JPS5849779A - Transparent green light-emitting material and photo- conversion material - Google Patents

Abstract

PURPOSE:To obtain the titled light-emitting material transparent in the visible wavelength range, and having excellent light-emitting property and high stability and weather resistance, by adding a specific amount of a light-emitting substance obtained by the reaction of a specific amount of a water-soluble salt of Tb, etc. with 5-sulfo-salicylic acid, etc., to a water-soluble polymer. CONSTITUTION:The objective light-emitting material can be obtained by adding a light-emitting substance obtained by the reaction of 1mol of 5-sulfosalicylic acid or 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt with 1/3-1mol of a water-soluble salt of Tb or (Tb1-xMx)(M is Y, la or Gd; 0<x<=0.9), to a water- soluble polymer (preferably PVA or polyvinyl pyrrolidone) in an amount of 0.05-12wt%. The above material can be converted to photo-conversion material by applying to the surface of a substrate which is trnsparent preferably in the visible wavelength range, e.g. soda glass, acrylic resin, etc., and insolubilizing by crosslinking. EFFECT:Suitable for mass production. USE:Expected to be used as a light-emitting material, displaying material, sensitizer, photocell, material for detecting the intensity of excitation source, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a transparent green luminescent material containing a luminescent substance consisting of 5-sulfosalicylic acid or Tyrone and Tb or (TbneyxMX), and a light conversion material using the same.

Conventionally, systems in which rare earth compounds are contained in poly-7 are known, as shown in US Pat. No. 4,037,172, etc., in which rare earth chelate compounds are used.

However, such systems use luminescent components that are inherently extremely poor in photostability, such as β-diketone type chelate of europium, so they cannot be applied industrially from the viewpoint of weather resistance and durability. has a fatal flaw. In addition, in order to obtain a chelate compound, 1. It is necessary to repeat processes such as recrystallization and purification, which poses problems in terms of operability and yield.

The present invention overcomes the problems mentioned in 1.
The object of the present invention is to provide a transparent green luminescent material and a light conversion material that are transparent to light having a wavelength of 410 to 800 nm, have excellent photostability and luminous ability, and are highly suitable for mass production.

- As a result of intensive research by the present inventors to obtain a transparent luminescent material with the above-mentioned characteristics, it was found that a transparent luminescent material obtained by combining a specific luminescent substance and a specific polymer has sufficient practical value. We have discovered that a certain light-converting luminous material can be used, and have completed the present invention.

That is, 1/3 mole to 1 mole of Tb or (Tb
A luminescent material made of a water-soluble polymer and a luminescent substance obtained by reacting a water-soluble salt of (XMX) (where M is at least one selected from Y, 'La, and Ga) and a water-soluble polymer. The present invention provides a transparent green light-emitting material, which is a transparent green light-emitting material, and is characterized in that the light-emitting substance is completely impregnated with the light-emitting substance in an amount of 0.05 to 12% by weight.

Furthermore, the present invention provides a light conversion material characterized in that the transparent green light emitter described above is provided on a substrate.

Incidentally, Tiron is a trade name meaning 1,2-dihydroxybenzene-3,5-disulfone disodium salt.

The transparent green light emitter and light conversion material of the present invention extremely effectively exhibit the green light emission characteristic of terbium ions, particularly under long wavelength ultraviolet light (320 to 370 nm). Furthermore, it has the great feature of effectively exhibiting the green luminescence characteristic of terbium ions even with short wavelength light (370 nm' to 400 nm light) in sunlight. In addition, it has great advantages from a functional and industrial standpoint, such as ease of production, mass productivity, and ease of molding into thinner films and larger areas.

In addition, since the luminescent material obtained by the present invention is colorless and transparent, it is extremely excellent in maintaining the purity of the luminescent color, and when used in combination with other substrates, it has the great advantage that the properties of the substrate, etc. can be used as they are under normal conditions. , and is also extremely excellent in terms of emission intensity. Moreover, the transparent green luminescent material obtained by the present invention is rich in thermal or chemical stability and greatly exceeds conventional β-diketone type chelates in terms of weather resistance.

In the present invention, the luminescent substance is a water-soluble substance obtained by reacting 173 mol to 1 mol of a water-soluble salt of Tb or (Tb1-XMX) with 1 mol of 5-sulfosalicylic acid or Tyron. Tbl-XMX) is 1/
If the amount is less than 3 moles, transparency will be significantly impaired;
If it exceeds a molar amount, the luminescence intensity of the transparent green light emitter will decrease significantly, which is not preferable. , In addition, in (TbxM, x), M is at least one type selected from Y, La, and Gd, and by using this solid M as the second component, the cost can be reduced and improved while having a large effect on the light emitting function. Not only is it possible to obtain a transparent luminescent polymer composition that does not give x-
1, that is, there are even cases where a synergistic effect appears, especially in terms of luminescence intensity, compared to the case of using Tb alone. A particularly preferable M is La.

In this (Tb knee X town), X satisfies O<x≦0.9, and when x>0.9, the emission intensity decreases significantly, which is not preferred in practice.

A more preferable range of X is O<x≦0.8, and an even more preferable range of X is O<x≦0.6.

Further, by using M in the composite, the effect of increasing weather resistance stability also appears.

What should be noted here is that M of the present invention can exhibit a unique synergistic effect even though it does not have an emission level by itself except for Gd. Furthermore, in the case of Gd, although it itself has an emission level, it can exhibit a unique synergistic effect despite the large difference between it and the emission level of Tb.

In the present invention, water-soluble polymers include, for example, cellulose derivatives such as carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and glycol xylene, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid and its copolymers, polymethacrylic acid, and Examples include copolymers thereof, polyethylene oxide, etc., and those having these as main structures, but it is preferable to select a combination of a light emitting substance and a polymer depending on the purpose. Preferred water-soluble polymers include polyvinyl alcohol and polyvinylpyrrolidone.

In the present invention, the weight ratio of the luminescent material to the water-soluble polymer is 0.05 to 12% by weight.

In this range, both the transparency and luminous intensity of the transparent green light emitter can become extremely remarkable. That is, when the weight ratio is less than 0.05% by weight, the luminous ability is poor in practical terms. Moreover, when the weight ratio exceeds 12% by weight, transparency is significantly impaired. Therefore, transparency can only be achieved by satisfying the weight ratio of 0.05 to 12% by weight, and a transparent luminescent material having a practically satisfactory luminous ability can be obtained. A preferred range of weight ratio is 0.5 to 10% by weight, and a more preferred range of weight ratio is 0.8 to 10% by weight.

The transparent green light emitter of the present invention contains 1/3 to 1 mole of Tb or (Tb to -XMx) water-soluble salts (e.g. chloride, nitrate, acetic acid) per mole of 5-sulfosalicylic acid or Tyron. It can be easily produced by reacting a salt, etc.) in pure water, adjusting the pH to 5 to 9, mixing it with the water-soluble polymer described above, and then drying it. Also, p
It can also be easily produced by drying a powdered luminescent material obtained from a reaction solution after H adjustment by means such as evaporation or evaporation to dryness, weighing an appropriate amount, dissolving it in a water-soluble polymer solution, and drying it. . It can also be easily produced by carrying out the above-mentioned reaction in a water-soluble polymer solution and then directly drying it. Therefore, it is possible to easily produce a transparent luminescent material with excellent transparency and luminescent function in large quantities, and it has great industrial significance.

The transparent green light-emitting material obtained by the present invention can be easily processed into a uniform sheet or film of any shape and used. Moreover, it can also be used as a paint-like luminescent material.

Furthermore, it is noteworthy that a transparent luminescent polymer composition was obtained which had excellent visible transmittance in the wavelength range of 410 to 800 nm, had no absorption maximum, and had excellent luminescent ability.

The light conversion material referred to in the present invention is one in which the above-mentioned transparent green light emitting material is provided on a substrate, and especially when provided on a transparent substrate, the light emitting material and the substrate can become a uniform transparent light emitting material. It has this great feature.

The transparent green light emitting material of the present invention has excellent moldability, and in addition, because of its high moldability, it also has the revolutionary property of being able to obtain a flexible transparent light emitting material with a large area. ing. Furthermore, it can be used as a transparent light conversion material by coating on a suitable substrate.

The substrate may be selected depending on the purpose from those that do not absorb the emitted color, but particularly when a transparent substrate is selected, the luminous effect is excellent. Furthermore, such transparent substrates include inorganic glasses such as soda glass, non-fluorescent glass, quartz, phosphate glass, and boric acid glass, and acrylic glasses such as polymethyl methacrylate-1 and its copolymers. Examples include resins, styrene resins such as polyethylene and copolymers thereof, epoxy resins, polycarbonate resins such as diethylene glycol bisallyl carbonate, polyesters, polyethylene and copolymers thereof, silicone resins, and the like. Preferred transparent substrates are 410-8
Particularly preferred are those having an absorption in the visible range of 0.00 nm and a transmittance of 90% or more.

Moreover, by having such properties, it exhibits remarkable characteristics when used as a transparent light emitter.

Furthermore, it is also possible to use a transparent substrate as a binder.

The method for producing the light conversion material of the present invention is to apply a luminescent substance-dissolved polymer aqueous solution obtained according to the above-mentioned method for producing a transparent green luminescent material onto a substrate by a well-known technique such as spraying or casting, and then dry it with hot air. Alternatively, it can be easily obtained through air drying. In addition, since it can be applied by coating, it can easily be applied to a large area, which has great industrial significance.

Further, by performing an insolubilization treatment using techniques such as post-crosslinking, it is possible to obtain a form with higher practicality.

The transparent luminescent polymer composition and light conversion material obtained in this way are transparent in the visible range and have excellent weather resistance, moldability, and wide applicability such as large-area formation compared to conventional systems. This is an epoch-making transparent luminous material.

The transparent green light emitting material and light conversion material of the present invention exhibit light emission characteristic of terbium in the green range, and can be used in the fields of light emitting materials, lighting materials, display materials, photographic materials, sensitizing materials, decorative materials, and photovoltaic cells. It is promising as a material.

In addition, a light conversion material structure in which a transparent luminescent material is provided on a substrate can be used as an optical waveguide for emitting light by appropriately selecting the substrate, and is promising as a material for position detection and excitation source intensity detection.

Hereinafter, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 3 50 ml of polyvinyl alcohol (Gohsenol NH-26, manufactured by Nippon Gosei Kagaku) was added to 500 cc of pure water, stirred, and immediately heated and kept at 90° C. to completely dissolve.

Next, the compositions shown in Table 1, &1 to 3 were reacted, and the pH was adjusted to 7. The obtained water-soluble luminescent substance was added to the above polymer aqueous solution, and the pH was maintained at 7 with sufficient stirring.

Table 1 Thereafter, the transparent luminescent films shown in Tables 2, &4 to A6 were obtained by casting the luminescent substance-containing polymer solution obtained above. The contents of A4 to A6 in the film were 4.1%, 5.4%, and 9.1% by weight, respectively.

When each film was measured using a spectrophotometer, the result was 41
No absorption band was observed in any case between 0 and 800 nm. Moreover, each film obtained was completely colorless, transparent, and smooth.

Table 2 Next, the luminescence intensity was measured with a fluorescence spectrophotometer and the result was A4.
When the emission intensity of the film was set as 100, results as shown in Table 2 were obtained. Also, the optimal excitation wavelength is 343 nm
Met.

Comparative Examples 1-2 Table 1 of Example 1. &9 to &9 in Table 4 in exactly the same manner as in Example 1 except that &1 is changed as shown in 7 to &8 in Table 3.
Each film shown in Section 10 was obtained.

In the film A10, precipitation of a luminescent substance was observed.

Further, when the A9 film was measured using a fluorescence spectrophotometer, the results shown in Table 4 were obtained, assuming that the emission intensity of the A4 film was 100.

Table 3 Examples 4 to 6 Examples 1 to 30 Each transparent luminescent film shown in Table 6 was obtained in exactly the same manner as in Example 1 except that Table 1 was changed as shown in Table 5.

The tyronterbium contents in each film shown in Table 6 are 1.89 (A 14 ) and 2.52 (A 15 ), respectively.
).

It was 4.40 (Al 6)% by weight.

When each of the obtained films was measured with a spectrophotometer, the result was 41
The transmittance in the range from 0 to 800 nm was 90% or more, and no absorption band was observed in any case. Moreover, the obtained film had good smoothness and was colorless and transparent.

Next, we measured the luminescence intensity and found that the A14 film was 10
When it was set to 0, results as shown in Table 6 (1) were obtained.

Comparative Examples 3-4 Table 8. Films shown in AI 7 to 18 were obtained. For the A20 film, precipitation of a luminescent substance was observed.

Also, A when the emission intensity of A14 film is taken as 100.
The relative luminescence intensity of film No. 19 was as shown in Table 8.

Examples 7-9 Table 1 of Example 1. Exactly the same as Example 1 except that A1 was changed as shown in A21 to A23 of Table 9. The films shown in Table 10 were obtained using the same method.

Table 9 Each film obtained had a transmittance of 90% or more in the range of 410 nm to 800 nm, and no absorption band was observed in this range.

Further, the film was highly smooth and colorless and transparent.

Further, Tb/Ln is 0.710.3.

Next, when the luminescence intensity of this film was measured, relative luminescence intensities as shown in Table 10 were obtained when the film of Example 1 was taken as 100. Further, the optimum excitation wavelength was 343 nm in all cases, and the content was 5.4% by weight.

Table 10 Example 10 and Comparative Example 5 Table 1 of Example 2. Each film was obtained in exactly the same manner as in Example 2, except that Boiled 2 was changed as shown in Tables 29 to 34 of Table 11.

The obtained film had a transmittance of 90% or more in the visible range and was colorless and transparent. Furthermore, when the emission intensity was measured, the results shown in FIG. 1 were obtained. (Tbl-XLa
When x>0.9 of X), the film of Example 2 (X=O
The relative luminescence intensity when the luminescence intensity of ) was set to 100 decreased significantly. The content was 5.4% by weight.

Examples 11 to 16 and Comparative Examples 6 to 7 Each of the films shown in Table 13 was obtained by dissolving the luminescent substances shown in Table 12 in the same polymer solution as in Example 1 and then performing a drying treatment.

Table 12 For A50, precipitation of the luminescent substance was observed and a transparent luminescent material could not be obtained.
A1.410~800n for ~&49 films
The transmittance in m was 90% or more, and it was colorless and transparent with no absorption band in this range.

Next, when the luminescence intensity was measured, the results shown in Table 13 were obtained, assuming that the luminescence intensity of the A47 film was 100.

Table 13 Examples 17-19 Example 2. Example 5. The luminescent material-containing polymer solutions obtained in A31 of Example 10 were added to A51 to A53 in Table 14, respectively.
The substrate shown in (thickness 21111, width 5Q+n.

After applying it thinly and uniformly to a length of 300111), a drying treatment was performed to obtain a light conversion material. Each of the obtained light conversion materials is colorless and transparent and integrated with a transparent substrate in each case,
When irradiated with black light, very strong green luminescence was observed.

In addition, strong green luminescence was observed when exposed to sunlight.

Table 14 Examples 20 to 21 When the transparent green light emitters obtained in Example 2 and A31 of Example 10 were placed in a sunshine weather meter and an exposure test was conducted, it was found that Example 10. A31
It was found that the system showed little deterioration in luminescence intensity. The results were as shown in Table 15.

Table 15 Examples 22-24 Example 2. To each luminescent substance-dissolved polymer solution obtained in Example 5 and Example 8, 1.2 g of diglycidyl acetate crosslinker Epiol (31-100 (manufactured by NOF) was added.
After adding , each film was obtained in the same manner as in Example 2.

Next, each film was heat-treated at 130 to 145° C. for 930 minutes to 60 cycles to obtain each film shown in Table 16.

It was confirmed that all of the obtained films were water-insoluble.

Furthermore, it was observed that the transmittance 2 emission intensity in the wavelength range of 410 to 800 nm was no different from that of the system without crosslinking treatment.

[Brief explanation of the drawing]

Figure 1 shows 5-sulfosalicyl (T) in Example 10.
In a polyvinyl alcohol transparent film containing 5.4% by weight of
It is a graph showing the relative luminescence intensity change when combined with. The luminescence intensity when La is not used is assumed to be 100, and the relative luminescence intensity with respect to it is plotted on the vertical axis and the molar concentration X of La is plotted on the horizontal axis. Applicant Asahi Dow Co., Ltd. Agent Yutaka 1) Yoshio

Claims (9)

[Claims] (1) 1/3 mol to 1 mol of 'rb or (TbneyXMx) per 1 mol of 5-sulfosalicylic acid or Tyrone
A luminescent substance obtained by reacting a water-soluble salt of
≦0.9) and a water-soluble polymer, and the transparent green luminescent material is characterized in that the luminescent substance is contained in an amount of 0.05 to 12% by weight. (2) The transparent green light emitter according to claim (1), wherein the water-soluble polymer is polyvinyl alcohol or polyvinylpyrrolidone. (3) A transparent green light emitter according to claim 11, wherein the luminescent polymer composition is insolubilized by crosslinking. (4) A luminescent substance obtained by reacting 1/3 mol to 1 mol of Tb or a water-soluble salt of (Tb□--4) with 1 mol of 5-sulfosalicylic acid or Tyrone (where M is Y,
At least one type selected from La and Ga, 0〈x≦0
9) A luminescent polymer composition comprising a water-soluble polymer and a transparent green luminescent material containing 0.05 to 12% by weight of the luminescent substance on a substrate. A light conversion material. (5) The light conversion material according to claim (4), wherein the substrate is transparent in the visible range. (6) The light conversion material according to claim (4), wherein the substrate is soda glass, non-fluorescent glass, or quartz. (7) The light conversion material according to claim (4), wherein the substrate is an acrylic resin, an acrylic resin, a polycarbonate resin, an epoxy resin, or a polyethylene resin. (8) The light conversion material according to claim (4), wherein the water-soluble polymer is polyvinyl alcohol or polyvinylpyrrolidone. (9) The light conversion material according to claim (4), wherein the transparent green light emitter is insolubilized by crosslinking.