JPH089683B2 - Manufacturing method of resin containing rare earth element - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a resin containing a rare earth element selected from the group consisting of lanthanum, cerium, praseodymium, dysprosium, thulium, ytterbium and lutetium. absorptivity derived to radiation and electromagnetic waves, to a rare earth element-containing resins of the production process with the various physical properties of the light emitting property and the like.

[0002]

2. Description of the Related Art Many azo, diazo, anthraquinone, and other oil-soluble dyes have been known as additives used to obtain a synthetic resin that selectively absorbs light having a specific wavelength in the visible region. ing. Although these have the advantage that they can be used by dissolving them in the resin raw material, the wavelength dependence of absorption shows that they absorb over a wide wavelength range. That is, the absorption is broad, and for example, if an attempt is made to sufficiently absorb a light beam having a wavelength of about 450 nm, a wide range of light beams having a wavelength of 350 nm to 500 nm will be absorbed, which is a drawback depending on the intended use of selective absorption. Further, these dyes generally have poor weather resistance, and in some cases, they are exposed to sunlight for about one week, or 180
Absorption often disappears or disappears at temperatures near ℃.

On the other hand, in absorbing X-rays and γ-rays, which are electromagnetic waves having a wavelength shorter than that of visible light, it is necessary to add a lead compound, a bismuth compound or the like to a synthetic resin to obtain a synthetic resin transparent in the visible region. It has been known. Looking at the mass absorption coefficient (cm ² / g) as a numerical value indicating the absorption capacity of photons, the absorption edge energy accompanying the orbital transition of the orbital electrons of the atom differs depending on the atom. The value of the mass absorption coefficient changes discontinuously. That is, comparing the mass absorption coefficients of lead and cerium, between the L ₃ absorption edge of cerium (5.723 keV) and the L ₃ absorption edge of lead (13.040 keV) and from the K absorption edge of cerium (40.440 keV). L ₃ -K absorption edge of the lead (74.
It is known that cerium has a mass absorption coefficient several times larger than that of lead in the range of 960 keV).

Similarly, the same applies to elements from thallium having an atomic number of 81 to palladium having an atomic number of 46.
Therefore, when the energy range of photons is limited, it is understood that each element has a unique photon absorption capacity larger than that of lead.

[0005]

[SUMMARY OF THE INVENTION The near infrared light, visible light, ultraviolet light and X-rays, with respect to electromagnetic waves of γ ray region
In general, organic synthetic resins do not show absorption, but by utilizing the fact that when they contain specific rare earth elements, they show sharp specific absorption unique to each, and it has been observed in the past. A resin having weather resistance that does not exist and selective absorption of electromagnetic waves was found.

[0006]

[Means for Solving the Problems] These specific rare earth elements
From the salts of these rare earth elements and certain unsaturated fatty acids
At least one selected from the group consisting of
Monomers containing steal as the main component or parts thereof
Rare earth elements are incorporated into the resin by copolymerizing with the polymer.
Can be included, which makes it particularly transparent without scattering
Various resins can be obtained.

That is, the present invention provides (a) methacrylic acid ester
-Containing monomers and their partial polymerization
A resin-forming raw material selected from the group consisting of the body, (b) lanthanum, cerium, praseodymium, dysprosiu
Consisting of aluminum, thulium, ytterbium and lutetium
Rare earth element and the general formula _{^{CH 2 = C (R 1)}} -COOH ( wherein selected from the group, R ₁ is hydrogen or a hydrocarbon residue having 1 to 3 carbon atoms
From the group consisting of salts with unsaturated fatty acids
At least one selected from the group consisting of: (c) a general formula R ₁ —COOH (1) having a solubility in the above components (a) and (b) (wherein R ₁ is a saturated or unsaturated group having 1 to 20 carbon atoms ); Carbonization of saturation
Is hydrogen _{residue); R 2 -OCO-R 3} -COOH (2) ( wherein, R ₂ is a hydrocarbon residue of 1-9 hydrogen or carbon
And R ₃ is a saturated or unsaturated hydrocarbon having 1 to 4 carbon atoms
Is a _{residue); CH 2 = C (R} 4) -COO - (- A 1 -O-) n H (3) ( wherein, R ₄ is hydrogen or methyl group, A ₁ is 2 carbon atoms
To 6 are alkylene groups, and n is 0 or an integer of 1 to 10.
In _{a); CH 2 = C (R} 5) -COO-R 6 -OH (4) ( wherein, R ₅ is hydrogen or methyl, R ₆ is 2 carbon atoms
Is a 6 alkylene _{group); R 7 -OH (5)} ( wherein, R ₇ is hydrocarbon saturated or unsaturated 3 to 10 carbon atoms
Is hydrogen residues); and _{R 8 = (- A 2 -O-} ) m H (6) ( wherein, R ₈ is a saturated or hydroxyl group or C1-10 non
A ₂ is a saturated hydrocarbon residue, and A ₂ is an alkyl group having 2 to 4 carbon atoms.
Is a xylene group and m is an integer of 1 to 10)
A mixture of at least one solvent selected from the group consisting of (d) a polymerization initiator and polymerizing in a mold.
A rare earth element-containing tree with excellent selective absorption of radiation and electromagnetic radiation
It is a method of producing fat.

The amount of the rare earth element used in the manufacturing method of the present invention is 0.001% to 35% based on the weight of the resin.
A%, less effect derived from the small and rare earth elements than 0.001%, not preferable since more than 35%, the impairment of mechanical properties of the resin composition.

Examples of the methacrylic acid ester used in the production method of the present invention include alkyl methacrylate such as methyl methacrylate and ethyl methacrylate, or cyclohexyl methacrylate, tetrahydrofuryl methacrylate, benzyl methacrylate, phenyl methacrylate, allyl methacrylate. , Methallyl methacrylate, β-naphthyl methacrylate, β-aminoethyl methacrylate, methacrylic acid 2
-Methoxyethyl, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate coat, penta Examples thereof include erythritol tetramethacrylate, trimethylolpropane trimethacrylate, and halogen-substituted methacrylates thereof.

The above general formulas (1), (2), (3), (4) and (5)
And the solvent represented by (6) is a cosolvent for uniformly dissolving the rare earth element compound in the resin-forming raw material, and specifically, for example, methacrylic acid, unsaturated carboxylic acids such as acrylic acid, and propionic acid. , Isobutyric acid, n-butyric acid, caproic acid, caprylic acid, capric acid, 2-ethylhexanoic acid,
Saturated or unsaturated fatty acids such as stearic acid and naphthenic acid, unsaturated alcohols such as α-hydroxyethyl acrylate and α-hydroxyethyl methacrylate, saturated aliphatic alcohols such as propyl alcohol and cyclohexyl alcohol, ethylene glycol, diethylene glycol and propylene glycol. And other polyhydric alcohols.

Among these solvents, monomers copolymerizable with methyl methacrylate such as methacrylic acid, acrylic acid, α-hydroxyethyl methacrylate and α-hydroxyethyl acrylate are preferred. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used cannot be unconditionally determined depending on the kind and amount of the rare earth element compound used, but 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 obtained resin composition are deteriorated, which is not preferable.

Examples of the polymerization initiator used in the above copolymerization include peroxides such as benzoyl peroxide and lauroyl peroxide, α, α′-azobisisobutyronitrile, α, α′-azobis. (2,4-
Dimethylvaleronitrile), α, α'-azobis (2,2
Known radical initiators such as azobis based ones such as 4-dimethyl-4-methoxyvaleronitrile) can be used. These polymerization initiators can be used alone or as a mixture of two or more kinds, and the amount thereof used is 0.1 with respect to 100 parts by weight of the resin raw material.
001 to 0.1 part by weight.

The copolymerization method for obtaining the resin of the present invention is not particularly limited, but a preferred copolymerization method is cast polymerization. In the case of this casting polymerization, the above-mentioned components
The mixture prepared from (a), (b), (c) and (d) is
For example, it is injected into a mold composed of a cell made of inorganic glass, stainless steel, nickel chrome or aluminum and a gasket and polymerized. For special applications, the radiation polymerization can be carried out at a low temperature below room temperature. Usually, the polymerization is completed at 45 to 95 ° C for 0.3 to 15 hours, and then at 100 to 145 ° C for 10 minutes to 5 hours.

In the present invention, if necessary, an ultraviolet absorber, a release agent, a heat stabilizer, a light absorber for absorbing light of other wavelengths, a light diffuser, a radiation shielding material, etc. may be added. it can. The rare earth element-containing resin of the present invention having the structure as described above has a property of increasing the refractive index of the base resin, X-rays, in addition to the light selective absorption performance due to the rare earth element.
It can be used for filters, lenses, lighting covers, image screens, radiation protection filters, scintillators, light emitters, etc. by imparting radiation absorption ability to γ rays, absorption ability to thermal neutron rays, etc. It is not limited to.

The present invention will now be described in more detail by way of examples, which should not be construed as limiting the present invention. Example 1 Lanthanum methacrylate 8 g, n-octylic acid 2 g, propylene glycol 1 g, α-hydroxyethyl methacrylate 1 g, styrene 5 g and methyl methacrylate 83
g were mixed. This mixed liquid was a colorless transparent liquid.

Next, 0.04 as a polymerization catalyst was added to this mixed solution.
g of α, α'-azobis (2,4-dimethylvaleronitrile) and 0.005 g of dioctyl sulfosuccinate sodium salt as a release agent were added and dissolved, and then degassed to obtain the product thickness in advance. Is poured into a conventional inorganic glass mold set to have a diameter of 2 mm, and this mold is
It was immersed in warm water of 5 ° C. for 180 minutes and then allowed to stand in an air bath of 110 ° C. for 120 minutes to complete the polymerization. The resin plate taken out from the mold was colorless and transparent.

Example 2 4 g of neodymium methacrylate and 4 lanthanum methacrylate
g, 4 g of lauric acid and 1 g of propylene glycol were mixed and dissolved in 87 g of methyl methacrylate, and cast polymerization was carried out under the same polymerization conditions as in Example 1. The obtained resin plate was pink and transparent.

Example 3 8 g of praseodymium methacrylate, 2 g of n-octylic acid,
1 g of propylene glycol, 1 g of α-hydroxyethyl methacrylate, 5 g of styrene and 83 g of methyl methacrylate were mixed, and cast polymerization was carried out under the same polymerization conditions as in Example 1. The obtained resin plate was a pale yellow-green transparent plate.

Example 4 4 g of neodymium methacrylate, 4 g of praseodymium methacrylate, 4 g of lauric acid and 1 g of propylene glycol were mixed and dissolved in 87 g of methyl methacrylate, and cast polymerization was carried out under the same polymerization conditions as in Example 1. The obtained resin plate was transparent and had a pale yellowish green color.

Example 5 Praseodymium methacrylate 20 g, lauric acid 7 g, propylene glycol 4 g and methyl methacrylate 69
g was mixed, and cast polymerization was performed under the same polymerization conditions as in Example 1. The obtained resin plate was yellowish green and transparent.

Example 6 20 g of praseodymium methacrylate, 7 g of lauric acid and 73 g of methyl methacrylate were mixed, and cast polymerization was carried out under the same polymerization conditions as in Example 1. The obtained resin plate was yellowish green and transparent.

Example 7 20 g of praseodymium methacrylate, 7 g of lauric acid and 73 g of tetrahydrofuryl methacrylate were mixed, and cast polymerization was carried out under the same polymerization conditions as in Example 1. The obtained resin plate was yellowish green and transparent.

Example 8 Thulium methacrylate 8 g, n-octylic acid 2 g, propylene glycol 1 g, α-hydroxyethyl methacrylate 1 g, styrene 5 g and methyl methacrylate 83
g was mixed, and cast polymerization was performed under the same polymerization conditions as in Example 1. The obtained resin plate was a pale red transparent plate.

Example 9 4 g of neodymium methacrylate, 4 g of dysprosium methacrylate, 4 g of lauric acid and 1 g of propylene glycol were mixed and dissolved in 87 g of methyl methacrylate, and cast polymerization was carried out under the same polymerization conditions as in Example 1. . The obtained resin plate was transparent and had a pale yellow color.

Comparative Example Spiron Yellow GRCH Special (product of Hodogaya Chemical Co., Ltd.) 0.002 g and Amaplast Yellow A
Example 1 was prepared by dissolving 0.005 g of GB (product of American Aniline Co., Ltd.) in 100 g of methyl methacrylate.
Cast polymerization was carried out under the same polymerization conditions as above. The obtained resin plates were pale yellow and transparent. Although the resin plates obtained in Examples and Comparative Examples both show absorption at a wavelength of around 450 nm, the Examples show sharp absorption and the Comparative Examples show broad absorption, as can be seen from the spectral transmittance curves in FIG. Is shown. Further, when these were exposed outdoors in Otake City, Hiroshima Prefecture for one month in summer, the absorption intensity did not change in the Examples, but almost all the colors disappeared in the Comparative Examples.

[0026]

Industrial Applicability The rare earth element-containing resin of the present invention has various physical properties such as selective absorption of radiation and electromagnetic waves derived from the rare earth element, luminescence, weather resistance, and a refractive index of the base resin. Filter, lens, lighting cover, video screen, radiation protection filter,
It can be used as a scintillator, a light emitter, and the like.

[Brief description of drawings]

FIG. 1 shows a spectral transmittance curve of a resin plate by a sunlight spectrophotometer MODEL 307, a curve a shows the case of the resin plate of Example 5, and a curve b shows a comparative example (Amaplast Yellow AG).
In the case of B) and the curve c, a comparative example (Spiron Yellow GR
CH special).

Claims (2)

[Claims] 1. A resin-forming raw material selected from the group consisting of (a) a monomer containing a methacrylic acid ester as a main component and partial polymers thereof, (b) lanthanum, cerium, praseodymium, dysprosium, thulium, A rare earth element selected from the group consisting of ytterbium and lutetium and a general formula CH ₂ ═C (R ¹ ) —COOH (in the formula, R ₁ is hydrogen or a hydrocarbon residue having 1 to 3 carbon atoms) . At least one selected from the group consisting of salts with unsaturated fatty acids, (c) a general formula R ₁ —COOH (1) (wherein R is R ₂ —COOH) having solubility in the above components (a) and (b) ₁ is a saturated or unsaturated hydrocarbon residue having 1 to 20 carbon atoms); R ₂ —OCO—R ₃ —COOH (2) (In the formula, R ₂ is hydrogen or a hydrocarbon having 1 to 9 carbon atoms. is a residue, R ₃ is carbon saturated or unsaturated having 1 to 4 carbon atoms Is hydrogen _{residue); CH 2 = C (R} 4) -COO - (- A 1 -O-) n H (3) ( wherein, R ₄ is hydrogen or methyl group, A ₁ is the number of carbon atoms Two
A 6 alkylene group, n is an integer of 0 or _{1~10); CH 2 = C (} R 5) -COO-R 6 -OH (4) ( wherein, R ₅ is hydrogen or a methyl group And R ₆ has 2 carbon atoms
R ₇ —OH (5) (wherein R ₇ is a saturated or unsaturated hydrocarbon residue having 3 to 10 carbon atoms); and R ₈ = (-A ₂ —O—) _m H (6) (In the formula, 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, m is an integer of 1 to 10) at least one solvent selected from the group consisting of compounds, and (d) a mixture of a polymerization initiator and the mixture are polymerized in a mold. A method for producing a rare earth element-containing resin having excellent selective absorption. 2. The method for producing a rare earth element-containing resin according to claim 1, wherein the amount of the rare earth element is 0.001 to 35% by weight as the rare earth element based on the weight of the resin.