JP2000007870A - Resin composition and its production, optical filter and device equipped with the same, athermanous filter, optical fiber and glass lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of effectively cutting near- infrared ray over a wide wavelength range, and a method for producing a resin composition high in near-infrared ray absorptivity and visible ray transmissivity. SOLUTION: This resin composition is of an acrylic-based resin containing a (substituted) amino group and metallic ion component, including copper ion. This method for producing the resin composition comprises a polymerization step which polymerizes a compound having a (substituted) amino group, copper compound and monomer composition containing an acrylic-based monomer, and another step of mixing the compound having a (substituted) amino group and copper compound in the acrylic-based resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition capable of absorbing near-infrared rays, a method for producing the same, an optical filter comprising the resin composition, and an application example thereof. A resin composition and an optical filter having excellent visible light transmittance, and a device equipped with the optical filter (camera, CCD imaging device, infrared communication environment maintenance device,
A plasma display device), a heat ray absorption filter, an optical fiber, and an eyeglass lens.

[0002]

2. Description of the Related Art In recent years, an optical filter (near-infrared cut filter) capable of cutting light in the near-infrared region is made of a resin composition that is lightweight and has good workability such as molding, cutting and polishing. Is being developed. As such a resin composition, there is known an acrylic resin containing copper ions (near infrared absorbing agent) (see Japanese Patent Publication No. 62-5190). Such a resin composition can be produced by polymerizing a monomer composition containing a copper compound that supplies copper ions, (meth) acrylic acid, and an acrylic monomer. (Ueno et al., Journal of Polymers, Vol. 51, 12, 819 (1
994)).

[0003]

However, in the above-mentioned optical filter made of a resin composition known in the art, a wavelength region of 1000 nm or more (for example, 100 nm or less).
(0 to 1500 nm), and did not exhibit a sufficient function as a near-infrared cut filter. Further, in the case of a conventionally known optical filter made of a resin composition, the light transmittance in the wavelength region of 800 to 1000 nm is not sufficiently low.

When such an optical filter is arranged on the front surface of a panel of a plasma display device, the near infrared rays from the panel cannot be cut sufficiently, and the near infrared rays around the plasma display device cannot be cut off. May cause a malfunction of the remote controller or the like. Also, when such an optical filter is mounted on an on-board camera for a personal computer, the red image element feels a little near-infrared light, resulting in a reddish image.

The present invention has been made based on the above circumstances. A first object of the present invention is to provide a resin composition that can effectively cut near infrared rays in a wide wavelength range (for example, 800 to 1500 nm). A second object of the present invention is to provide a light source having a wavelength of 800 to 1200 nm.
To provide a resin composition capable of cutting near-infrared rays in a wavelength region of high efficiency. A third object of the present invention is to provide a near-infrared absorbing acrylic resin composition having excellent visible light transmittance. A fourth object of the present invention is to provide a method for producing a resin composition having excellent near-infrared absorption and visible light transmission. A fifth object of the present invention is to provide an optical filter that can effectively cut near infrared rays in a wide wavelength range. A sixth object of the present invention is to provide a camera provided with an optical filter capable of effectively cutting off near infrared rays in a wide wavelength range as a visibility correction filter for a light receiving element.
A seventh object of the present invention is to provide an optical filter capable of effectively cutting near infrared rays in a wide wavelength range by using a C filter.
An object of the present invention is to provide an imaging device provided as a visibility correction filter for a CD. An eighth object of the present invention is to
An object of the present invention is to provide an infrared communication environment maintenance device including, as a noise cut filter, an optical filter capable of effectively cutting near infrared rays in a wide wavelength range. A ninth object of the present invention is to provide a plasma display device in which an optical filter capable of effectively cutting off near infrared rays in a wide wavelength range is arranged on the front surface of a panel. A tenth object of the present invention is to
An object of the present invention is to provide a heat ray absorbing filter capable of effectively cutting near infrared rays in a wide wavelength range.
An eleventh object of the present invention is to provide an optical fiber that can effectively cut near infrared rays in a wide wavelength range. A twelfth object of the present invention is to provide a spectacle lens that can effectively cut near infrared rays in a wide wavelength range and has an effect of suppressing the onset of cataract.

[0006]

According to the present invention, the dispersibility of copper ions in an acrylic resin can be enhanced by including a substituted or unsubstituted amino group in the acrylic resin, and a wide wavelength range can be obtained. It has been found that a resin composition capable of effectively cutting near infrared rays in a region can be obtained, and has been completed based on such findings.

That is, the resin composition of the present invention is characterized in that a substituted or unsubstituted amino group and a metal ion component containing a copper ion are contained in an acrylic resin. The resin composition of the present invention is characterized in that an N, N-dimethylamino group and a metal ion component containing a copper ion are contained in an acrylic resin.

The method for producing a resin composition of the present invention comprises a step of polymerizing a monomer composition containing a compound having a substituted or unsubstituted amino group, a copper compound, and an acrylic monomer. It is characterized by including. The method for producing a resin composition of the present invention includes a step of mixing a compound containing a substituted or unsubstituted amino group with a copper compound in an acrylic resin. The method for producing a resin composition of the present invention includes a step of mixing a reaction product of a compound having a substituted or unsubstituted amino group with a copper compound in an acrylic resin.

The optical filter of the present invention is characterized by comprising the above resin composition (the resin composition of 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 plasma display device of the present invention is characterized in that the above-mentioned optical filter (the optical filter of the present invention) is arranged on the front surface of the panel. 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. A spectacle lens of the present invention is characterized by comprising the above optical filter (optical filter of the present invention).

In the present invention, the “substituted or unsubstituted amino group” refers to a group represented by the following formula (1).

[0011]

Embedded image

(In the formula, R ¹¹ and R ¹² each represent a hydrogen atom, a substituted or unsubstituted alkyl group or a phenyl group, which may be the same or different.)

[0013]

The compound having a substituted or unsubstituted amino group and a copper ion form a complex structure represented by the following formula (2). Thus, by using the “compound containing a substituted or unsubstituted amino group” as a ligand of a copper complex, a high concentration of copper ions can be dissolved in the acrylic resin. According to the resin composition of the present invention having such a complex structure, 800 to 100
Not only near-infrared rays in a wavelength region of 0 nm, but also light beams in a wavelength region of 1000 to 1500 nm, which could not be sufficiently cut by a conventionally known resin composition, can be effectively cut off. A cutting function can be exhibited. Further, according to the resin composition of the present invention having such a complex structure, even if the content of copper ions is small (for example, 0.05 to 1.0 part by mass per 100 parts by mass of the resin component), a wide wavelength range is obtained. Region (80
(0 to 1500 nm) can be effectively cut off.

[0014]

Embedded image

(In the formula, R ^{21 to} R ²⁶ each represent a hydrogen atom, a substituted or unsubstituted alkyl group or a phenyl group, which may be the same or different.)

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. <Resin Composition> The resin composition of the present invention contains a substituted or unsubstituted amino group represented by the above formula (1) and a metal ion component containing a copper ion in an acrylic resin.

<Acrylic Resin> The acrylic resin constituting the resin composition of the present invention is a resin obtained from a (meth) acrylate monomer (hereinafter referred to as “acrylic monomer”). Combination can be preferably used. Specific examples of such acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate,
n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, t-butyl (meth)
Acrylate, n-hexyl (meth) acrylate, n
-Alkyl (meth) such as octyl (meth) acrylate
Acrylates, glycidyl (meth) acrylate, 2
-Modified (meth) such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isobornyl (meth) acrylate, methoxypolyethylene (meth) acrylate, and phenoxy (meth) acrylate Acrylates, 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) acryloxyethoxy] phenylpropane, 2
-Hydroxy-1- (meth) acryloxy-3- (meth) acryloxypropane, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth)
Examples include polyfunctional (meth) acrylates such as acrylate. These monomers can be used alone or in combination of two or more.

The acrylic resin may be a copolymer of the above acrylic monomer and a copolymerizable monomer copolymerizable therewith. Specific examples of such a copolymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, styrene, α -Aromatic vinyl compounds such as methylstyrene, chlorostyrene, dibromostyrene, methoxystyrene, vinylbenzoic acid, and hydroxymethylstyrene.

In the above, when only a monofunctional monomer is used as the monomer, a thermoplastic acrylic resin is obtained, whereby an acrylic resin composition that can be molded by melting is prepared. be able to. When a polyfunctional resin is used as a part or all of the monomer, a thermosetting acrylic resin is obtained. In the present invention, the intended use of the obtained acrylic resin composition,
A thermoplastic acrylic resin or a thermosetting acrylic resin can be selected and used depending on the use, processing method, and the like.

The acrylic resin constituting the resin composition of the present invention can be prepared by radical polymerization of a monomer composition containing the above acrylic monomer as an essential component. Here, the radical polymerization method is not particularly limited, and known methods such as a bulk (cast) polymerization method, a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method using a usual radical polymerization initiator are used. Can be adopted. Further, a photopolymerization method in which a photopolymerization initiator is used and a polymerization reaction is performed by radiation such as ultraviolet rays and visible rays can also be employed.

<Substituted or unsubstituted amino group>"Substituted or unsubstituted amino group" refers to a compound containing the amino group in its molecular structure (hereinafter simply referred to as "amino group-containing compound").
That. ) Can be introduced into the acrylic resin. The amino group-containing compound may be a polymerizable (monofunctional / polyfunctional) compound containing an unsaturated group or a non-polymerizable compound.

Specific examples of such an amino group-containing compound include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine and n-butylamine.
Pentylamine, isopentylamine, tert-pentylamine, cyclopentylamine, n-hexylamine, isohexylamine, tert-hexylamine,
Cyclohexylamine, heptylamine, isoheptylamine, tert-heptylamine, octylamine,
Nonylamine, decylamine;

Dimethylamine, diethylamine, di-n
-Propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-tert-butylamine, di-n-pentylamine, diisopentylamine, di-tert-pentylamine, dicyclopentylamine, di-n-hexyl Amines, diisohexylamine, di-tert-hexylamine, dicyclohexylamine, diheptylamine, diisoheptylamine,
Di-tert-heptylamine, dioctylamine, dinonylamine, didecylamine, diphenylamine;

Trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-
tert-butylamine, tri-n-pentylamine,
Triisopentylamine, tri-tert-pentylamine, tricyclopentylamine, tri-n-hexylamine, triisohexylamine, tri-tert-hexylamine, tricyclohexylamine, triheptylamine, trisoheptylamine, tri-tert Heptylamine, trioctylamine, trinonylamine, tridecylamine, triphenylamine;

Dimethylaminoethane, dimethylaminopropane, dimethylaminobutane, dimethylaminobutene, dimethylaminopentane, dimethylaminohexane, dimethylaminoheptane, diethylaminoethane,
Diethylaminopropane, diethylaminobutane, diethylaminobutene, diethylaminopentane, diethylaminohexane, diethylaminoheptane;

Aniline, N-methylaniline, N, N-
Dimethylaniline, N-ethylaniline, N, N-diethylaniline, p-toluidine, p-fluoroaniline, p-chloroaniline, p-bromoaniline, p-iodoaniline, p-anisidine, p-nitroaniline,
o-toluidine, o-fluoroaniline, o-chloroaniline, o-bromoaniline, o-iodoaniline, o
-Anisidine, o-nitroaniline, m-toluidine,
m-fluoroaniline, m-chloroaniline, m-bromoaniline, m-iodoaniline, m-anisidine, m
-Nitroaniline;

Methylenediamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, N, N, N ',
N'-tetramethylmethylenediamine, N, N, N ',
N'-tetramethylethylenediamine, N, N, N ',
N′-tetramethyl-1,3-propanediamine, N,
N, N ', N'-tetramethyltetramethylenediamine, N, N, N', N'-tetramethylpentamethylenediamine, N, N, N ', N'-tetramethylhexamethylenediamine, N, N , N ', N'-tetramethylheptamethylenediamine, N, N, N', N'-tetramethyloctamethylenediamine, N, N, N ',
N'-tetramethylnonamethylenediamine, N, N,
N ′, N′-tetramethyldecamethylene diamine,
N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethylbutenediamine, N, N, N ′, N′-tetramethylpentenediamine, N, N, N ', N'-tetramethylhexenediamine, N, N, N', N'-tetraethylmethylenediamine, N, N, N ', N'-tetraethylethylenediamine, N, N, N', N'-tetraethyltrimethylene Diamine, N, N, N ', N'-tetraethyltetraethylenediamine, N, N, N', N'-tetraethylpentamethylenediamine, N, N, N ', N'-tetraethylhexamethylenetylenediamine, N, N , N ', N'
-Tetraethylheptamethylenediamine, N, N,
N ′, N′-tetraethyloctamethylenediamine,
N, N, N ′, N′-tetraethylnonamethylenediamine, N, N, N ′, N′-tetraethyldecamethylenediamine;

1,3 bis (dimethylamino) -2-propanol, acrylic acid-1,3 bis (dimethylamino)
-2-propane, methacrylic acid-1,3 bis (dimethylamino) -2-propane, acetic acid-1,3 bis (dimethylamino) -2-propane, N, N, N ', N'-tetramethyl-2 -Butene-1,4-diamine, triisopropanolamine, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dimethylamino) ethyl acrylate, acetic acid-2- (N, N-dimethylamino) ethyl, 3- (N, N-dimethylamino) propyl methacrylate, 3- (N, N-dimethylamino) propyl acrylate, 3- (N, N-dimethylamino) propyl acetate 4- (N, N-dimethylamino) butyl methacrylate, 4- (N, N-dimethylamino) butyl acrylate, 4- (N, N-dimethylamino) butyl acetate, N- (3 Dimethylaminopropyl) methacrylamide, N- (2-dimethylaminoethyl) methacrylamide, N- (4-dimethylaminobutyl) methacrylamide, N- (3-dimethylaminopropyl) acrylamide, N- (2-dimethylaminoethyl) ) Acrylamide, N- (4-dimethylaminobutyl) acrylamide, dimethylaminomethanol, dimethylaminoethanol, dimethylaminopropanol, dimethylaminobutanol, dimethylaminopentanol, dimethylaminohexanol, dimethylaminoheptanol,
Dimethylaminooctamethylene alcohol, dimethylaminononamethylene alcohol, dimethylaminodecamethylene alcohol, ethylenediaminetetraacetic acid, dimethylaminoacetaldehyde diethylacetal, 3- (dimethylamino) acrylonitrile, 3- (dimethylamino) methacrylonitrile, 1- (2 -Dimethylaluminoethyl) -4-methylpiperidine, N, N-dimethylaminomethylenemalonic acid dimethyl ester, dimethylaminomethylnitrile, dimethylaminoethylylnitrile, dimethylaminopropiononitrile, dimethylaminobutyrylnitrile, dimethylaminopentylnitrile , Dimethylaminohexylnitrile;

1,3 bis (diethylamino) -2-propanol, acrylic acid-1,3 bis (diethylamino)
-2-propane, methacrylic acid-1,3 bis (diethylamino) -2-propane, acetic acid-1,3 bis (diethylamino) -2-propane, N, N, N ′, N′-tetramethyl-2-butene -1,4-diamine, triisopropanolamine, 2- (N, N-diethylamino) ethyl methacrylate, 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-diethylamino) acetic acid Ethyl, 3- (N, N-diethylamino) propyl methacrylate, 3- (N, N-diethylamino) propyl acrylate, 3- (N, N-diethylamino) propyl acetate, 4- (N-methacrylic acid) , N-diethylamino) butyl, 4- (N, N-diethylamino) butyl acrylate, 4- (N, N-diethylamino) butyl acetate, N- (3 Diethylaminopropyl) methacrylamide, N- (2-diethylaminoethyl) methacrylamide, N- (4-diethylaminobutyl) methacrylamide, N- (3-diethylaminopropyl) acrylamide, N- (2-diethylaminoethyl) acrylamide, N- (4-diethylaminobutyl) acrylamide, diethylaminomethanol, diethylaminoethanol, diethylaminopropanol, diethylaminobutanol, diethylaminopentanol, diethylaminohexanol, diethylaminoheptanol,
Diethylaminooctamethylene alcohol, diethylaminononamethylene alcohol, diethylaminodecamethylene alcohol, ethylenediaminetetraacetic acid, diethylaminoacetaldehyde diethylacetal, 3- (diethylamino) acrylonitrile, 3- (diethylamino) methacrylonitrile, 1- (2-diethylaminoethyl) -4 -Methylpiperidine, N, N-diethylaminomethylenemalonic acid dimethyl ester, diethylaminomethylnitrile, diethylaminoethylylnitrile, diethylaminopropiononitrile, diethylaminobutyrylnitrile, diethylaminopentylnitrile, diethylaminohexylnitrile and the like.

Of these, compounds containing an N, N-dimethylamino group [(CH ₃ ) ₂ N—] are preferred from the viewpoint of particularly improving the dispersibility of copper ions in the acrylic resin. .

The content of the amino group-containing compound in the resin composition of the present invention is preferably 0.001 to 20 parts by mass, more preferably 0.005 to 15 parts by mass, per 100 parts by mass of the acrylic resin. And particularly preferably 0.01 to 10 parts by mass. This ratio is 0.001
When the amount is less than parts by mass, it becomes difficult to disperse copper ions in the acrylic resin, and it becomes difficult to obtain an acrylic resin composition having high near infrared absorption efficiency.
On the other hand, if this proportion exceeds 20 parts by mass, the resulting acrylic resin composition becomes too soft, impairing practicality.

<Metal ion component containing copper ion> The copper ion constituting the resin composition of the present invention can be obtained by adding an appropriate copper compound (copper salt) to a monomer or an acrylic resin for obtaining an acrylic resin. And by subjecting this system to a polymerization treatment, it can be contained in the acrylic resin. Specific examples of the above copper compounds include copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethyl acetoacetate, copper pyrophosphate, copper naphthenate, copper citrate,
Examples include anhydrides or hydrates such as copper sulfate, copper nitrate, and copper carbonate, but are not limited to these copper compounds.

The content ratio of the copper ion is as follows.
The amount is preferably 0.005 to 20 parts by mass, more preferably 0.01 to 15 parts by mass, particularly preferably 0.02 to 10 parts by mass, per 100 parts by mass. If this ratio is less than 0.005 parts by mass, it will be difficult to obtain an acrylic resin composition that absorbs near infrared rays with high efficiency. On the other hand, when this proportion exceeds 20 parts by mass, it becomes difficult to disperse copper ions in the acrylic resin, and a resin composition having excellent visible light transmittance may not be obtained.

In the resin composition of the present invention, a complex structure represented by the above formula (2) is formed by the copper ion and the amino group-containing compound, and the resin composition containing the complex structure is , Wide wavelength range (800-150
0 nm) can be effectively absorbed, and particularly near infrared rays in a wavelength region of 800 to 1200 nm can be efficiently absorbed.

The resin composition of the present invention may contain metal ions other than copper ions (hereinafter, referred to as “other metal ions”) as metal ion components. Specific examples of such other metal ions include sodium, potassium, calcium, barium, iron, manganese, cobalt,
Magnesium, nickel, vanadium, aluminum,
Examples include ions of metals such as titanium, chromium, and zinc. These other metal ions can be contained in the acrylic resin in the same manner as copper ions.

The content ratio of copper ions in the metal ion component is preferably 50% by mass or more.
It is more preferably at least 70% by mass, particularly preferably at least 80% by mass. When this ratio is less than 50% by mass, it becomes difficult to obtain a resin composition having high near-infrared absorption efficiency.

<Method for Producing Resin Composition> The resin composition of the present invention is obtained by subjecting a monomer composition containing an amino group-containing compound, a copper compound, and an acrylic monomer as essential components to a polymerization treatment. It can be suitably manufactured by a method including a step of carrying out. Specifically, in a monomer for obtaining an acrylic resin (an acrylic monomer (essential) and a copolymerizable monomer (optional)), a metal compound having a copper compound as an essential component,
By adding and mixing with an amino group-containing compound,
A method in which a monomer composition in which a metal ion component and an amino group-containing compound are dissolved and prepared is prepared, and the monomer composition is subjected to polymerization treatment.

The resin composition of the present invention can also be suitably produced by a method in which a metal compound essentially containing a copper compound and an amino group-containing compound are added to an acrylic resin and mixed. Specifically, (1) a method of adding and mixing a metal compound and an amino group-containing compound into an acrylic resin melted by heating (hereinafter, referred to as a “post-addition method”), and (2) an acrylic resin. A method of dissolving or swelling the resin with an organic solvent, adding a metal compound and an amino group-containing compound to the obtained resin solution or the swelled acrylic resin, and mixing the resulting solution.

As an example of the post-addition method of the above (1), there is a method in which a metal compound and an amino group-containing compound are directly mixed, and the obtained mixture is added and mixed in an acrylic resin. Here, when a mixed solution is prepared by mixing the metal compound and the amino group-containing compound, a suitable organic solvent may be added as necessary for viscosity adjustment or the like. Before mixing into the resin, it may be removed from the mixture.

As another example of the post-addition method of the above (1), a solution is prepared by dissolving an amino group-containing compound in a small water-soluble organic solvent (a hydrocarbon solvent such as toluene, xylene, and kerosene). Then, by bringing an aqueous solution that dissolves copper ions into contact with the solution, copper ions are transferred into the solution (hereinafter, referred to as “cation extraction method”), and a solution containing copper ions and an amino group-containing compound is obtained. (Hereinafter, also referred to as “copper ion-amino group-containing solution”)
And a method in which a solvent is removed from the copper ion-amino group-containing solution, if necessary, and this system is added to and mixed with an acrylic resin.

The organic solvent used in the method (2) is not particularly limited as long as it dissolves or swells the acrylic resin. Preferably, it can be easily removed after mixing. Specific examples of such organic solvents 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, dichloromethane, dichloroethane, methylene chloride and the like. And amide solvents such as dimethylacrylamide, dimethylacetamide, dimethylformamide and N-methylpyrrolidone.

From the viewpoint of preventing an increase in hygroscopicity and a decrease in thermal stability of the resin composition, the resin composition of the present invention contains an anion (counter ion of a metal ion component) and an acid component derived therefrom. Preferably, it is not contained. For this reason, it is preferable to adopt a production method as shown in the following (a) to (c) or to perform a treatment as shown in the following (d) on the obtained resin composition.

(A) A production method comprising a step of polymerizing a monomer composition containing an amino group-containing compound, a copper compound, and an acrylic monomer as essential components. (B) A production method including a step of mixing a copper ion-amino group-containing solution obtained by a cation extraction method with an acrylic resin. (C) An acid derived from an anion from the monomer composition by cooling the monomer composition containing the anion (acid component) (an acid having low solubility in the monomer composition)
And separating the mixture by filtration. (D) A treatment for extracting and removing an acid derived from an anion from the resin composition by bringing a resin having a strong affinity for the anion into contact with the resin composition containing the anion (acid component). .

The "solvent having a strong affinity for anions" used in the extraction treatment (d) is capable of dissolving a released acid component and has an appropriate affinity for the acrylic resin used. (Affinity that does not dissolve the acrylic resin but permeates the acrylic resin)
Is not particularly limited as long as it has
Specific examples of such a solvent include methyl alcohol,
Ethyl alcohol, n-propyl alcohol, lower aliphatic alcohols such as isopropyl alcohol, acetone,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethers such as diethyl ether and petroleum ether, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, chloroform, methylene chloride, carbon tetrachloride and the like Examples thereof include halides, aromatic hydrocarbons such as benzene, toluene, and xylene. Of these, methyl alcohol having excellent affinity for benzoate ions is preferable.

The resin composition of the present invention thus obtained can be formed into a desired shape such as a plate, a column, or a lens, depending on the use. Since the resin composition of the present invention contains copper ions in a state of being dispersed at a high concentration in the acrylic resin, it can efficiently absorb near infrared rays in a wide wavelength range and transmit visible light. Also excellent in nature. Further, the resin composition of the present invention can effectively cut near-infrared rays in a wide wavelength range even if the content of copper ions is small. The resin composition of the present invention can be suitably used as a constituent material of an optical filter such as a heat ray absorbing filter such as a window material, a near infrared cut filter, and a near infrared cut lens. Hereinafter, such an optical filter (the optical filter of the present invention) and its application example will be described.

<Optical Filter of the Present Invention> The optical filter of the present invention comprises the acrylic resin composition of the present invention. According to the filter of the present invention, it effectively cuts near infrared rays in a wide wavelength range. be able to.

<Application Examples of Optical Filter of the Present Invention> The optical filter of the present invention has excellent optical characteristics (an efficient cut function of near-infrared rays in a wide wavelength range) for various uses as described below. Can be applied. 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 unit of a camera. Here, the "visibility correction filter" composed of the optical filter of the present invention includes a converging lens and the like in addition to the visibility correction filter which is independently arranged in the optical path to the light receiving element. According to the camera equipped with the optical filter of the present invention (camera of the present invention), the light receiving element (silicon photodiode)
Light incident on the light source can be substantially limited to light in the visible region, and as a result, 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 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.

Further, by arranging the optical filter of the present invention on the front surface of the panel of the plasma display device, it is possible to efficiently cut the 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.

The optical filter of the present invention is a heat ray absorbing filter, specifically, a window material in a building such as a house or a building, a window material of a car or a train car, or a translucent member of a greenhouse for agriculture or the like. 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.

The optical filter of the present invention can be suitably used as a spectacle lens. 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.

[0054]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by these.

Example 1 According to the formulation shown in Table 1 below, 100 g of methyl methacrylate and N, N, N ', N'-tetramethyl-1,3- represented by the following formula (3) were used.
1.72 g (copper ion content = 0.54 g) of copper acetate was added to a mixture consisting of 1.23 g of propanediamine, and the mixture was stirred at 60 ° C. for 1 hour to dissolve copper acetate, thereby obtaining a monomer composition. Was prepared. 0.1 g of t-butyl peroxyneodecanate was added to the obtained monomer composition, and the monomer composition was poured into a disk molding mold (for molding a 2 mm-thick disk). At 50 ° C. for 3 hours and 90 ° C. for 1 hour to obtain a transparent disk (optical filter) having a thickness of 2 mm and made of the optical material of the present invention.

[0056]

Formula (3): (H ₃ C) ₂ N— (CH ₂ ) ₃ —N
(CH ₃ ) ₂

<Examples 2 to 3> The amounts of N, N, N ', N'-tetramethyl-1,3-propanediamine and the amount of copper acetate added were changed according to the formulation shown in Table 1 below. Except for the above, a monomer composition was prepared in the same manner as in Example 1, and cast polymerization was carried out to obtain a transparent disk (optical filter) having a thickness of 2 mm and comprising the optical material of the present invention.

Example 4 According to the recipe shown in Table 1 below, instead of N, N, N ', N'-tetramethyl-1,3-propanediamine, 5.94 g of 2-dimethylaminoethyl methacrylate was used. A monomer composition was prepared in the same manner as in Example 1 except that 2.90 g of copper benzoate (copper ion content = 0.54 g) was added instead of copper acetate, and cast polymerization was performed. As a result, a transparent disk (optical filter) having a thickness of 2 mm made of the optical material of the present invention was obtained.

<Examples 5 to 8> A monomer composition was prepared in the same manner as in Example 1 except that the type and amount of the amino group-containing monomer were changed according to the formulation shown in Table 1 below. By performing cast polymerization, a transparent disk (optical filter) having a thickness of 2 mm and comprising the optical material of the present invention was obtained.

Example 9 To 100 g of polymethyl methacrylate melted by heating, 5.73 g of copper acetate (content of copper ion = 1.80 g) and N, N, N ′, N′-tetramethyl-1, 4.10 g of 3-propanediamine was mixed and added to obtain an optical material of the present invention, and a transparent disk (optical filter) having a thickness of 3 mm was obtained using the optical material.
I got

Comparative Example 1 According to the formulation shown in Table 1 below, 5.0 g of copper acetate, 5.6 g of methacrylic acid, and 20.0 g of diethylene glycol dimethacrylate were added to 65.5 g of methyl methacrylate and mixed. By stirring for an hour, copper acetate was dissolved to prepare a monomer composition. 0.1 g of t-butyl peroxyneodecanate was added to the obtained monomer composition, and the monomer composition was poured into a disk molding mold (for molding a 2 mm-thick disk). For 5 hours, 60 ° C for 3 hours, 9
By performing casting polymerization at 0 ° C. and sequentially at different temperatures for 1 hour, a disk (optical filter) having a thickness of 2 mm made of a comparative optical material was obtained.

[0062]

[Table 1]

<Evaluation of Optical Material> Using the disks according to Examples 1 to 9 and Comparative Example 1 as test pieces, the spectral transmittance curves of the test pieces were measured with a spectrophotometer “U-4000” (manufactured by Hitachi, Ltd.). did. 500 nm, 800 nm, 90
Table 2 also shows the spectral transmittance of each test piece at 0 nm, 1000 nm, 1200 nm, 1300 nm, and 1500 nm, and FIG. 1 shows the spectral transmittance curve (250 to 1200 nm) of the disk according to Example 1.

[0064]

[Table 2]

As is clear from the results shown in Table 2, the disks according to Examples 1 to 9 had wavelengths of 800 to 1500 nm.
(Especially transmittance at 800 to 1200 nm)
, It can effectively cut near-infrared rays in a wide wavelength range, and has a transmittance at 500 nm of 70% or more, and is excellent in visible light transmittance.
On the other hand, the disks according to Comparative Example 1 were 800 to 1
The transmittance at 500 nm was high, and did not exhibit a sufficient function as a near-infrared cut filter.

[0066]

The resin composition of the present invention can effectively cut near infrared rays in a wide wavelength range (800 to 1500 nm), and particularly cuts near infrared rays in a wavelength range of 800 to 1200 nm with high efficiency. Can be. Moreover, the resin composition of the present invention is also excellent in visible light transmittance.

The production method of the present invention can produce a resin composition having excellent near-infrared absorption and visible light transmission. The optical filter of the present invention can cut off near-infrared rays in a wide wavelength range, and has excellent visible light transmittance.

According to the camera of the present invention, light incident on the light receiving element can be substantially limited to light in the visible region, and accurate photometry (exposure operation) can be performed. 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. According to the plasma display device of the present invention, a malfunction of the remote controller due to near-infrared rays does not occur around the plasma display device. 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 included in the light guided and emitted by the optical fiber, the temperature rise near the light emitting portion (in the apparatus / in the room) is suppressed. be able to. 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.

[Brief description of the drawings]

FIG. 1 is a spectral transmittance curve measured for a disk according to Example 1.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2H048 CA04 CA05 CA12 CA19 4F070 AA32 AB05 AC06 AC18 AC45 FA04 FA08 FB05 FB09 4J002 BG041 BG051 BG061 DD077 DE247 DF006 DF037 DG047 EG047 EG077 EG087 EN009 EN0106 EN0066 EN0066 GP01

Claims (14)

[Claims] 1. A resin composition comprising a substituted or unsubstituted amino group and a metal ion component containing a copper ion contained in an acrylic resin. 2. A resin composition characterized in that an N, N-dimethylamino group and a metal ion component containing copper ions are contained in an acrylic resin. 3. A resin composition comprising a step of polymerizing a monomer composition containing a compound having a substituted or unsubstituted amino group, a copper compound, and an acrylic monomer. Method of manufacturing a product. 4. A method for producing a resin composition, comprising a step of mixing a compound containing a substituted or unsubstituted amino group with a copper compound in an acrylic resin. 5. A method for producing a resin composition, comprising a step of mixing a reaction product of a compound containing a substituted or unsubstituted amino group with a copper compound in an acrylic resin. 6. An optical filter comprising the resin composition according to claim 1 or 2. 7. A camera equipped with the optical filter according to claim 6, as a visibility correction filter for a light receiving element. 8. An imaging device equipped with the optical filter according to claim 6, as a visibility correction filter for a CCD. 9. An infrared communication environment maintenance device equipped with the optical filter according to claim 6 as a noise cut filter. 10. A plasma display device comprising the optical filter according to claim 6 disposed on a front surface of a panel. 11. A heat ray absorbing filter comprising the optical filter according to claim 6. 12. An optical fiber comprising the optical filter according to claim 6. 13. An optical fiber, wherein the optical filter according to claim 6 is provided in a lighting part. 14. A spectacle lens comprising the optical filter according to claim 6.