pigment solution was coated on the surface of the second white phosphorescent pigment layer and then dried at 100 캜 for 48 hours.

Composition of first white phosphorescent pigment solution: 70 parts by weight of MEK (Ethyl Ketone) / 20 parts by weight of DMF (Dimethylformamide) / 10 parts by weight of TOL (Toluene) per 100 parts by weight of polyurethane resin (solid content 40% 4 parts by weight of boron oxide (ZnS: Cu) / 4 parts by weight of nano pearl / 8 parts by weight of ACCEL (accelerator) / 7 parts by weight of opaque white pigment (TiO ₂ )

The binder solution was applied to the surface of the first white phosphorescent pigment layer and then dried at 70 DEG C for 48 hours.

Composition of binder solution: 100 parts by weight of transparent binder resin / DMF (Dimethylformamide) 30 parts by weight / TOL (Toluene) 20 parts by weight / ACCEL (accelerator) 8 parts by weight / curing agent 10 parts by weight.

After the fibers were adhered onto the binder layer, they were dried in a maturing chamber at 100 캜 for 48 hours. After drying, the PET film attached to the glass bottle was removed. The ink fixing resin was coated on the surface from which the PET film was removed and dried in a maturing chamber at 100 캜 for 48 hours. The temperature and speed of the chambers in each of the processes are as follows: Chamber 1: 80 캜 - Chamber 2: 120 캜 - Chamber 3: 80 캜, Speed: 4.5 - 5 m / min.

≪ Example 2 >

The glass beads were applied on the PET film coated with the pressure-sensitive adhesive at uniform intervals and attached. The second white phosphorescent pigment solution was coated on the surface of the glass beads and then dried at 100 DEG C for 48 hours.

Composition of the second white phosphorescent pigment solution: 100 parts by weight of polyurethane resin (solid content: 40%) / MEK (Methyl Ethyl Ketone) 70 parts by weight / DMF (Dimethylformamide) 20 parts by weight / TOL (Toluene) 3 parts by weight of luminous pigment (Aluminum Oxide), 6.5 parts by weight of ZnS (Cu), Nano Pearl, 4 parts by weight of ACCEL (Accelerator), 8 parts by weight of transparent white pigment (Sb ₂ O ₃ ) 10 parts by weight.

The first white phosphorescent pigment solution was coated on the surface of the second white phosphorescent pigment layer and then dried at 100 캜 for 48 hours.

Composition of first white phosphorescent pigment solution: 70 parts by weight of MEK (Ethyl Ketone) / 20 parts by weight of DMF (Dimethylformamide) / 10 parts by weight of TOL (Toluene) per 100 parts by weight of polyurethane resin (solid content 40% 4 parts by weight of boron oxide (ZnS: Cu) / 4 parts by weight of nano pearl / 8 parts by weight of ACCEL (accelerator) / 7 parts by weight of opaque white pigment (TiO ₂ )

The binder solution was applied to the surface of the first white phosphorescent pigment layer and then dried at 70 DEG C for 48 hours.

Composition of binder solution: 100 parts by weight of transparent binder resin / DMF (Dimethylformamide) 30 parts by weight / TOL (Toluene) 20 parts by weight / ACCEL (accelerator) 8 parts by weight / curing agent 10 parts by weight.

After the fibers were adhered onto the binder layer, they were dried in a maturing chamber at 100 캜 for 48 hours. After drying, the PET film attached to the glass bottle was removed. The transparent binder solution was applied to the surface from which the PET film was removed and dried in the aging chamber at 100 캜 for 48 hours. PVC was attached on the side coated layer where the PET film was removed, and then dried in the aging chamber at 100 캜 for 48 hours. On the fiber (support layer), a removable pressure-sensitive adhesive was applied and a liner for protecting the pressure-sensitive adhesive was attached, followed by drying in a maturing chamber at 100 ° C for 48 hours. The temperature and speed of the chambers in each of the processes are as follows: Chamber 1: 80 캜 - Chamber 2: 120 캜 - Chamber 3: 80 캜, Speed: 4.5 - 5 m / min.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. For example, if the techniques described are performed in a different order than the described methods, and / or if the described components are combined or combined in other ways than the described methods, or are replaced or substituted by other components or equivalents Appropriate results can be achieved.

Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (20)

Supporting layer;
A binder layer formed on the support layer;
A first white phosphorescent pigment layer formed on the binder layer;
A second white phosphorescent pigment layer formed on the first white phosphorescent pigment layer;
A bead shaped reflector formed on the second white phosphorescent pigment layer; And
And a transparent protective layer formed on the protruded surface of the bead-shaped reflector,
Wherein the first white phosphorescent pigment layer, the second white phosphorescent pigment layer and the bead shaped reflector are embedded in a structure protruding from the binder layer.
The method according to claim 1,
Further comprising an ink fixing layer and a printing layer between the bead shaped reflector and the transparent protective layer,
Wherein the ink fixing layer and the printing layer are formed on a protruded surface of the bead-shaped reflector.
Supporting layer;
A binder layer formed on the support layer;
A first white phosphorescent pigment layer formed on the binder layer;
A second white phosphorescent pigment layer formed on the first white phosphorescent pigment layer;
A bead shaped reflector formed on the second white phosphorescent pigment layer;
A coating layer forming an upper part of the plane while filling up the protruded structure of the bead-shaped reflector not buried in the binder layer; And
And a surface layer formed on the application layer.
The method of claim 3,
And a printing layer formed on the surface layer.
The method of claim 3,
On the surface layer,
A print layer, and a transparent protective layer.
The method according to claim 1 or 3,
Wherein the support layer further comprises an adhesive layer and a release film layer.
The method according to claim 1 or 3,
Wherein the first white phosphorescent pigment layer is at least one selected from the group consisting of Zinc Sulfide Copper Doped (ZnS: Cu), Boron Oxide, Alkaline Aluminate, and Alkali- One single-axis phosphorescent pigment, a polyurethane, and an opaque white pigment,
Wherein the second white phosphorescent pigment layer comprises at least one long-axis phosphorescent pigment selected from the group consisting of aluminum oxide, calcium oxide, strontium oxide and Europium oxide, a zinc phosphide doped ZnS: At least one uniaxially-incandescent phosphorescent pigment selected from the group consisting of copper (Cu), boron oxide, alkaline earth aluminate, and alkaline earth silicate, polyurethane, nanopearl, and transparent white pigment , A printed sheet.
8. The method of claim 7,
Wherein the first white phosphorescent pigment layer comprises 2 to 5 parts by weight of the uniaxial light phosphorescent pigment and 5 to 8 parts by weight of the opaque white pigment based on 100 parts by weight of the polyurethane,
Wherein the second white phosphorescent pigment layer comprises, based on 100 parts by weight of the polyurethane, 2 to 5 parts by weight of the phosphorescent pigment in the long axis light, 5 to 8 parts by weight of the phosphorescent pigment in the short axis, 3 to 5 parts by weight, And 7 to 12 parts by weight of the transparent white pigment.
3. The method of claim 2,
Wherein the ink fixing layer comprises a base resin, a wetting agent, and a surfactant.
The method according to claim 2 or 4,
Further comprising a binder layer for bonding and a fiber layer on the printing layer.
Attaching a bead shaped reflector on the carrier film;
Forming a second white phosphorescent pigment layer on a protruded surface of the bead shaped reflector;
Forming a first white phosphorescent pigment layer on the second white phosphorescent pigment layer;
Forming a binder layer on the first white phosphorescent pigment layer;
Attaching a support layer on the binder layer; And
And removing the carrier film attached to the bead-shaped reflector.
12. The method of claim 11,
After the step of removing the carrier film,
Forming a print fixing layer on the side of the side where the carrier film is removed, on the projected surface of the bead-shaped reflector;
Forming a print layer on the print fixing layer; And
And forming a transparent protective layer on the printing layer.
Attaching a bead shaped reflector on the carrier film;
Forming a second white phosphorescent pigment layer on a protruded surface of the bead shaped reflector;
Forming a first white phosphorescent pigment layer on the second white phosphorescent pigment layer;
Forming a binder layer on the first white phosphorescent pigment layer;
Attaching a support layer on the binder layer;
Removing the carrier film attached to the bead-shaped reflector;
Forming a coating layer on a side where the carrier film is removed; And
And forming a surface layer on the coating layer,
Wherein the coating layer forms a plane while filling up the protruding structure of the bead-shaped reflector.
14. The method of claim 13,
And forming a printing layer on the surface layer.
14. The method of claim 13,
Forming a print layer on the surface layer; And
And forming a transparent protective layer on the printing layer.
14. The method according to claim 11 or 13,
Forming an adhesive layer below the support layer; And
And forming a release film layer below the adhesive layer.
14. The method according to claim 11 or 13,
Wherein the first white phosphorescent pigment layer is at least one selected from the group consisting of Zinc Sulfide Copper Doped (ZnS: Cu), Boron Oxide, Alkaline Aluminate, and Alkali- One single-axis phosphorescent pigment, a polyurethane, and an opaque white pigment,
Wherein the second white phosphorescent pigment layer comprises at least one long-axis phosphorescent pigment selected from the group consisting of aluminum oxide, calcium oxide, strontium oxide and Europium oxide, a zinc phosphide doped ZnS: At least one uniaxially-incandescent phosphorescent pigment selected from the group consisting of copper (Cu), boron oxide, alkaline earth aluminate, and alkaline earth silicate, polyurethane, nanopearl, and transparent white pigment , And a method for manufacturing a printing sheet.
18. The method of claim 17,
Wherein the first white phosphorescent pigment layer comprises 2 to 5 parts by weight of the uniaxial light phosphorescent pigment and 5 to 8 parts by weight of the opaque white pigment based on 100 parts by weight of the polyurethane,
Wherein the second white phosphorescent pigment layer comprises, based on 100 parts by weight of the polyurethane, 2 to 5 parts by weight of the phosphorescent pigment in the long axis light, 5 to 8 parts by weight of the phosphorescent pigment in the short axis, 3 to 5 parts by weight, And 7 to 12 parts by weight of the transparent white pigment.
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