JP2007230955A - Copolymerizable rare earth metal complex, method of producing the same and resin composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copolymerizable rare earth metal complex which undergoes graft copolymerization with a matrix resin, particularly an EVA resin, to form a composition in which a rare earth metal complex powder is chemically uniformly dispersed in a synthetic resin. <P>SOLUTION: The rare earth metal complex has an organic carboxylic acid derivative having a graft-copolymerizable ethylenically unsaturated bond as a ligand. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention provides a stable composition by graft copolymerization with a matrix resin when a composition of a rare earth metal complex and a synthetic resin is used as a solar cell sealing material, a light emitting resin panel, a fluorescent film forming material, or the like. The present invention relates to a novel rare earth metal complex capable of forming a product, a production method thereof, and a resin composition using the same.

  Rare earth metals are usually most stable in oxidation state 3, but Eu, Yb, Sm can also form complexes of oxidation state 2, and Ce forms a tetravalent compound. The bond is highly ionic and tends to have a higher coordination number, so after reacting with the anionic ligand necessary to neutralize the positive charge (usually 3+), further neutral organic A rare earth metal complex can be obtained by reacting a ligand.

And so far, many rare earth metal complexes having, for example, C ₅ H ₅ , C ₅ (CH ₃ ) ₅ and C ₈ CH ₈ as neutral organic ligands are known, and some of them are compounds Are used as synthetic intermediates, polymerization catalysts, and the like (see Non-Patent Document 1). Many rare earth metal complexes having cyclopentadienyl, pentamethylcyclodienyl, cyclooctatetraene, bipyridyl, and phenanthroline are also known.

  As a result of recent progress in research on the development of conjugates of organic compounds and metal ions, NMR chiral shift reagents containing rare earth metal complexes with 6- to 8-dentate amino acid derivatives as active ingredients An optical resolution reagent (see Patent Document 1), a complex of an aromatic carbonyl compound such as naphthaldehyde, acetonaphthone or 10-methylacridone and a metal ion such as magnesium ion, lutetium ion, ytterbium ion or scandium ion. A light emitting material (see Patent Document 2) is proposed.

  On the other hand, when the phosphor powder is mixed with a resin material to form a light-emitting panel, or when the phosphor is mixed with a matrix resin and a solvent to form a phosphor film forming composition, the resin material or the matrix resin is ethylene. -It is known to use a vinyl acetate copolymer (hereinafter referred to as EVA) (see Patent Documents 3 and 4).

  In addition, the present inventors previously used a fluorescent rare earth metal complex powder that absorbs light of 450 nm or less and emits light in the visible region, and uniformly disperses it in the EVA resin and uses it as a solar cell sealing material. Proposed (see Patent Documents 5 and 6).

  By the way, when using the phosphor powder dispersed in the EVA resin matrix in this way, until now it has been made a uniform composition by physical dispersion, but if this can be chemically dispersed, it becomes more uniform. In spite of being able to make a stable composition, such a composition has not been known so far.

JP 2002-20358 A (Claims and others) JP 2003-183639 A (Claims and others) JP 2004-249644 A (claims and others) JP-A-8-102257 (Claims and others) Japanese Patent Application No. 2005-118666 (Claims and others) Japanese Patent Application No. 2005-120126 (Claims and others) "Fourth Edition Experimental Chemistry Lecture 18 Organometallic Complex", published by Maruzen Co., Ltd., The Chemical Society of Japan, p. 36-48

  In the present invention, when a rare earth metal complex powder is used as a composition uniformly dispersed in a synthetic resin, a chemically uniform dispersed composition is formed by graft copolymerization with a matrix resin, particularly an EVA resin. Therefore, the present invention has been made for the purpose of providing a rare earth metal complex having copolymerizability.

  In order to obtain a fluorescent rare earth metal complex that can form a stable composition by chemically reacting with a matrix resin when mixed with a synthetic resin to form a composition, the present inventors have made extensive studies. As a result, by introducing an organic compound derivative capable of graft copolymerization with a matrix resin, that is, an organic carboxylic acid derivative having an ethylenically unsaturated bond capable of graft copolymerization, as the ligand of the fluorescent rare earth complex, The inventors have found that it can be achieved, and have reached the present invention based on this finding.

  That is, the present invention relates to a copolymerizable fluorescent rare earth metal complex having an organic carboxylic acid derivative having an ethylenically unsaturated bond that can be graft copolymerized as a ligand, an organic solvent and an inorganic acid. Suspend the rare earth metal oxide powder in the mixture, heat-react until a homogeneous solution is formed, and then in the reaction mixture, an organic carboxylic acid having an ethylenically unsaturated bond capable of graft copolymerization and a neutralizing amount The present invention provides a method for producing a fluorescent rare earth metal complex having copolymerizability and a resin composition, characterized by adding an organic amine to cause a reaction, and precipitating the deposited precipitate.

  Although the rare earth metal is used as the central metal in the metal complex of the present invention, there is no particular limitation on the rare earth metal, that is, a metal belonging to the rare earth, that is, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, Any of terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium and scandium can be used.

  In addition, since the organic carboxylic acid derivative coordinated to the central metal is a ligand for neutralizing the positive charge (3+) of the central metal, it is necessary to coordinate three molecules per atom of the rare earth metal. There is. As a source of the ligand, an organic carboxylic acid or a salt thereof, for example, an alkali metal salt such as a sodium salt or a potassium salt is used. As this organic carboxylic acid, it is necessary to use what has a copolymerizable ethylenically unsaturated bond.

であらわされる３，４‐ジウンデセニルオキシ安息香酸である。 Examples of such organic carboxylic acids include unsaturated fatty acids such as acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, tiglic acid, 2-decenoic acid and elaidic acid, and hydroxy acids such as vinyl glycolic acid and propenyl glycolic acid. Examples include unsaturated fatty acids, alkoxy-unsaturated fatty acids such as 2-methoxypropenoic acid and 4-methoxybutenoic acid, and preferred are those represented by the general formula R _n —Ar—COOH (I)
(In the formula, Ar is an aromatic ring group, R is an alkenyl group or an alkenyloxy or alkenylthioxy group, and n is an integer of 1 to 3)
The aromatic ring group in this formula includes an aromatic carbocyclic group and an aromatic heterocyclic group.
Is a substituted aromatic carboxylic acid represented by Examples of such substituted aromatic carboxylic acids include alkenyl-substituted benzoic acids such as 4-vinylbenzoic acid, 3,4-divinylbenzoic acid, 3-butenylbenzoic acid, 4-hexenylbenzoic acid, and 3-vinyloxybenzoic acid. 4-vinyloxybenzoic acid, 4-butenyloxybenzoic acid, 3,4-dihexenyloxybenzoic acid, 4-decenyloxybenzoic acid, 4-undecenyloxybenzoic acid, 3,4-didecenyloxybenzoic acid, 3,4-diun Decenyloxybenzoic acid, 3,6-diundecenyloxynaphthoic acid, 4-undecenyloxy-1-naphthoic acid, 6,7-diundecenyloxy-2-naphthoic acid, 7-undece Alkenyloxy-substituted aromatics such as nyloxy-4-fluorenecarboxylic acid, 3-undecenyl-2-thiophenecarboxylic acid It can be mentioned carboxylic acid or alkenyl-substituted aromatic carboxylic acids.
Particularly preferred among these substituted aromatic carboxylic acids are those of the general formula

3,4-diundecenyloxybenzoic acid represented by

  In the above general formula (I), R is an alkenyloxy group and n is a compound of 2, but such a compound is produced by reacting, for example, dihydroxybenzoic acid with two molecules of a halogen-substituted alkene. be able to.

  The neutral organic ligand introduced as a ligand in addition to the organic carboxylic acid derivative in the complex of the present invention is an organic amine and an organic phosphorus compound. As this organic amine, tertiary amines such as phenanthroline, bipyridine, quinoquine and pyridine are preferable, and as the organic phosphorus compound, triphenylphosphoric acid, trithiophenylphosphoric acid, tri (4-butoxyphenyl) phosphoric acid, etc. Is preferred.

The fluorescent copolymerizable rare earth metal complex of the present invention can be produced, for example, as follows.
That is, a rare earth metal oxide powder is suspended in an organic solvent, an inorganic acid is added thereto, and the mixture is reacted until a uniform, almost transparent solution is formed. At this time, if desired, the reaction can be promoted by stirring. If a uniform solution is formed, an organic carboxylic acid and an organic amine that can be graft-copolymerized are introduced into the solution, and a white solid is precipitated. After sufficiently depositing a white solid, this is filtered off, and the organic solvent is washed with water and dried under reduced pressure. In this way, the desired complex is obtained in a yield of 70% or more based on the rare earth metal oxide used. The fact that this product is the target complex can be identified by, for example, elemental analysis values and infrared absorption spectra.

Examples of rare earth metal oxides used in the above reaction include Sc ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , Eu ₂ O ₃ , Sm ₂ O ₃ , and Tb ₄ O ₇ . These rare earth metal oxides are used in the form of powder having a particle size of 100 μm or less, preferably 10 μm or less, dispersed in an organic solvent.

  The organic solvent can be arbitrarily selected from those conventionally used in the production of organic rare earth metal complexes. Examples of such organic solvents include methanol, ethanol, propanol, acetonitrile, dimethylformamide (DMF), diethylacetamide, tetrahydroxyfuran (THF), acetone, chloroform, methylene chloride, ethyl acetate, butyl acetate, dimethyl sulfoxide, diethyl Examples include sulfoxide.

  In the method of the present invention, the rare earth metal oxide powder is added to the organic solvent and uniformly dispersed by stirring. The ratio of the organic solvent used in this case is selected in the range of 1:30 to 1: 300, preferably 1:50 to 1: 200, by mass ratio with respect to the rare earth metal oxide.

  In addition, as the inorganic acid used at this time, strong acids such as hydrochloric acid, chloric acid, sulfuric acid, and nitric acid are used. The amount of the inorganic acid used should be at least stoichiometric, preferably slightly excessive, relative to the rare earth metal powder.

  Moreover, there is no restriction | limiting in particular as heating temperature, Usually, 40 degreeC or more, Preferably it selects in the range of 60-100 degreeC. This heat treatment is continued until the dispersion becomes a substantially transparent solution. This treatment time depends on the kind of rare earth metal, the kind of inorganic acid, the concentration of inorganic acid, etc., but is usually in the range of 10 minutes to 5 hours.

  The fluorescent rare earth metal complex of the present invention thus obtained is mixed with EVA, added with a catalyst if necessary, and heated and graft-copolymerized easily to form a chemically uniform composition. To do.

  In this case, the mixing ratio of EVA and the complex is usually selected in an amount not exceeding 10% based on the mass of EVA, preferably in the range of 0.01 to 8%, particularly 0.05 to 1%. If the amount of the complex is less than 0.01%, the desired fluorescence intensity cannot be obtained, and if it exceeds 10%, the fluorescence intensity is not improved even if the amount of the complex used is increased, which is economically undesirable.

  An organic peroxide is added to the composition composed of EVA and the complex, and this is thermally decomposed to form a crosslinked structure and improve the mechanical strength.

Any organic peroxide can be used as long as it generates radicals at 100 ° C. or higher. However, if the stability at the time of blending is taken into consideration, the decomposition temperature with a half-life of 10 hours is 70 ° C. or higher. Are preferred.
For example, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, di-t- Butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxyisopropyl) benzene, n-butyl-4 , 4-Bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butyl) Peroxy) 3,3,5-trimethylcyclohexane, t-butyl peroxybenzate, benzoyl peroxide and the like.
The blending amount of the organic peroxide is sufficient up to 5% by mass with respect to EVA.

In the composition, a crosslinking aid can be added to improve the degree of crosslinking and improve durability.
As this crosslinking aid, trifunctional crosslinking aids such as triallyl isocyanurate and triallyl isocyanate, and monofunctional crosslinking aids such as NK ester are used. The blending amount of the crosslinking aid is sufficient up to 10% by mass with respect to EVA.

In addition, a stabilizer such as hydroxyquinone, hydroxyquinone monomethyl ether, P-benzoquinone or methylhydroquinone can be added to the composition in order to improve the stability.
The blending amount of the stabilizer is sufficient up to 5% by mass with respect to EVA.

  Furthermore, an ultraviolet absorber, an antiaging agent, a discoloration preventing agent and the like can be added to the composition.

  Examples of ultraviolet absorbers include benzophenone series such as 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, and 2- (2′-hydroxy5-methylphenyl) benzo A hindered amine type such as benzotriazole type such as triazole, phenyl salicylate, or pt-butylphenyl salicylate is used.

  Antiaging agents include amines, phenols, bisphenyls, hindered amines such as di-t-butyl-p-cresol, bis (2,2,6,6-tetramethyl-4-piperazyl) sebacate, etc. Is used.

  The solar cell encapsulant prepared by mixing the fluorescent rare earth complex of the present invention with EVA has the effect of being more uniform and dispersible than the conventional one and being able to be used in a stable state over a long period of time. .

  Next, the best mode for carrying out the present invention will be described by way of examples, but the present invention is not limited thereto.

Reference example 1
9.8 g (54 mmol) of ethyl 3,4-dihydroxybenzoate and 17 g (120 mmol) of potassium carbonate are suspended in 120 ml of dimethylformamide, into which a dimethylformamide solution of 11-bromo-1-undecene (0.86M concentration) 150 ml is gradually added dropwise and allowed to react for 18 hours while stirring at 90 ° C.
Subsequently, the obtained reaction mixture was cooled to room temperature, the reaction product was extracted with ether, the extract was dried over magnesium sulfate, and then the solvent was distilled off to obtain a light brown solid as a residue. This solid was recrystallized with ethanol to obtain 22 g of ethyl 3,4-diundecenyloxybenzoate. The yield based on ethyl 3,4-dihydroxybenzoate was 84%.

Next, ¹ H-NMR, ¹³ C-NMR and IR characteristic values of this product are shown.
¹ H-NMR (δ, ppm): 1.34 (—CH ₂ —and—CH ₃ , m, 23H), 1.45 (—CH ₂ —, m, 4H), 1.83 (—CH ₂ —) , m, 4H), 2.04 ( -CH 2 -, q, J = 7.2Hz, 4H), 4.04 (-CH 2 -, td, J 1 = 6.7Hz, J 2 = 1.6Hz _{, 4H), 4.34 (-OCH 2} -, q, J = 7.2Hz, 2H), 4.93 (= CH 2, d, J = 10.2Hz, 2H), 4.99 (= CH 2 , d, J = 17.2Hz, 2H ), 5.79 (-CH =, m, 2H), 6.86 (-C 6 H 3 -, d, J = 8.4Hz, 1H), 7.54 (−C ₆ H ₃ −, d, J = 7.4 Hz, 1H), 7.64 (−C ₆ H ₃ −, dd, J ₁ = 8.5 Hz, J ₂ = 2.1 Hz, 1H); ¹³ C-NMR (δ, ppm): 14.8 ( _{-CH 3), 26.4 (-CH 2} -), 26.4 (-CH 2 -), 29.3 (-CH 2 -), 29.5 (-CH 2 -), 29.6 (- _{CH 2 -), 29.8 (-CH} 2 -), 29.9 (-CH 2 -), 30.0 (-CH 2 -), 34.2 (-CH 2 -), 61.1 (- _{CH 2 -), 69.4 (-OCH} 2 -), 69.7 (-OCH 2 -), 112.4,114.5 (= CH 2), 114.7,123.2,123.8, 139.6 (-CH =), 148.9, 153.5, 166.9 (-COO-); IR (KBr): 3070, 2978, 2919, 2849, 1708, 1642, 1421, 1390, 1366, 1348 , 1293, 1278, 1069, 1031, 1105, 1069, 1031, 991, 914, 869, 761 m ^-1.

  Next, a solution prepared by dissolving 9.8 g (20 mmol) of ethyl 3,4-diundecenyloxybenzoate and 4.0 g of sodium hydroxide in 200 ml of ethanol was refluxed for 12 hours, Until cooled. To this reaction mixture, 200 ml of ether and 150 ml of 1M hydrochloric acid were added and shaken. The ether layer was separated and dried over magnesium sulfate, and then the solvent was distilled off. The remaining pale yellow solid was purified by recrystallization from methanol to obtain 8.7 g (18.9 mmol) of 3,4-diundecenyloxybenzoic acid. The yield based on ethyl 3,4-diundecenyloxybenzoate was 95%.

Next, ¹ H-NMR, ¹³ C-NMR and IR characteristic values of this product are shown.
¹ H-NMR (δ, ppm): 1.30 (—CH ₂ —, m, 20H), 1.43 (—CH ₂ —, m, 4H), 1.71 (—CH ₂ —, m, 4H) ), 2.00 (—CH ₂ —, q, J = 7.0 Hz, 4H), 3.34 (—OH, br, 1H), 3.98 (—CH ₂ —, dt, J ₁ = 20. 0 Hz, J ₂ = 6.3 Hz, 4H), 4.92 (= CH ₂ , dd, J ₁ = 10.2 Hz, J ₂ = 1.1 Hz, 2H), 4.99 (= CH ₂ , dd, J ₁ = 17.1 Hz, J ₂ = 1.9 Hz, 2H), 5.77 (−CH =, m, 2H), 7.01 (−C ₆ H ₃ −, d, J = 8.6 Hz, 1H) 7.42 (−C ₆ H ₃ −, d, J = 1.9 Hz, 1H), 7.53 (−C ₆ H ₃ −, dd, J ₁ = 8.4 Hz, J ₂ = 21.9 Hz, 1H); ¹³ C-NMR (δ, ppm) ): 26.4 (—CH ₂ —), 26.4 (—CH ₂ —), 29.3 (—CH ₂ —), 29.5 (—CH ₂ —), 29.8 (—CH ₂ —) ), 29.8 (—CH ₂ —), 30.0 (—CH ₂ —), 34.2 (—CH ₂ —), 69.4 (—OCH ₂ —), 69.6 (—OCH ₂ —) _{), 112.4,114.5 (= CH 2)} , 114.9,121.8,124.9,139.6 (-CH =), 148.9,154.3,172.31 (-COO -); IR (KBr): 3079,2923,2849,1670,1643,1597,1520,1467,1444,1416,1393,1350,1307,1114,1071,1014,911,803,769,725,674cm - ¹ .

Reference example 2
11 g (64 mmol) of ethyl 2-hydroxybenzoate and 10 g (71 mmol) of potassium carbonate were suspended in 70 ml of dimethylformamide, and 120 ml of a dimethylformamide solution (concentration of 0.54 M) of 11-bromo-1-undecene was gradually added thereto. And is allowed to react for 18 hours while stirring at 90 ° C.
Subsequently, the obtained reaction mixture was cooled to room temperature, the reaction product was extracted with ether, the extract was dried over magnesium sulfate, and the solvent was distilled off to obtain a pale brown oily residue as a residue. . This oil was produced by chromatography (silica gel, methylene chloride) to obtain 17 g of ethyl 2-undecenyloxybenzoate. The yield based on ethyl 2-hydroxybenzoate was 85%.

Next, ¹ H-NMR, ¹³ C-NMR and IR characteristic values of this product are shown.
¹ H-NMR (δ, ppm): 1.34 (—CH ₂ —and—CH ₃ , m, 23H), 1.47 (—CH ₂ —, m, 4H), 1.82 (—CH ₂ —) , m, 4H), 2.04 ( -CH 2 -, q, J = 7.2Hz, 4H), 4.04 (-CH 2 -, td, J 1 = 6.7Hz, J 2 = 2.0Hz _{, 4H), 4.34 (-OCH 2} -, q, J = 7.2Hz, 2H), 4.93 (= CH 2, d, J = 10.2Hz, 2H), 4.99 (= CH 2 , d, J = 15.6Hz, 2H ), 5.81 (-CH =, m, 2H), 6.86 (-C 6 H 3 -, d, J = 8.6Hz, 1H), 7.54 (−C ₆ H ₃ −, d, J = 2.0 Hz, 1H), 7.59 (−C ₆ H ₃ −, s, 1H), 7.64 (−C ₆ H ₃ −, dd, J ₁ = 8.4 Hz, J ₂ = 2.0 Hz, 1H); ¹³ C-NMR (δ, ppm): 14.7 (—CH ₃ ), 26.4 (—CH ₂ —), 28.9 (—CH ₂ —), 29.3 (—CH ₂ —), 29. 5 (—CH ₂ —), 29.6 (—CH ₂ —), 29.8 (—CH ₂ —), 29.9 (—CH ₂ —), 34.2 (—CH ₂ —), 61. _{1 (-O-CH 2 -)} , 69.2 (-OCH 2 -), 113.5,114.5 (= CH 2), 120.3,121.3,131.9,133.5 (- CH =), 139.5, 158.9 (-COO-); IR (KBr): 2991, 2968, 2947, 2897, 1510, 1487, 1424, 1393, 1308, 1208, 1157, 1127, 1030, 1007, 924, 841, 725, 677, 663 cm ⁻¹ .

  Next, a solution obtained by dissolving 4.5 g (14 mmol) of ethyl 2-undecenyloxybenzoate and 1.0 g of sodium hydroxide in 50 ml of ethanol was refluxed for 12 hours and then cooled to room temperature. . After 70 ml of ether and 60 ml of 1M hydrochloric acid were added to the reaction mixture and shaken, the ether layer was separated and dried over magnesium sulfate, and then the solvent was distilled off. The remaining pale yellow oil was purified by recrystallization from ether to obtain 3.7 g (13 mmol) of 2-undecenyloxybenzoic acid. The yield based on ethyl 2-undecenyloxybenzoate was 90%.

Next, ¹ H-NMR, ¹³ C-NMR and IR characteristic values of this product are shown.
¹ H-NMR (δ, ppm): 1.31 (—CH ₂ —, m, 10H), 1.47 (—CH ₂ —, m, 2H), 2.04 (—CH ₂ —, q, J = 6.9Hz, 2H), 4.25 ( -OCH 2 -, t, J = 6.6Hz, 2H), 4.93 (= CH 2, dd, J 1 = 10.1Hz, J 2 = 0. 8 Hz, 1 H), 4.99 (= CH ₂ , d, J ₁ = 17.5 Hz, ₁ H), 5.80 (= CH−, m, 1 H), 7.05 (Ar, d, J = 8. 4 Hz, 1 H), 7.13 (Ar, t, J = 7.5 Hz, 1 H), 7.55 (Ar, t, J = 7.5 Hz, 1 H), 8.19 (Ar, d, J = 7) .8 Hz, 1 H); ¹³ C-NMR (δ, ppm): 26.3 (—CH ₂ —), 29.3 (—CH ₂ —), 29.4 (—CH ₂ —), 29.6 ( -CH ₂ -), 29.7 (- _{CH 2 -), 29.8 (-CH} 2 -), 34.2 (-CH 2 -), 70.7 (-OCH 2 -), 113.0,114.6 (= CH 2), 118. 1,122.6, 134.2, 135.4, 139.5 (-CH =), 158.0, 165.8 (-CO-); IR (KBr): 3074, 2925, 2855, 1698, 1640 , 1603, 1578, 1493, 1467, 1421, 1397, 1312, 1251, 1168, 1143, 1088, 992, 950, 914, 839, 757, 659 cm ⁻¹ .

Europium oxide 0.18 g (0.50 mmol) was suspended in a mixture of 0.6 M of 12 M hydrochloric acid and 30 ml of ethanol, and the mixture was refluxed until a uniform solution was obtained.
Next, 0.94 g (3.2 mmol) of 3,4-diundecenyloxybenzoic acid obtained in Reference Example 1 was added, and trimethylamine was further added until the reaction solution became neutral. This treatment resulted in the precipitation of a white solid, which was filtered off, washed with water and ethanol, and dried under reduced pressure. In this way, three 3,4-diundecenyloxybenzoic acid derivatives (0.96 mmol) were obtained. The yield based on europium oxide was 96%. Further, as a result of infrared absorption spectrum analysis, this was found to be IR (KBr): 3077, 2924, 2835, 1614, 1599, 1521, 1437, 1398, 1271, 1226, 1120, 993, 909, 778, 723, 649 cm ^{−. It has 1} peak, and from this, it was confirmed to have a chemical structure represented by the following formula.

Reference example 3
0.2 parts by mass of the europium complex obtained in the examples and 1.5 parts by mass of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane with respect to 100 parts by mass of EVA (hydrolysis rate 72%) A part was dissolved in 20 parts by mass of ethanol and added, and the mixture was stirred and reacted at 60 ° C. for 2 hours.
Next, the composition thus obtained was molded into a plate-like body (50 × 50 × 0.5 mm) and irradiated with ultraviolet rays. As a result, red fluorescence was emitted.
Moreover, when this plate-shaped surface was observed with the microscope, it was recognized that it was a uniform state over the whole surface.

It is useful as a cell sealing material for silicon crystal solar cell modules by mixing with EVA resin.

Claims (8)

  A fluorescent rare earth metal complex having a copolymerizability characterized by having an organic carboxylic acid derivative having an ethylenically unsaturated bond capable of graft copolymerization as a ligand.   2. The fluorescent rare earth metal complex having copolymerizability according to claim 1, wherein the organic carboxylic acid derivative having an ethylenically unsaturated bond capable of graft copolymerization is an aromatic carboxylic acid derivative having an alkenyloxy group.   3. The fluorescent rare earth metal complex having copolymerizability according to claim 2, wherein the aromatic carboxylic acid derivative having an alkenyloxy group is a 3,4-diundecenyloxybenzoic acid derivative.   Suspend rare earth metal oxide powder in a mixture of organic solvent and inorganic acid, heat reaction until a uniform solution is formed, and then organically graftable copolymerizable ethylenically unsaturated bond in the reaction mixture A method for producing a copolymerizable fluorescent rare earth metal complex, which comprises adding a carboxylic acid and a neutralizing amount of an organic amine to cause a reaction, and separating the deposited precipitate.   5. The method for producing a copolymerizable fluorescent rare earth metal complex according to claim 4, wherein the inorganic acid is hydrochloric acid.   6. The process for producing a copolymerizable fluorescent rare earth metal complex according to claim 4 or 5, wherein the organic amine is a tertiary amine.   The resin composition for solar cell sealing materials which consists of a composition which mix | blended the fluorescent rare earth metal complex which has the copolymerizability in any one of Claims 1 thru | or 3 with respect to ethylene-vinyl acetate copolymer.   The resin composition for a solar cell sealing material according to claim 7, wherein the blending ratio of the copolymerizable fluorescent rare earth metal complex is in a range not exceeding 10% based on the mass of the ethylene / vinyl acetate copolymer.