WO2000050932A1 - Materiau optique et element optique obtenu a partir du materiau optique - Google Patents

Materiau optique et element optique obtenu a partir du materiau optique Download PDF

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Publication number
WO2000050932A1
WO2000050932A1 PCT/JP2000/001104 JP0001104W WO0050932A1 WO 2000050932 A1 WO2000050932 A1 WO 2000050932A1 JP 0001104 W JP0001104 W JP 0001104W WO 0050932 A1 WO0050932 A1 WO 0050932A1
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Prior art keywords
group
mass
phosphate
optical material
parts
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PCT/JP2000/001104
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English (en)
Japanese (ja)
Inventor
Hiroki Katono
Tomoyoshi Koizumi
Masuhiro Shouji
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Kureha Kagaku Kogyo Kabushiki Kaisha
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Priority claimed from JP11049003A external-priority patent/JP2000247986A/ja
Priority claimed from JP11049002A external-priority patent/JP2000247985A/ja
Application filed by Kureha Kagaku Kogyo Kabushiki Kaisha filed Critical Kureha Kagaku Kogyo Kabushiki Kaisha
Priority to AU26930/00A priority Critical patent/AU2693000A/en
Publication of WO2000050932A1 publication Critical patent/WO2000050932A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds

Definitions

  • the present invention relates to an optical material and an optical member using the optical material. More specifically, the present invention relates to an optical material having a characteristic of absorbing or emitting light in a specific wavelength range (specific wavelength light) with high efficiency, and using the optical material.
  • Optical member Background art
  • the present inventors have earnestly studied the above-mentioned conventional optical materials, and have obtained the following findings.
  • the phosphate group-containing compound has a tendency to be unstable thermally and chemically (for example, heating, irradiation of ultraviolet rays, etc.), and it is preferable that the resin composition is polymerized and solidified for use.
  • the present invention has been made in view of such circumstances, and it has been found that heat absorption or emission characteristics of specific wavelength light by a metal ion such as a rare-earth metal ion is maintained while maintaining heat absorption characteristics. It is an object of the present invention to provide an optical material and an optical member having excellent mechanical and chemical stability and capable of improving moldability.
  • the present inventors have conducted intensive studies and found that a phosphate group-containing compound having an unsaturated double bond in the molecule can affect the polymerization shrinkage of the resin composition.
  • the present invention has been reached.
  • Component (A) a component comprising a rare earth metal ion and a phosphate compound represented by the following formula (1):
  • Component (B) a component comprising a phosphate ester rare earth metal compound represented by the following formula (2) or (3):
  • R independently represents a group represented by the following formula (4), (5), (6) or (7), M represents a rare earth metal ion, and n Is 1 or 2.
  • the function of the phosphate group contained in the component (A) and / or the component (B) secures the same or higher dispersion of rare earth metal ions as before. Is done.
  • the phosphate ester compound (A) and the phosphate rare earth metal compound (B) have good releasability when mixed with a resin and polymerized in a mold.
  • the phosphate ester compound (A) and the phosphate rare earth metal compound (B) are hard to be hardened by ultraviolet rays and are stable and hard to deteriorate even if they are not polymerized with the resin.
  • rare earth metals have, for example, the property that trivalent neodymium ions sharply absorb light near a wavelength of 580 nm, and the property that erbium ions sharply absorb light near a wavelength of 520 nm.
  • an optical member having an excellent antiglare property for visible light can be formed, or used for a laser for medical treatment, processing, and the like.
  • An optical member with excellent eye protection against laser light (wavelength: about 500 nm) can be formed.
  • these rare-earth metal ions emit fluorescence with high efficiency among the rare-earth metal ions or emit laser light, it is possible to obtain an optical material capable of exhibiting an excellent optical amplification function. .
  • the amide group-containing compound is preferably a compound represented by the following formula (8), formula (9) or formula (10).
  • R 4 , R 5 , 18 and 13 ⁇ 41 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and may be the same or different. good.
  • R 6, R 7, R 11 and R 12 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, and may be the same or different.
  • R 9 represents an alkylene group having 1 to 6 carbon atoms.
  • Ring A represents a 4-membered ring, a 5-membered ring, a 6-membered ring or a hetero ring thereof.
  • the total content of the amide group and the phosphate group is 0.8 to 50% by mass, preferably 1 to 40% by mass, and the ratio of the amide group to the phosphate group is The ratio is 10:90 to 70:30, preferably 15:85 to 60:40, and the content of the total metal ion component is the composition containing the metal ion component. It is more preferable that the content is 0.005 to 30% by mass, and preferably 0.01 to 26% by mass.
  • the total content of the amide group and the phosphate group is less than 0.8% by mass, it tends to be difficult to sufficiently disperse the metal ion component in the composition.
  • the content exceeds 50% by mass, the dispersibility of the metal ion component is reduced, and the obtained optical material tends to have high hygroscopicity, which is not preferable in practical use.
  • the ratio of the amide group to the phosphate group is less than 10% by mass, the dispersibility of the metal ion component tends to be difficult to be improved. On the other hand, if this ratio exceeds 70% by mass, the effect according to the amide group ratio tends to be saturated.
  • the content of the metal ion component is less than 0.05% by mass in the composition, an optical material that absorbs light in a wavelength range corresponding to the metal ion with high efficiency tends not to be obtained. . On the other hand, if this proportion exceeds 30% by mass, it tends to be difficult to disperse the metal ion component in the composition.
  • the optical material of the present invention is characterized by further comprising a compound having a substituted or unsubstituted amino group (hereinafter, referred to as “amino group-containing compound”).
  • amino group-containing compound a compound having a substituted or unsubstituted amino group
  • the dispersibility of the metal ion in the composition is further enhanced as compared with the case where the phosphate group is used alone. This is because the formation of a salt by an amino group and a phosphate group suppresses the aggregation of the phosphate groups, and the presence of the salt mitigates the rapid reaction between the phosphate group and the metal ion. And metal It is considered that ions are easily introduced uniformly.
  • amino group-containing compound is more preferably a compound represented by the following formula (11) or (12).
  • R 13 , R 14 and R 15 represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, pheninole,
  • H 2 C C (X) COOR 16 — or
  • R 18 , R 19 , R 2Q and R 21 represent a hydrogen atom, an alkyl group or a phenyl group, which may be the same or different.
  • R 22 represents an alkylene group.
  • the total content of the amino group and the phosphate group is 0.05 to 50% by mass, preferably 0.1 to 40% by mass, and the ratio of the amino group and the phosphate group is a mass ratio. 10: 90-70: 30, and the content of all metal ion components is 0.005-30% by mass, particularly 0.01-26% by mass in the composition containing the metal ion components. Is preferred.
  • the total content of amino groups and phosphate groups is less than 0.05% by mass, It tends to be difficult to contain the ON component in a sufficiently high ratio.
  • the content exceeds 50% by mass, the optical material tends to have high hygroscopicity and coloring property, which tends to be unfavorable in practical use.
  • the ratio of the amino group to the phosphate group is less than 10% by mass, the dispersibility of the metal ion component tends to be hardly sufficiently increased.
  • this ratio exceeds 70% by mass, the effect according to the ratio of the amino group tends to be saturated.
  • the content of the metal ion component is less than 0.05% by mass, the optical function of the metal ion tends not to be sufficiently exhibited. On the other hand, if the content exceeds 30% by mass, it tends to be difficult to disperse the metal ion component in the composition.
  • the optical material of the present invention further contains a compound having a sulfinyl group (hereinafter, referred to as “sulfinyl group-containing compound”) or a compound having a sulfonyl group (hereinafter, referred to as “sulfonyl group-containing compound”). Is also preferred.
  • sulfinyl group-containing compound a compound having a sulfinyl group
  • sulfonyl group-containing compound a compound having a sulfonyl group
  • metal ions can be dispersed in the composition at a higher ratio than when a phosphate group is used alone. This is because these compounds have a strong interaction or coordination ability with metal ions, and the metal ions are liable to be in a solvated state. For example, these compounds may form an intermediate layer between the metal ions and the resin layer. It is thought to play a role.
  • a compound having a functional group such as a thiol-containing thiol, sulfenic acid, thioaldehyde, thioketone, thioacetal, thiocarboxylic acid or the like is included as a base material of the optical material or a part of the base material. It is suitable.
  • the compound represented by the following R notation (13) —a, formula (13) —b, formula (13) —c, formula (13) —d or formula (13o) —e it is more preferable that the compound represented by the following R notation (13) —a, formula (13) —b, formula (13) —c, formula (13) —d or formula (13o) —e .
  • R 1 represents an alkyl group having 1 to 20 carbon atoms
  • R 2 represents an alkylene group having 1 to 6 carbon atoms
  • R 3 represents an alkylene group having 1 to 10 carbon atoms
  • Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • m is an integer of 1 to 6
  • k is an integer of 0 to 5.
  • the organic solvent used in the reaction between the specific alcohol and phosphorus pentoxide is an organic solvent that does not react with phosphorus pentoxide, such as hexane and cyclohexane.
  • Hydrocarbon solvents such as butane, heptane, octane, benzene, toluene, xylene, petroleum spirit, halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, dichloroethane, and cyclobenzene, geethylether, diisopropyl ether, Examples thereof include ether solvents such as dibutyl ether and tetrahydrofuran, and ketone solvents such as acetone, methyl ethyl ketone and dibutyl ketone. Of these, toluene and xylene are preferable.
  • reaction conditions of the specific alcohol represented by the formula (14) or the formula (15) with phosphorus pentoxide are such that the reaction temperature is 0 to 100 ° C, preferably 40 to 80 ° C. And the reaction time is 1 to 24 hours, preferably 4 to 9 hours.
  • reaction conditions between the specific alcohol represented by the formula (16) or the formula (17) and phosphorus pentoxide are as follows.
  • reaction conditions of the specific alcohol and the phosphorus oxyhalide are such that the reaction temperature is 0 to 110 ° C, preferably 40 to 80 ° C, and the reaction time is 1 to 20 hours. Is 2 to 8 hours.
  • a monoester can be obtained by using a specific alcohol and phosphorus oxyhalide in a molar ratio of 1: 1.
  • the ratio of these specific alcohols to phosphorus oxyhalide and the reaction conditions are selected, and an appropriate reaction catalyst is used.
  • a mixture of a monoester and a diester can be obtained by using a hydrochloric acid killer or by-produced hydrochloric acid. At this time, the molar ratio is adjusted within the range of 99: 1 to 1:99. Is done.
  • the ratio of these specific alcohols to phosphorus oxyhalide and the reaction conditions are selected, and the Lewis acid catalyst and A mixture of a monoester and a diester is obtained by using the hydrochloric acid catching agent in combination, and the ratio is adjusted in such a manner that the molar ratio is in the range of 99: 1 to 1:99.
  • the amount of the reaction catalyst to be used is 0.05 to 0.2 mol, preferably 0.01 to 0.05 mol, per mol of phosphorus oxyhalide.
  • a phosphonate ester compound is synthesized by reacting a specific alcohol with phosphorus trihalide in a solvent-free or appropriate organic solvent, and then obtaining This is a method of oxidizing the obtained phosphonate compound.
  • the phosphorus trihalide it is preferable to use phosphorus trichloride or phosphorus tribromide, and particularly preferable is phosphorus trichloride.
  • reaction conditions of the specific alcohol and the phosphorus trihalide are as follows: the reaction temperature is 0 to 90 ° C, preferably 40 to 75 ° C, and the reaction time is 1 to 10 hours, preferably 2 to 10 hours. ⁇ 5 hours.
  • a means for synthesizing a phosphorohalolidate compound by reacting a halogen such as chlorine gas with the phosphonate ester compound and hydrolyzing the phosphorohalolidate compound is used.
  • the reaction temperature of the phosphonate compound with the halogen is preferably 0 to 40 ° C, particularly preferably 5 to 25 ° C.
  • the phosphonate compound is distilled, and in the third method, for example, a specific alcohol and phosphorus trihalide are removed. By using a molar ratio of 3: 1, the diester can be obtained with high purity.
  • the ratio of the specific alcohol to the phosphorus trihalide and the reaction conditions a mixture of a monoester and a diester can be obtained, and the ratio is a molar ratio of 99: 1 to 1:99. It is adjusted within the range.
  • preferred specific examples of the specific phosphate compound having a group R represented by the formula (4) or (5) include compounds represented by the following formulas (18) to (41). Are enumerated.
  • Preferred examples of the group represented by the formula (6) include groups represented by the following formula (42). Among the groups represented by the formula (7), And a group represented by the following formula (43).
  • R 4Q represents an alkyl group having 1 to 20 carbon atoms
  • R 41 represents an alkylene group having 1 to 10 carbon atoms
  • R 42 and R 43 represent a hydrogen atom or a carbon atom.
  • specific examples of the specific phosphate compound having a group R represented by the formula (42) include compounds represented by the following formulas (44) to (75).
  • a specific phosphate compound constituting the component (A) has an alkoxy group or an oxycarbonyl group having a certain degree of polarity in its molecular structure. Since it exists, it can be used in media such as solvents and resins. Good solubility or dispersibility.
  • the above-mentioned (meth) acrylic ester based simple A copolymer of a monomer and another copolymerizable monomer that can be copolymerized with the (meth) acrylate monomer is also used.
  • a copolymerizable monomer such as
  • Unsaturated carboxylic acids such as (meth) acrylic acid, 2- (meth) acryloyloxetyl succinic acid, 2- (methyl) acryloyloxetyl phthalic acid, N, N-dimethylacrylamide
  • aromatic vinyl compounds such as styrene, permethylstyrene, chlorostyrene, dibromostyrene, methoxystyrene, vinylbenzoic acid, and hydroxymethylstyrene. These monomers are used alone or in combination of two or more.
  • thermoplastic acryl-based resin when only a monofunctional one is used as a monomer, a thermoplastic acryl-based resin is obtained, and when a part or all of the monomer is a polyfunctional one, Since a thermosetting acrylic resin can be obtained, by appropriately selecting these acrylic resin compositions, it is possible to obtain an optical material according to the purpose of use, application, processing method, and the like. Use of such a material facilitates remolding after curing and improves moldability.
  • resins having high compatibility with specific phosphate ester compounds include poly (ethylene terephthalate) (PET), polyethylene, polypropylene, polyvinyl chloride, polycarbonate, styrene, polymethylstyrene, and chlorostyrene. And polymers such as aromatic vinyl compounds such as dibromostyrene, methoxystyrene, vinylbenzoic acid, and hydroxymethylstyrene.
  • PET ethylene terephthalate
  • polyethylene polyethylene
  • polypropylene polyvinyl chloride
  • polycarbonate polycarbonate
  • styrene polymethylstyrene
  • chlorostyrene chlorostyrene
  • polymers such as aromatic vinyl compounds such as dibromostyrene, methoxystyrene, vinylbenzoic acid, and hydroxymethylstyrene.
  • the component (B) is a phosphate ester rare earth metal compound represented by the formula (2) or (3) (hereinafter, referred to as a “specific phosphate ester rare earth metal compound”). It is.
  • a specific phosphate ester rare earth metal compound can be obtained by reacting the aforementioned specific phosphate ester compound with the aforementioned rare earth metal salt. The reaction between the specific phosphate compound and the rare earth metal salt is carried out by bringing the two into contact under appropriate conditions. Examples of such a method include the following fourth method, fifth method, and sixth method.
  • the fifth method is a method in which a specific phosphate compound and a rare earth metal salt are reacted in an appropriate organic solvent.
  • the phosphate ester rare earth metal compound is produced by the above-mentioned fourth method, after the specific phosphate ester compound and the rare earth metal salt are reacted, the generated acid component can be removed by distillation.
  • the ester rare earth metal compound is produced by the fifth method, a specific phosphate ester compound is reacted with a rare earth metal salt, and then the generated acid component and organic solvent are removed. It can be removed by distillation.
  • the specific phosphate compound may be any of a monoester in which the number n of hydroxyl groups is 2 and a diester in which the number n of hydroxyl groups is 1 in the above formula (1).
  • the ester is a triester in which the value of n is 0, it does not have a hydroxyl group capable of coordinating and / or ionic bonding with a rare earth metal ion. It is difficult to disperse ions in the resin.
  • R 2 in the formulas (6) and (7) is an alkylene group having 1 to 6, preferably 1 to 4, more preferably 3 to 4, and particularly preferably 3 carbon atoms. That is, examples of the alkyleneoxy group include a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, a pentyleneoxy group, a hexyleneoxy group, and the like, and a propyleneoxy group and a butyleneoxy group are particularly preferable.
  • the alkyl group R 2 has more than 6 carbon atoms, it is difficult to disperse the alkyl group R 2 in a solvent or a resin at a high ratio.
  • R 3 in the formula (5) is an alkylene group having 1 to 10, preferably 3 to 6, more preferably 3 to 4, and particularly preferably 3 carbon atoms. This alkylene If the number of carbon atoms in the group R 3 is greater than 1 0, Ru tended to decrease dispersibility in a solvent or resin.
  • Z in the formulas (4) and (5) is an alkyl group having 1 to 4 carbon atoms. That is, examples of the alkyleneoxy group in the formulas (4) and (5) include a propylene oxide group and a butylene oxide group, and a propylene oxide group is particularly preferable. When the number of carbon atoms in the alkyl group Z exceeds 4, it tends to be difficult to disperse the compound in the composition at a high ratio.
  • examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol; glycol ethers such as methyl cellosolve and ethyl cellosolve; ethers such as methyl ether and diisopropyl ether; acetone; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, isopropyl acetate, butyl acetate, and butyl acetate; aromatic compounds such as benzene, toluene, and xylene; hexane; Kerosene, petroleum ether, etc. are used.
  • alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol
  • glycol ethers such as methyl cellosolve and ethyl cellosolve
  • ethers such
  • This seventh method is based on the fact that (A) component (here, a mixture of a phosphate compound and a rare earth metal salt) and ( B) A method comprising preparing a monomer composition containing at least one of the components, and subjecting the monomer composition to a radical polymerization treatment.
  • the specific method of the radical polymerization treatment of the monomer composition is not particularly limited, and a radical polymerization method using a usual radical polymerization initiator, for example, a bulk (cast) polymerization method, Known methods such as a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method can be used.
  • a means generally used as a melt kneading method for a thermoplastic resin is used as a means for kneading the acrylic resin and at least one of the components (A) and (B).
  • a means generally used as a melt kneading method for a thermoplastic resin is used.
  • means for melt-kneading with a mixing roll, means for pre-mixing with a Henschel mixer or the like, and then melt-kneading with an extruder are mentioned.
  • such a solvent examples include lower aliphatic alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Ethers such as petroleum ether and petroleum ether; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-form, methylene chloride, carbon tetrachloride, etc .; And aromatic hydrocarbons such as benzene, toluene and xylene.
  • lower aliphatic alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol
  • ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • Ethers such as petroleum ether and petroleum ether
  • the obtained optical material tends to have insufficient light absorption characteristics and / or light emission characteristics characteristic of the rare earth metal ions contained therein. is there.
  • the rare earth metal ion is neodymium ion
  • the light absorption characteristic at around 580 nm tends to be insufficient.
  • the content ratio of the rare earth metal ion exceeds 30 parts by mass, the rare earth metal ion tends to be hardly uniformly contained in the composition.
  • the content ratio of the total metal ions to the content is from 0.1 to 45 parts by mass, preferably from 0.1 to 40 parts by mass, and more preferably from 0.3 to 30 parts by mass.
  • the dispersibility of the metal ion component can be further enhanced by including the amide group together with the phosphate group, as compared with the case where the phosphate group is used alone.
  • the reasons for this have not been fully elucidated, but the fact that the coordination bond between the phosphate group and the metal ion component is promoted, that the metal ion component coordinates with the amide group to form a complex, Alternatively, it is considered that the compatibility between the complex and the acryl-based resin is increased.
  • amide group-containing compound represented by the formula (9) examples include N, N, -methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylamide, N, Polymerization wherein R 7 or R 11 in formula (9) such as N, N-propylenebis (meth) acrylamide, N, N, butylenebis (meth) acrylamide is an alkenyl group having 2 to 3 carbon atoms
  • Amide group-containing compound, N, N'-ethylene bisformamide, N, N, propylene bisformamide, N, N'-butylene bisformamide, N, N, monoethylene bisacetamide, N, N R 7 or R 11 in formula (9) such as N, 1-propylene bisacetamide, N, N'-butylene bisacetamide is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the use ratio of the specific amide group-containing compound is preferably 1 to 60% by mass, and particularly preferably 1 to 50% by mass of the whole composition. Further, the content ratio of the amide group in the optical material of the present invention is preferably from 0.3 to 30% by mass, particularly preferably from 0.4 to 20% by mass. If the specific amide group-containing compound is used in an amount of less than 1% by mass, the metal ion component cannot be dispersed at a high ratio, and an optical material having the desired performance such as anti-glare properties cannot be obtained. It tends not to be obtained. On the other hand, when the use ratio of the specific amide group-containing compound exceeds 60% by mass, it becomes difficult to disperse the specific amide group-containing compound in the optical material or its raw material. The obtained optical material is likely to be highly hygroscopic, which is not practically preferable.
  • the optical material containing an amide group of the present invention is a resin composition such as an acrylic resin composition
  • the optical material is preferably polymerized by the radical polymerization method described in the above ⁇ Resin composition>.
  • an acid component is contained in the resin as a by-product.
  • Such an acid component can be obtained by an appropriate method, for example, a method of filtering crystals. It can be removed by a method of evaporating at a high temperature, a method of solvent extraction, a method of washing with water, or the like, or a method described in, for example, the description of ⁇ Resin composition> above.
  • the amino group-containing compound used in the present invention is a typical basic compound, and forms a salt by reaction with an acid.
  • This acid-base reaction is a well-known phenomenon.
  • the reaction with a phosphate group stabilized by forming a salt represented by the above formula (84) forms such a salt. It is considered that the reaction is more difficult than the reaction with a free phosphoric acid group, and as a result, a reaction suppressing effect appears.
  • the above-mentioned amide group-containing compound and the donor as an electron donor of this amino group-containing compound are about 25 to 30 for the former and about 55 to 6 ° for the latter (by V. Gutman, Otaki Hitoshi. Okada, Translated by Donor and Axep Yuichi, pp. 22-23, First Edition, March 10, 1988, March 10 (published by Gakkai Shuppan Center), amino-containing compounds.
  • the doughness of the product is overwhelmingly higher than that of the amino group-containing compound, and therefore, the amino group-containing compound has a stronger bond with the acid.
  • the ability of the amino group-containing compound to solubilize metal components such as rare earth metals is higher than that of the amide group-containing compound.
  • the amino group-containing compound it is preferable to use a compound represented by the above formula (11) or the above formula (12) (hereinafter referred to as “specific amino group-containing monomer”).
  • the specific amino group-containing compound represented by the formula (11) has a (meth) acryloyl group ((meth) acryloxyalkyl group or (meth) acrylamide alkyl group) in the molecular structure.
  • Examples of the specific amino group-containing compound include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N- Amino group-containing monomer having a (meth) acryloxyalkyl group as a substituent, such as acetylaminopropyl (meth) acrylate; N- (2-dimethylaminoethyl) (methyl) acryl Amid, N— (2-getylaminoethyl) (meth) acrylamide, N— (3-dimethylaminopropyl) (meth) acrylamide, N— (3—ethyl (Meth) acrylamide such as (aminopropyl) (meth) acrylamide, etc. Amino group-containing compounds having an alkyl group as a substituent can be used. These can be
  • Specific examples of the specific amino group-containing compound represented by the formula (12) include: Alkylene diamines such as tylene diamine, trimethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, N, N, N, N-tetramethyl ethylene diamine; N, N, N, N-tetramethyltrimethylenediamine, N, N, N, N-tetramethylpropylenediamine, N, N, N-tetramethyltetramethylenediamine, N, N N, N, N, N-tetraalkylalkylenediamines such as N, N, N-tetramethylpentamethylenediamine, N, N, N, N-tetramethylhexamethylenediamine Can be mentioned.
  • the above specific amino group-containing compounds can be used alone or in combination of two or more.
  • a metal compound such as a rare earth metal salt which is a supply source of the metal ion component is added to 100 parts by mass of the raw material other than the metal compound. It is preferably used in an amount of 0.01 to 80 parts by mass, particularly 0.02 to 75 parts by mass. By satisfying such conditions, it is possible to surely dissolve or disperse the composition in the composition, and to form an optical composition in which a phosphate group, an amino group, and a metal ion component are contained in the above-mentioned preferred ratios, respectively. The material is obtained.
  • the optical material containing an amino group of the present invention is a resin composition such as an acryl-based resin composition
  • the optical material may be polymerized by the radical polymerization method described in the above ⁇ Resin composition>. Can be more suitably produced.
  • an acid component is contained in the resin as a by-product.
  • Such an acid component can be formed by an appropriate method, for example, a method of filtering crystals, evaporation , A solvent extraction method, a method of washing with water, or the like, or a method described, for example, in the description of ⁇ Resin composition> above.
  • the sulfinyl group or the sulfonyl group may be contained by dispersing the sulfinyl group-containing compound or the sulfonyl group-containing compound in the composition, or may be a polymer constituting the resin as a component of the composition. It may be contained in the structure in a chemically bonded state.
  • the metal ion component has little deterioration over time due to release from the composition component, and the durability is low.
  • the sulfinyl group or the sulfonyl group is contained in a state of being chemically bonded in the structure of the polymer constituting the resin.
  • the total content of the sulfinyl group or the sulfonyl group and the phosphate group is 1 to 50% by mass in the composition as a component of the optical material, particularly It is preferably from 1 to 40% by mass.
  • the total content of the sulfinyl group or the sulfonyl group and the phosphoric acid group exceeds 50% by mass, the dispersibility of the metal ion component tends to decrease, and the obtained optical material has a hygroscopic property. Tend to be high.
  • the ratio between the sulfinyl group or the sulfonyl group and the phosphate group is such that the mass ratio of the sulfinyl group or the sulfonyl group: the phosphate group is 10:90 to 70:30, particularly 15:85 to 60. : 40 is preferred.
  • the ratio of the sulfinyl group or the sulfonyl group to the phosphate group is less than 10% by mass, the effect of including the sulfinyl group or the sulfonyl group, that is, the effect of increasing the dispersibility of the metal ion component is sufficiently obtained. Tend not to be.
  • the content ratio of the metal ion component in the composition is preferably 0.05 to 30% by mass, and particularly preferably 0.01 to 26% by mass. If this ratio is less than 0.05% by mass, it tends to be difficult to obtain an optical material that absorbs light in a wavelength range corresponding to metal ions with high efficiency. On the other hand, when this proportion exceeds 30% by mass, it tends to be difficult to disperse the metal ion component in the composition.
  • the optical member of the present invention is formed by using the above-described optical material of the present invention, and the following three types are preferable.
  • Glass formed of the optical material of the present invention comprising a resin composition such as an acryl-based resin containing at least one of the component (A) and the component (B), or glass Alternatively, this optical material is bonded to a transparent substrate made of a transparent resin plate or the like.
  • the optical characteristics characteristic of the rare earth metal ion are exhibited.
  • the first embodiment is manufactured by polymerizing a resin monomer containing at least one of the components (A) and (B). At this time, the phosphoric ester compound in the component (A) and / or the component (B) has, as shown in the above formulas (4) to (7), an unsaturated diester in the molecular structure. Since it does not have a heavy bond, when the resin monomer is polymerized and cured in a mold, the releasability of the cured resin composition is remarkably improved as compared with the related art.
  • a resin composition containing at least one of the components (A) and (B) has thermoplasticity and is thermally stable, so that remolding after molding is possible. Yes, it is possible to significantly improve the moldability of the optical member as compared with the related art. Therefore, not only a plate-shaped, sheet-shaped, or film-shaped optical member but also a fiber-shaped or linear optical member can be formed very easily.
  • an acrylic resin, a polycarbonate resin, a styrene resin examples thereof include those made of polyester resin, cellulose resin, and the like.
  • an acrylic resin having adhesiveness may be used as the acrylic resin.
  • Such an acrylic resin having adhesiveness can be obtained by polymerizing a monomer composition containing an acrylic resin monomer constituting an adhesive component.
  • the window member and the covering member can be adhered to the base material without using an adhesive. Can be easily obtained. Further, since the component (A) and the component (B) are thermally and chemically stable, it is possible to reliably obtain an optical member that is hardly deteriorated even when exposed to heat or ultraviolet rays.
  • an optical member having excellent optical performance can be formed as compared with the case of using an adhesive. Furthermore, a film plate or the like is further adhered on such an adhesive optical member, so that an optical member having excellent protection can be easily obtained.
  • plasticizers can be contained.
  • phosphate ester plasticizers such as tricresyl phosphate and triphenyl phosphate
  • phthalic plasticizers such as octyl phthalate and dibutyl phthalate, dibutyl sebacate, butyl ricinoleate, and methyl phthalate.
  • Fatty acid plasticizers such as cetyl ricinoleate and butyl succinate
  • glycol plasticizers such as butyl phenyl butyl glycolate, triethylene glycol dibutyrate, and triethylene glycol di-2-ethylene glycol, and polyethylene glycol; No.
  • the optical member can also be formed by spraying and applying the component (B) itself or a powder containing the component (B) using a powder spray or the like. Note that these powders may be attached via an adhesive material such as an adhesive.
  • the optical member according to the third embodiment is manufactured as a film- or plate-like molded product by, for example, press-molding a component consisting only of the component (A) and the component Z or (B). Is done.
  • the optical member thus formed may be in the form of a plate (including a disc, a lens, or the like), a sheet or a film (including a composite body in which these are laminated), a fibrous, a linear, It has excellent moldability in the form of a sticky substance and has a high content of rare-earth metal ions, so the optical function of rare-earth metal ions (light of a specific wavelength range with high efficiency) Absorption function / function to emit light in a specific wavelength range with high efficiency) is equal to or better than conventional. Therefore, such an optical member of the present invention has high functional efficiency as an optical member, and when an optical device is obtained using this optical member, the size and length of the optical device can be reduced.
  • a phosphoric acid ester compound As a phosphoric acid ester compound, 1.4272 g of a mixture of a monoester represented by the formula (30) and a diester represented by the formula (31) was placed in a flask, and 10 g of styrene was used as a solvent. The mixture was stirred at room temperature for several minutes. To this solution was added 0.5 g of neodymium acetate monohydrate, and the mixture was stirred and mixed at room temperature for 2 hours to obtain a liquid optical material. Neodymium acetate monohydrate was completely dissolved, and it was confirmed that the solubility was good.
  • FIG. 1 shows the result of measuring the spectral transmittance curve of this optical material. As shown in FIG. 1, this optical material clearly showed absorption near a wavelength of 580 nm characteristic of neodymium ions.
  • a phosphate compound As a phosphate compound, a mixture of 1.4272 g of a mixture of a monoester represented by the formula (30) and a diester represented by the formula (31) is placed in a flask, and 10 g of methacrylic acid is used as a solvent. Was added and stirred at room temperature for several minutes. To this solution was added 0.5 g of neodymium acetate monohydrate, and the mixture was stirred and mixed at room temperature for 2 hours to obtain a liquid optical material. Neodymium acetate monohydrate was completely dissolved, and it was confirmed that the solubility was good.
  • FIG. 2 shows the result of measuring the spectral transmittance curve of this optical material. As shown in FIG. 2, this optical material clearly showed absorption near a wavelength of 580 nm characteristic of neodymium ions.
  • a monomer composition was prepared in the same manner as in Example 9 except that this monomer mixture was used, to produce a transparent plate-shaped optical material having a thickness of 2 mm.
  • the light absorption and the water absorption were measured in the same manner as in Example 8, the light absorption was about 26%.
  • the water absorption was about 1%.
  • a monomer composition was prepared in the same manner as in Example 9 except that this monomer mixture was used, to produce a transparent plate-shaped optical material having a thickness of 2 mm.
  • the light absorption and the water absorption were measured in the same manner as in Example 8. As a result, the light absorption was about 21% and the water absorption was about 1%.
  • the monomer composition prepared in this way is molded into a disk molding mold (thickness 2).
  • Example 18 the mixture was cast under the same conditions as in Example 18 to obtain a transparent disk-shaped optical member having a thickness of 20 mm and made of the optical material of the present invention.
  • the light absorption and the water absorption were measured in the same manner as in Example 8. As a result, the light absorption at a wavelength of 52 O nm was about 18%, and the water absorption was about 1%.
  • neodymium acetate monohydrate the content of neodymium ion was 6.37 parts per 100 parts of the monomer mixture
  • 7.0 parts of braseodymium acetate dihydrate The content of praseodymium ion is 2.79 parts per 100 parts of the monomer mixture
  • 2.0 parts of t-butylpropyloxyneodecanoate (polymerization initiator) are added, and the mixture is sufficiently stirred.
  • the monomer composition thus prepared was poured into a disk molding mold, and subjected to casting polymerization under the same conditions as in Example 18 to obtain a 2 mm thick optical material of the present invention.
  • the light absorption and the water absorption were measured in the same manner as in Example 8. As a result, the light absorption at a wavelength of 520 nm was about 52%, and the water absorption was about 2%.
  • This monomer mixture was mixed with 18.0 parts of erbium acetate tetrahydrate (7.23 parts of erbium ion based on 100 parts of the monomer mixture) and t-butyl peroxy neodecanoate (polymerization). (Initiator) 2.0 parts, and the mixture was sufficiently stirred and mixed to prepare a monomer composition.
  • the monomer composition thus prepared was poured into a disk molding mold, and subjected to casting polymerization under the same conditions as in Example 18 to obtain a 2 mm thick optical material of the present invention.
  • the light absorption and the water absorption were measured in the same manner as in Example 8. As a result, the light absorption at a wavelength of 520 nm was about 50%, and the water absorption was about 1%.
  • a neodymium salt of a mixture of a phosphate compound represented by the formula (30) and a phosphate compound represented by the formula (31), and a conventional phosphate compound represented by the above formula (85) The thermal decomposition characteristics of a mixture with the conventional phosphate ester compound represented by the above formula (86) with a neodymium salt were measured using the following measuring device and measuring conditions and compared.
  • FIG. 7 shows a pyrolysis chart of the neodymium salt of a mixture of the phosphate compound represented by the formula (30) and the phosphate compound represented by the formula (31).
  • FIG. 8 is a pyrolysis chart of the neodymium salt of a mixture of the conventional phosphate compound represented by the formula (85) and the conventional phosphate compound represented by the formula (86). Comparing Fig. 7 and Fig. 8, the former neodymium salt shown in Fig. 7 does not decrease in weight until around 270 ° C, whereas the latter neodymium salt (conventional) shown in Fig. 8 has 200 The weight gradually decreases from just before ° C. Thus, it was confirmed that the neodymium salt of the phosphate compound used in the present invention is thermally more stable than before.
  • a mixture of 1.472 g of a mixture of the monoester represented by the formula (30) and the diester represented by the formula (31) as a phosphate compound is placed in a flask, and toluene 8: and dimethylsulfoxide 2 g are used as a solvent.
  • the mixture was stirred at room temperature for several minutes.
  • To this solution was added 0.5 g of neodymium acetate monohydrate (the content of neodymium ions in 100 parts of the total mixture was 1.86% by mass), and the mixture was stirred and mixed at room temperature for 2 hours to obtain a liquid optical material.
  • neodymium acetate monohydrate the content of neodymium ions in 100 parts of the total mixture was 1.86% by mass
  • the content of the phosphoric acid group and the sulfinyl group in this liquid optical material was as follows: the phosphoric acid group was 5.6% by mass, the sulfinyl group was 10.8% by mass, and the total was 16.4% by mass.
  • the content of the phosphate group and the sulfinyl group in this liquid optical material was 10.1% by mass for the phosphate group, 24.1% by mass for the sulfinyl group, and 34.2% in total. %, And the ratio of the sulfinyl group to the phosphate group is 70:30 in terms of mass ratio: sulfiel group: phosphate group. Neodymium acetate monohydrate was completely dissolved, and it was confirmed that the solubility was good.
  • 0.2 g of phosphate neodymium salt synthesized in Example 27 was added to 20 g of MMA, and the mixture was stirred at room temperature for several minutes so that the concentration of neodymium phosphate was 0.99% by weight.
  • a liquid monomer composition as an optical material of the present invention was obtained.
  • This phosphate neodymium salt was completely dissolved in a short time, and it was confirmed that the solubility was very good.
  • 0.0404 g of methyl styrene was sufficiently mixed with the monomer composition, and a mixture obtained by adding 0.404 g of t-butyl vinyl octanoate was filled in a glass mold. Then, it was polymerized and solidified to produce a film as an optical material or an optical member of the present invention.
  • FIG. 9 shows the result of measuring the spectral transmittance curve of this film. As shown in FIG. 9, this film clearly showed absorption around 580 nm, which is characteristic of neodymium ions.
  • Example 27 1 g of the neodymium phosphate ester synthesized in Example 27 was added to 20 g of MMA, and the mixture was stirred at room temperature for several minutes, and the concentration of the neodymium phosphate ester was 4.76% by weight. A liquid monomer composition as a material was obtained. This phosphate neodymium salt was completely dissolved in a short time, and it was confirmed that the solubility was very good. 0.042 g of methyl styrene was sufficiently mixed with the monomer composition, and a mixture of 0.42 g of t-butyl peroxy latex was added to a glass mold. The film was filled and polymerized and solidified to produce a film as an optical material or an optical member of the present invention.
  • FIG. 10 shows the result of measuring the spectral transmittance curve of this film. As shown in FIG. 10, this film clearly showed absorption around 580 nm, which is characteristic of neodymium ions.
  • Example 27 2 g of the neodymium phosphate ester synthesized in Example 27 was added to 20 g of MMA, and the mixture was stirred at room temperature for several minutes, and the concentration of the neodymium phosphate ester was 99.9% by weight. A liquid monomer composition as a material was obtained. This phosphate neodymium salt was completely dissolved in a short time, and it was confirmed that the solubility was very good.
  • 0.044 g of methyl styrene was sufficiently mixed with the monomer composition, and a mixture of 0.444 g of t-butyl pentoxide was further added to a glass mold. Then, it was polymerized and solidified to produce a film as the optical material or optical member of the present invention.
  • FIG. 11 shows the result of measuring the spectral transmittance curve of this film. As shown in FIG. 11, this film clearly showed absorption near a wavelength of 580 nm, which is characteristic of neodymium ions.
  • phosphate neodymium salt synthesized in Example 27 was added to 20 g of MMA, and the mixture was stirred at room temperature for several minutes.
  • the present invention wherein the concentration of neodymium phosphate was 20.0% by weight.
  • a liquid monomer composition as an optical material was obtained.
  • This phosphate neodymium salt was completely dissolved in a short time, confirming that the solubility was very good.
  • 0.05 g of methyl styrene was sufficiently mixed with the monomer composition, and a mixture obtained by adding 0.5 g of t-butyl peroxy latex was filled in a glass mold. Then, a film as an optical material or an optical member of the present invention was produced by polymerization and solidification.
  • FIG. 12 shows the result of measuring the spectral transmittance curve of this film. As shown in FIG. 12, this film clearly showed absorption near a wavelength of 580 nm, which is characteristic of neodymium ions.
  • Example 27 5 g of the phosphate neodymium salt synthesized in Example 27 was added to 10 g of MMA, and the mixture was stirred at room temperature for several minutes to obtain a phosphoric acid neodymium salt having a concentration of 33.333% by weight according to the present invention. A liquid monomer composition as an optical material was obtained. This phosphate neodymium salt was completely dissolved in a short time, confirming that the solubility was very good. 0.03 g of methyl styrene was sufficiently mixed with this monomer composition, and a mixture of 0.3 g of t-butylpropyl oxynoate was added to a glass mixture.
  • the optical material of the present invention or a film as an optical member was produced by filling the mixture into a mold and polymerizing and solidifying.
  • FIG. 13 shows the result of measuring the spectral transmittance curve of this film. As shown in FIG. 13, this film clearly showed absorption near a wavelength of 580 nm, which is characteristic of neodymium ions.
  • Example 27 0.5 g of the phosphate neodymium salt synthesized in Example 27 was added to 2 g of methylethyl ketone as a solvent, and the mixture was stirred at room temperature for several minutes to give a phosphate ester neodymium salt having a concentration of 20.0% by weight. A liquid optical material of the present invention was obtained. This ester neodymium phosphate salt was completely dissolved in a short time, and it was confirmed that the solubility was very good.
  • FIG. 14 shows the results of measuring the spectral transmittance curve of this liquid optical material. As shown in FIG. 14, this liquid optical material clearly showed the absorption around 580 nm, which is characteristic of neodymium ions, similarly to Examples 28 to 32 described above.
  • the monomer mixture is obtained.
  • the content of phosphate groups and amide groups in this monomer mixture is determined by polymerization Phosphoric acid groups in the active ingredient were 15.3% by mass, amide groups were 8.5% by mass, and the total was 23.8% by mass.
  • neodymium acetate monohydrate (the content of trivalent neodymium ions is 19.5 parts based on 100 parts of the polymerizable component), and the mixture is sufficiently stirred and mixed.
  • a monomer composition was prepared.
  • Cast polymerization was carried out using this monomer composition in the same manner as in Example 8 to produce a transparent plate-shaped optical material having a thickness of 2 mm. Further, when the light absorption and the water absorption were measured in the same manner as in Example 8, the light absorption was about 52% and the water absorption was about 4%.
  • neodymium acetate monohydrate (the content of trivalent neodymium ions relative to 100 parts of the polymerizable component was 4.3 parts) was added, and the mixture was sufficiently stirred and mixed.
  • a monomer composition was prepared. Casting polymerization was performed using this monomer composition in the same manner as in Example 8, to produce a transparent plate-shaped optical material having a thickness of 2 mm. Further, when the light absorption and the water absorption were measured in the same manner as in Example 8, the light absorption was about 23% and the water absorption was about 1%.
  • a monomer mixture was prepared by sufficiently mixing 28 parts of a mixture of the phosphate ester compounds represented by the formulas (69) to (73), 16 parts of DMAA, and 56 parts of MMA.
  • the content of phosphate groups and amide groups in this monomer mixture is determined by polymerization
  • the phosphoric acid group in the active ingredient was 8.57% by mass
  • the amide group was 6.8% by mass
  • the total was 15.37% by mass.
  • C Phosphoric acid group 44.2: 55.8.
  • To this monomer mixture is added 16 parts of neodymium acetate monohydrate (the content of trivalent neodymium ions is 6.8 parts based on 100 parts of the polymerizable component), and the mixture is sufficiently stirred and mixed.
  • a monomer composition was prepared.
  • Cast polymerization was carried out using this monomer composition in the same manner as in Example 8 to produce a transparent plate-shaped optical material having a thickness of 2 mm.
  • the light absorption and the water absorption were measured in the same manner as in Example 8. As a result, the light absorption was about 32%, and the water absorption was about 2%.
  • the monomer A mixture was prepared.
  • the content of the phosphate group and the amide group in the monomer mixture was 1.53% by mass of the phosphoric acid group in the polymerizable component, 0.4% by mass of the amide group, and 1.93% by mass in total. %,
  • neodymium acetate monohydrate 0.2 part of trivalent neodymium ion based on 100 parts of polymerizable component
  • a monomer composition was prepared.
  • Cast polymerization was carried out using this monomer composition in the same manner as in Example 8, to produce a transparent plate having a thickness of 2 mm.
  • An optical material having a thickness of 10 mm was manufactured. The light absorption and the water absorption of the test piece of this optical material were measured in the same manner as in Example 8, and the light absorption was about 10% and the water absorption was about 1%.
  • the monomer mixture By thoroughly mixing 17 parts of DMAA and 8 parts of 2 EHA, the monomer mixture was prepared.
  • the content of the phosphate group and the amide group in this monomer mixture was 23.0% by mass of the phosphoric acid group in the polymerizable component, 7.2% by mass of the amide group, and 30.2% by mass in total.
  • To this monomer mixture was added 70 parts of neodymium acetate monohydrate (the content of trivalent neodymium ions was 29.7 parts per 100 parts of the polymerizable component), and the mixture was thoroughly stirred and mixed.
  • a monomer composition was prepared.
  • Cast polymerization was carried out using this monomer composition in the same manner as in Example 8 to produce a transparent plate-shaped optical material having a thickness of 2 mm. Further, when the light absorption and the water absorption were measured in the same manner as in Example 8, the light absorption was about 56% and the water absorption was about 4%.
  • the monomer mixture is obtained.
  • the content of phosphoric acid groups and amide groups in this monomer mixture was 5.2 mass% for the phosphoric acid groups and 6.6 mass% for the amide groups in the polymerizable component, for a total of 11.8 mass%.
  • a monomer composition was prepared in the same manner as in Example 9 except that this monomer mixture was used, to produce a transparent plate-shaped optical material having a thickness of 2 mm.
  • the light absorption and the water absorption were measured in the same manner as in Example 8. As a result, the light absorption was about 26% and the water absorption was about 1%.
  • a monomer mixture was prepared by thoroughly mixing 25 parts of a mixture of the phosphate ester compounds represented by the formulas (69) to (73), 5 parts of MBAA, and 70 parts of MMA.
  • the content of the phosphate group and the amide group in this monomer mixture was as follows: 7.7% by mass of the phosphate group and 2.7% by mass of the amide group in the polymerizable component, and 10.4% by mass in total.
  • a monomer composition was prepared in the same manner as in Example 9 except that this monomer mixture was used, to produce a transparent plate-shaped optical material having a thickness of 2 mm. Further, when the light absorption and the water absorption were measured in the same manner as in Example 8, the light absorption was about 21% and the water absorption was about 1%.
  • a monomer mixture is obtained.
  • neodymium acetate monohydrate 8 parts of trivalent neodymium ion based on 100 parts of polymerizable component
  • praseodymium acetate dihydrate 10 parts of praseodymium acetate dihydrate
  • Cast polymerization was carried out using this monomer composition in the same manner as in Example 8 to produce a transparent plate-shaped optical material having a thickness of 2 mm. Further, when the light absorption and the water absorption were measured in the same manner as in Example 8, the light absorption was about 40% and the water absorption was about 4%.
  • Example 1 was repeated except that praseodymium acetate dihydrate was replaced by 10 parts of holmium acetate tetrahydrate (the content of trivalent holmium ion was 4.0 parts based on 100 parts of the polymerizable component). 2 mm thick transparent plate-shaped optical material as in 42 Made. Further, when the light absorption and the water absorption were measured in the same manner as in Example 8, the light absorption was about 33% and the water absorption was about 3%.
  • a thickness of 2 was obtained in the same manner as in Example 41 except that 8 parts of DMA cA was used instead of 5 parts of MB AA, and the amount of MMA was changed from 70 parts to 67 parts to prepare a monomer mixture.
  • a transparent plate-shaped optical material of mm was manufactured.
  • the content of the phosphoric acid group and the amide group in the above monomer mixture is 7.7% by mass for the phosphoric acid group and 3.9% by mass for the amide group in the polymerizable component, and the total is 11.6% by mass. %,
  • the light absorption and the water absorption were measured in the same manner as in Example 8. As a result, the light absorption was about 22% and the water absorption was about 7%.
  • the monomer composition thus prepared is poured into a disc molding mold (for molding a 2 mm-thick disc), and is heated at 35 ° C for 1 hour and from 35 ° C to 60 ° C for 6 hours. The temperature is raised from 60 ° C to 80 ° C in 2 hours, from 80 ° C to 100 ° C in 1 hour, and the mixture is heated at 100 ° C for 2 hours to perform casting polymerization.
  • Optical material thus, a transparent disk-shaped optical member having a thickness of 2 mm was obtained.
  • the light absorption and the water absorption were measured in the same manner as in Example 8. As a result, the light absorption at a wavelength of 520 nm was about 55%, and the water absorption was about 1%.
  • a monomer mixture comprising 30.3 parts of N- (3-dimethylaminopropyl) methacrylamide (specific amino group-containing monomer) and 37.7 parts of methyl methacrylate was prepared.
  • the content of the phosphoric acid group and the amino group in this monomer mixture was 9.8% by mass for the phosphoric acid group, 2.49% by mass for the amino group, and 12.3% by mass in total.
  • the monomer composition thus prepared was poured into a disk molding mold, and subjected to casting polymerization under the same conditions as in Example 45, to thereby obtain a 2 mm-thick film made of the optical material of the present invention.
  • the light absorption and the water absorption were measured in the same manner as in Example 8. As a result, the light absorption at a wavelength of 520 nm was about 56%, and the water absorption was about 2%.
  • a simple mixture comprising 53 parts of a mixture of the phosphoric ester compounds represented by the formulas (69) to (73) and 47.0 parts of N, N-dimethylaminoethyl methacrylate (a specific amino group-containing monomer)
  • a monomer mixture was prepared.
  • the content of the phosphoric acid group and the amino group in this monomer mixture was 16.2% by mass for the phosphoric acid group and 4.19% by mass for the amino group, and the total was 20.39% by mass.
  • Acetic acid is added to this monomer mixture.
  • the monomer composition thus prepared was poured into a disk molding mold, and subjected to casting polymerization under the same conditions as in Example 45, to thereby obtain a 2 mm-thick film made of the optical material of the present invention.
  • the light absorption and the water absorption were measured in the same manner as in Example 8. As a result, the light absorption at a wavelength of 520 nm was about 82%, and the water absorption was about 3%.
  • the monomer composition thus prepared was poured into a disk molding mold (for molding a 20 mm thick disk), and cast polymerization was carried out under the same conditions as in Example 45.
  • a transparent disk-shaped optical member having a thickness of 20 mm made of the above optical material was obtained.
  • the light absorption and the water absorption were measured in the same manner as in Example 8. As a result, the light absorption at a wavelength of 52 O nm was about 18%, and the water absorption was about 1%.
  • Example 49 20 parts of a mixture of the phosphoric ester compounds represented by the formulas (69) to (73), 70.0 parts of N, N-dimethylaminoethyl methacrylate (specific amino group-containing monomer), A monomer mixture consisting of 10.0 parts of methyl methacrylate was prepared.
  • the content of the phosphoric acid group and the amino group in this monomer mixture was 6.12% by mass of the phosphoric acid group, 6.24% by mass of the amino group, and 12.36% by mass in total.
  • This monomer mixture was mixed with 18.0 parts of erbium acetate tetrahydrate (7.23 parts of erbium ion based on 100 parts of monomer mixture) and t-butyl peroxyneodecanoe. To the mixture (polymerization initiator) was added 2.0 parts, and the mixture was sufficiently stirred and mixed to prepare a monomer composition.
  • the monomer composition thus prepared was poured into a disk molding mold, and subjected to casting polymerization under the same conditions as in Example 45, to thereby obtain a 2 mm-thick film made of the optical material of the present invention.
  • the light absorption and the water absorption were measured in the same manner as in Example 8. As a result, the light absorption at a wavelength of 520 nm was about 50%, and the water absorption was about 1%.
  • a monomer mixture was prepared.
  • the content of the phosphoric acid group and the amino group in this monomer mixture was 7.2% by mass for the phosphoric acid group, 2.77% by mass for the amino group, and 9.97% by mass in total.

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Abstract

La présente invention concerne un matériau optique comprenant des ions de métal de terres rares et des composés d'esters phosphoriques correspondant respectivement aux formules suivantes (30) et (31). Ce matériau présente une excellente stabilité thermique et chimique ainsi qu'une aptitude au moulage tout en préservant une propriété d'absorption et d'émission de lumière dans une zone de longueur d'onde donnée grâce aux ions de métal de terres rares.
PCT/JP2000/001104 1999-02-25 2000-02-25 Materiau optique et element optique obtenu a partir du materiau optique WO2000050932A1 (fr)

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JP11049003A JP2000247986A (ja) 1999-02-25 1999-02-25 光学材料及び該光学材料を用いた光学部材
JP11/49002 1999-02-25
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005073312A1 (fr) * 2004-01-30 2005-08-11 Kureha Corporation Composition de resine et element optique

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0702249A1 (fr) * 1994-09-13 1996-03-20 Kureha Kagaku Kogyo Kabushiki Kaisha Matière plastique pour l'optique et son procédé de fabrication
JPH1095890A (ja) * 1996-07-31 1998-04-14 Kureha Chem Ind Co Ltd プラスチック製光学材料およびその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0702249A1 (fr) * 1994-09-13 1996-03-20 Kureha Kagaku Kogyo Kabushiki Kaisha Matière plastique pour l'optique et son procédé de fabrication
JPH1095890A (ja) * 1996-07-31 1998-04-14 Kureha Chem Ind Co Ltd プラスチック製光学材料およびその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005073312A1 (fr) * 2004-01-30 2005-08-11 Kureha Corporation Composition de resine et element optique

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