JPH035402B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a methacrylic resin composition containing europium and having excellent optical and mechanical properties, and a method for producing the same. Methacrylic resin is used in a variety of fields due to its excellent transparency, weather resistance, and mechanical properties. However, since methacrylic resin does not have radiation shielding ability, it cannot be used for these purposes. Ta. Therefore, in recent years, radiation shielding materials containing lead in methacrylic resin have been developed (Special Publications Publication No.
No. 2360, Japanese Patent Publication No. 53-9994, No. 53-9995, No. 53
-9996, and 53-63310, etc.). However, although the lead-containing radiation shielding materials described above effectively shield radiation from electromagnetic waves such as X-rays and γ-rays and charged particles such as α-rays and β-rays, they do not shield against neutron radiation. Not enough. On the other hand, it is also known to add a boron compound to polyethylene or methacrylic resin as a polymeric material for shielding neutron beams (Japanese Unexamined Patent Publication No. 144597-1987).
issue). However, although this method also has a large neutron beam absorption capacity, the helium and lithium produced in the neutron absorption reaction have almost no neutron absorption capacity, so their capacity tends to decrease as the amount of neutron absorption increases. However, the optical and mechanical properties have not yet reached a satisfactory level. In addition to the boron compounds mentioned above, europium, a rare earth element with an atomic number of 63, is known to have an even greater ability to absorb thermal neutrons than boron as a substance that absorbs neutrons. However, since europium is a metallic solid, it has poor compatibility with methacrylic polymers, and methacrylic resins with excellent optical and mechanical properties have not yet been produced. The inventor of the present invention has arrived at the present invention as a result of various studies in view of the above circumstances. A methacrylic resin composition containing a europium compound in an amount of 0.01 to 10% by weight based on the total composition. The resin composition of the present invention is achieved by incorporating a europium compound into a methacrylic resin containing methyl methacrylate as a main component. Therefore, the method for obtaining the composition of the present invention is not particularly limited, and various manufacturing methods can be applied. For example, a method of blending a europium compound and a methacrylic resin, a method of mixing and polymerizing a europium compound with a monomer whose main component is methyl methacrylate or a partial polymer thereof, or a method of mixing and polymerizing a europium compound with a monomer whose main component is methyl methacrylate. The polymer may be polymerized by mixing it with a partially polymerized product thereof and a solvent. The resin forming raw material used to constitute the resin composition of the present invention is a methyl methacrylate monomer, a monomer mixture containing methyl methacrylate as a main component, or a partial polymer thereof. The monomer mixture containing methyl methacrylate as a main component consists of methyl methacrylate and another vinyl monomer copolymerizable with methyl methacrylate. Other vinyl monomers copolymerizable with methyl methacrylate are not particularly limited, but include those having 1 to 4 carbon atoms.
alkyl acrylate, alkyl methacrylate having 2 to 4 carbon atoms, styrene, α-methylstyrene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol acrylate, Examples include pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, allyl acrylate, allyl methacrylate, and the like. The amount of these used is 50% by weight or less in the monomer mixture. Further, it is desirable that the polymer content in the partially polymerized resin raw material used be as small as possible so as not to impair the optical properties of the finally obtained polymer. The europium used to constitute the composition of the invention can be obtained by reacting a europium compound, such as an oxide of europium, europium carbonate, europium hydroxide, or an oxide of europium, with an inorganic or organic acid. europium nitrate, europium methacrylate,
Tris(acetylacetonato)europium or tris(benzoylacetonato)europium obtained by reacting a europium salt of an inorganic or organic acid such as europium acrylate, or an oxide of europium with acetylacetone, benzoylacetone, etc. Examples include europium complex compounds. The amount of these europium compounds used is such that the weight concentration of europium atoms is 0.01 to 10% by weight, preferably 1 to 10% by weight based on the total weight of the resin composition.
5% by weight is desirable. If the amount is less than 0.01% by weight, the resulting resin composition will have little neutron beam shielding effect, and if it exceeds 10% by weight, the optical properties or mechanical strength will deteriorate. Although these europium compounds cannot be determined unconditionally depending on the intended use, they can be blended with methacrylic resin, mixed with resin-forming raw materials and polymerized, or mixed with resin-forming raw materials and a solvent and polymerized to form methacrylic resin. It can be contained inside. Particularly, the method using the latter solvent is suitable for obtaining transparent resin products without scattering. europium oxide, when blended with europium compounds or added to resin-forming raw materials;
Preferred examples include those selected from europium carbonate, europium hydroxide compounds, and complex compounds of europium. In addition, when using a europium compound in a mixture with a resin-forming raw material and a solvent, europium nitrate, europium methacrylate, and europium acrylate obtained by reacting an oxide of europium with an inorganic or organic acid can be used. Tris(acetylacetonato)europium or tris(benzoylacetonato)europium obtained by reacting europium salts of inorganic or organic acids such as europium salts and double salts thereof, or oxides of europium with acetylacetone, benzoylacetone, etc. Preferable examples include europium complex compounds such as . The solvent used when producing the resin composition of the present invention has the following general formula which shows solubility for the resin forming raw material and the europium compound. (In the formula, R ₁ is a saturated or unsaturated hydrocarbon residue having 1 to 20 carbon atoms) (In the formula, R ₂ is hydrogen or a saturated or unsaturated hydrocarbon residue having 1 to 9 carbon atoms, and R ₃ is a saturated or unsaturated hydrocarbon residue having 1 to 9 carbon atoms.
4 saturated or unsaturated hydrocarbon residues) (In the formula, R ₄ is hydrogen or a methyl group, A ₁ is an alkyl group having 2 to 6 carbon atoms, and n is 0 or an integer of 1 to 10) (In the formula, R ₅ is hydrogen or a methyl group, and R ₆ is an alkylene group having 2 to 6 carbon atoms.) R ₇ −OH (5) or (In the formula, R ₇ is a saturated or unsaturated group having 3 to 10 carbon atoms.) R ₈ (-A ₂ -O)- _n H (6) (wherein, R ₈ is a hydroxyl group or a saturated or unsaturated hydrocarbon residue having 1 to 10 carbon atoms, A ₂ is an alkylene group having 2 to 4 carbon atoms, and m is an integer of 2 to 10). The solvents represented by the general formulas (1), (2), (3), (4), (5) and (6) are cosolvents for uniformly dissolving the europium compound in the resin forming raw material. For example, unsaturated carboxylic acids such as methacrylic acid and acrylic acid, saturated or unsaturated fatty acids such as propionic acid, octylic acid, isobutyric acid, hexanoic acid, octylbenzoic acid, stearic acid, palmitic acid, naphthenic acid, and 2-hydroxyethyl acrylate. , unsaturated alcohols such as 2-hydroxyethyl methacrylate, saturated aliphatic alcohols such as propyl alcohol and cyclohexyl alcohol, and glycols such as ethylene glycol, diethylene glycol and propylene glycol. Among these solvents, monomers copolymerizable with methyl methacrylate, such as methacrylic acid, acrylic acid, 2-hydroxyethyl methacrylate, and 2-hydroxyethyl acrylate, are preferred. These solvents can be used alone or in combination of two or more. The amount of the solvent used in the present invention cannot be absolutely determined depending on the type and amount of the europium compound used, but it is 40% by weight or less, preferably 10% by weight or less. If the amount used exceeds 40% by weight, the mechanical and thermal properties of the resulting resin composition will deteriorate, which is not preferred. Examples of the polymerization initiator used in the present invention include peroxides such as benzoyl peroxide and lauroyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4
Known radical initiators such as azobis-based initiators such as -dimethylvaleronitrile) and 2,2'-azobis-(2,4-dimethyl-4-methoxy-valeronitrile) can be used. These polymerization initiators can be used alone or in combination of two or more, and the amount used is 0.001 to 0.1 per 100 parts by weight of resin raw material.
Parts by weight. The polymerization method used to obtain the resin composition of the present invention is not particularly limited, but cast polymerization is a preferred polymerization method. In the case of this cast polymerization, the polymerization mixture prepared from the above components (a), (b) and (c) is mixed with a soft material such as an inorganic glass plate, stainless steel plate, nickel chrome plate or aluminum plate. The mixture is injected into a mold consisting of a vinyl chloride gasket and allowed to polymerize. Mold polymerization is
0.3-15 hours at 45-95℃, followed by 10 hours at 100-145℃
Polymerization is completed over a period of minutes to 5 hours. In the present invention, if necessary, an ultraviolet absorber,
A mold release agent, a heat stabilizer, a coloring agent, a light diffusing agent, and other neutron shielding compounds, lead compounds, etc. can also be added. The europium-containing methacrylic resin composition of the present invention, which has the above-described structure and has excellent optical and mechanical properties, can be easily manufactured in the same manufacturing process as acrylic resins, and can shield radiation mainly composed of neutrons. Can be used as a material. Furthermore, when a lead compound is used in combination with the composition of the present invention, X-rays and γ
It becomes possible to shield from both radiation and neutron radiation. Although the methacrylic resin composition of the present invention is particularly useful as a neutron shielding material, it can also be used in other applications such as optical filters, optical lenses, light conversion materials, lighting materials, and the like. EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited thereto. Reference Example 1 Synthesis of europium methacrylate 0.3 g of hydroquinone monomethyl ether as a polymerization inhibitor was uniformly dissolved in a mixture of 280 g of methacrylic acid and 1000 g of toluene, and after heating this to 60°C, europium oxide powder was added to this solution.
Add 176 g over 20 minutes and continue stirring for 1 hour. The reaction solution was then allowed to stand for one day, and then filtered.
The liquid is removed to obtain europium methacrylate.
The yield was 350g. Reference Example 2 Synthesis of europium nitrate A slight excess of europium oxide is heated and dissolved in concentrated nitric acid and reacted. After 1 hour, the liquid was cooled to precipitate europium nitrate crystals. The yield was 65%. Reference example 3 Synthesis of tris(acetylacetonato)europium Acetylacetone 100 c.c. and europium oxide 174
g was suspended in 3000 c.c. of anhydrous diethyl ether and refluxed for 2 hours, followed by distilling off the diethyl ether to obtain crystals of tris(acetylacetonato)europium. The yield was 70%. Example 1 3 g of europium nitrate synthesized in Reference Example 2 was
- Dissolve in a mixture of 17 g of hydroxyethyl methacrylate and 2 g of propylene glycol, add 78 g of methyl methacrylate to this solution, and stir to mix. This liquid mixture was a transparent liquid. Next, add 0.04g of 2 as a polymerization catalyst to this mixed solution.
After adding and dissolving 2'-azbis-(2,4-dimethylvaleronitrile) and 0.005 g of dioctyl sulfosuccinate sodium salt as a mold release agent, it was degassed and the plate thickness was set in advance to be 3 mm. The mixture was poured into an inorganic glass mold using a conventional method, and the mold was immersed in warm water at 65°C for 180 minutes, and then kept in an air bath at 110°C for 120 minutes to complete polymerization. The resin plate taken out from the mold was transparent. Example 2 1.5 g of europium nitrate synthesized in Reference Example 2 was
Dissolve in 8.5 g of 2-hydroxyethyl methacrylate, add this to 90 g of methyl methacrylate, and mix with stirring. This mixture was transparent. The same type and amount of polymerization catalyst and mold release agent as used in Example 1 were added to this mixed solution, and cast polymerization was carried out under the same conditions as in Example 1. The obtained resin plate was transparent. Example 3 1.5 g of tris(acetylacetonato)europium synthesized in Reference Example 3 is dissolved in 8.5 g of methacrylic acid, and this solution is added to 90 g of methyl methacrylate and mixed by stirring. The same polymerization catalyst and mold release agent as in Example 1 were added to this mixed solution, and the same cast polymerization as in Example 1 was performed.
After completion of polymerization, the resin plate peeled from the mold was transparent. Example 4 8 g of europium methacrylate synthesized in Reference Example 1, 2 g of n-octylic acid, 1 g of propylene glycol, 1 g of 2-hydroxyethyl methacrylate, 5 g of styrene, and 83 ml of methyl methacrylate.
The cast polymerization was repeated under the same polymerization conditions as in Example 1. The obtained resin plate was transparent. Example 5 Partial polymer of methyl methacrylate (polymerization rate 18
%) 100 parts by weight, α,α′-azobis-(2,4-dimethylvaleronitrile) 0.04 as a polymerization catalyst
Parts by weight, 0.005 parts by weight of dioctyl sulfosuccinate sodium salt as a mold release agent, average particle size 2μ
Add and mix 2.0 parts by weight of europium oxide, which is
After degassing, it was poured into a mold made of tempered glass with a thickness of 3 mm and a soft vinyl chloride gasket, immersed in hot water at 70°C for 60 minutes, and then placed in an air bath at 130°C. The polymerization was completed after being left for 80 minutes to obtain a resin plate. Example 6 Methacrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name
Acrypet VH) Average particle size per 100 parts by weight
Add 2.0 parts by weight of europium hydroxide with a particle size of 0.5 μ and 1.0 part by weight of europium carbonate with an average particle size of 2 μ, thoroughly mix in a tumbler to make the mixture homogeneous, and then extrude using an extruder using a conventional method to obtain a sheet with a thickness of 3 mm. Ta. The results of total light transmittance (%), haze value (%), bending fracture strength (Kg/cm ² ), and neutron shielding ability (thermal neutron absorption cross section) of the methacrylic resin plates obtained in Examples 1 to 6 are shown below. It is shown in Table 1. In addition, total light transmittance and haze value are ASTM-D
-1003-61, bending fracture strength was measured according to ASTM-D-790. The thermal neutron absorption cross section was determined using the numerical values described in Experimental Chemistry Course (12) Radiochemistry (Maruzen) and the following formula. S = (W ₁ /M ₁ ×S ₁ +W ₂ /M ₂ ×S ₂ +... +Wn / Mn × Sn) × N where S: Thermal neutron absorption cross section per 100 g of composition (cm ² ) Mi; i Atomic weight of seed element Wi; Abundance of i-type element Si; Thermal neutron absorption cross section of i-type element (barns) N; Avogadro number (i=1...n)

【table】

【table】

Claims (1)

[Scope of Claims] 1. A methacrylic resin composition containing a europium compound in a methacrylic resin whose main component is methyl methacrylate so that the weight concentration of europium atoms is 0.01 to 10% by weight based on the total composition. thing. 2 (a) Methyl methacrylate monomer or a monomer mixture containing methyl methacrylate as a main component,
or a resin-forming raw material selected from a partial polymerization thereof; (b) a polymerization mixture consisting of a europium compound in an amount such that the weight concentration of europium atoms is 0.01 to 10% by weight based on the total composition; and (c) a polymerization initiator. 1. A method for producing a methacrylic resin composition, which comprises polymerizing a methacrylic resin composition. 3. The method for producing a methacrylic resin composition according to claim 2, wherein the europium compound is selected from europium oxide, europium carbonate, europium hydroxide, and europium complex compounds. 4 The following general formula showing solubility for resin forming raw materials and europium compounds (In the formula, R ₁ is a saturated or unsaturated hydrocarbon residue having 1 to 20 carbon atoms) (In the formula, R ₂ is hydrogen or a saturated or unsaturated hydrocarbon residue having 1 to 9 carbon atoms, and R ₃ is a saturated or unsaturated hydrocarbon residue having 1 to 9 carbon atoms.
4 saturated or unsaturated hydrocarbon residues) (In the formula, R ₄ is hydrogen or a methyl group, A ₁ is an alkyl group having 2 to 6 carbon atoms, and n is 0 or an integer of 1 to 10) (In the formula, R ₅ is hydrogen or a methyl group, and R ₆ is an alkylene group having 2 to 6 carbon atoms.) R ₇ −OH (5) (In the formula, R ₇ is a saturated or unsaturated group having 3 to 10 carbon atoms. ) or R ₈ (-A ₂ -O)- _n H (6) (wherein R ₈ is a hydroxyl group or a saturated or unsaturated hydrocarbon residue having 1 to 10 carbon atoms, A ₂ is an alkylene group having 2 to 4 carbon atoms, and m is an integer of 2 to 10. Method of manufacturing the composition. 5 The europium compound is europium nitrate,
5. The method for producing a methacrylic resin composition according to claim 4, wherein the methacrylic resin composition is selected from europium salts of organic acids or complex compounds of europium. 6. The europium compound is selected from europium methacrylate, europium acrylate or tris(acetylacetonato)europium, and the solvent is octylic acid and propylene glycol and/or 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate. 5. A method for producing a methacrylic resin composition according to claim 4.