KR20110098950A - Light accumulating laminated body - Google Patents

Abstract

The present invention has suitable flexibility, conformation, thinness and excellent light accumulation capability for corrugated surfaces (with indentations and protrusions) such as interior and exterior road surfaces, stairs, wall surfaces, etc. It provides a laminate.

Description

Light accumulation laminated body {LIGHT ACCUMULATING LAMINATED BODY}

The present invention relates to a light accumulation laminate. In particular, the present invention relates to a light accumulating laminate in which an acrylic type white adhesive layer is laminated.

Sheets or flooring using light accumulating materials can be used in practice. In the use of such sheets or floorings, a material can be selected that generates light in the dark from the energy of light absorbed by the light accumulating material. These sheets or floorings can be used as disaster prevention signs, safety signs, or as different types of design indicators. At the point where the light accumulating material generates light on its rear surface, the light accumulating ability is further increased if a light suppressing layer is provided. Because of this, a material having suppressive properties can be provided on the rear surface of the layer containing the light accumulating material. In this case, an adhesive layer can be provided on such a layer having suppressive properties.

The present invention relates to a light accumulation layer comprising a light accumulation layer and a layer laminated on the light accumulation layer. The lamination layer may be an acrylic type white adhesive layer. The adhesive layer may contain carboxyl radical containing (meth) acrylic type polymers, white pigments, and (meth) acrylic type polymers containing amino radicals and no aromatic vinyl monomers.

<Figure 1>
BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows an example of the light accumulation laminated material which concerns on this invention.
2A and 2B.
2A and 2B are views showing an example of the light accumulation laminated material according to the present invention, where FIG. 2A shows a three-dimensional drawing, and FIG. 2B shows a sectional view.
3,
3 is a cross-sectional view showing an example of the light accumulation laminated material according to the present invention.
<Figure 4>
4 is a graph showing the ratio of the luminance decrease occurring in the black portion measured according to the reference actual test 1. FIG.
<Figure 5>
FIG. 5 is a graph showing 90 degree peel adhesion force (N / 25 mm) after 24 hours (1 day), which is a measured value according to Reference Actual Test 2. FIG.
6,
FIG. 6 is a graph showing 90 degree peel adhesion force (N / 25 mm) after the one week period which is the measured value according to the reference actual test 2. FIG.
7A, 7B, and 7C.
7A, 7B, and 7C are photographs taken when each individual sample is adhered to a sheet used for testing of concealment properties according to Reference Test 1.

The present invention provides a light accumulating laminate having suitable flexibility properties for wavy surfaces (with indentations and protrusions), such as interior and exterior road surfaces, stairs, wall surfaces, and the like. The laminate has compliant characteristics, is thin and has excellent light accumulation capability.

The present invention provides a light accumulating laminate having appropriate flexible properties to the corrugated surface (with indentations and protrusions), having conforming properties, being thin and having excellent light accumulating ability. The present invention also proposes a light accumulating laminate which can maintain adhesion (bonding) properties at places such as interior and exterior road surfaces or wall surfaces, and stairs, which can be wetted by water.

1 is a cross-sectional view showing an example of a light accumulation laminate according to the present invention. This is a figure which shows schematically an example of sectional drawing of the light accumulation laminated body 100 which concerns on this invention. The light accumulating laminate 100 is a laminate in which a light accumulating layer 102 and an acrylic type white adhesive layer (or laminate) 104 are laminated.

The light accumulation layer 102 is formed from a resin containing a light accumulation fluorescent material. There is no particular limitation regarding the resin material. For example, materials used according to the prior art can be used. However, it is possible to use any one type of the following materials or mixtures of two or more types thereof: among other things, polyurethanes having transparent and flexible properties, vinyl chloride type polymers, acrylic type polymers, polyesters, Polyolefin, polystyrene, silicone, fluorinated type polymer, or epoxy type polymer. Then, optionally, it is also possible to add crosslinkers and crosslink these polymer materials. With regard to the resin material, it may also be a material containing a surface improver, a curing agent, a colorant, an antibacterial agent, an additive, or another performance enhancer.

Regarding the light accumulating fluorescent material, it is possible to appropriately select a material known from the prior art such as, for example, an aluminum acid salt type light accumulating fluorescent material or a sulfide compound type fluorescent light material, and there is no particular limitation. For example, in certain embodiments, GLL-300, G-300 (produced by Basic Specialty Science Company, strontium salt of europium doped (activated) -dysprosium inter-doped aluminum acid (SrAlO 4: Eu, Dy)), or GSS (manufactured by Basic Specialty Science Company, copper doped—zinc sulfide (ZnS: Cu)).

The light accumulating layer according to the invention is a layer which can be formed of resin in pellet, paste or powder form. Light accumulating fluorescent materials are added to the desired mixture, which are formed through methods known from the prior art such as calendering, extrusion or orientation (elongation) and the like.

There is no particular limitation with regard to the thickness of the light accumulating layer, but it may range from about 0.1 mm to about 5 mm.

The laminate, or acrylic type white adhesive layer 104 contains a carboxyl radical containing (meth) acrylic type polymer, a white pigment, and an (meth) acrylic type polymer containing amino radicals and no aromatic vinyl monomers. .

In the description of the present invention, the term "(meth) acryl" has the meaning of "acrylic or methacryl". The term "carboxy radical containing (meth) acrylic type polymer" is also referred to as "carboxy radical containing polymer", and the term "(meth) acrylic type polymer containing amino radicals and free of aromatic vinyl monomer" is referred to as "amino Radical-containing polymer ".

Regarding the acrylic type white adhesive, a carboxyl radical containing polymer which is a polymer obtained as a carboxyl radical containing monomer is used as a structural component, which is polymerized. In addition, amino radical containing polymers which are polymers obtained as amino radical containing monomers are used as structural components, which are polymerized. These two radicals are mixed and combined, with the mixture improving the properties of the white pigment material inside the adhesive and keeping the white pigment material stable inside the adhesive. For this reason, it is possible to propose the white adhesive containing a larger amount of pigment material.

With respect to the acrylic type white adhesive, particularly preferred adhesives are from about 25 parts by weight to about (i) carboxyl radical-containing (meth) acrylic type adhesive polymer and also (ii) the carboxyl radical-containing (meth) acrylic type polymer described above. It is formed from an amino radical containing (meth) acrylic type polymer that does not contain an aromatic vinyl monomer in an amount of 150 parts by weight of a white pigment material.

It is possible to stably disperse even larger quantities of white pigment material inside the adhesive through the incorporation of the colorants described above, ie through the pre-dispersion of the white pigment material in the polymer material.

Carboxyl Radical  contain ( MET ) Acrylic type polymer

Regarding the carboxyl radical-containing (meth) acrylic type polymers described above, this is a polymer material having a monoethylenically unsaturated monomer as a main component, a part of which is a carboxyl radical-containing monoethylenically unsaturated monomer (carboxyl radical-containing monoethylenic Unsaturated monomer). With regard to the monoethylenically unsaturated monomers described above, it is a material whose main component is a polymer, usually it is of the formula CH ₂ = CR ¹ COOR ² (wherein R ¹ represents hydrogen or methyl radical and R ² is straight, cyclic Or branched type alkyl radicals or phenyl radicals, alkoxyl alkyl radicals, phenoxy alkyl radicals, hydroxy alkyl radicals, cyclic ether radicals). Suitable monomer materials can be selected, for example, from the following materials: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-amyl (meth) acrylate, n- Hexyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, iso-octyl (meth) acrylate, iso-nonyl (meth) acrylate, decyl (meth) acrylate, or dodecyl (meth) acrylate Alkyl (meth) acrylates such as cyclohexyl (meth) acrylate; Phenoxy alkyl (meth) acrylates such as phenoxy ethyl (meth) acrylate; Alkoxyl alkyl (meth) acrylates such as methoxy propyl (meth) acrylate and 2-methoxy butyl (meth) acrylate; Hydroxy alkyl (meth) acrylates such as 2-hydroxy ethyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate and 4-hydroxy butyl (meth) acrylate; Cyclic type ether-containing (meth) acrylates such as glycidyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate. Depending on the requirements (optionally), it is also possible to use one type or two or more types of mono ethylenically unsaturated monomers.

The carboxyl radical-containing mono ethylenically unsaturated monomers include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Unsaturated di-carboxylic acids such as itaconic acid, fumaric acid, citraconic acid and maleic acid; ω-carboxy polycaprolactone mono acrylate, β-carboxy ethyl acrylate, 2- (meth) acryloyl oxy ethyl succinic acid and the like.

The carboxyl radical-containing (meth) acrylic type polymer can be obtained by copolymerizing, for example, at a ratio of 80 to 99.5 parts by weight of the aforementioned mono ethylenically unsaturated monomer and 0.5 to 20 parts by weight of the aforementioned carboxyl radical containing mono ethylenically unsaturated monomer. Can be. Alternatively, it can be obtained by keeping the amount of the mono ethylenically unsaturated monomer in the range of 90 to 99 parts by weight and the amount of the carboxyl radical-containing mono ethylenically unsaturated monomer in the range of 1 to 10 parts by weight.

There is no particular limitation regarding the weight average molecular weight of the carboxyl radical containing (meth) acrylic type polymer, but it may be a material having a weight average molecular weight in the range of about 100,000 to about 2,000,000 or about 300,000 to about 1,000,000.

With respect to the carboxyl radical containing (meth) acrylic type polymer, it can be used as the main component of the acrylic type white adhesive, the compounding amount of which is about 35 parts by weight to about when the total amount of the acrylic type white adhesive is set as 100 parts by weight It may be in the range of 80 parts by weight.

Amino free of aromatic vinyl monomers Radical  contain ( MET ) Acrylic type polymer

The amino radical containing (meth) acrylic type polymer which does not contain the aromatic vinyl monomer described above has a monoethylenically unsaturated monomer as its main component, a partially amino radical containing unsaturated monomer is contained, and the aromatic vinyl monomer is a structural material of the polymer material. It is a polymer which is not contained as a component. With respect to such mono ethylenically unsaturated monomers, this is the same as the carboxyl radical-containing (meth) acrylic type polymer in the adhesive, and the aforementioned aromatic vinyl monomers include styrene, α-methyl styrene, vinyl toluene, vinyl naphthalene, vinyl anthracene, vinyl anthracene Quinones, (meth) acrylamide aromatic amines, (meth) acrylates of hydroxyl radical-containing aromatic compounds, and the like. The aromatic amines can be aniline, benzyl amines, naphthyl amines, amino anthracenes, amino anthraquinquinones, or derivatives thereof. The hydroxyl radical containing aromatic compound may be a hydroxyl radical containing compound corresponding to the aromatic amine described above. As a method for obtaining an amino radical containing (meth) acrylic type polymer, it is possible to use the method of copolymerizing a mono ethylenically unsaturated monomer and an amino radical containing unsaturated monomer.

In the case of amino radical-containing unsaturated monomers, the following monomers may be used: dialkyl amino alkyls such as N, N-dimethyl amino ethyl acrylate (DMAEA), N, N-dimethyl amino ethyl methacrylate (DMAEMA) (Meth) acrylates; Dialkyl amino alkyl (meth) acrylamides such as N, N-dimethyl amino propyl acrylamide (DMAPAA), N, N-dimethyl amino propyl methacrylamide; Dialkyl amino alkyl vinyl ethers such as N, N-dimethyl amino ethyl vinyl ether and N, N-diethyl amino ethyl vinyl ether; Or mixtures thereof.

Amino radical containing polymers can be obtained, for example, by copolymerizing mono ethylenically unsaturated monomers in an amount ranging from about 80 to about 99.5 parts by weight with amino radical containing unsaturated monomers in an amount ranging from about 0.5 to about 20 parts by weight. Alternatively, the amount of mono ethylenically unsaturated monomer can be set in the range of about 90 to about 99 parts by weight and the amount of amino radical-containing unsaturated monomer in the range of about 1 to about 10 parts by weight.

There is no particular limitation regarding the weight average molecular weight of the amino radical containing polymer, but for example, the weight average molecular weight may be in the range of about 1,000 to about 500,000, about 5,000 to about 200,000, or about 10,000 to about 100,000.

Regarding the compounding amount of the amino radical-containing polymer, when the total amount of the acrylic type white adhesive is taken as 100 parts by weight, it may be in the range of about 5 parts by weight to about 20 parts by weight. In addition, when the acrylic type white adhesive contains a white color agent, it is possible to be used as one component of a suitable colorant.

Copolymerization of these polymers can be carried out by radical polymers. In this case, it is possible to use solution polymerization, suspension polymerization or flocculation polymerization or other well known polymerization methods. As the initiator, it is possible to use the following formulations: organic peroxides such as benzoyl peroxide, lauroyl peroxide, bis (4-tert-butyl cyclohexyl) peroxy dicarbonate, or 2,2'- Azo bis iso-butylonitrile, 2, 2'- azo bis-2-methyl butyronitrile, 4,4'- azo bis-4'-cyano valeric acid, 2, 2'- azo bis (2-methyl Propionic acid) azo type polymerization initiators such as dimethyl ester, azobis 2,4-dimethyl valeronitrile (AVN) and the like. As the usage-amount of these polymerization initiators, when a monomer mixture material is taken as 100 weight part, it may be set so that it may exist in the range of 0.05-5 weight part.

White pigment material

White pigment materials can be selected, for example, from the following materials: zinc carbonate (zinc salt of carbonate), zinc sulfide, or titanium oxide (titanium dioxide). It is also possible to optionally use talc, kaolin, calcium carbonate. These white pigment materials can be used individually as a single material or it is possible to mix two or more types and use these mixtures. In addition, these white pigment materials may be in any type of form, or it is also possible that they have undergone different types of dispersion treatments according to methods well known from the prior art.

The content of the white pigment material can be chosen approximately to match the desired hiding properties. For example, with respect to 100 parts by weight of the carboxyl radical-containing (meth) acrylic type polymer described above, the content may be in the range of about 25 parts by weight to about 150 parts by weight.

coloring agent

The colorant contains a white pigment material and an amino radical containing (meth) acrylic type polymer that does not contain aromatic vinyl monomers. Here, amino radical containing (meth) acrylic type polymers free of white pigment material and aromatic vinyl monomers are correspondingly according to the descriptions reported above.

In the description of the invention, amino radical containing (meth) acrylic type polymers which do not contain aromatic vinyl monomers in colorants are reported as "colorant polymers". In addition, polymers not originally present in the colorant are reported as "adhesive polymers".

Regarding the colorant polymer, a polymer compatible with the above-described adhesive polymer is preferable in view of maintaining long-term stability characteristics.

The colorant may be obtained when the white pigment material described above and the colorant polymer described above are mixed according to the methods of the prior art. For example, this can be accomplished using a paint shaker, sand grind mill, ball mill, attritor mill, or three-body roll mill. Can be obtained by mixing. At this time, it is also possible (optionally) to add a solvent medium of aqueous or organic type.

The colorant is preferably a material in which the pigment particles do not agglomerate and remain well dispersed immediately after preparation, as well as after a long period of time after preparation and preparation (eg up to approximately one month level). These conditions are relatively high, for example, in the case of preparation and manufacture using a device having a relatively strong mixing force such as a sand grind mill, a ball mill, an atliter mill, or a three body roll mill, as well as a paint shaker or the like. The same applies to the use of devices with weak mixing forces. When devices with relatively weak mixing forces are used, mixing and combining for a relatively short period of time (eg approximately 10 minutes), so that they remain well dispersed immediately after preparation and even after a long time after preparation and preparation It is possible to obtain the material to be made.

Crosslinker

The acrylic type white adhesive may optionally also contain a crosslinking agent. Such formulations may be selected from among the following materials, among others: bis amide type crosslinkers (eg 1,1′-iso-phthaloyl bis (2-methyl aziridine)), aziridine type crosslinking Binders (e.g. Chemilite PZ33 manufactured by Nippon Catalyst Company, NeoCryl CX-100 manufactured by Abishia), carbodi di-imide Type crosslinkers (eg Carbodilite V-03, V-05, V-07) manufactured by Nishinbo Company, Epoxy type crosslinkers (eg Soken Kagaku) E-AX, E-5XM, E5C) manufactured by Soken Kagaku Company, isocyanate type crosslinkers (e.g., Coronate L, manufactured by Nippon Polyurethane) Nate HK, Desm manufactured by Bayer Company odur) H, Desmodur W, Desmodur I).

With respect to the amount of crosslinker added, this can be made 0.01 to 0.5 equivalents relative to the carboxyl radicals in the carboxyl radical-containing polymer, or relative to the amino radicals in the amino radical-containing polymer.

White colorants can be obtained when the white pigment material described above and the amino radical containing (meth) acrylic type polymers that do not contain the aforementioned aromatic vinyl monomers are mixed according to the prior art methods.

For example, this can be obtained when the respective components are introduced into the mixing apparatus almost simultaneously and mixed using a paint shaker, sand grind mill, ball mill, atliter mill, three body roll mill, or the like. It is then possible (in accordance with the requirements) to optionally use the aforementioned crosslinkers or well-known aqueous or organic type solvent media. It is also possible for the aforementioned white pigment material to be mixed in an aqueous or organic type solvent medium, after which it is mixed with the remaining components.

In addition, when the acrylic type white adhesive contains a colorant, it can be obtained when the carboxyl radical containing acrylic type polymer and the colorant are mixed and combined according to the prior art methods.

The acrylic type white adhesive layer has inherently adhesive properties and due to the fact that it contains a significant amount of white pigment material, it also has sufficient hiding properties. By laminating such an adhesive layer on the light accumulating layer of the light accumulating laminate according to the present invention, it becomes necessary to use two layers, namely a layer having concealment properties and an adhesive layer. Therefore, even if the thickness of the white adhesive layer is made thin, it is possible to obtain sufficient hiding characteristics. And, for that reason, it is possible to limit the thickness of the entire body of the light accumulation laminate.

The thickness of the acrylic type white adhesive layer is not particularly limited. For example, this can be from about 0.02 mm to about 0.1 mm.

At the point where the light accumulating layer generates light, it can be reflected by the acrylic type white adhesive layer, thereby increasing the light generating efficiency.

2A is a three-dimensional view illustrating an example of the light accumulation stack according to the present invention. FIG. 2B is a cross-sectional view illustrating the light accumulation stack of FIG. 2A.

The light accumulating layer 202 may be a layer having a structure formed of a light accumulating portion 203 made of a resin containing a light accumulating fluorescent material and a supporting portion 205 formed from a resin which does not actually contain the light accumulating fluorescent material. have. In the example shown in Figs. 2A and 2B, there is no particular limitation with regard to the resin that can be used for the light accumulating portion 203 and the supporting portion 205. For example, it is possible to use resins having transparent and flexible properties as reported according to the description of FIG. 1.

There is no particular limitation with respect to the shape of the light accumulating portion 203 and the supporting portion 205, the surface area ratio of the light accumulating portion 203 and the supporting portion 205, or their volume ratios, and these may be appropriately selected according to different conditions. Can be. In order to increase the light generating efficiency of the light accumulating portion 203, it is preferable that the light accumulating portion 203 and the acrylic type white adhesive layer 204 are in contact.

It is sectional drawing which shows an example of the light accumulation laminated body which concerns on this invention. The light accumulation stack 300 has a structure that can be formed of a light accumulation layer 302, an acrylic type white adhesive layer 304, and a bottom surface adhesive layer 306. The bottom surface adhesive 306 is effective for maintaining the bonding strength at the point when the light accumulating laminate 300 adheres to the surface. This is true for surfaces with protrusions and indentations, or when bonded to places of high humidity, such as outdoors, or where it can be easily wetted by water from rain or snow.

With regard to the bottom surface adhesive, it is possible to use adhesives according to the prior art, with no particular limitation. For example, it is possible to use acrylic type adhesives, silicone type adhesives, rubber type adhesives, urethane type adhesives and the like. In view of water resistance and compliance properties, rubber type adhesives (eg NBR, etc.) may be mentioned as preferred formulations. Also, in many cases, conventional ground road materials are materials having low polarity characteristics, and therefore, the use of adhesives having low polarity characteristics such as silicone type adhesives or rubber type adhesives is preferable because their bonding properties are excellent.

There is no particular limitation with regard to the thickness of the bottom surface adhesive layer, for example the thickness may range from approximately 0.01 mm to approximately 0.5 mm, or approximately 0.03 mm to approximately 0.2 mm.

In order to protect the adhesive layer, a liner may be provided on the light accumulating laminate. With regard to this liner, it is a good choice as long as it is a liner commonly used in the adhesive tape industry and the like, and there are no restrictions on specific materials. Suitable liners include, for example, paper; Plastic materials such as polyethylene, polypropylene, polyester, or cellulose acetate; Or materials such as paper materials covered or laminated with such plastic materials. These liners can be used as they are and are good choices, but they are possible to be the materials obtained after a treatment has been performed to improve their release properties using silicon treatment or other methods.

With respect to the light accumulating laminate, it may also be desirable to include a functional layer such as a surface protective layer or a primer layer. In addition, this is an excellent choice if the general-use primer is coated on the surface to be adhered at the time when the light accumulating laminate is adhered to the material to be adhered. Typically, by such a primer treatment, the adhesion between the light accumulating laminate and the material to be adhered can be increased.

It is also possible to provide a hemispherical or pyramidal micro-structure (fine protrusions) on the surface (on part or on the entire surface) of the light accumulating layer. By providing such a fine micro-structure, it is possible to obtain an anti-slip effect or an anti-staining effect.

[Example]

Light accumulation layer

A layer of polyvinyl chloride (TUJ-7854, manufactured by Shinets Polymer Company) was prepared containing 30 parts by weight of light accumulating fluorescent material (GLL-300M, manufactured by Basic Specialty Science Company).

Manufacture of acrylic type white adhesive layer

10 parts by weight of acrylic resin 1 (methyl methacrylate (MMA) / butyl methacrylate (BMA) / dimethyl-amino-ethyl-methacrylate, DEMAEMA) copolymer-60: 34: 6 (weight ratio) With respect to an ethyl acetate solution having a molecular weight (Mw) of 68,000 and a Tg of 63 ° C. (calculated value), wherein the solids are 39%), and 50 parts by weight of pigment material 1 (white pigment material, DuPont) To Ti Pure R960 manufactured by (DuPont), titanium dioxide, 40 parts by weight of methyl iso-butyl ketone were added and, using a paint shaker (ARE250 manufactured by Tinky Company), It stirred for 10 minutes and obtained the pigment material premix solution.

Thereafter, 100 parts by weight of adhesive 1 (butyl acrylate (BA) / acrylonitrile (AN) / acrylic acid (AA) copolymer) having a composition ratio of 92: 3: 5 (as weight ratio), an acrylic type adhesive, where solvent The agent is ethyl acetate, with a weight average molecular weight of 360,000 and a Tg of −46 ° C. (calculated), the adhesive and the premix described above are mixed so that the pigment material is 40 parts by weight and the acrylic resin 1 is 8 parts by weight. Thus, a white adhesive composition material solution was prepared. For 100 parts by weight of adhesive 1, 0.2 parts by weight of crosslinker 1 (toluene solution of 1,1'-iso-phthaloyl-bis (2-methyl aziridine), wherein the solids content is 5%) ) Was added. The adhesive composition material described above was coated using a knife coater to the surface of the release paper formed from a base paper on which polyethylene was laminated on both sides, so as to have a thickness of 30 micrometers after drying, which was then 90 ° C. for 5 minutes. Dried at a temperature of and dried and crosslinked (cured).

Floor surface with adhesive layer

A rubber type adhesive (GRN-13B manufactured by Big technos Company) and a polyisocyanate crosslinker (Coronate L-55E manufactured by Nippon Polyurethane Industries) were used in a ratio of 100: 1 (weight ratio). Was mixed with toluene as a solvent, it was adjusted to approximately 30% solids, and using a knife coater, on the surface of the release paper formed from the base paper from which polyethylene was laminated on both sides, the thickness after drying was 30 It was coated to a micrometer, which was then dried at a temperature of 90 ° C. for 5 minutes, which was dried and crosslinked (cured).

Example  One

An adhesive type laminate was obtained by bonding and combining the acrylic type white adhesive layer and the bottom surface adhesive layer. A primer (N200 manufactured by Sumitomo Company) was coated and dried on the resultant light accumulating layer described above, and light accumulated by adhesion and combination through lamination to the acrylic type white adhesive layer of the above-described adhesive layer laminate. A laminate was obtained.

Example  2

The laminate was prepared as described in Example 1. Rear of polyvinyl chloride resin layer (TUJ-7854 manufactured by CINETS Polymer Company) containing 30 parts by weight of light accumulating fluorescent material (GLL-300M manufactured by Basic Specialty Chemicals Company) On the cotton, a primer (N-200 manufactured by Sumitomo Company) was coated and dried, and then a polyisocyanate crosslinker (Coronate L-55E manufactured by Nippon Polyurethane Industries) was mixed at 100: 1. Solution) was coated using a knife coater so as to have a thickness of 80 micrometers after drying, and it was dried to obtain a light accumulation laminate.

Example  3

The laminate was prepared as described in Example 1. On the rear face of the polyvinyl chloride resin layer (TUJ-7854 manufactured by the Shinnets Polymer Company) containing 30 parts by weight of a light accumulation fluorescent material (GLL-300M manufactured by Basic Specialty Chemicals Company), a primer (Sumitomo N-200 manufactured by the company) was coated and dried, and then rubber containing the bottom surface adhesive solution (50 parts by weight of white pigment material (BW9310 (Alkyd White Pigment Dispersion) manufactured by Sumitomo Company)). A solution obtained as a type adhesive (GRN-13B manufactured by Big Technos Company), and a polyisocyanate crosslinker (Coronate L-55E manufactured by Nippon Polyurethane Industries) were mixed in a 100: 1, knife coater Was coated so as to have a thickness of 80 micrometers after drying, and it was dried to obtain a light accumulation laminate.

Reference Practical Test 1: Measurement of Light Accumulation Performance

Both the black and white were printed and the sheet used for the concealment performance test was adhered to the light accumulating laminated material obtained according to Examples 1, 2 and 3, and according to the procedure of JIS Z 9107 6.3.2, And using a luminance measuring system to measure the afterglow luminance as the light accumulation capability of the corresponding black and white portions (after abruptly darkening after irradiating with the commonly used light source lamp D65 for 20 minutes at 200 Lux). It was. The bonded samples of Examples 1, 2 and 3 are shown in FIGS. 7A, 7B and 7C. The afterglow luminance values are shown in Table 1, and the luminance reduction ratio of the black portion is correspondingly shown in FIG.

TABLE 1

Adhesive property performance

The light accumulating laminate materials of Examples 2 and 3 were cut to 25 mm width, adhered to the mortar plates, and after 24 hours (1 day) and 1 week after in a moisture proof installation (65 ° C., 95%). The 90 degree peel force (N / 25mm) was measured by the digital force meter (made by Imada Company, Inc. each), and the adhesive characteristic was measured. Results for day 1 are correspondingly shown in FIG. 5. Similarly, results for one week are shown in FIG. 6 for two mortar surface finishes (flat / flat, and non-flat / wave). The value of both graphs is the adhesive strength (N / 25 mm + standard deviation).

Claims (5)

Light accumulation layer; And a laminate located on the light accumulating layer, the laminate comprising (i) a carboxyl radical containing (meth) acrylic type polymer, (ii) a white pigment, and (iii) an amino radical containing nonaromatic vinyl (meth ) Light accumulation laminate comprising acrylic type polymer. The light accumulating laminate according to claim 1, wherein the laminate comprises 25 to 150 parts by weight of a white pigment based on 100 parts by weight of a carboxyl radical-containing (meth) acrylic type polymer. The light accumulation laminate according to claim 1 or 2, wherein the laminate has a thickness in the range of 0.02 mm to 0.1 mm. The light accumulating laminate according to any one of claims 1 to 3, wherein the light accumulating layer comprises a light accumulating portion and a supporting portion. The light accumulating laminate according to any one of claims 1 to 4, further comprising a bottom surface adhesive layer, wherein the bottom surface adhesive is laminated to the light accumulating laminate.

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