JP2002006101A - Optical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical material which can improve molding processability as compared with a prior art while obtaining an excellent absorption characteristic or emission characteristic of a light of a specific wavelength. SOLUTION: The composition of matter of the present invention having the near-infrared light absorption characteristic is characterized in that it is composed by including either a phosphonic compound such as etyl-phosphonic acid, vinylphosphonic acid, or a phosphinic acid compound such as dimetyl- phosphinic acid, diphenyl-phoshinic acid, and a metal ion such as copper ion, a rare earth metal ion, in a solvent or in a resin. The composition can thus obtain the absorption characteristic or emission characteristic of a light of a specific wavelength and, on top of that, doesn't undergo pyrolysis so often as before.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical material, and more particularly, to an optical material having an absorption characteristic or a light emission characteristic with respect to light having a specific wavelength (specific wavelength light) specific to metal ions.

[0002]

2. Description of the Related Art Conventionally, as an optical material utilizing absorption or emission characteristics of light of a specific wavelength expressed by metal ions,
For example, a material constituting the optical filter described in International Publication WO9926952 by the present applicant can be mentioned. This optical material contains a phosphate ester compound and copper ions, and has near infrared light absorption characteristics. In addition, JP-A-2000-98130 discloses that
There is a description about an optical filter obtained by adding a copper salt when polymerizing a phosphinic acid compound having a (meth) acrylic group and a resin.

[0003]

However, such conventional optical materials and optical filters do not always have sufficient moldability and, more specifically, chemical stability in thermoforming. In some cases, devitrification or discoloration to the extent that it is difficult to use as an optical material occurs. And to improve the simplicity of molding and the variety of shapes,
A material that can further increase the molding temperature when a resin composition is formed has been desired. Further, the optical filter using the phosphinic acid compound described in JP-A-2000-98130 has a tendency to exhibit thermosetting properties due to the formation of a crosslinked structure, thereby being easily restricted by molding. .

Accordingly, the present invention has been made in view of such circumstances, and an optical material having excellent absorption characteristics or emission characteristics of light of a specific wavelength and capable of improving molding workability as compared with the related art. The purpose is to provide.

[0005]

In order to solve the above-mentioned problems, an optical material according to the present invention comprises a phosphonic acid compound represented by the formula (1) or a phosphinic acid compound represented by the formula (2) and a metal ion Is contained in a solvent or a resin. Here, the metal ion is not particularly limited, and is preferably an alkali metal, an alkaline earth metal, a transition metal, or a rare earth metal ion, and the optical material according to the present invention is a transition metal among these metal ions. Alternatively, a material containing a rare earth metal is preferable. In the present invention, “transition metal” refers to a compound having an atomic number of 21.
(Scandium) to 30 (zinc), 39 (yttrium) to 48 (cadmium), 72 (hafnium) to 80
(Mercury) indicates a metal.

[0006] These metals (ions) exhibit light absorption characteristics or light emission characteristics peculiar to the atomic structure, and when these are used, optical materials having various optical characteristics can be obtained. In particular, transition metals and rare earth metals exhibit near-infrared light absorption properties, which are considered to be due to electronic transitions in d-orbital or f-orbital, and absorb or emit visible light at a specific wavelength. Can be formed.

Further, among these metals, sodium, potassium, magnesium, calcium, iron, manganese, nickel, cobalt, chromium, copper, neodymium, praseodymium, europium, thulium, erbium, terbium, dysprosium, samarium, lanthanum, Gadolinium, holmium and the like are useful metals. Among them, as the optical material of the present invention, metal ions include iron, manganese, nickel, cobalt, chromium, copper, neodymium,
Praseodymium, europium, thulium, erbium,
Terbium, dysprosium, samarium, lanthanum,
Suitably, it is an ion of at least one metal of gadolinium and holmium.

[0008] In particular, copper is coordinated or bonded to a phosphonic acid or phosphinic acid compound and can exhibit excellent near-infrared light absorption characteristics and visible light transmission characteristics. In addition, neodymium, praseodymium, europium, thulium, or erbium has a large and steep absorption peak at the absorption wavelength, has excellent wavelength component selectivity, and tends to have high luminous efficiency such as fluorescence.

The thermal stability of the optical material using the phosphonic acid compound represented by the formula (1) or the phosphinic acid compound represented by the formula (2) according to the present invention and the conventional optical material are shown. As a result of the evaluation, it was confirmed that the optical material according to the present invention was less likely to be thermally decomposed than in the past.

It is considered that the heat resistance of the metal salt of the compound represented by the formula (1) or (2) is improved due to the bonding stability of the compound. Details are unknown, but
Specifically, in addition to including a PC bond having a large bond energy as a bond of a phosphorus atom, it is presumed that this does not include a specific ester structure having a smaller bond energy (eg, an ester group derived from a methacryloyl group). Is done. However, the function and mechanism are not limited to this.

Further, in the optical material of the present invention, the properties and properties according to the solvent and resin used are dissolved or dispersed in the optical material and / or a molded product thereof (polymerizable solvent or monomer constituting the resin). Is obtained by polymerizing the product. Therefore, an optical material suitable for various uses can be obtained by appropriately selecting these solvents and resins.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the optical material according to the present invention and optical members and the like using the optical material will be described below.

<Metal Ion> The metal ion constituting the optical material of the present invention is not particularly limited as to the kind of metal, but alkali metal, alkaline earth metal, transition metal or rare earth metal ions are preferably used. Can be These metal ions have light absorption characteristics or light emission characteristics peculiar to the electronic structure of each metal atom, and an optical material exhibiting various optical characteristics can be obtained. In particular, transition metals and rare earth metals exhibit near-infrared light absorption characteristics, which are considered to be due to electronic transitions in d orbitals and f orbitals, respectively, and also exhibit visible light absorption or emission characteristics of a specific wavelength, and thus have excellent functionality. Optical materials can be formed.

Specific examples of such a metal ion include:
Lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper,
Zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, lutetium Examples include ions of hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury and the like.

The metal ion source is not particularly limited as long as it contains such a metal. However, such a metal ion source is not limited to acetic acid, formic acid, stearic acid, benzoic acid, ethyl acetoacetic acid, Acids, pyrophosphoric acid, naphthenic acid, organic acids such as citric acid, or sulfuric acid, hydrochloric acid, nitric acid, salts with inorganic acids such as hydrofluoric acid, basic carbonates, hydroxides, oxides, their anhydrides or Hydrates or hydrates are exemplified.

Among these metal ions, sodium, potassium, magnesium, calcium, iron, manganese, nickel, cobalt, chromium, copper, neodymium, praseodymium, europium, thulium, erbium, terbium, dysprosium, samarium, lanthanum, gadolinium , Ions such as holmium are more preferred, especially iron, manganese, nickel, cobalt, chromium, copper,
Neodymium, Praseodymium, Europium, Thulium, Erbium, Terbium, Dysprosium, Samarium,
More preferably, it is an ion of at least one metal of lanthanum, gadolinium and holmium.

In particular, copper is light in the near infrared region (near infrared light)
It has good absorption characteristics and visible light transmission characteristics for NIR, and more specifically, near-infrared light is selectively absorbed by the electronic transition of the d-orbit of copper ions, resulting in excellent near-infrared light absorption. The property is developed. Thereby, it is possible to obtain an optical material suitable for various uses such as visibility correction, photometry, near-infrared light and infrared light cut, heat ray absorption, and brightness adjustment.

Neodymium, praseodymium, europium, thulium or erbium have excellent absorption characteristics and selectivity for light having a wavelength specific to each ion (specifically, the absorption peak is large and steep). For example, trivalent neodymium ions have a property of sharply absorbing light near a wavelength of 580 nm, and erbium ions have a property of sharply absorbing light near a wavelength of 520 nm.

Such an optical material containing a rare earth metal ion can form an optical member having excellent antiglare property for visible light, and can be used for laser light (wavelength of about 520 nm) used in medical or processing lasers. An optical member having excellent eye protection can be formed. Furthermore, among these rare earth metal ions, among the rare earth metal ions, fluorescent light is emitted with high efficiency or laser light is emitted. Therefore, by using these rare earth metal ions, an excellent light amplification function can be exhibited. Optical materials can be formed.

These metal ions are used alone or in combination of two or more. At this time, the amount of the metal ions used is adjusted so that the content ratio in the optical material is preferably 2 to 60% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 25% by mass. You.
If the content of the metal ions is less than 2% by mass, it tends to be difficult to obtain sufficient absorption characteristics for light of a specific wavelength depending on the thickness of the optical material. On the other hand, when this content ratio is 6
If it exceeds 0% by mass, it tends to be difficult to uniformly dissolve or disperse the metal ions in the optical material, depending on the type of the metal ions.

The content of copper ions and / or rare earth metal ions in the optical material is, for example, 5% of the total metal ion amount.
It is suitable that the content is 0% by mass or more, preferably 70% by mass or more. By doing so, an optical material having optical characteristics specific to copper ions and / or rare earth metal ions can be reliably obtained.

<Phosphonic acid compound and phosphinic acid compound> The optical material of the present invention contains a phosphonic acid compound represented by the following formula (1) or a phosphinic acid compound represented by the following formula (2).

[0023]

Embedded image

Here, R ¹ , R ² and R ³ in the formula represent a branched, linear or cyclic alkyl, alkenyl, alkynyl, aryl or aryl group having 1 to 30 carbon atoms. Wherein at least one hydrogen atom is a halogen atom, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, an acyl group, an aldehyde group, a carboxyl group, a hydroxyl group, or a group having an aromatic ring May or may not be substituted.

Examples of the phosphonic acid compound represented by the formula (1) include ethylphosphonic acid, vinylphosphonic acid, n-
Butylphosphonic acid, 2-ethylhexylphosphonic acid, 3
-Bromopropylphosphonic acid, 3-methoxybutylphosphonic acid, benzenephosphonic acid, 4-methoxyphenylphosphonic acid, and the like, that is, phosphonic acid compounds represented by the following formulas (3) to (10).

[0026]

Embedded image

Examples of the phosphinic acid compound represented by the formula (2) include dimethylphosphinic acid, diphenylphosphinic acid, bis (1,1,3,3-tetramethylbutyl) phosphinic acid, and 2-phenylphosphinic acid. Examples include finopropanoic acid and the like, that is, phosphinic acid compounds represented by the following formulas (11) to (14).

[0028]

Embedded image

Here, when the number of carbon atoms of the group R ¹ in the formula (1) and the groups R ² and R ³ in the formula (2) exceeds 20, the phosphonic acid compound represented by the formula (1) or When the phosphinic acid compound represented by the formula (2) is contained in a resin to be described later, the compatibility with the resin may be reduced, and this tends to make it difficult to disperse metal ions in the resin. is there.

<Optical Material> The optical material according to the present invention comprises the above-mentioned phosphonic acid compound or phosphinic acid compound and the above-mentioned compound containing a metal ion (metal ion source), in other words, phosphonic acid obtained by the reaction thereof. A metal compound or a metal phosphinate (hereinafter collectively referred to as "specific metal compound" for convenience of description) is contained in a solvent or a resin. Preferred embodiments of such an optical material include, for example, the following. [First Embodiment]: Liquid composition containing a specific metal compound [Second Embodiment]: Resin composition containing a specific metal compound [Third Embodiment]: Adhesiveness containing a specific metal compound Composition

<First Embodiment> The optical material of this embodiment is a liquid composition in which a specific metal compound is contained in a solvent (solvent). As the liquid composition, the thin film or thin layer formed by evaporating the solvent is preferably transparent to light having a wavelength other than the absorption wavelength of metal ions, and the liquid composition itself is transparent. , Translucent or opaque.

As the solvent, water or an organic solvent can be used. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol, and glycol ethers such as methyl cellosolve and ethyl cellosolve. , Diethyl ether,
Ethers such as diisopropyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, ethyl acetate, isopropyl acetate, butyl acetate, esters such as butyl acetate cellosolve, aromatic compounds such as benzene, toluene, xylene,
Hexane, kerosene, petroleum ether and the like are used. Further, as other solvents, for example, organic solvents such as (meth) acrylates such as (meth) acrylate and the like and aromatic vinyl compounds such as styrene and α-methylstyrene can be used.

Note that the "meta" enclosed in parentheses ()
Is a description method that is used for convenience to simplify the description when it is necessary to describe both acrylic acid or a derivative thereof and methacrylic acid or a derivative thereof, and is also adopted in this specification. It was done.

When an organic solvent is used as a solvent, the liquid composition can be produced, for example, by reacting a phosphonic acid compound or a phosphinic acid compound with a salt as a metal ion source in an appropriate organic solvent.

The organic solvent is not particularly limited as long as it can dissolve or disperse the phosphonic acid compound or the phosphinic acid compound used. Examples thereof include aromatic compounds such as benzene, toluene and xylene, and furan such as tetrahydrofuran. Or furan derivatives, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, glycol ethers such as methyl cellosolve and ethyl cellosolve, ethers such as diethyl ether, diisopropyl ether and dibutyl ether, acetone,
Examples include ketones such as methyl ethyl ketone, esters such as ethyl acetate, hexane, kerosene, petroleum ether and the like. Further, organic solvents having polymerizability such as (meth) acrylates such as (meth) acrylate, aromatic vinyl compounds such as styrene and α-methylstyrene are also used.

As another production method, a specific metal compound obtained by mixing a phosphonic acid compound or a phosphinic acid compound with a salt serving as a metal ion source to allow them to react with each other is dissolved in an appropriate solvent. Alternatively, it can be prepared by dispersing. In these methods, a dissolution aid for promoting the dissolution of the metal compound serving as the metal ion source in the phosphonic acid compound or the phosphinic acid compound or in the solvent may be added.

The content ratio of the specific metal compound contained in the liquid composition varies depending on the type of the solvent used, the use of the optical material or the purpose of use, etc., but from the viewpoint of the viscosity after preparation, the solvent is usually used. 0.1 parts per 100 parts by mass
The amount is adjusted within the range of 1 to 1900 parts by mass, preferably 1 to 900 parts by mass, particularly preferably 5 to 400 parts by mass.

Second Embodiment The optical material of this embodiment is a composition in which a specific metal compound is contained in a resin. The specific metal compound has excellent compatibility with the resin, and the metal ions can be well dispersed in the resin. The resin is not particularly limited as long as the resin has excellent compatibility or dispersibility with a phosphonic acid compound or a phosphinic acid compound and / or a specific metal compound. As such a resin, for example, a resin such as an acrylic resin shown below can be preferably used.

As the acrylic resin, a (meth) acrylate monomer or a polymer obtained therefrom is preferably used. Specific examples of (meth) acrylate monomers having a monofunctional group include methyl (meth) acrylate, ethyl (meth) acrylate, n-
Alkyl (meth) acrylates such as propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, n-hexyl (meth) acrylate, and n-octyl (meth) acrylate , Glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isobornyl (meth) acrylate, methoxypolyethylene (meth) acrylate, phenoxy ( Modified (meth) acrylates such as meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth)
Acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 2-hydroxy-1,3-di (meth) acrylate, 2,2-bis [4- (meth) acryloxyethoxyphenyl] propane, 2-hydroxy-1- (meth) acryloxy-3- Multifunctional (meth) such as (meth) acryloxypropane, trimethylolpropane tri (meth) acrylate, pentaerythrit tri (meth) acrylate, pentaerythrit tetra (meth) acrylate
Acrylates and the like.

As another resin, the above (meth)
Other copolymerizable monomers capable of copolymerizing the acrylate monomer and the (meth) acrylate monomer are also used. Specific examples of such a copolymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, and 2- (meth) acryloyloxyethylphthalic acid; , N-
Examples include acrylamides such as dimethylacrylamide, and aromatic vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, dibromostyrene, methoxystyrene, vinylbenzoic acid, and hydroxymethylstyrene.

Further, examples of the resin polymer (polymer) include polyethylene terephthalate (PET), polyethylene, polypropylene, polyvinyl chloride, various polycarbonates (polycarbonates), various polyurethanes, various epoxy resins, and the like. Is styrene, α-
Methyl styrene, chlorostyrene, dibromostyrene,
Examples include polymers of aromatic vinyl compounds such as methoxystyrene, vinylbenzoic acid, hydroxymethylstyrene, and divinylbenzene.

Here, when only a monofunctional monomer is used as the monomer constituting the resin, a thermoplastic molded product is obtained, and a part or all of the monomer is polyfunctional. When a thermosetting material is used, a thermosetting molded body is obtained. Therefore, by appropriately selecting these resins, it is possible to obtain a molded article of an optical material according to the purpose of use, application, molding method, and the like. Of these,
If a thermoplastic material is used, remolding after polymerization becomes easy, so that moldability is improved.

The specific method for preparing the resin composition is not particularly limited, but it is preferable to use the following two methods.

[First Method for Preparing Resin Composition]: In this method, a phosphonic acid compound or a phosphinic acid compound and a metal ion source, or a specific metal compound obtained by the reaction of both are added to a monomer. This is a method of preparing a monomer composition by incorporating the compound. This monomer composition can be used as it is as an optical material without being polymerized, or this monomer composition may be subjected to radical polymerization treatment to be used as an optical material.

In this method, specific examples of the radical polymerization treatment of the monomer composition include a radical polymerization method using a usual radical polymerization initiator, for example, a bulk (cast) polymerization method, a suspension polymerization method, Known methods such as an emulsion polymerization method and a solution polymerization method can be used. However, the polymerization treatment method is not limited to these. In addition, from the viewpoint of improving the weather resistance and heat resistance of the molded article of the optical material obtained by polymerization of the monomer composition, the monomer composition may include various high-absorbing agents such as an ultraviolet absorber and a light stabilizer. It is preferred to add a molecular additive. Various colorants may be added to adjust the color tone of the optical material.

Examples of such an ultraviolet absorber include salicylates such as p-tert-butylphenyl salicylate, 2,4-dihydroxybenzophenone,
Benzophenones such as 2-hydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-3'-ter
Benzotriazoles such as t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-octylphenyl) benzotriazole, ethyl-2-cyano-3,3-diphenyl Ultraviolet absorbers such as cyanoacrylates such as acrylates are exemplified.

As the light stabilizer, for example, bis (1,2,2,6,6 pentamethyl-4-piperidyl)
Sebacate, bis (2,2,6,6-tetramethyl-4
-Piperidyl) sebacate, di (1,2,2,6,6-
Pentamethyl-4-piperidyl) -butyl (3 ′, 5 ′
-Di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2- (3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -4- (3- (3, 5-di-tert-butyl-4
-Hydroxyphenyl) propionyloxy) -2,
2,6,6-tetramethylpiperidine, poly {(6-
{1,1,3,3-tetramethylbutyl) amino}-
1,3,5-triazine-2,4-diyl) (1,6-
{2,2,6,6-tetramethyl-4-piperidinyl}
Aminohexamethylene)}, poly {6- (morpholino) -S-triazine-2,4-diyl} 1,6-
(2,2,6,6-tetramethyl-4-piperidyl) amino {hexamethylene}, 4-hydroxy-2,2,
Various hindered amine light stabilizers such as a dimethyl succinate polymer with 6,6-tetramethyl-1-piperidinethanol can be used.

Further, as the radical polymerization initiator, an ordinary organic peroxide-based polymerization initiator can be used.
tert-butyl peroxy neodecanoate, tert
-Butylperoxydecanoate, tert-butylperoxypivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxylaurate,
peroxyesters such as tert-butylperoxy-3,5,5-trimethylhexanoate; diacyl peroxides such as lauroyl peroxide and 3,5,5-trimethylhexanoyl peroxide; 1,1-
Peroxy ketals such as bis (tert-butylperoxy) -3,5,5-trimethylcyclohexane are preferably used.

Alternatively, 2,2-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis (cyclohexane-
An azo radical polymerization initiator such as 2-carbonitrile) is also preferably used.

[Second resin composition preparation method]: This method comprises adding a phosphonic acid compound or a phosphinic acid compound and a metal ion source or a specific metal compound obtained by the reaction of both to a resin. It is a method of mixing. This method is effective when used when a thermoplastic resin is used as the resin. Specifically, the following two methods are exemplified.

(1) a method in which a phosphonic acid compound or a phosphinic acid compound and a metal ion source or a specific metal compound are added to a molten resin and kneaded, and (2) the resin is dissolved in an appropriate organic solvent. There is a method of dissolving, dispersing or swelling, adding a phosphonic acid compound or a phosphinic acid compound and a metal ion source or a specific metal compound to the solution and mixing them, and then removing the organic solvent from the solution. In any of these methods, it is effective to add various solubilizers in order to enhance the solubility of the metal ion source. Therefore, such a treatment is preferable.

Among the above two preparation methods, the kneading means in the former method (method (1)) is a means generally used as a method for melt-kneading thermoplastic resins, for example, melt-kneading with a mixing roll. Means, premixing with a Henschel mixer or the like, and then melt kneading with an extruder.

On the other hand, the organic solvent used in the latter method (method (2)) is not particularly limited as long as it can dissolve, disperse or swell the resin, and specific examples thereof include: , Alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene and xylene, chlorinated hydrocarbons such as methylene chloride, dimethylacrylamide and dimethylform Examples include amide compounds such as amides.

Here, although the content ratio of the specific metal compound in the optical material of the present embodiment, that is, the resin composition, differs depending on the use of the optical material, the purpose of use, etc., usually, from the viewpoint of moldability, the resin 100% For parts by mass,
The amount is adjusted within the range of 0.1 to 400 parts by mass, preferably 0.3 to 200 parts by mass, particularly preferably 1 to 100 parts by mass. Further, the content ratio of the metal ion in the resin composition is adjusted so as to be preferably 2 to 60% by mass with respect to the entire resin composition as described above.

Third Embodiment The optical material of this embodiment is an embodiment of a resin composition in which a specific metal compound is contained in an adhesive resin (hereinafter referred to as “adhesive resin”). A composition comprising: Examples of such an adhesive resin include an acrylic resin having adhesiveness, polyvinyl butyral, an ethylene-vinyl acetate copolymer, or a partially saponified product thereof. The adhesive composition of the present embodiment is obtained by mixing a phosphonic acid compound or a phosphinic acid compound and a metal ion source or a specific metal compound with these adhesive resins.

The adhesive composition may further contain a benzotriazole-based, benzophenone-based or salicylic acid-based ultraviolet absorber, other antioxidants, stabilizers, and the like. Further, various plasticizers can be contained. Such plasticizers include phosphate plasticizers such as tricresyl phosphate and triphenyl phosphate, phthalic plasticizers such as dioctyl phthalate and dibutyl phthalate, dibutyl sebacate, butyl ricinolate, and methyl acetyl ricinolate. And butyl succinate and the like, and glycol-based plasticizers such as butyl phthalyl butyl glycolate, triethylene glycol dibutyrate, triethylene glycol di-2-ethyl butyrate, and polyethylene glycol.

In the optical material of the present invention described above, an oxygen atom derived from a hydroxyl group of a phosphonic acid compound or a phosphinic acid compound is bonded to a metal ion through a coordination bond and / or an ionic bond. Therefore, since the metal ion is dissolved or dispersed in the composition in a state surrounded by the phosphonic acid group or the phosphinic acid group, the light absorption characteristic or the emission characteristic specific to the atomic structure of the metal (ion) used is good. Is expressed in Therefore, it is possible to obtain an optical material having optical characteristics according to the light absorption characteristics, light transmission characteristics, or light emission characteristics of the metal ion.

In the phosphonic acid compound represented by the formula (1) or the phosphinic acid compound represented by the formula (2), the bond of the phosphorus atom in the molecule is determined by the method of P By containing a PC bond stronger than a -OC bond, heat resistance and the like are improved as compared with such a conventional phosphoric acid type compound.

Further, the phosphonic acid compound represented by the formula (1) or the phosphinic acid compound represented by the formula (2) has a specific ester structure contained in a conventional phosphonic acid compound having a (meth) acrylic group, That is, it does not have an ester group derived from a (meth) acryloyl group. Such an ester structure has a smaller binding energy than a P-O-C bond.

Therefore, the optical material according to the present invention can further improve the thermal stability as compared with such a phosphonic acid compound having a specific ester structure, and further, as compared with the phosphinic acid compound. However, the operation is not limited to these. Therefore, the optical material according to the present invention is less likely to be thermally decomposed than in the past, and in particular, the molding temperature when forming a resin composition can be increased, and the moldability can be improved.

As the phosphonic acid compound represented by the formula (1) or the phosphinic acid compound represented by the formula (2),
When R ¹ , R ² and R ³ in the formula use a substituted or unsubstituted alkyl group or aryl group, the stability of the optical material itself against heat and ultraviolet rays is enhanced. Furthermore, when a resin composition is used, a crosslinked structure between the phosphonic acid compound or the phosphinic acid compound and the resin is not formed, so that the development of thermosetting properties can be suppressed, and the moldability of the optical material can be further improved.

Further, among the above-mentioned metal ions, sodium, potassium, magnesium, calcium, iron, manganese, nickel, cobalt, copper, neodymium, praseodymium, europium, thulium, erbium, terbium, dysprosium, samarium, holmium, etc. When ions are used, it is possible to obtain an optical material having an excellent optical function.

In particular, copper can be coordinated or bonded to a phosphonic acid compound or a phosphinic acid compound to exhibit extremely excellent near-infrared light absorption characteristics and visible light transmittance, and to correct luminous efficiency,
An optical material suitable for various uses such as photometry, near-infrared light and infrared light cut, heat ray absorption, and brightness adjustment can be obtained.

Further, neodymium, praseodymium, europium, thulium, erbium, terbium, dysprosium, samarium, and holmium have a large and steep absorption peak in the absorption wavelength. Moreover, while having excellent wavelength component selectivity, fluorescence emission efficiency tends to be high,
Alternatively, laser light is emitted. So from these things,
It is possible to form an optical material suitable for various uses such as visibility correction, optical amplification, protective shielding, and the like.

Further, since the phosphonic acid compound represented by the formula (1) and / or the phosphinic acid compound represented by the formula (2) and the above-mentioned metal ion are contained in the solvent or the resin, the The properties and properties according to the solvent and the resin can be imparted to the optical material or the optical member that is a molded product thereof. Therefore, by appropriately selecting these solvents and resins, a high-performance optical material suitable for various uses can be easily and reliably produced.

Furthermore, since the optical material can be in various forms (specific metal compound itself, liquid composition, resin composition, adhesive composition, etc.), excellent properties according to each form, for example, molding Processability, thermoplasticity, thermosetting, transparency, weather resistance, light weight, adhesiveness, easy handling, ease of application, drying property, etc. can be imparted to the optical material and / or its molded product. Therefore, a versatile optical material applicable to various uses can be obtained.

<Optical Member> By using the optical material according to the present invention, optical members suitable for various uses can be formed. Examples of the form of the optical member include, for example, an optical material itself, a material combined with a light-transmitting material, a molded material, and the like. Specifically, powder, liquid, adhesive, paint, film Various shapes such as a shape, a plate shape, a tube shape, and a lens shape can be adopted.

Such an optical member has excellent durability, weather resistance, optical characteristics, versatility, economy, and the like, and further has excellent moldability realized by the present invention. Correction member, photometry member, heat ray absorption member, composite optical filter, lens member (eyeglasses, sunglasses, goggles, optical system, optical waveguide system), fiber member (optical fiber), or other light receiving element Noise cut member, display cover or display filter such as plasma display front plate, projector front plate, light source heat ray cut member, color tone correction member, illumination brightness adjustment member, optical element (optical amplification element, wavelength conversion element, etc.), Faraday element , Optical communication function devices such as isolators, optical disk elements, and the like.

[0069]

EXAMPLES Hereinafter, specific examples according to the present invention will be described, but the present invention is not limited to these examples.

<Synthesis Example 1> Tetrahydrofuran 18.0
0.91 g of ethylphosphonic acid was dissolved in g. 0.50 g of anhydrous copper acetate was added thereto, and the mixture was stirred for 2 hours while being heated so that the internal temperature became 60 ° C. After filtering the precipitate, 4
Vacuum drying was performed overnight at 0 ° C. to obtain a copper complex.

<Synthesis Example 2> A copper complex was obtained in the same manner as in Synthesis Example 1, except that 0.89 g of vinylphosphonic acid was used instead of ethylphosphonic acid.

<Synthesis Example 3> Instead of ethylphosphonic acid
A copper complex was obtained in the same manner as in Synthesis Example 1 except that 1.14 g of n-butylphosphonic acid was used.

<Synthesis Example 4> A copper complex was obtained in the same manner as in Synthesis Example 1, except that 0.32 g of 2-ethylhexylphosphonic acid was used instead of ethylphosphonic acid.

<Synthesis Example 5> A copper complex was obtained in the same manner as in Synthesis Example 1 except that 1.68 g of 3-bromopropylphosphonic acid was used instead of ethylphosphonic acid.

<Synthesis Example 6> A copper complex was obtained in the same manner as in Synthesis Example 1, except that 2.00 g of 3-methoxybutylphosphonic acid was used instead of ethylphosphonic acid.

<Synthesis Example 7> A copper complex was obtained in the same manner as in Synthesis Example 1 except that 1.32 g of benzenephosphonic acid was used instead of ethylphosphonic acid.

Synthesis Example 8 A copper complex was obtained in the same manner as in Synthesis Example 1 except that 1.55 g of 4-methoxyphenylphosphonic acid was used instead of ethylphosphonic acid.

Synthesis Example 9 A copper complex was obtained in the same manner as in Synthesis Example 1, except that 18.0 g of ethanol was used instead of tetrahydrofuran and 0.32 g of dimethylphosphinic acid was used instead of ethylphosphonic acid. .

<Synthesis Example 10> 0.5 g of copper acetate anhydride was dissolved in 20.0 g of ethanol, and 1.09 g of diphenylphosphinic acid was added thereto. After stirring at 60 ° C. for 2 hours, the precipitate was filtered and vacuum dried at 40 ° C. overnight to obtain a copper complex.

<Synthesis Example 11> 4.79 g of bis (1,1,3,3-tetramethylbutyl) phosphinic acid (manufactured by Nippon Chemical Co., Ltd., product name: Hostar) was dissolved in 18.0 g of ethanol. To this, 0.50 g of copper acetate monohydrate was added, and the mixture was stirred for 2 hours while being heated to an internal temperature of 60 ° C. Then, after all of the anhydrous copper acetate was dissolved, the solution was allowed to stand overnight, and the precipitated blue crystals were filtered to obtain a copper complex.

<Synthesis Example 12> 2 in 18.0 g of ethanol
-1.18 g of phenylphosphinopropanoic acid (manufactured by Nippon Chemical Co., Ltd., product name: diphosmer PC-6HA) was dissolved. 0.50 g of copper acetate monohydrate was added thereto, and the internal temperature was 6
The mixture was stirred for 2 hours while being heated to 0 ° C. The precipitate was filtered and dried to obtain a copper complex.

Comparative Example 1 Monomethyl phosphoric acid 0.62 represented by the following formula (15) instead of ethylphosphonic acid:
g, and a copper complex was obtained in the same manner as in Synthesis Example 1 except that 0.69 g of dimethyl phosphoric acid represented by the following formula (16) was used.

[0083]

Embedded image

<Comparative Example 2> Instead of ethylphosphonic acid, 1.20 g of mono-2-ethylhexyl phosphoric acid represented by the following formula (17) and di-diethyl represented by the following formula (18)
A copper complex was obtained in the same manner as in Synthesis Example 1 except that 1.80 g of 2-ethylhexyl phosphoric acid was used.

[0085]

Embedded image

Comparative Example 3 0.5 g of copper acetate anhydride was dissolved in 20.0 g of ethanol, 1.25 g of diphenylphosphoric acid represented by the following formula (19) was added, and the internal temperature was adjusted to 60 ° C. And stirred for 2 hours. After completion of the reaction, the reaction solvent and acetic acid produced as a by-product are distilled off from the reaction solution,
Vacuum drying was performed at 40 ° C. overnight to obtain a copper complex.

[0087]

Embedded image

Comparative Example 4 0.32 g of a phosphoric ester compound represented by the following formula (20) was added to 18.0 g of toluene.
In addition, 0.45 g of a phosphate compound represented by the following formula (21) was dissolved. To this, copper acetate monohydrate 0.5
0 g was added, and the mixture was stirred for 2 hours while being heated to an internal temperature of 60 ° C. After the completion of the reaction, the reaction solvent and acetic acid produced as a by-product were distilled off, followed by vacuum drying at 40 ° C. overnight to obtain a copper complex.

[0089]

Embedded image

<Thermal Stability Test> The thermal decomposition characteristics of the optical materials (copper complexes) obtained in Synthesis Examples 1 to 12 and Comparative Examples 1 to 4 were measured using the following measuring apparatus and measuring conditions: a) Measuring apparatus: METTLER TA4000 thermal analysis system manufactured by Hitachi, Ltd. b) Measurement conditions: heating rate; 10 ° C./min, temperature range: 30
３００300 ° C. in a nitrogen atmosphere. Table 1 shows the measurement results of the temperature (pyrolysis temperature) when the weight was reduced by 1% and 5% from that before heating.

[0091]

[Table 1]

From these results, it was confirmed that the phosphonic acid compound and the complex of the phosphinic acid compound and the copper ion used in the present invention have extremely high thermal stability as compared with the prior art.

Example 1 0.31 g of the copper complex prepared in Synthesis Example 4 was finely crushed, and 9.69 g of methyl methacrylate and 10.0 g of cyclohexyl methacrylate were obtained.
g and α-methylstyrene 0.04 g to obtain a prepared solution (monomer solution). To this monomer solution, t-butylperoxydecanoate was added as a radical initiator in 0.1 ml.
Add 20 g, place in a test tube, and add
Polymerization was carried out by sequentially raising the temperature to 8 ° C. for 8 hours and 100 ° C. for 3 hours to obtain a cylindrical optical material.

Example 2 0.50 g of the copper complex prepared in Synthesis Example 1 was finely crushed, and this was
Y-105 (manufactured by Mitsubishi Rayon Co., Ltd., product name: MMA syrup) was mixed with 19.50 g to prepare a prepared solution (monomer solution).
I got As a radical initiator, t-
Add 0.20 g of butylperoxydecanoate, place in a test tube, at 45 ° C. for 16 hours, 60 ° C. for 8 hours, 100
The temperature was sequentially raised to a different temperature at 3 ° C. for 3 hours to carry out polymerization to obtain a columnar optical material.

Example 3 A cylindrical optical material was prepared in the same manner as in Example 1 except that the copper complex prepared in Synthesis Example 1 was replaced by 0.50 g of the copper complex prepared in Synthesis Example 7. Obtained.

Comparative Example 5 0.50 g of the copper complex prepared in Comparative Example 4 was finely crushed, and methyl methacrylate 1
9.50 g and 0.04 g of α-methylstyrene were mixed to obtain a preparation solution (monomer solution). To this monomer solution, 0.20 g of t-butyl peroxydecane as a radical initiator was added, and the mixture was placed in a test tube.
The temperature was sequentially raised to different temperatures of 60 ° C. for 8 hours and 100 ° C. for 3 hours to carry out polymerization to obtain a columnar optical material.

Comparative Example 6 17 g of a phosphoric ester compound represented by the following formula (22), 18 g of a phosphoric ester compound represented by the following formula (23), and methyl methacrylate 3
64.6 g and 0.9 g of α-methylstyrene were mixed to obtain a preparation solution.

[0098]

Embedded image

To this was added 32 g of copper benzoate, and the internal temperature was 6
The mixture was heated to 0 ° C. and stirred for 2 hours. After the copper benzoate is dissolved, the monomer solution is left in a refrigerator at −20 ° C. for 24 hours to crystallize and precipitate benzoic acid (melting point: 122 ° C.). Separated by filtration below. To the obtained monomer solution, 2.0 g of t-butyl peroxyoctanoate as a radical initiator was added, and the mixture was placed in a test tube and kept at 45 ° C for 16 hours for 6 hours.
Polymerization was performed by sequentially raising the temperature to different temperatures of 0 ° C. for 8 hours and 100 ° C. for 3 hours to obtain a cylindrical optical material.

<Heat Press Test> A heat press test was performed on the optical materials prepared in Examples 1 to 3 and Comparative Examples 5 and 6. FIG. 1A is a cross-sectional view schematically illustrating a state in which an optical material is arranged on a heating press machine in a heating press test, and FIG. 1B is a schematic view illustrating a state in which the optical material is pressed in a heating press test. It is sectional drawing. First, as shown in FIG. 1A, an optical material 10 is disposed between two opposing press plates 1 via a ferro plate 2, and a rectangular cross section of 3 mm on both sides of the optical material 10. Spacers were provided. Next, as shown in FIG. 1B, 40 kgf / cm is applied to the optical material thus arranged from two directions.
A pressure of ² was applied and the temperature was kept at 200 ° C. for 10 minutes.

The shape and internal state of the optical material 10 were visually observed before and after pressing. Table 2 summarizes the results for each optical material. In the table, after pressing, crushing, cracking,
Those that did not cause any trouble such as foaming were marked with “○”, and those that fractured or foamed were marked with “x”.

[0102]

[Table 2]

From these results, it was confirmed that the optical material of the comparative example as a conventional optical material could cause problems such as crushing and foaming during thermal deformation by a hot press.
On the other hand, the optical material according to the present invention does not cause any serious problems such as crushing and foaming even by the heat press under the above conditions, and can be subjected to pressure molding at a higher temperature than before. confirmed.

[0104]

As described above, according to the present invention, it is possible to obtain an optical material which has excellent absorption characteristics or emission characteristics of light of a specific wavelength and which can be improved in molding workability as compared with the prior art. It is.

[Brief description of the drawings]

FIG. 1A is a cross-sectional view schematically showing a state in which an optical material is arranged in a heating press machine in a heating press test, and FIG. 1B is a state in which the optical material is pressed in the heating press test. It is sectional drawing which shows typically.

[Explanation of symbols]

 10 Optical materials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 C09K 11/06 C09K 11/06 660 660 G02B 5/22 G02B 5/22 / / C09K 3/00 105 C09K 3/00 105 (72) Inventor Tomoyoshi Koizumi 16 Nishikicho Ochiai, Iwaki-shi, Fukushima Kureha Chemical Industry Inside Nishiki Plant (72) Inventor Masuhiro Shoji 16 Nishimachi Ochiai, Iwaki-shi, Fukushima Kureha Chemical F-term in the Nishiki Plant of Industrial Co., Ltd. (reference) FD040 FD050 FD070 FD340 GP00 GP01

Claims (2)

[Claims] 1. The following formula (1) or the following formula (2): (Wherein, R ¹ , R ² and R ³ are a branched, linear or cyclic alkyl group or alkenyl group having 1 to 30 carbon atoms,
An alkynyl group, an aryl group or an allyl group, wherein at least one hydrogen atom is a halogen atom, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, an acyl group, an aldehyde group, a carboxyl group, a hydroxyl group Or a group having an aromatic ring, or may not be substituted. An optical material characterized by comprising a phosphonic acid compound or a phosphinic acid compound represented by the formula (1) and a metal ion in a solvent or a resin. 2. The metal ion is at least one metal selected from iron, manganese, nickel, cobalt, chromium, copper, neodymium, praseodymium, europium, thulium, erbium, terbium, dysprosium, samarium, lanthanum, gadolinium and holmium. The optical material according to claim 1, wherein the ion is