JP2003327958A - Biodegradable luminous sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare a biodegradable luminous sheet which accumulates energy when irradiated with light, emits light in high brightness, has a long afterglow time, can produce a dark hall to exhibit an advertising function or a specific effect in the dark place, and can be attached to a balloon to fly the balloon while emitting light. <P>SOLUTION: A luminous composition having high brightness comprising an inorganic luminous fluorophor or an organic luminous phosphor and a transparent biodegradable resin is used. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a phosphorescent sheet which is soluble in water and biodegradable.

[0002]

2. Description of the Related Art Conventionally, a printed material, a material which is woven into a thermoplastic polymer and made into a film, which uses a phosphorescent material capable of displaying even in the dark, has an A coat layer on one side of a pure white roll paper, two layers of a light stabilizer, and There is known an optical paper (utility model registration No. 3012389) that is formed by sequentially stacking thick plastics and films, and having a cursor stop layer on the opposite surface, but these are soluble over time. However, because it does not biodegrade, we could not release the phosphorescent sheet by attaching it to the balloon from the viewpoint of environmental pollution. Also, it was not possible because the treatment after using the phosphorescent sheet was difficult due to the production at the venue.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a technique of a phosphorescent sheet which is biodegradable and does not attenuate the storability or brightness of the luminescent luminous body.

[0004]

[Means for Solving the Problems] In order to solve the above problems, this phosphorescent sheet is made of biodegradable resin, Sr and A.
20 ~ 200 phosphorescent powder for aluminate system including l
Although it is mixed in a weight percentage or is face-bonded to form a sheet. In the case of surface-attachment, a biodegradable phosphorescent sheet characterized in that a phosphorescent material is adhered to a biodegradable resin to form a phosphorescent material layer, and another water-soluble resin is heat-bonded, pressure-bonded or adhered. Is.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION As a base material sheet for the light-saving sheet of the present invention, treatment of plastic waste has become a major environmental problem. As one of the countermeasures, degradable resin has been in the spotlight, photodegradable resin that decomposes by light,
And two main biodegradable resins that are decomposed by microorganisms. The latter is mainly composed of natural materials such as starch and cellulose, and is further divided into chemically synthesized systems such as polycaprolactone, polylactic acid and polyvinyl alcohol, and microbial systems such as polycopolymers. Both are decomposed into low molecular weight compounds, and finally carbon dioxide and water.
Use a substance that has the characteristic of being soluble in water.

Therefore, as the substrate sheet of the light-saving sheet of the present invention, Kuraray water-soluble vinylon film "Claria" is used.
(Kuraray Co., Ltd.) uses polyvinyl alcohol as a raw material, and has resins and plastic films, and is effective in environmental issues, safety, etc. Popar of the raw material is obtained by saponifying polyvinyl acetate insoluble in water. . As a result of saponification, the number of hydrophobic vinyl ester groups in the molecule is decreased and the number of hydrophilic hydroxyl groups is increased, so that partially saponified poplar is water-soluble. If the degree of saponification is higher than that, the number of hydroxyl groups is increased and the substance becomes hydrophilic. On the other hand, the number of hydrogen bonds between hydroxyl groups increases, and _the number of bond portions into which water does not easily enter increases, so that the compound exhibits hot water solubility rather than cold water solubility. Partially saponified poplar with a saponification degree of about 88 mol% has the best water solubility, and the film shows cold water solubility. Films composed of highly saponified intermediate-saponified poplar and fully saponified poplar exhibit solubility in cold water.

Inorganic crystals are often used as host crystals of the light stabilizer used in the present invention, and white microcrystals such as sulfides, oxysulfides, and double oxides are used. As a host crystal, it has a high efficiency of receiving excitation energy by incident light and transmitting it to an activator, little deterioration during stool use, and chemically stable and easy to process into a composition like a paint. Etc. are preferred. Specifically, zinc sulfide, calciu, mousstrontium-based sulfide, strontium aluminate and the "Phosphor Handbook", and the 224th Proc. (Amiya, Honda, etc.) _, 229th (Masaaki Morita, etc.), 229th ₍
Sato, Toki et al.), The same 230th (Takaki et al.), The 24th
8 times (Matsuzawa, Takeuchi et al.) And 250 times (Koike et al.) And the like. If the base material contains transition metals such as Fe, Co, and Ni as impurities (in this case, called killer), the luminous efficiency is significantly reduced. Therefore, for zinc sulfide and the like, it is necessary to set these to several PPm or less. Organic substances can be used for the host crystal, and specific examples thereof include fluorescent dyes such as rhodamine and eosin, and fluorescent pigments such as rhodamine tungstate.

Examples of the phosphorescent agent of the phosphorescent sheet of the present invention include strontium aluminate (SrAl2O4: Eu, etc.)
Is mainly studied. For the composition, see JP 2000
-34480, "A divalent eurobium-activated alkaline earth metal aluminate bioluminescent phosphor, the chemical composition formula of which is RO.a (AI1-XGX) 2O3.bMnOn.
・ CB2O3 ・ dEu2 + (50, but R is at least one selected from the group consisting of alkaline earth metals such as Ba, Sr, and CMg, and Zn, and M is at least selected from Y, Sc, and Si. 1 or more), a, b, c, d, x are 0.3 ≦ a ≦ 8, 0 <b ≦ 0.2, 0.001 ≦ c ≦ 0.3, 0.00, respectively.
1 ≦ d ≦ 0.3, 0 ≦ x <1.0, which is disclosed as “photoluminescent phosphor,” containing at least one selected from yttrium oxide, scandium oxide, and silicon oxide. According to the disclosure, it was possible to "improve afterglow brightness and afterglow time at the same time", but as a further hydroxybutyrate / valerate film, for example, an ink containing a light stabilizer is printed on a substrate. A printed one, a film made by kneading a light stabilizer into a thermoplastic polymer, and A on one side of pure white roll paper
Known is a light-protecting paper (utility model registration No. 3012389) in which a coat layer, two light-absorbing agent layers, and a plastic film having a specific thickness are sequentially laminated, and a cursor stop layer is provided on the opposite surface. However, since they are insoluble in water and do not biodegrade,
At the event etc., I could not hang the animal light sheet on the balloon and fly it, so there is a need for an animal light sheet that dissolves in water and biodegrades, but since the animal light agent is oxidized by the water-soluble solvent, It loses shelf life and does not emit light.

The light stabilizer used in the present invention is not particularly limited as long as it accumulates light energy such as sunlight and electric light and emits light in a dark place, and various conventionally known ones can be used. Examples of such a material include zinc sulfide, zinc silicate, zinc sulfide, strontium sulfide, calcium tungstate, and the like, which are usually used in the form of fine particles having an average particle diameter of 0.1 μm to 5 μm.
It is 00 μm, preferably 100 μm to 500 μm. The mixing ratio of this phosphorescent agent and the resin binder can be selected according to the brightness of the resulting phosphorescent layer film, but if it is less than 50% by weight relative to the resin binder, the brightness is low and it is not suitable for normal use. However, if it exceeds 300%, it is not possible to obtain the brightness corresponding to the blended amount. Therefore, from the viewpoint of brightness and economical efficiency, the blending amount of the phosphorescent agent to the resin binder is 50 to 300% by weight. , Preferably, 100 to 25
It is recommended to set it to 0% by weight.

The photoluminescent agent used in the present invention is not limited in its color tone, such as green, white, red, orange, and yellow, which can be arbitrarily selected, such as a mixed color of two or more kinds thereof, in terms of both fluorescent light emission and luminous light emission.

As the luminescent agent, fluorescent agents such as FZ-2000 series (Shin Loihi Chemical Co., Ltd.) and SW-10 series (Shin Loihi Chemical Co., Ltd.), sulfurous sulfide and lead calcium sulfide, and a radio assotope fixed thereto. And Luminova, (Nemoto Special Co., Ltd.) and other phosphorescent agents. Further examples include optical brighteners such as Uvitex (Ciba Specialty Chemicals) 11Iumi, narl (Showa Denko) and Whitex (Sumitomo Chemical).

[0012]

EXAMPLES Next, the present invention will be described with reference to examples. At a banquet, you can attach a phosphorescent sheet to a rubber balloon, release the balloon in the night sky, and use it in the production of the venue. Also, it is easy to process after arranging with fresh flowers and it is widely used. I was able to do things.

Example 1 200 parts by weight of a resin binder (product name: Cranol, permanent glue Co., Ltd.) (100 parts by weight of solid content) was poured into a resin container having a diameter of about 100 mm and a depth of 15 mm, and 100 parts by weight of a phosphorescent agent was added. After mixing and dispersing, it was dried and peeled from the container to obtain a phosphorescent sheet.

Example 2 100 parts by weight of a resin binder (product name: Cranol, permanent glue Co., Ltd.) (solid content: 50 parts by weight) was poured into two resin containers A and B each having a diameter of about 100 mm and a depth of 15 mm. After drying, it is peeled off, the surface of A is coated with a phosphorescent agent, and the surface of B is coated with a resin binder 10 times.
After dropping about a drop, the surface on which the phosphorescent agent A was adhered was bonded to the surface on which about 10 drops of the resin binder B were joined and dried again to obtain a phosphorescent sheet after drying.

Example 3 100 parts by weight of resin binder (product name: Clanol, permanent glue, Inc.) (solid content: 50 parts by weight) was poured into two resin containers A and B each having a diameter of about 100 mm and a depth of 15 mm, After drying, it is peeled off, the surface of A is coated with a phosphorescent agent, and the surface of B is coated with a resin binder 10 times.
After dropping about a drop, the surface of the phosphorescent agent of A is attached to the surface of the resin binder of B about 10 drops, and thermocompression bonded,
I got a phosphorescent sheet.

Example 4 Diameter of about 100 mm, depth of 15 m
Approximately 1 g of phosphorescent agent and acetic anhydride 1-2 ml in a resin container of m
After addition and mixing, 3 g (solid name: 1.5 g) of a resin binder (product name: Cranol, permanent glue, Inc.) was added, mixed again, dried, and peeled from the container to obtain a phosphorescent sheet.

Example 5 Diameter of about 100 mm, depth of 15 m
3g (solid content 1.5g) of resin binder (product name: Clanol, Permanent Glue Co., Ltd.) in a resin container of m,
After adding 0.2 to 0.5 g of boric acid and mixing, 1 g of a phosphorescent agent was added, and the mixture was stirred, dried and peeled from the container to obtain a phosphorescent sheet.

[0018]

According to the present invention, by using a biodegradable (environmentally friendly) phosphorescent sheet, it is attached to a rubber balloon and released at an event, a wedding reception, etc., a molded article in which the phosphorescent sheet is entangled, or a phosphorescent sheet. After directing with the sheet itself, it is possible to use even if it is not possible to collect, and the range of production has expanded.

Claims (3)

[Claims] 1. A biodegradable phosphorescent sheet comprising a phosphorescent material and a biodegradable resin mixed to form a sheet.
2. A biodegradable phosphorescent sheet, characterized in that a phosphorescent material surface is adhered to a biodegradable resin to form a phosphorescent material layer, and another water-soluble resin is heat-bonded, pressure-bonded or adhered. . 3. The phosphorescent material according to claim 1, wherein Sr and
It is characterized in that it is an aluminate-based material containing Al and is made of polyvinyl alcohol-based resin as a biogenic resin.