JP2000038396A - Multifunctional phosphate, multifunctional copper phosphate, resin composition, optical fiber, apparatus equipped with the same filter, heat-absorbing filter, optical fiber, and lens for glasses - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound capable of giving a resin composition for optical filter excellent in near infrared absorption property and moisture resistance by being copolymerized with a comonomer. SOLUTION: This new compound is expressed by formula I R is expressed by formula II [X is H or methyl; R1 is a 1-6C hydrocarbon; (m) is 1-6; (p) is 2-6]; (n) is 1 or 2} and is e.g. a monoester of phosphoric acid, expressed by formula III. The compound of formula I is obtained e.g. as a 1:1 mixture of a diester of phosphoric acid of formula I [(n) is 1] with a monoester of phosphoric acid of formula I [(n) is 2] by reacting 3 mol. alcohol of formula R-OH with 1 mol. phosphorus pentoxide in an organic solvent. It is pref. that the solvent is toluene or xylene, and the reaction is carried out at 40-80 deg.C for 4-9 h. A resin composition obtained by copolymerizing the compound of formula I with a comonoer can give optical filter scarcely causing withening and devitrification behavior with time even when it is used under a highly humid condition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyfunctional phosphoric acid ester compound, a polyfunctional phosphoric acid ester copper compound, a resin composition, an optical filter, and applied equipment thereof.
More specifically, a polyfunctional phosphoric acid ester compound having a specific structure, a polyfunctional phosphoric acid ester copper compound, and a compound obtained by polymerizing these polyfunctional phosphoric acid ester (copper) compounds to obtain a near-infrared wavelength A resin composition and an optical filter capable of efficiently cutting light and having excellent moisture resistance, devices including the optical filter (cameras, CCD imaging devices, infrared communication environment maintenance devices, plasma display devices), heat rays It relates to an absorption filter, an optical fiber and an eyeglass lens.

[0002]

2. Description of the Related Art Heretofore, as a photometric filter (visibility correction filter) of a camera or a CCD image pickup device, a glass optical filter in which copper ions are contained in a special phosphate glass has been used.

However, these glass optical filters have a problem that they have a large hygroscopicity and are liable to cause whitening and devitrification over time. In addition, glass optical filters also have a manufacturing problem that processing such as molding, cutting, and polishing is difficult.

As a means for solving the above-mentioned problems, the present inventors have developed a resin component containing a phosphate group,
An optical filter made of a synthetic resin containing an ionic metal component containing copper ions as a main component has been proposed (Japanese Patent Application Laid-Open No. Hei 6 (1994) -207).
-118228, 9-184914). According to such a synthetic resin optical filter, wavelength light in the near infrared region can be efficiently cut,
Moreover, the optical filter is light, easily processed, excellent in productivity, and has a certain degree of moisture resistance.

However, optical filters used in high-humidity environments and the like are required to have even better moisture resistance (small hygroscopicity and no whitening and devitrification phenomenon over time).

[0006]

SUMMARY OF THE INVENTION The present invention has been made based on the above circumstances. A first object of the present invention is to provide a novel polyfunctional phosphate compound which is useful as a constituent of a resin composition having excellent near infrared (700 to 1000 nm) absorption characteristics and excellent moisture resistance. is there. A second object of the present invention is to provide a novel copper salt of a polyfunctional phosphate ester which is useful as a constituent of a resin composition having excellent near-infrared absorption characteristics and moisture resistance. A third object of the present invention is to provide a resin composition having excellent near-infrared absorption characteristics. A fourth object of the present invention is to provide a resin composition which is excellent in moisture resistance and does not cause whitening and devitrification over time even when used in a high humidity environment. A fifth object of the present invention is to
An object of the present invention is to provide a resin composition which is lightweight and easy to process such as molding, cutting and polishing. A sixth object of the present invention is to provide an optical filter having excellent near-infrared absorption characteristics. A seventh object of the present invention is to provide a resin optical filter which is more excellent in moisture resistance than conventionally known optical filters and which does not cause whitening and devitrification over time even when used in a high humidity environment. It is in. An eighth object of the present invention is to provide a camera provided with an optical filter having excellent near-infrared absorption characteristics and moisture resistance as a visibility correction filter for a light receiving element. A ninth object of the present invention is to
It is an object of the present invention to provide an image pickup apparatus including an optical filter having excellent near-infrared absorption characteristics and moisture resistance as a visibility correction filter for a CCD. A tenth object of the present invention is to provide an infrared communication environment maintenance device including an optical filter having excellent near-infrared absorption characteristics and moisture resistance as a noise cut filter. An eleventh object of the present invention is to provide a plasma display device in which an optical filter having excellent near-infrared absorption characteristics and moisture resistance is arranged on the front surface of a panel. A twelfth object of the present invention is to provide a heat ray absorbing filter having excellent near-infrared absorption characteristics and excellent moisture resistance. A thirteenth object of the present invention is to provide an optical fiber having excellent near-infrared absorption characteristics and moisture resistance. A fourteenth object of the present invention is to provide a spectacle lens excellent in near-infrared absorption characteristics (effect of suppressing cataract development) and moisture resistance.

[0007]

Means for Solving the Problems The polyfunctional phosphate compound of the present invention is characterized by being represented by the following formula (1).

[0008]

Embedded image

[0009] The multifunctional phosphoric acid ester copper compound of the present invention is characterized by being represented by the following formula (2).

[0010]

Embedded image

[0011] The polyfunctional phosphate copper compound of the present invention is characterized by being represented by the following formula (3).

[0012]

Embedded image

[0013] The resin composition of the present invention comprises a polyfunctional phosphate compound represented by the above formula (1) and a resin component obtained by copolymerizing a monomer copolymerizable therewith. Is characterized by being contained. Further, the resin composition of the present invention is obtained by copolymerizing a polyfunctional phosphate copper compound represented by the formula (2) and a monomer copolymerizable therewith. Further, the resin composition of the present invention is obtained by copolymerizing a polyfunctional phosphoric acid ester copper compound represented by the formula (3) and a monomer copolymerizable therewith.

The optical filter of the present invention is characterized by comprising the above resin composition (the resin composition of the present invention).

A camera according to the present invention is characterized in that the above optical filter (optical filter according to 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. An infrared communication environment maintenance device of the present invention is characterized in that the above-described optical filter (the optical filter of the present invention) is used as a noise cut filter. 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. The spectacle lens of the present invention,
It is characterized by comprising the above-mentioned optical filter (the optical filter of the present invention).

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. <Polyfunctional phosphate compound> A polyfunctional phosphate compound represented by the above formula (1) [hereinafter, also referred to as “polyfunctional phosphate compound (A)”. Is a polyfunctional unsaturated compound having a plurality (2 to 12) of acryloyloxy groups or methacryloyloxy groups, which are radically polymerizable functional groups, in the molecular structure.

This polyfunctional phosphate compound (A)
Is R-OH [wherein, R represents the same group as R in the above formula (1). Can be prepared by reacting the alcohol represented by the formula [1] with phosphorus pentoxide in an appropriate organic solvent.

Here, the organic solvent used in the reaction can be selected from solvents which do not react with phosphorus pentoxide. For example, hexane, cyclohexane, heptane, octane, benzene, toluene, xylene , Hydrocarbon solvents such as petroleum spirits, halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, acetone, methyl ethyl ketone,
Examples thereof include ketone solvents such as dibutyl ketone. Of these, toluene and xylene are preferable. The reaction conditions include a reaction temperature of 0 to 100 ° C, preferably 40 to 80 ° C, and a reaction time of 1 to 24 hours.
Preferably, it is 4 to 9 hours.

In this preparation method, for example, R
By reacting 3 moles of an alcohol represented by -OH with 1 mole of phosphorus pentoxide, the polyfunctional phosphate compound (A) (monophosphate phosphate) wherein the number n of hydroxyl groups in the above formula (1) is 2 Ester) and a polyfunctional phosphoric ester compound (phosphoric diester) in which the number n of hydroxyl groups in the above formula (1) is 1 (molar ratio) is about 1: 1.
The following mixture can be obtained. In addition, the above R-OH
By appropriately selecting the ratio of the alcohol represented by the formula and phosphorus pentoxide and the reaction conditions, the ratio (molar ratio) of the phosphoric acid monoester and the phosphoric acid diester to be formed is 9
It can be adjusted in the range of 9: 1 to 40:60.

As described above, an example of the method for preparing the polyfunctional phosphate compound [polyfunctional phosphate compound (A)] of the present invention has been described. Can also be prepared. Here, as another preparation method, (i) an alcohol represented by R-OH and phosphorus oxyhalide are mixed in an appropriate organic solvent (a solvent having no reactivity with phosphorus oxyhalide). (Ii) reacting an alcohol represented by R-OH and phosphorus trihalide with an appropriate organic solvent (reaction with phosphorus trihalide). (A solvent having no properties) to oxidize the resulting phosphonate ester compound.

<Copper Polyfunctional Phosphate Copper Compound> The polyfunctional phosphoric acid copper ester compound represented by the above formula (2) has a plurality of (meth) acryloyloxy groups which are radically polymerizable functional groups in the molecular structure. The polyfunctional unsaturated compound having (2 to 6) polyfunctional unsaturated copper compounds represented by the above formula (3) has a plurality of (4 to 24) (meth) acryloyloxy groups in the molecular structure. It is a polyfunctional unsaturated compound having two

A copper salt of a polyfunctional phosphate ester represented by the above formula (2) or (3) [hereinafter, these are also referred to as "copper copper salt of a polyfunctional phosphate (B)". ]
It can be prepared by reacting the above polyfunctional phosphate compound (A) with a copper salt.

The copper salt used to obtain the copper compound (B) is copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethyl acetoacetate, pyrroline. Examples include, but are not limited to, anhydrides or hydrates such as copper acid, copper naphthenate, copper citrate, copper sulfate, copper nitrate, and copper carbonate.

The reaction between the polyfunctional phosphate compound (A) and the copper salt is carried out by bringing them into contact under appropriate conditions. Specifically, (1) a method of mixing a polyfunctional phosphate compound (A) and a copper salt to react them, and (2) a method of mixing the polyfunctional phosphate compound (A) and copper in an appropriate solvent. (3) contacting an organic solvent layer containing a polyfunctional phosphate compound (A) in an organic solvent with an aqueous layer in which a copper salt is dissolved, Functional phosphate compound (A)
With a copper salt.

The polyfunctional phosphate compound (A)
The reaction conditions for the copper salt and the reaction temperature are 0 to 200 ° C, preferably 40 to 150 ° C, more preferably 60 to 100 ° C.
And the reaction time is 30 seconds to 10 hours, preferably 3 minutes to 7 hours, more preferably 5 minutes to 5 hours.

The solvent used in the above method (2) is not particularly limited as long as it can dissolve the polyfunctional phosphate compound (A). Examples of the solvent include aromatic waters such as distilled water, benzene, toluene and xylene. Aromatic compounds; 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; ketones such as acetone and methyl ethyl ketone; Esters such as hexane, kerosene, petroleum ether and the like.

The organic solvent used in the method (3) is not particularly limited as long as it is insoluble or hardly soluble in water and can dissolve the polyfunctional phosphate compound (A). For example, among those exemplified as the organic solvent used in the method (2), aromatic compounds, ethers, esters, hexane, kerosene,
(Meth) acrylates and the like.

In the reaction between the polyfunctional phosphate compound (A) and the copper salt, an acid component as an anion is released from the copper salt. Since such an acid component may cause a decrease in moisture resistance and thermal stability of a resin composition obtained by polymerizing the acid component, the acid component is preferably removed as necessary.

In the case of preparing the polyfunctional phosphate ester copper compound (B) by the above method (1) or (2), after reacting the polyfunctional phosphate ester compound (A) with a copper salt, The generated acid component [the generated acid component and the organic solvent in the method of (2)] can be removed by distillation or filtration.

When the polyfunctional phosphoric acid ester copper compound (B) is produced by the method (3), the following method can be mentioned as a preferable method for removing the acid component. After neutralization by adding an alkali component to an organic solvent layer containing a polyfunctional phosphate compound (A) in an organic solvent insoluble or hardly soluble in water, the organic solvent layer and the copper salt are dissolved. A method of reacting a polyfunctional phosphate compound (A) with a copper salt by contacting the aqueous layer with the resulting aqueous layer, and thereafter separating the organic solvent layer and the aqueous layer. Here, examples of the alkali component include sodium hydroxide, potassium hydroxide, and ammonia, but are not limited thereto. According to such a method, a water-soluble salt is formed by the acid component and the alkali component released from the copper salt, and the salt migrates to the aqueous layer, and the resulting polyfunctional phosphate copper compound ( Since B) moves to the organic solvent layer, the acid component can be removed by separating the aqueous layer and the organic solvent layer.

<Resin Composition> The resin composition of the present invention includes:
Resin comprising copper ion in a resin component obtained by copolymerizing polyfunctional phosphate compound (A) represented by the above formula (1) and a monomer copolymerizable therewith. Composition [hereinafter, also referred to as “resin composition (A)”. And a resin composition obtained by copolymerizing a multifunctional phosphate copper compound (B) represented by the above formula (2) or (3) with a monomer copolymerizable therewith. [Hereinafter, it is also referred to as “resin composition (B)”. ] Is included.

<Resin Composition (A)> As a monomer for obtaining the resin component of the resin composition (A), a polyfunctional phosphate compound (A) is used. As represented by the above formula (1), the polyfunctional phosphate compound (A)
It has a phosphate group capable of binding to copper ions in its molecular structure, whereby it is possible to impart the solubility of copper ions to the obtained resin component. The copolymer holding copper ions via the phosphate group exhibits light absorption characteristics characteristic in the near infrared region. In the present invention, “phosphate group” is “PO (OH) _n −” (n is 1
Or 2. ) Is meant.

Furthermore, the polyfunctional phosphate compound (A) has a plurality (2 to 12) of (meth) acryloyloxy groups, which are radically polymerizable functional groups, in its molecular structure. In view of the polymerizability, it becomes possible to copolymerize with various monomers. In addition, a crosslinked structure of the polyfunctional phosphate compound (A) is introduced into the resin component obtained by copolymerization, and a copper complex site (copper ion-phosphate group bonding site) is introduced into the resin component. Is covered by the crosslinked structure. As a result, the water that tends to penetrate into the copper complex site from the outside is blocked by the crosslinked structure, and the reaction between the copper complex and water, which causes the whitening and devitrification phenomenon, is suppressed. As a result, the obtained resin composition (A) exhibits water repellency and has much better moisture resistance than conventionally known resin compositions constituting an optical filter.

In the above formula (1) representing the molecular structure of the polyfunctional phosphate compound (A), the alkylene group (-C
_m H _2m - number of carbon atoms of) (m) is the integer from 1 to 6, preferably 1 to 4, particularly preferably 1. The value of m is 6
When it exceeds, the crosslinked structure introduced around the copper ion (copper complex site) does not become dense, and the obtained resin composition does not have the expected moisture resistance.

In the above formula (1), the hydrocarbon group (R ¹ ) has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
It is particularly preferably 2. When the number of carbon atoms in the hydrocarbon group exceeds 6, the effect of introducing a cross-linked structure around copper ions (copper complex sites) cannot be sufficiently exerted, and the resulting resin composition is insufficient. It does not have the initial moisture resistance.

Further, in the above formula (1), [CH ₂
= C (X) COO-C m H 2m - number of groups represented by] (p) is a 2-6, preferably 3-6, particularly preferably 3. When the value of p is 1, the obtained resin composition does not have sufficient moisture resistance. On the other hand, when the value of p exceeds 6, the crosslinked structure to be introduced becomes too dense, the resulting resin composition becomes hard and brittle, and the practicality as an optical filter is impaired.

In the above formula (1), the number (n) of hydroxyl groups of the polyfunctional phosphate compound (A) can be selected from 1 or 2 depending on the purpose of use of the optical filter. Good. Here, according to the polyfunctional phosphate compound (A) in which the value of n is 1, a resin composition having a high crosslinking density can be obtained. In addition, the polyfunctional phosphate compound (A) in which the value of n is 2 has a high binding property to copper ions. Furthermore, it is preferable to use a polyfunctional phosphate compound (A) in which the value of n is 1 and a polyfunctional phosphate compound (A) in which the value of n is 2 in combination. When the polyfunctional phosphoric ester compound (A) is used in such a ratio that each becomes almost equimolar, the copper salt (the salt used for introducing copper ions into the resin composition) of the mixed monomer is used. It is preferable because solubility is improved.

As a monomer for obtaining the resin component of the resin composition (A), a polyfunctional phosphate compound (A) and a monomer copolymerizable therewith (a copolymerizable monomer) are used. Used. The copolymer obtained by copolymerizing the polyfunctional phosphate compound (A) and the copolymerizable monomer has low hygroscopicity, satisfies the hardness conditions required for optical filters, and has heat resistance and shape. Excellent retention. Therefore, according to the resin composition containing such a copolymer as a resin component, it is possible to obtain a molded article (for example, an optical filter) excellent in various performances.

The copolymerizable monomer is (1) uniformly dissolved and mixed with the polyfunctional phosphate compound (A),
It is not particularly limited as long as it satisfies (2) good radical copolymerizability with the polyfunctional phosphate compound (A) and (3) an optically transparent copolymer can be obtained. Not something.

Specific examples of the copolymerizable monomer satisfying these conditions include monofunctional acrylates and monofunctional methacrylates (eg, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl acrylate). Alkyl acrylates such as methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, alkyl methacrylate, glycidyl acrylate, glycidyl methacrylate , 2-hydroxyethyl acrylate, 2
-Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, modified alkyl acrylates and modified alkyl methacrylates such as 2-hydroxybutyl methacrylate, etc.); polyfunctional acrylates or polyfunctional methacrylates (for example, Ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 1,
3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate,
1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane , 2-hydroxy-
1-acryloxy-3-methacryloxypropane, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, etc.); acrylic acid Carboxylic acids such as methacrylic acid, 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxyethyl phthalic acid; styrene, α-methylstyrene, chlorostyrene, dibromostyrene, methoxystyrene, divinylbenzene, vinylbenzoic acid, hydroxymethyl styrene,
Examples thereof include aromatic vinyl compounds such as trivinylbenzene. These can be used alone or in combination of two or more.

In the mixed monomer for obtaining the resin component of the resin composition (A), the ratio of the polyfunctional phosphoric acid ester compound (A) to the copolymerizable monomer is defined as “polyfunctional phosphoric acid”. The "ester compound (A): copolymerizable monomer (weight)" is preferably in the range of 3:97 to 80:20, and more preferably 10:90 to 60:40. When the proportion of the polyfunctional phosphate compound (A) is less than 3% by weight, light absorption characteristics suitable as an optical filter are hardly exhibited. On the other hand, when this proportion exceeds 80% by weight, the obtained copolymer (resin component) tends to be flexible which cannot satisfy the hardness condition required for the optical filter.

The copolymer constituting the resin component of the resin composition (A) is obtained by radical polymerization of a mixed monomer comprising the polyfunctional phosphate compound (A) and a copolymerizable monomer. . The radical polymerization method is not particularly limited, and a known method 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 is used. Can be.

The resin composition (A) comprises the above resin component (copolymer) containing copper ions. The copper ions have a function of efficiently absorbing light in the near-infrared region due to interaction with a phosphate group contained in the resin component. Copper ions can be introduced using copper salts. Here, as the copper salt used to introduce copper ions, compounds exemplified as those used to obtain the polyfunctional phosphate copper compound (B) (copper acetate, copper chloride, copper formate, stearin) Anhydrides or hydrates such as copper acid, copper benzoate, copper ethyl acetoacetate, copper pyrophosphate, copper naphthenate, copper citrate, copper sulfate, copper nitrate, and copper carbonate).

The content of copper ions in the resin composition (A) is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the copolymer as the resin component. １５15 parts by weight. If this proportion is less than 0.05 parts by weight, a resin composition having excellent near-infrared absorption properties cannot be obtained, while
If the amount is more than 100 parts by weight, it is difficult for the copper salt, which is the source of copper ions, to be uniformly dispersed in the mixed monomer or copolymer.

The method for preparing the resin composition (A) by incorporating copper ions in the copolymer is not particularly limited, but the following two methods can be mentioned as preferred methods. .

(1) A method in which a copper salt is added and dissolved in the mixed monomer before radical polymerization of the mixed monomer is performed. This method contains a copper salt, the copper salt,
A monomer mixture comprising the polyfunctional phosphate compound (A) and a copolymerizable monomer is prepared, and the monomer mixture is subjected to radical polymerization.

(2) A method in which a copper salt is added and mixed into a copolymer (resin component) obtained by performing radical polymerization of a mixed monomer. In this case, as a method for adding the copper salt, a method in which the copolymer is dissolved in an organic solvent and added to the solution can be used.

In the step of preparing the resin composition (A), the phosphoric acid group derived from the polyfunctional phosphoric acid ester compound (A) reacts with the copper salt, so that an acid component as an anion is liberated from the copper salt. Is done. Such an acid component is preferably removed as necessary for the same reason as described above. As a method of removing such an acid component, a method of extracting the acid component by immersing the resin composition (A) in an appropriate organic solvent, and a method of extracting the acid component before polymerizing the monomer mixture. A method of precipitating and separating the acid component by subjecting the monomer mixture to a cooling treatment is exemplified.

As the organic solvent used in the above method (extraction method), an organic solvent capable of dissolving a released acid component and having an appropriate affinity for the resin component of the resin composition (A) is used. If there is, it is not particularly limited. Specific examples of such a solvent include lower aliphatic alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as diethyl ether and petroleum ether. , N-pentane, n-hexane, n-heptane, chloroform, methylene chloride, aliphatic hydrocarbons such as carbon tetrachloride and their halides, and aromatic hydrocarbons such as benzene, toluene and xylene. No. When the above-mentioned method (precipitation method) is adopted, it is preferable to use a copper salt in which a liberated acid component (acid derived from the copper salt) is hardly dissolved in a monomer, and specifically, It is preferable to use a copper salt of a carboxylic acid having an aromatic ring such as benzoic acid.

The resin composition (A) may contain other metal ions together with copper ions. here,
Other metal ions include sodium, potassium, calcium, iron, manganese, cobalt, magnesium, nickel and the like. Further, other metal ions can be contained in the resin component by a method similar to the method of containing copper ions. As the content ratio of other metal ions, 20% by weight of all metal ions including copper ions is used from the viewpoint of exhibiting near infrared absorption characteristics.
The following is preferred.

A copolymer containing copper ions (resin composition (A)) can be obtained by the method as described in (1) and (2) above. This resin composition (A) can be formed as it is or in a desired shape such as a plate shape, a column shape, a lens shape or the like according to the purpose and application.

<Resin composition (B)> Resin composition (B)
Is obtained by copolymerizing a polyfunctional phosphoric acid ester copper compound (B) and a monomer copolymerizable therewith (copolymerizable monomer). In the above formulas (2) and (3) showing the molecular structure of the polyfunctional phosphate ester copper compound (B), the group represented by R is the same group as R in the polyfunctional phosphate ester compound (A) It is. Therefore, the polyfunctional phosphoric acid ester copper compound (B) represented by the above formula (2) has a plurality of (meth) acryloyloxy groups in the molecular structure (2 to 6), and the formula (3) The polyfunctional phosphoric acid ester copper compound (B) represented has a plurality (8 to 24) of (meth) acryloyloxy groups in the molecular structure.

The polyfunctional phosphoric acid ester copper compound (B) is considered to be extremely copolymerizable, and can be copolymerized with various monomers. Moreover, the resin composition (B) obtained by copolymerization is introduced with a crosslinked structure of the polyfunctional phosphate copper compound (B),
In the resin composition (B), a copper complex site (copper ion-phosphate group bonding site) is covered with a crosslinked structure. As a result, the water that tends to penetrate into the copper complex site from the outside is blocked by the crosslinked structure, and the reaction between the copper complex and water, which causes the whitening and devitrification phenomenon, is suppressed.
As a result, the resin composition (B) exhibits water repellency, and has much better moisture resistance than conventionally known resin compositions constituting an optical filter.

The copolymerizable monomer for obtaining the resin composition (B) is the same as the compound exemplified as the copolymerizable monomer for obtaining the resin component of the resin composition (A) [ Monofunctional (meth) acrylate, polyfunctional (meth) acrylate, carboxylic acid, aromatic vinyl compound] and the like, and these can be used alone or in combination of two or more. In the mixed monomer for obtaining the resin composition (B), the ratio of the polyfunctional phosphoric acid ester copper compound (B) and the copolymerizable monomer used is defined as “polyfunctional phosphoric acid ester copper compound (B ): Copolymerizable monomer (weight) ”is preferably in the range of 3:97 to 80:20, more preferably 10:90 to 60:40. The proportion of the polyfunctional phosphate copper compound (B) is 3
When the content is less than the weight%, it is difficult to exhibit light absorption characteristics suitable as an optical filter. On the other hand, this ratio is 80
When the content is more than 10% by weight, the obtained copolymer [resin composition (B)] tends to be flexible which cannot satisfy the hardness condition required for the optical filter.

The copolymer constituting the resin composition (B) is
It is obtained by radically polymerizing a mixed monomer comprising a polyfunctional phosphoric acid ester copper compound (B) and a copolymerizable monomer. The radical polymerization method is not particularly limited, and a known method 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 is used. Can be.

By the above-mentioned method, a copolymer containing a copper ion [resin composition (B)] is obtained. This resin composition (B) can be formed as it is or in a desired shape such as a plate, a column, or a lens depending on the purpose and application.

<Optical Filter> The optical filter of the present invention is obtained by molding the resin composition of the present invention [resin composition (A) or resin composition (B)]. The optical filter of the present invention has excellent near-infrared absorption characteristics due to the interaction between the phosphate group and copper ions in the resin composition constituting the optical filter. In addition, the optical filter of the present invention is configured in such a manner that the binding site (copper complex site) between the phosphate group and the copper ion is covered with the crosslinked structure, so that the optical filter is far superior to the conventionally known optical filter. Has moisture resistance. The optical filter of the present invention can be subjected to a surface treatment using an organic or inorganic hard coat agent. Thereby, it is possible to achieve antistatic, improvement of surface hardness, prevention of surface reflection, and the like. Further, the optical filter of the present invention and other optical materials (for example, a quartz plate)
Can be laminated to produce a composite material.

<Application Example of Optical Filter> 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 made 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 incident on the light receiving element (silicon photodiode) can be substantially limited to light in the visible region. ,
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, a source of near-infrared rays (for example, an automatic door or a remote controller) is covered by the “noise cut filter” including the optical filter of the present invention, and the generation of noise during communication is performed by blocking infrared rays from the source. Can be reliably prevented.

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 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.

The optical filter of the present invention is used as a heat ray absorbing filter, specifically, a window material in a building such as a house or a building, a window material of an automobile or a train, a translucent member of a greenhouse, and a lighting cover. It can be suitably used as such.

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 protect the eyes from heat rays and near infrared rays that cause cataracts.

[0065]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited by these examples. In the following, “parts” means “parts by weight”.

Example 1 In a flask, a solution was prepared by dissolving 86.3 g of an alcohol represented by the following formula (4) in 100 g of dibutyl ether (reaction solvent), and the temperature of the solution was reduced to 5 ° C. 12. While maintaining, phosphorus pentoxide
7 g was added slowly. Next, the temperature of the system was gradually increased, and the system was heated at 60 ° C. for 10 hours to react an alcohol represented by the following formula (4) with phosphorus pentoxide. The obtained reaction solution was transferred to a distillation apparatus, and the reaction solvent was distilled off to obtain 105 g of a reaction product containing the polyfunctional phosphate compound (A). The obtained reaction product was subjected to spectroscopic analysis by infrared absorption spectrum, and contained a phosphoric diester represented by the following formula (5) and a phosphoric acid monoester represented by the following formula (6). Was confirmed. The yield of the polyfunctional phosphate compound (A) (phosphoric diester and phosphoric monoester) was determined to be 94% by weight. Further, when the composition ratio of the polyfunctional phosphoric acid ester compound (A) (phosphoric acid diester / phosphoric acid monoester) was determined, the phosphoric acid diester was 52 mol% and the phosphoric acid monoester was 48 mol%.

[0067]

Embedded image

[0068]

Embedded image

Example 2 In a flask, the polyfunctional phosphate compound (A) 2 obtained in Example 1 was placed.
0.0 g [phosphate diester 1 represented by the above formula (5)
A mixture of 3.0 g (52 mol%) and 7.0 g (48 mol%) of the phosphoric acid monoester represented by the above formula (6)]
And 100 g of toluene (reaction solvent) and 5 g of anhydrous copper acetate monohydrate, gradually raising the temperature, stirring at 40 ° C. for 1 hour, and further stirring at 80 ° C. for 3 hours. Each of the phosphoric diester represented by the formula (5) and the phosphoric acid monoester represented by the formula (6) was reacted with anhydrous copper acetate monohydrate. The obtained reaction solution was transferred to a distillation apparatus, and the reaction solvent was distilled off, whereby 19.5 g of a reaction product containing the polyfunctional phosphate copper compound (B) was obtained. The obtained multifunctional phosphoric acid copper ester compound (B) is composed of a compound having a structure represented by the following formula (7) (33 mol%) and a compound having a structure represented by the following formula (8) (67 Mol%), and the yield of the polyfunctional phosphate copper compound (B) was 89.7%.

[0070]

Embedded image

Example 3 26.0 parts of the phosphoric diester represented by the above formula (5), 14.0 parts of the phosphoric monoester represented by the above formula (6), and 1,6-hexane 20.0 parts of diol dimethacrylate, 39.5 parts of methyl methacrylate, and 0.5 part of α-methylstyrene were mixed to prepare a mixed monomer. Here, the molar ratio between the phosphoric diester and the phosphoric monoester is 52:48. To this mixed monomer was added 17 parts of copper benzoic anhydride (3.5 parts of copper ions based on 100 parts of the mixed monomer), and the mixture was sufficiently dissolved by stirring and mixing at 80 ° C. A monomer mixture in which ions were dissolved in the mixed monomer was obtained.

The monomer mixture thus prepared was cooled at -20 ° C. for 24 hours to precipitate benzoic acid as an acid component, and the benzoic acid was separated by filtration. Next, 2.0 parts of t-butyl peroxyoctanoate was added to the monomer mixture, and the monomer mixture was poured into a glass mold, and the mixture was heated at 45 ° C. for 8 hours, at 60 ° C. for 4 hours, at 100 ° C. The mixture was heated at a different temperature for 3 hours in order to carry out casting polymerization, thereby obtaining a 2 mm-thick optical filter (optical filter of the present invention) composed of the resin composition (A). The specific gravity of this optical filter was as small as 1.251, and the refractive index was 1.501.

Example 4 26.7 parts (33 mol%) of a copper phosphate compound (B) represented by the above formula (7)
And 17.3 parts (67 mol%) of the copper phosphate ester compound (B) represented by the above formula (8), 20.0 parts of 1,6-hexanediol dimethacrylate, and 35.5 parts of methyl methacrylate. And 0.5 part of α-methylstyrene were mixed to prepare a mixed monomer. This mixed monomer has t
-2.0 parts of butyl peroxyoctanoate are added,
This was poured into a glass mold and heated at 45 ° C. for 8 hours for 6 hours.
A 2 mm-thick optical filter (the optical filter of the present invention) made of the resin composition (B) is obtained by heating at 0 ° C. for 4 hours and then heating at 100 ° C. for 3 hours sequentially at different temperatures to perform cast polymerization. Was. The specific gravity of this optical filter is 1.25.
0 and the refractive index was 1.502.

Comparative Example 1 25.0 parts of a comparative phosphoric diester represented by the following formula (9) and 15.0 parts of a comparative phosphoric monoester represented by the following formula (10): ,
A mixed monomer was prepared by mixing 20.0 parts of 1,6-hexanediol dimethacrylate, 39.5 parts of methyl methacrylate, and 0.5 part of α-methylstyrene. Here, the molar ratio between the phosphoric diester and the phosphoric monoester is 50:50. To this mixed monomer was added 20 parts of anhydrous copper benzoate (the content of copper ions was 4.15 parts based on 100 parts of the mixed monomer), and the mixture was sufficiently dissolved by stirring and mixing at 80 ° C. A monomer mixture in which ions were dissolved in the mixed monomer was obtained. Except that this monomer mixture was used, benzoic acid was separated by filtration and cast polymerization was performed in the same manner as in Example 3 to obtain an optical filter (optical filter for comparison) having a thickness of 2 mm. Was. This optical filter has a specific gravity of 1.283 and a refractive index of 1.5.
09.

[0075]

Embedded image

<Evaluation of Performance of Optical Filter> (1) Absorption Characteristics of Near Infrared Ray: For each of the optical filters obtained in Examples 3 to 4 and Comparative Example 1, a spectral transmittance curve (250) was obtained using a spectrophotometer. １０００1000 nm). The results are shown in Table 1 below.

(2) Moisture resistance: After drying the optical filters obtained in Examples 3 and 4 and Comparative Example 1 at 80 ° C. for 5 hours, each of the optical filters was subjected to a temperature of 60.
500 ℃ in a thermo-hygrostat set at 90 ℃ and 90% relative humidity
After leaving for a period of time, the presence or absence (occurrence time) of the occurrence of the whitening / devitrification phenomenon is measured.
% Was measured after standing for 24 hours in a thermo-hygrostat set at%. The results are shown in Table 1 below. The water absorption (%) is calculated based on the weight w before immersion or before standing.
₁ (g) and weight w ₂ after immersion or after standing
From (g), it was determined by the following equation.

[0078]

(Formula 1): W = (w ₂ −w ₁ ) / w ₁ × 100 (%)

[0079]

[Table 1]

As is clear from the results shown in Table 1, the optical filters obtained in Examples 3 and 4 and Comparative Example 1
It is understood that near infrared rays (700 to 1000 nm) are efficiently absorbed. Further, the optical filters obtained in Examples 3 and 4 did not cause whitening and devitrification even when left for 500 hours in a high-temperature and high-humidity environment, and were superior to the optical filters obtained in Comparative Example 1. It is understood that it has excellent water resistance.

[0081]

The polyfunctional phosphate compound of the present invention is useful as a constituent of a resin composition having excellent near-infrared absorption properties and moisture resistance. The polyfunctional phosphoric acid ester copper compound of the present invention is useful as a constituent of a resin composition having excellent near-infrared absorption characteristics and moisture resistance. INDUSTRIAL APPLICABILITY The resin composition of the present invention has excellent near-infrared absorption properties, excellent moisture resistance, and does not cause whitening and devitrification over time even when used in a high humidity environment. Furthermore, the resin composition of the present invention is lightweight and easy to process such as molding, cutting, polishing and the like. The optical filter of the present invention has excellent near-infrared absorption properties, is more excellent in moisture resistance than conventionally known optical filters, and does not cause temporal whitening and devitrification even when used in a high humidity environment. .

According to the camera of the present invention, the 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.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 1/04 G02B 1/04 G02C 7/04 G02C 7/04 H01L 31/0232 H01L 31/02 D (72 Inventor Tomoyoshi Koizumi 16 Nishimachi, Nishikicho, Iwaki-shi, Fukushima Prefecture Kureha Chemical Industry Nishiki Plant Co., Ltd. (72) Inventor Katsuichi Machida 16 Nishimachi, Nishimachi, Iwaki-shi, Fukushima Prefecture Kishiha Chemical Industry Nishiki Plant F-term (reference) 2H006 BE00 4H050 AA01 AA03 AA05 AB46 AB92 4J002 BG021 DD076 DE246 DF036 DG046 DH056 EG046 EG056 EG076 EG086 GP00 4J100 AB02P AB03P AB07P AB08P AB09P AB15P AB16P AG08P AJ02P AL03P AL04P AL03P AL08P AL08P AL08P AL08P AL08P AL09P 5F088 BB01 BB03 JA13 LA03

Claims (15)

[Claims] 1. A polyfunctional phosphate compound represented by the following formula (1). Embedded image 2. A polyfunctional phosphate copper compound represented by the following formula (2). Embedded image 3. A polyfunctional phosphate copper compound represented by the following formula (3). Embedded image 4. Copper ions are contained in a resin component obtained by copolymerizing the polyfunctional phosphate compound represented by the formula (1) according to claim 1 and a monomer copolymerizable therewith. A resin composition characterized by being contained. 5. A resin composition obtained by copolymerizing a polyfunctional phosphate copper compound represented by the formula (2) according to claim 2 and a monomer copolymerizable therewith. object. 6. A resin composition obtained by copolymerizing a polyfunctional phosphate copper compound represented by the formula (3) according to claim 3 and a monomer copolymerizable therewith. object. 7. An optical filter comprising the resin composition according to claim 4. Description: 8. A camera equipped with the optical filter according to claim 7, as a visibility correction filter for a light receiving element. 9. An imaging apparatus comprising the optical filter according to claim 7 as a visibility correction filter for a CCD. 10. An infrared communication environment maintenance device comprising the optical filter according to claim 7 as a noise cut filter. 11. A plasma display device, wherein the optical filter according to claim 7 is arranged on a front surface of a panel. 12. A heat ray absorbing filter comprising the optical filter according to claim 7. 13. An optical fiber comprising the optical filter according to claim 7. 14. An optical fiber, wherein the optical filter according to claim 7 is provided in a lighting part. 15. A spectacle lens comprising the optical filter according to claim 7.