JPH10221523A - Optical filter, device with it, spectacle lens, heat ray absorbing filter, and optical fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical filter through which hue in the same level as a natural light is perceived and which is near achromatic color by containing copper ions (II) in a synthetic resin and setting the chroma to a specific value. SOLUTION: An optical filter is formed by containing copper ions (II) in a synthetic resin and has chroma of 0-12. This optical filter is formed by containing the copper ions (II), metal ions for absorbing the light of wavelength 450-600nm, and/or a coloring substance in the synthetic resin and has the chroma 0-12. It is preferable that the metal ions and the coloring substance constituting the optical filter have the absorption peak in the wavelength 500-550nm. It is also preferable that cobalt ions (II) are contained as the metal ions for constituting the optical filter. This constitution can efficiently cut near infrared rays and provide a suitable one as a near infrared rays cutting filter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical filter and an application example thereof, and more particularly, to an optical filter made of a synthetic resin which is capable of efficiently cutting off near-infrared rays and is almost transparent and achromatic. The present invention relates to a device including a filter (plasma display device / camera / CCD imaging device / infrared communication environment maintenance device), an eyeglass lens for cataract prevention, a heat ray absorption filter, and an optical fiber.

[0002]

2. Description of the Related Art In recent years, synthetic filters made of synthetic resin have been developed as optical filters for cutting off near infrared rays.
BACKGROUND ART Optical filters made of synthetic resins have attracted attention because they are lightweight, have excellent workability, and have a wide range of applications, and are suitably used as, for example, front plates of plasma displays and spectacle lenses for preventing cataracts.

[0003] However, copper ion (II) is known as a substance for exhibiting a near-infrared cut-off function, and according to an optical filter in which copper ion (II) is contained in a synthetic resin, a visible light region is required. Of the near-infrared region and the ultraviolet region can be efficiently cut.

[0004]

However, in an optical filter containing copper ions (II),
Because it absorbs a part of the light in the blue region and the light in the red region and the transmittance of the light in the green region becomes relatively large,
The optical filter exhibits green to bluish green.

[0005] When the thus-colored optical filter is used as a front panel of a plasma display, there arises a problem that the color balance of the plasma display is impaired. In addition, when the optical filter is used as a spectacle lens, a sense of incompatibility with an unnatural hue is felt.

The present invention has been made based on the above circumstances. A first object of the present invention is to provide an optical filter close to an achromatic color capable of perceiving a hue comparable to that of natural light. A second object of the present invention is to
Another object of the present invention is to provide an optical filter capable of efficiently cutting off near infrared rays and suitable as a near infrared cut filter. A third object of the present invention is to provide an optical filter which has an excellent color balance and can be suitably used as a front plate of a plasma display device and a material for an eyeglass lens. A fourth object of the present invention is to provide a plasma display device in which an achromatic optical filter capable of efficiently cutting off near infrared light is arranged as a front panel of a panel. A fifth object of the present invention is to provide a near-achromatic spectacle lens which has an effect of suppressing the onset of cataract by efficiently cutting off near infrared rays and can perceive a hue comparable to that of natural light. It is in. A sixth object of the present invention is to
It is an object of the present invention to provide a camera provided with a near-achromatic optical filter capable of efficiently cutting off near infrared rays as a visibility correction filter for a light receiving element.
A seventh object of the present invention is to provide an image pickup apparatus including a near-achromatic optical filter capable of efficiently cutting off near infrared rays as a visibility correction filter for a CCD. An eighth object of the present invention is to provide an infrared communication environment maintenance device including, as a noise cut filter, an optical filter close to an achromatic color capable of efficiently cutting off near infrared rays. A tenth object of the present invention is to provide a near achromatic heat ray absorbing filter capable of efficiently cutting off near infrared rays. An eleventh object of the present invention is to provide an achromatic optical fiber capable of efficiently cutting off near infrared rays.

[0007]

The optical filter of the present invention is characterized in that the synthetic resin contains copper ion (II) and has a saturation of 0 to 12. The optical filter of the present invention comprises copper ion (II) and a wavelength of 450 to 600 n.
m, a metal ion and / or a coloring substance capable of absorbing light of m.
-12. The metal ion and the coloring substance constituting the optical filter of the present invention have a wavelength of 500
It preferably has an absorption peak at ~ 550 nm. Further, it is preferable that cobalt ion (II) is contained as a metal ion constituting the optical filter of the present invention.

In the optical filter of the present invention, a phosphoric acid group-containing monomer represented by the following formula (1) (hereinafter referred to as “specific phosphoric acid group-containing monomer”) and a monomer copolymerizable therewith. It is preferable that the synthetic resin be composed of a phosphate group-containing copolymer obtained by copolymerizing a monomer (hereinafter, referred to as a “copolymerizable monomer”).

[0009]

Embedded image

It is preferable that the optical filter of the present invention contains a phosphate group-containing compound represented by the following formula (2) (hereinafter, referred to as a “specific phosphate group-containing compound”).

[0011]

Embedded image

A plasma display device according to the present invention is characterized in that the above-described optical filter (optical filter according to the present invention) is arranged as a front plate of a panel. A spectacle lens for cataract prevention according to the present invention is characterized by comprising the above optical filter (optical filter according to the present invention). The camera of the present invention is characterized in that the above optical filter (optical filter of the present invention) is mounted as a visibility correction filter for a light receiving element. The imaging device of the present invention is characterized in that the above optical filter (the optical filter of the present invention) is mounted as a visibility correction filter for a CCD. The infrared communication environment maintenance device of the present invention includes the above-described optical filter (optical filter of the present invention) as a noise cut filter.
Is mounted. The heat ray absorption filter of the present invention is characterized by comprising the above optical filter (the optical filter of the present invention). The optical fiber of the present invention is characterized by comprising the above optical filter (the optical filter of the present invention). The optical fiber of the present invention is characterized in that the above optical filter (the optical filter of the present invention) is provided in a lighting part.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The optical filter of the present invention contains a substance (metal ion and / or coloring substance) capable of absorbing light (450 to 600 nm) including a green to bluish green region, so that copper ions (II) can be removed. Despite being contained, it exhibits a state close to an achromatic color (a range where the saturation is 0 to 12).

The optical filter of the present invention is constituted by containing a copper ion (II) for efficiently absorbing light in the near infrared region in a synthetic resin.

As methods for uniformly dispersing and containing copper ions (II) in a synthetic resin, [1] a method of polymerizing a monomer holding copper ions (II), and [2] a method of dispersing copper ions (II) A method of copolymerizing a monomer to be retained and a monomer copolymerizable therewith, [3] a method of polymerizing a monomer in the presence of a compound that retains copper ion (II), [4] ] A method of kneading and dispersing a compound holding copper ion (II) in a polymer can be exemplified.

Copper ion (II) in optical filter
As the content ratio, based on 100 parts by mass of the resin component,
It is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 15 parts by mass. If the proportion of copper ions (II) is too small, it is not possible to obtain an optical filter that efficiently cuts near infrared rays. On the other hand, when the proportion of the copper ion (II) is excessively large, the dispersibility of the copper ion (II) is reduced, and an optical filter having good transparency cannot be obtained.

As the synthetic resin constituting the optical filter of the present invention, for example, acrylic resin, vinyl chloride resin, polycarbonate resin, polyester resin, fluorine resin and the like can be used.

From the viewpoint of improving the dispersibility of copper ion (II), it is preferable that the synthetic resin contains a phosphate group.
I) is contained in the synthetic resin in a state of being bonded (for example, a coordinate bond) to a phosphate group. Here, the “phosphate group”
It refers to a group represented by “PO (OH) _n −” (n is 1 or 2).

Means for causing a phosphate group to be contained in the synthetic resin include [1] a "specific phosphate group-containing monomer" and a "copolymerizable monomer" represented by the above formula (1). Means for obtaining a phosphoric acid group-containing copolymer by copolymerizing [2] a "specific phosphoric acid group-containing compound" represented by the above formula (2) into a mixed monomer. Means for polymerizing the monomer composition may be mentioned.

<Polyphosphate-Containing Copolymer> In a preferred embodiment of the present invention, an optical filter is constituted by containing copper ions (II) in the phosphate-containing copolymer. Hereinafter, the phosphate group-containing copolymer will be described.

The phosphate group-containing copolymer constituting the optical filter of the present invention can be obtained by copolymerizing a specific phosphate group-containing monomer and a copolymerizable monomer. The specific phosphate group-containing monomer has a phosphate group capable of binding to copper ion (II) in its molecular structure and a radical polymerizable functional group via an ethylene oxide group. Since it has a certain acryloyloxy group or methacryloyloxy group, it is considered to be very copolymerizable and can be copolymerized with various monomers.

In the formula (1) showing the molecular structure of a specific phosphoric acid group-containing monomer, the group R ¹ is an acryloyloxy group (when X is a hydrogen atom) or a methacryloyloxy group (to which X is a hydrogen atom) bonded to an ethylene oxide group. X is a methyl group). Here, the repeating number m of the ethylene oxide group is an integer of 1 to 5. When the value of m exceeds 5, the obtained copolymer may not have sufficient hardness, and may reduce the practicality as an optical filter.

In the formula (1), the number n of the hydroxyl groups is 1 or 2, and the specific value of the specific phosphoric acid group containing n is 1 depending on the molding method and the purpose of use of the obtained optical filter. Either one or both of the monomer and the specific phosphate group-containing monomer having a value of n of 2 can be used, and when both are used, the mixing ratio thereof can be selected. .

More specifically, when the value of n is 2, that is, when the number of radically polymerizable functional groups bonded to the phosphorus atom is 1, the specific phosphate group-containing monomer is a copper ion Has a high binding property to On the other hand, if the value of n is 1
In other words, the specific phosphoric acid group-containing monomer in which the number of radically polymerizable functional groups bonded to the phosphorus atom is 2 has crosslinking polymerizability. Therefore, when an optical filter is obtained by a molding method applied to a thermoplastic resin, it is preferable to use a large mixing ratio of a specific phosphate group-containing monomer having a value of n of 2.

As described above, the value of n can be selected according to the performance of the optical filter, the molding method and the purpose of use, but from the viewpoint of the solubility of copper ion (II) in the monomer, n A specific phosphate group-containing monomer having a value of 1 and n
It is preferable to use a specific phosphate group-containing monomer having a value of 2 in combination. In particular, these two types of specific phosphate group-containing monomers are each in a ratio of approximately equimolar amounts. For example, it is preferable to use a molar ratio of 40 to 60:60 to 40, preferably 45 to 55:55 to 45.

The copolymerizable monomer subjected to a copolymerization reaction with a specific phosphoric acid group-containing monomer suppresses the hygroscopicity of the resulting phosphoric acid group-containing copolymer and is required for an optical filter. And imparts excellent heat resistance, shape retention, and the like. Therefore, according to the phosphoric acid group-containing copolymer obtained by using the copolymerizable monomer, an optical filter excellent in various performances can be constituted.

Such copolymerizable monomers include:
[1] homogeneously dissolving and mixing with a specific phosphate group-containing monomer, [2] good radical copolymerizability with the specific phosphate group-containing monomer, [3] optically There is no particular limitation as long as it satisfies that a transparent copolymer can be obtained.

Specific examples of the copolymerizable monomer include lower alkyl groups having 1 to 8 carbon atoms, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate and n-propyl methacrylate. Alkyl acrylates and lower alkyl methacrylates; modified alkyl acrylates and modified alkyl methacrylates in which the alkyl group is substituted by a glycidyl group or a hydroxy group, such as glycidyl acrylate, glycidyl methacrylate, 2-hydroxybutyl acrylate, and 2-hydroxybutyl methacrylate , Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol diacrylate 1,4-butanediol dimethacrylate, 2,2-bis [4-methacryloxyethoxyphenyl] propane, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetra Polyfunctional acrylates and polyfunctional methacrylates such as acrylate and pentaerythritol tetramethacrylate; unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and aromatic compounds such as styrene, α-methylstyrene, halogenated styrene, methoxystyrene and divinylbenzene And the like. These can be used alone or in combination of two or more.

In the mixed monomers for obtaining the phosphoric acid group-containing copolymer, the ratio of the specific phosphoric acid group-containing monomer to the copolymerizable monomer is defined as “a specific phosphoric acid group-containing copolymer”. Monomer:
The copolymerizable monomer (mass ratio) "is preferably in the range of 3:97 to 90:10, more preferably 10:90.
~ 80: 20. When the proportion of the specific phosphoric acid group-containing monomer is less than 3% by mass, it is difficult to obtain a phosphoric acid group-containing copolymer having light absorption characteristics suitable as an optical filter. On the other hand, when the proportion exceeds 90% by mass, the obtained phosphoric acid group-containing copolymer may not satisfy the hardness condition required for the optical filter.

The phosphate group-containing copolymer constituting the optical filter of the present invention is usually obtained by radical polymerization of a mixed monomer comprising a specific phosphate group-containing monomer and a copolymerizable monomer. Obtained. The radical polymerization method is not particularly limited, and a known method such as a cast polymerization method using a known radical polymerization initiator, a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method can be employed.

The thus obtained phosphoric acid group-containing copolymer (synthetic resin) contains copper ions (II) to constitute the optical filter of the present invention. This copper ion (II)
Is covalently bound with a phosphate group as a ligand, is retained and contained in the phosphate group-containing copolymer, and efficiently absorbs light in the near infrared region by forming a complex with the phosphate group. .

The method for obtaining the phosphoric acid group-containing copolymer containing copper ions (II), which is a constituent material of the optical filter of the present invention, includes [1] co-polymerization with a specific phosphoric acid group-containing monomer. A method of adding copper ion (II) to a mixed monomer comprising a polymerizable monomer, for example, in the form of a copper compound, and subjecting the resulting monomer composition to a polymerization treatment; [2] phosphate group A method in which the content-containing copolymer is heated and melted, and a copper compound is added to and mixed with the phosphate-containing copolymer. [3] The phosphate-containing copolymer is dissolved in an organic solvent to obtain A method of adding a copper compound to a solution and mixing the solution can be used.

The copper compound which is a source of copper ions (II) includes copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethyl acetoacetate, copper pyrophosphate, copper naphthenate, Examples thereof include anhydrides and hydrates such as copper citrate.

In the constituent material of the optical filter, it is preferable that an acid component (organic acid / inorganic acid) generated by the reaction between the copper compound and the phosphoric acid group is removed. Preferably, the acid component is extracted and removed with a solvent. This acid component extraction and removal step
Regardless of before and after the radical polymerization treatment, at any stage of the method for producing an optical filter, for example, after adding a copper compound to a mixed monomer, polymerizing the monomer composition, and then forming the filter material It can be carried out any time after the above. As a solvent used in the acid component extraction and removal step, the acid component can be dissolved and has a suitable affinity for the phosphate group-containing copolymer (it does not dissolve the phosphate group-containing copolymer, (A degree of affinity that can penetrate into the phosphate group-containing copolymer). Specific examples of such solvents include water, aliphatic lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl ether, petroleum ether and the like. Ethers, n-pentane, n-hexane, n
-Aliphatic hydrocarbons such as heptane, chloroform, methylene chloride, and carbon tetrachloride and halides thereof, and aromatic compounds such as benzene, toluene, and xylene. These solvents may be used alone or as a solvent. More than one kind can be mixed and used. Of these, water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methylene chloride
It is particularly preferable from the viewpoint that it hardly remains in the phosphate group-containing copolymer. The amount of the acid component removed in the acid component extraction and removal step is preferably 30% by mass or more, more preferably 40% by mass or more of the generated acid component. After completion of the acid component extraction and removal step, it is preferable to wash and dry the extract to remove the residual solvent used for the extraction. The optical filter manufactured by extracting and removing the acid component described above hardly generates bleed on the filter surface, and clouding and devitrification phenomena due to the bleed in a high humidity atmosphere.

<Phosphoric acid group-containing compound> As a means for incorporating a phosphoric acid group into the synthetic resin, a specific phosphoric acid group-containing compound represented by the above formula (2) is added to the mixed monomer to form a simple compound. A means for obtaining a monomer composition and polymerizing the monomer composition may be employed.

The specific phosphate group-containing compound is a non-polymerizable compound (phosphate ester / phosphonate ester) having a phosphate group capable of binding to copper ion (II) in its molecular structure.

Specific examples of the specific phosphate group-containing compound include monomethyl phosphate, dimethyl phosphate, monoethyl phosphate, diethyl phosphate, monopropyl phosphate, dipropyl phosphate, monoisopropyl phosphate, and diisopropyl phosphate. Fate, mono n-butyl phosphate,
Di-n-butyl phosphate, mono (2-ethylhexyl) phosphate, di (2-ethylhexyl) phosphate, mono n-decyl phosphate, di n-decyl phosphate, monoisodecyl phosphate, diisodecyl phosphate, mono Phosphate esters such as oleyl phosphate, dioleyl phosphate, monoisostearyl phosphate, diisostearyl phosphate, monophenyl phosphate, diphenyl phosphate; mono (2-ethylhexyl) 2-
Examples include phosphonate esters such as ethylhexyl phosphonate, monomethyl methyl phosphonate, monoethyl ethyl phosphonate, monobutyl butyl phosphonate, and monodecyl decyl phosphonate.

The proportion of the specific phosphoric acid group-containing compound used is preferably 1 to 10 mol, more preferably 1 to 5 mol, per 1 mol of copper ion (II). When the use ratio of the specific phosphate group-containing compound is too small, the dispersibility of copper ion (II) tends to decrease. On the other hand, if this ratio is too large, it may adversely affect mechanical properties such as hardness. When a metal ion other than copper ion (II) is contained in the synthetic resin, it is preferable to increase the usage ratio of the specific phosphate group-containing compound according to the usage amount of the metal ion.

<Acrylic Resin> When a specific phosphate group-containing compound is used to contain a phosphate group in the synthetic resin, the synthetic resin is preferably an acrylic resin. Specific examples of the monomer used to obtain such an acrylic resin include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, and t-butyl acrylate. Butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isodecyl acrylate,
Isodecyl methacrylate, n-lauryl acrylate, n-lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, n-stearyl acrylate, n-stearyl methacrylate, isobonyl acrylate, isobonyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl Acrylate, ethoxyethyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate and the like can be mentioned, and these are
They can be used alone or in combination of two or more. Among these, a polymer having high solubility of a complex of a specific phosphate group-containing compound and copper ion (II) can be obtained, and thus t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate,
-Ethylhexyl methacrylate, isobonyl acrylate, isobonyl methacrylate are preferred. Further, as a monomer for obtaining an acrylic resin, together with the above monofunctional acrylates or monofunctional methacrylates, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 2,
Polyfunctional acrylates and polyfunctional methacrylates such as 2-bis [4-methacryloxyethoxyphenyl] propane, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, and pentaerythritol tetraacrylate may be used. By using acrylates and / or polyfunctional methacrylates, the mechanical properties of the finally obtained optical filter can be improved.

<Green Region Absorbing Material> Metal ions and / or metal ions capable of selectively absorbing green to blue-green light (450 to 600 nm) together with copper ions (II) are provided in the optical filter of the present invention. A coloring substance (hereinafter, also referred to as a “green region absorbing substance”) is contained.

By containing the green region absorbing substance, the optical filter of the present invention can be in a state close to an achromatic color (saturation = color) despite containing copper ions (II).
0-12). Here, “saturation” is defined as L ^* a ^* b ^* color system [CIE (International Commission on Illumination)
1976 (L ^* a ^* b ^* ) color space] and values obtained from the values of a ^* and b ^* according to the following formula. A ^* and b ^* indicate the hue and the degree thereof, respectively.

[0042]

[Number 1] C ^* = ^{[(a *) 2 + (b} *) 2 ] ^0.5

Such a green region absorbing material does not absorb light in the blue and red regions but selectively absorbs light in the green to blue-green region (450 to 600 nm), and preferably has a wavelength of 500 to 550 nm. Selected from metal ions and coloring substances having an absorption peak at

As a metal ion which can be suitably used as a green region absorbing material, cobalt ion (II)
Can be mentioned. As a method for uniformly dispersing and containing the cobalt ion (II) in the synthetic resin, a method similar to the method for dispersing and containing the copper ion (II), that is,
[1] a method of polymerizing a monomer holding cobalt ion (II) (for example, the above-mentioned phosphate group-containing monomer),
[2] a method of copolymerizing a monomer holding cobalt ion (II) and a monomer copolymerizable therewith, [3] a compound holding cobalt ion (II) (for example, (4) a method of polymerizing a monomer in the presence of an acid group-containing compound, [4] kneading a compound retaining cobalt ion (II) into a polymer (for example, the above-mentioned phosphate group-containing copolymer). Dispersion methods and the like can be mentioned. When a metal ion such as cobalt ion (II) is used as the green region absorbing substance, the obtained optical filter is preferable because it has good weather resistance.

The method for incorporating cobalt ion (II) into the synthetic resin comprising the above-mentioned phosphate group-containing copolymer is as follows: [1] A specific phosphate group-containing monomer and a copolymerizable monomer Cobalt ion (I
I) is added, for example, in the form of a cobalt compound, and the resulting monomer composition is subjected to polymerization treatment. [2] The phosphate group-containing copolymer is heated and melted, , A method of adding and mixing a cobalt compound, [3]
For example, a method of dissolving a phosphate group-containing copolymer in an organic solvent, adding a cobalt compound to the resulting solution, and mixing the resulting solution can be used.

Cobalt compounds which are sources of cobalt ions (II) include cobalt acetate, cobalt formate, cobalt benzoate, cobalt naphthenate, cobalt bromide,
Anhydrides and hydrates such as cobalt chloride, cobalt nitrate and cobalt sulfate can be exemplified.

Coloring materials that can be suitably used as a green region absorbing material include quinones, quinolines, and the like.
Dyes and organic dyes capable of absorbing light of 450 to 600 nm, such as imidazole, oxazoline, fulgide, polyene, azo, indico, diphenylmethane, triphenylmethane, polymethine, and naphthoquinone, etc. Can be mentioned.

The coloring substance which is a green region absorbing substance is contained in the synthetic resin containing copper ions (II) or by adding it to a mixed monomer for obtaining the same. Can be.

The content of the green region absorbing substance in the optical filter differs depending on the content of copper ion (II) and the like. When the green region absorbing substance is an organic dye, the content is based on 100 parts by mass of the resin component. And 0.000
It is preferably 1 to 0.1 part by mass, more preferably 0.0005 to 0.01 part by mass, and when the green region absorbing substance is a metal ion, based on 100 parts by mass of the resin component, It is preferably 0.001 to 1.00 parts by mass, more preferably 0.01 to 0.50 parts by mass. Further, the saturation may be measured at each stage of the optical filter manufacturing method, and the content ratio (addition amount) of the green region absorbing substance may be adjusted based on the measured value.

<Other Constituents> In the synthetic resin constituting the optical filter of the present invention, in addition to the copper ion (II) and the green region absorbing substance, the near infrared ray cut performance is not impaired, and the obtained optical filter is obtained. Other metal ions, including those that do not act as a green region absorbing substance, may be contained within a range in which the saturation of does not exceed 12. Such metal ions include sodium ions, potassium ions,
Examples thereof include calcium ions, iron ions, manganese ions, magnesium ions, and nickel ions.

The optical filter of the present invention has a copper ion (I
I), manufactured by molding and polishing a filter material containing a green region absorbing substance and an optional component in a synthetic resin into a plate, column, lens, etc. shape according to the purpose and application. can do.

<Application Example of Optical Filter of the Present Invention> The optical filter of the present invention has excellent optical characteristics (has transparency close to achromatic color, and can efficiently cut light in the near infrared region). Depending on the characteristics), it can be applied to various uses as described below.

By using the optical filter of the present invention as a front panel of a panel in a plasma display device, it is possible to efficiently cut off near infrared rays emitted from the panel. As a result, a malfunction of the remote controller due to near infrared rays does not occur around the plasma display device. Moreover, since the optical filter of the present invention is close to an achromatic color, the color balance of the plasma display device is not impaired.

The optical filter of the present invention can be suitably used as a spectacle lens for preventing cataract. According to such a spectacle lens (the spectacle lens of the present invention), it is possible to reliably protect the eyes from heat rays and near infrared rays which cause cataracts. Moreover, since the optical filter of the present invention is close to an achromatic color, it can perceive the same hue as natural light.

The optical filter of the present invention can be suitably used as a visibility correction filter for a light receiving element (for example, a photoelectric conversion element formed of a silicon photodiode) in a photometry section of a camera. Here, the "visibility correction filter" comprising the optical filter of the present invention includes:
In addition to the visibility correction filter that is independently arranged in the optical path to the light receiving element, a condenser lens and the like are included. According to the camera equipped with the optical filter of the present invention (camera of the present invention), the light incident on the light receiving element (silicon photodiode) can be substantially limited to light in the visible region. And accurate photometry (exposure operation) can be performed.

The optical filter of the present invention can be suitably used as a visibility correction filter for a CCD (for example, a photoelectric conversion element composed of a silicon photodiode) in an imaging device. Here, the "visibility correction filter" composed of the optical filter of the present invention includes a visibility, a filter, and a lid, a lens, a protective plate, and the like, in addition to a visibility correction filter independently disposed in an optical path to a CCD. . Examples of the imaging device equipped with a CCD include a video camera, a digital camera, a board camera, a color scanner, a color fax, a color copying machine, and a color videophone device. According to the imaging device equipped with the optical filter of the present invention (the imaging device of the present invention), a CCD (silicon photodiode)
The incident light on the light can be substantially limited to light in the visible region. As a result, accurate photometry (exposure operation) can be performed, and further, the reproduction of the red component and the color balance are not hindered. Never do.

The optical filter of the present invention can be suitably used as a noise cut filter in an environment where an infrared communication device (a communication device using light of 850 to 950 nm as a medium) is used. Here, the "noise cut filter" comprising the optical filter of the present invention blocks infrared rays from a source of near-infrared rays (for example, an automatic door or a remote controller), thereby reliably preventing the generation of noise during communication. it can.

The optical filter of the present invention is a heat ray absorbing filter, specifically, a window material for buildings such as houses and buildings, a window material for cars and trains, and a translucent member for greenhouses for agricultural use. It can be suitably used as a lighting cover or the like.

The optical filter of the present invention can be suitably used as a constituent material of an optical fiber. Further, the optical filter of the present invention may be provided in a lighting part of an optical fiber.

[0060]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited to these examples. In the following, “parts” means “parts by mass”.

Example 1 13.4 parts of a specific phosphoric acid group-containing monomer represented by the following formula (3) and a specific phosphoric acid group-containing monomer represented by the following formula (4) 8.0 parts, 28.1 parts of methyl methacrylate, 20.0 parts of n-butyl methacrylate, and phenoxyethyl methacrylate
0 parts, and diethylene glycol dimethacrylate 20.
0 parts and 0.5 part of α-methylstyrene were sufficiently stirred and mixed to prepare a mixed monomer. To this mixed monomer,
6.0 parts of anhydrous copper benzoate (the content of copper ions with respect to 100 parts of the mixed monomer is 1.26 parts) and 0.3 part of cobalt acetate tetrahydrate (the amount of cobalt ions with respect to 100 parts of the mixed monomer is And a monomer composition in which copper ion (II) and cobalt ion (II) are dissolved in the mixed monomer. I got

[0062]

Formula (3)

[0063]

Formula (4)

To the monomer composition obtained as described above, 2.0 parts of t-butyl peroxypivalate was added, and the monomer composition was poured into a mold.
Time, 2 hours at 50 ° C, 6 hours from 50 ° C to 60 ° C,
The copper ions (II) and The optical filter of the present invention having a thickness of 2.0 mm made of a phosphate group-containing copolymer containing cobalt ions (II) [this is referred to as “filter (A)”. ] Was obtained.

<Example 2> Example 1 was repeated except that the addition amount of cobalt acetate tetrahydrate was changed to 0.5 part (the content of cobalt ion was 0.118 part relative to 100 parts of the mixed monomer). In the same manner as described above, the optical filter of the present invention [this is referred to as “filter (B)”. ] Was obtained.

Example 3 Instead of cobalt acetate, 500
Red dye “Sumiplast, RED H3G” for coloring synthetic resins having an absorption peak in nm [Sumitomo Chemical Co., Ltd.
The optical filter of the present invention is referred to as "filter (C)" in the same manner as in Example 1 except that 0.001 part is added. ] Was obtained.

<Example 4> Instead of cobalt acetate, 500
Red dye “Sumiplast, RED AS” for coloring synthetic resins having an absorption peak at nm [manufactured by Sumitomo Chemical Co., Ltd.]
The optical filter of the present invention [this is referred to as “filter (D)” in the same manner as in Example 1 except that 0.001 part was added. ] Was obtained.

Example 5 Methyl methacrylate
To a mixed monomer prepared by mixing 0 parts and 50.0 parts of isobonyl methacrylate, 9.06 parts of di (2-ethylhexyl) phosphate was added and mixed. Next, 2.04 parts of anhydrous copper acetate was added to the mixed monomer (the content of copper ion was 0.71 part based on 100 parts of the mixed monomer).
And 0.0005 parts of a synthetic resin coloring red dye “Sumiplast, RED H3G” (manufactured by Sumitomo Chemical Co., Ltd.) having an absorption peak at 500 nm, and sufficiently dissolved by stirring and mixing to obtain copper ions. (II) and 5
There was obtained a monomer composition in which a red dye for coloring a synthetic resin having an absorption peak at 00 nm was dissolved in a mixed monomer.
Using the monomer composition thus obtained, Example 1
By performing cast polymerization in the same manner as described above, the optical filter of the present invention [this is referred to as “filter (E)”. ] Was obtained.

<Example 6> Methyl methacrylate 50.
To a mixed monomer prepared by mixing 0 parts and 50.0 parts of t-butyl methacrylate, 4.53 parts of di (2-ethylhexyl) phosphate was added and mixed. Next, 1.02 parts of anhydrous copper acetate was added to the mixed monomer (the content of copper ion was 0.35 parts with respect to 100 parts of the mixed monomer).
And 0.0003 parts of a red dye “Sumiplast, RED H3G” (manufactured by Sumitomo Chemical Co., Ltd.) having a absorption peak at 500 nm for coloring a synthetic resin, and sufficiently dissolved by stirring and mixing to obtain copper ions. (II) and 5
There was obtained a monomer composition in which a red dye for coloring a synthetic resin having an absorption peak at 00 nm was dissolved in a mixed monomer.
Using the monomer composition thus obtained, Example 1
By performing cast polymerization in the same manner as described above, the optical filter of the present invention [this is referred to as “filter (F)”. ] Was obtained.

Comparative Example 1 An optical filter for comparison [this is referred to as “filter (g)” in the same manner as in Example 1 except that cobalt acetate was not added. ] Was obtained.

[0071]

[Table 1]

<Evaluation of Optical Filter> (1) Spectral transmittance: filters (A) to (F) of the present invention
And 25 g for each of the comparative filters (g).
The spectral transmittance in the wavelength range of 0 to 1200 nm was measured using a spectrophotometer “U-4000” (manufactured by Hitachi, Ltd.). It was found that it was well absorbed. Further, the filters (A) to
In the spectral transmission curve measured for (F), the wavelength 52
A small valley was observed near 0 nm. In addition, wavelength 250nm, 400nm, 500nm, 520nm, 5
Table 2 shows the light transmittance at 50 nm, 600 nm, 700 nm, and 1200 nm, and FIG. 1 shows the spectral transmission curve of the filter (A) of the present invention.

(2) Saturation: color difference meter "CR-300"
Using Minolta Camera Co., Ltd., a ^* and b ^* were measured based on L ^* a ^* b ^* color system. Where a ^*
And b ^* indicate the hue and its degree, respectively.
The closer the values of a ^* and b ^* are to 0, the closer to colorless. Further, the chroma C ^* was obtained according to the above formula. When the value of the saturation C ^* is from 0 to 12, the color is felt as colorless or pale, when the value is from 12 to 30, the color is felt as a medium dark color, and when the value exceeds 30, the color is very dark. I can feel it. Table 2 shows the results.

[0074]

[Table 2]

[0075]

According to the present invention, it is possible to provide an almost achromatic optical filter capable of perceiving the same hue as natural light despite containing copper ions (II). . The optical filter of the present invention can efficiently cut off near infrared rays, and is suitable as a near infrared cut filter. The optical filter of the present invention,
It has an excellent color balance and can be suitably used as a front plate of a plasma display and a material for eyeglass lenses.

According to the plasma display device of the present invention, a malfunction of the remote controller due to near infrared rays does not occur in the vicinity thereof. Moreover, the plasma display device of the present invention has a good color balance. ADVANTAGE OF THE INVENTION According to the spectacle lens of this invention, an eye can be protected from heat rays and near-infrared rays which are the cause of cataract onset. In addition, since the spectacle lens of the present invention is close to an achromatic color, it can perceive the same hue as natural light.
ADVANTAGE OF THE INVENTION According to the camera of this invention, the light which injects into a light receiving element can be substantially limited to the light of a visible region, and can perform accurate photometry (exposure operation). According to the imaging apparatus of the present invention, the light incident on the CCD can be substantially limited to light in the visible region, and as a result, accurate photometry (exposure operation) can be performed, and the red component of the red component can be measured. Excellent reproducibility. According to the infrared communication environment maintenance device of the present invention, noise during communication can be reliably prevented. ADVANTAGE OF THE INVENTION According to the heat ray absorption filter of this invention, the temperature rise in a room etc. can be suppressed reliably. According to the optical fiber of the present invention, since heat rays (near-infrared rays) are hardly contained in the light guided and radiated by the optical fiber, a rise in temperature near the light radiating portion (in the apparatus / in the room) is suppressed. be able to.

[Brief description of the drawings]

FIG. 1 is a spectral transmission curve diagram for a filter of the present invention.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C08F 30/02 C08F 30/02 299/02 299/02 C08L 43/02 C08L 43/02 (72) Inventor Takeo Ogiwara Fukushima 2-3-6, Nishikicho, Iwaki-shi

Claims (14)

[Claims] 1. An optical filter comprising a synthetic resin containing copper ion (II) and having a saturation of 0 to 12. 2. A synthetic resin comprising copper ion (II), a metal ion capable of absorbing light having a wavelength of 450 to 600 nm and / or a coloring substance, and having a saturation of 0 to 12. An optical filter, characterized in that: 3. It has an absorption peak at a wavelength of 500 to 550 nm and a copper ion (II).
An optical filter comprising a synthetic resin containing a metal ion and / or a coloring substance capable of absorbing light of 0 to 600 nm, and having a saturation of 0 to 12. 4. A cobalt ion (II) as a metal ion
The optical filter according to claim 3, wherein 5. A synthetic resin comprising a phosphate group-containing monomer represented by the following formula (1) and a phosphate group-containing copolymer obtained by copolymerizing a monomer copolymerizable therewith. The optical filter according to any one of claims 1 to 4, wherein: Embedded image 6. The optical filter according to claim 1, further comprising a phosphate group-containing compound represented by the following formula (2). Embedded image 7. A plasma display device, wherein the optical filter according to claim 1 is arranged as a front plate of a panel. 8. A spectacle lens for preventing cataract, comprising the optical filter according to any one of claims 1 to 6. 9. A camera comprising the optical filter according to claim 1 as a visibility correction filter for a light receiving element. 10. An imaging apparatus comprising the optical filter according to claim 1 as a visibility correction filter for a CCD. 11. An infrared communication environment maintenance device, wherein the optical filter according to any one of claims 1 to 6 is mounted as a noise cut filter. 12. A heat ray absorbing filter comprising the optical filter according to any one of claims 1 to 6. 13. An optical fiber comprising the optical filter according to claim 1. Description: 14. An optical fiber, wherein the optical filter according to claim 1 is provided in a lighting part.