JP2005314569A - Composition for fluorescent resin and fluorescent resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for an inexpensive and easy to handle composition for fluorescent resin and a fluorescent resin using the same. <P>SOLUTION: A composition including a dialkoxy anthracene, a photocationic polymerization initiator and a cationically polymerizable compound is cured with UV rays of 366 nm, then a part of the cured product is radiated with UV rays of 254 nm to eliminate the fluorescence of the radiated part thereby providing a fluorescent resin that can display information, for example, arbitrary characters, figures and the like. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a composition for a fluorescent resin containing dialkoxyanthracene, a fluorescent resin obtained by curing the composition, and an information recording method using the composition.

It is known to display a display body drawn with a fluorescent light-emitting paint by emitting light using a black light. Moreover, although it is known that a dialkoxyanthracene compound is used as a sensitizer of a photopolymerizable compound, an example using it for a fluorescent resin is not known.
JP 2000-204284 A

  However, fluorescent paints are expensive and problematic for industrial use in large quantities. In addition, to use these fluorescent paints for display, it is necessary to draw or print with a pen, etc., and the solvent used to dissolve the paint is released into the atmosphere at the time of drying and may cause environmental pollution. There was sex.

  As a result of intensive studies on the physical properties of dialkoxyanthracene, the present inventor has found that a resin obtained by curing a cationically polymerizable compound containing dialkoxyanthracene with UV having a specific wavelength has fluorescence, and further has a specific wavelength. It was found that the fluorescence presumed to be unique to dialkoxyanthracene disappears by irradiating UV, and the present invention was completed.

That is, the gist of the present invention is as follows.
(1) A composition for a fluorescent resin containing a dialkoxyanthracene, a cationic photopolymerization initiator and a cationically polymerizable compound.
(2) The dialkoxyanthracene is 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene or 9,10-bis (2-ethylhexyloxy) anthracene in (1) The composition for fluorescent luminescent resin of description.
(3) The composition for fluorescent light-emitting resins according to (1), wherein the cationic photopolymerization initiator is a sulfonium salt or an iodonium salt.
(4) The composition for a fluorescent light-emitting resin according to (1), wherein the cationically polymerizable monomer is an alicyclic epoxy compound, an aromatic glycidyl compound, an epoxy-modified silicone or vinyl ether.
(5) A fluorescent resin, wherein the composition for fluorescent resin according to any one of (1) to (4) is cured with UV light of 366 nm.
(6) A fluorescent light-emitting resin, characterized in that the composition for fluorescent light-emitting resin according to any one of (1) to (4) is applied to a substrate and then cured with UV light of 366 nm.
(7) By curing the composition for fluorescent light-emitting resin according to any one of (1) to (4) with UV light of 366 nm, and then irradiating a part of the cured product with UV light of 254 nm A fluorescent light-emitting resin characterized by quenching the fluorescence of the irradiated portion.
(8) The composition for fluorescent light-emitting resin described in any one of (1) to (4) is applied to a substrate, cured with UV light at 366 nm, and then UV light at 254 nm using a photomask. , And quenching the fluorescence of the irradiated part.
(9) An information recording resin obtained by curing the fluorescent light-emitting resin composition according to any one of (1) to (4) with UV light of 366 nm.
(10) By curing the composition for fluorescent light-emitting resin according to any one of (1) to (4) with UV light of 366 nm, and then irradiating a part of the cured product with UV light of 254 nm An information recording method comprising quenching fluorescence of the irradiated portion.
(11) The composition for fluorescent light-emitting resin according to any one of (1) to (4) is applied to a substrate, cured with 366 nm UV light, and then 254 nm UV light using a photomask. , And quenching the fluorescence of the irradiated portion.
(12) A method of emitting fluorescence by irradiating the fluorescent light-emitting resin according to any one of (5) to (8) with black light.

The production of the fluorescent film of the present invention is very easy, does not use any environmentally dangerous solvent, and the obtained film can be used as an image display by irradiation with black light.

The composition for fluorescent light-emitting resin of the present invention is a composition containing dialkoxyanthracene, a photocationic polymerization initiator, and a cationically polymerizable compound.
The dialkoxyanthracene of the present invention is a compound having a structure represented by the following formula 1.

(In the formula, R represents an alkyl group, an aryl group, an aralkyl group, an allyl group, a glycidyl group, or a hydroxyalkyl group.)
Examples of the alkyl group in the above formula include a methyl group, an ethyl group, a butyl group, an amyl group, and a 2-ethylhexyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Examples of the aralkyl group include a benzyl group and a 2-phenylethyl group. Examples of the hydroxyl group include a 2-hydroxypropyl group, a 2-hydroxylbutyl group, and a 2-hydroxy-3-butoxypropyl group.

    The photopolymerization initiator of the present invention includes, as a sulfonium salt, S, S, S ′, S′-tetraphenyl-S, S ′-(4,4, ′-thiodiphenyl) disulfonium bishexafluorophosphate, Examples include diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate. For example, UVI6992 manufactured by Dow can be used. On the other hand, as the iodonium salt, 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, 4-isopropylphenyl-4'-methylphenyliodonium tetrakispentafluorophenylborate For example, Ciba CGI-552 and Rhodia 2074 can be used.

    Examples of the cationically polymerizable compound of the present invention include epoxy compounds and vinyl ethers. Commonly used epoxy compounds are alicyclic epoxy compounds, aromatic glycidyl compounds, and epoxy-modified silicones. Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate. For example, UVR6105 and UVR6110 manufactured by Dow can be used. . Aromatic glycidyl compounds include 2,2′-bis (4-glycidyloxyphenyl) propan. Examples of the epoxy-modified silicone include UV-9300 manufactured by Toshiba GE Silicone. Examples of the vinyl ether include methyl vinyl ether, vinyl ethyl ether, vinyl isobutyl ether, and vinyl-2-ethylhexyl ether.

    The composition for fluorescent light-emitting resin of the present invention is a composition comprising the above cationic polymerizable compound, a cationic polymerization initiator, and dialkoxyanthracene. The content of the cationic polymerization initiator is in the range of 0.01% to 10% by weight, preferably 0.3% to 3% by weight, based on the cationically polymerizable compound. If it is 0.01% by weight or less, the curing rate is too slow, and if it is 10% by weight or more, the properties of the resin are adversely affected. On the other hand, the content of dialkoxyanthracene is in the range of 0.01% to 10% by weight, preferably 0.3% to 3% by weight, based on the cationically polymerizable compound. If it is 0.01% by weight or less, the fluorescence intensity may be weakened, and if it is 10% by weight or more, the properties of the resin are adversely affected.

    In curing the composition for the fluorescent light-emitting resin, an arbitrary shape can be selected, but it is convenient and preferable to handle it to form a film or the like.

    The present fluorescent composition is formed into a film as follows. That is, a composition for fluorescent light-emitting resin is applied on a substrate using a bar coater. The substrate is not particularly limited, such as a film, paper, aluminum foil, or metal. As the film, a polyester film, for example, Toyo Rayon Luminer can be used. The film thickness of the Luminer film is usually about 100μ. The rod number of the bar coater to be used is not specified, but a bar coater having a rod number such that the film thickness is several μ to several tens μ is used.

  Curing of the composition of the present invention is performed by irradiation with 366 nm UV light. When the composition is irradiated with UV light, a solid material is obtained, and when the applied material applied to the substrate is irradiated, a film is obtained. Here, UV irradiation at 366 nm means that UV irradiation is performed using a light source having a substantial light intensity peak mainly at 366 nm. Specifically, a lamp containing 366 nm light, for example, a metal halide lamp, a fusion D bulb can be used. The irradiation time depends on the intensity of the lamp, but if it is a solid material, it will be cured in several minutes to several tens of minutes.

    Next, by irradiating a part of the polymer with UV light having a wavelength of 254 nm, the fluorescence emission property of the irradiated portion disappears, so that information such as arbitrary characters and figures can be recorded. Here, the UV irradiation of 254 nm means that UV irradiation is performed using a light source having a substantial light intensity peak mainly at 254 nm. In order to irradiate a part of the polymer with UV light, a method of irradiating with UV of 254 nm by applying a photomask can be used. The lamp used in this case can be a strong lamp around 254 nm, such as a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, or a fusion H bulb. In this way, a film that emits a fluorescent image can be created.

    When this fluorescent film is irradiated with black light, the fluorescence at the 254 nm irradiated portion disappears and only the non-irradiated portion emits fluorescence, so that it can be used for image display.

  EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited by the following description examples, unless the meaning is exceeded.

“Creation of fluorescent film” Dow epoxy compound UVR-6105 5g, Dow sulfonium type initiator UVI-6992 0.12g, bis (2-ethylhexyl) anthracene 0.02g are mixed, and a luminaire is used using a bar coater. Apply on a film (film pressure 100μ) to make a 12μ thick coating layer. Next, UV irradiation of 366 nm (intensity 0.2 mw / cm 2) was irradiated for 2 minutes to cure the whole. Next, the film was masked with a photomask obtained by cutting out an aluminum foil, and irradiated with UV light of 254 nm for 10 minutes.
"Image display using black light"
When the fluorescent film prepared in Example 1 is irradiated with black light, an image as shown in FIG. 1 can be obtained. In the UV irradiation part, the dialkoxyanthracene compound is dimerized to quench the fluorescence, and the text part is dark, and since the UV is not irradiated, the character part is brightly fluorescent by black light irradiation.

  The fluorescent light-emitting resin of the present invention can be produced at low cost, can record and display information such as arbitrary characters and figures, and can be used for various applications.

It is the figure which showed the fluorescence emission of the fluorescence resin by this invention. In addition, the height of the character in a figure is about 2 cm.

Claims (12)

A composition for a fluorescent resin containing a dialkoxyanthracene, a cationic photopolymerization initiator and a cationically polymerizable compound. The fluorescence according to claim 1, wherein the dialkoxyanthracene is 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, or 9,10-bis (2-ethylhexyloxy) anthracene. Composition for luminescent resin. The composition for a fluorescent light-emitting resin according to claim 1, wherein the cationic photopolymerization initiator is a sulfonium salt or an iodonium salt. The composition for a fluorescent light-emitting resin according to claim 1, wherein the cationic polymerizable monomer is an alicyclic epoxy compound, an aromatic glycidyl compound, an epoxy-modified silicone, or vinyl ether. A fluorescent light-emitting resin, wherein the composition for a fluorescent light-emitting resin according to claim 1 is cured with UV light of 366 nm. A fluorescent light-emitting resin, characterized in that the composition for fluorescent light-emitting resin according to any one of claims 1 to 4 is applied to a substrate and then cured with UV light of 366 nm. The composition for a fluorescent light-emitting resin according to any one of claims 1 to 4 is cured with 366 nm UV light, and then the irradiated part is irradiated with 254 nm UV light. Fluorescent light-emitting resin characterized by quenching the fluorescence. The composition for fluorescent light-emitting resin according to any one of claims 1 to 4 is applied to a substrate, cured with UV light of 366 nm, and then irradiated with UV light of 254 nm using a photomask. Fluorescent light-emitting resin characterized by quenching the fluorescence of the irradiated part. An information recording resin obtained by curing the composition for a fluorescent light-emitting resin according to any one of claims 1 to 4 with UV light of 366 nm. The composition for a fluorescent light-emitting resin according to any one of claims 1 to 4 is cured with UV light of 366 nm, and then the irradiated part is irradiated with UV light of 254 nm. A method for recording information, wherein the fluorescence of the light is quenched. The composition for fluorescent light-emitting resin according to any one of claims 1 to 4 is applied to a substrate, cured with UV light of 366 nm, and then irradiated with UV light of 254 nm using a photomask. A method of recording information, wherein the fluorescence of the irradiated portion is quenched. A method for emitting fluorescence by irradiating the fluorescent light-emitting resin according to any one of claims 5 to 8 with black light.

Images