WO2003065082A1

WO2003065082A1 - Optical material

Info

Publication number: WO2003065082A1
Application number: PCT/JP2002/010092
Authority: WO
Inventors: Naoki Hayashi; Hiroki Katono; Katsuichi Machida
Original assignee: Kureha Chemical Industry Company, Limited
Priority date: 2002-01-25
Filing date: 2002-09-27
Publication date: 2003-08-07
Also published as: JP2003215325A; JP4071003B2

Abstract

An optical material which comprises a resin comprising constituent units derived from a first monomer such as methyl methacrylate and a second monomer such as isobornyl methacrylate or t-butyl methacrylate and, contained in the resin, an unpolymerized phosphoric ester compound and copper ions. This optical material is excellent in absorption of lights having specific wavelengths and in moldability. It can retain high stability for long even in a high-temperature high-humidity environment.

Description

Specification

Optical materials

Technical field

The present invention relates to an optical material, and more particularly, to an optical material that exhibits absorptivity to light of a specific wavelength.

Background art

Conventionally, as an optical material or an optical member having a near-infrared light absorption property utilizing a specific wavelength light absorption characteristic of copper ions, for example, Japanese Patent Application Laid-Open Nos. 2001-83318 and 2001- No. 83890, Japanese Unexamined Patent Application Publication No. 2001-154015, International Publication No. 01Z77250 (WOO 1/77250) Optical materials, optical members, etc. containing a phosphate ester compound and copper ions described in Pamphlet Small etc. Is received.

Disclosure of the invention

In recent years, the demand for such optical members has been increasing as absorption filters for various optical systems, heat ray absorbing materials, and the like. With the miniaturization and space saving of devices on which the optical members are mounted or installed, specific wavelengths have been increased. It is required to reduce the thickness while maintaining high light absorption characteristics.

In order to respond to this, it is necessary to increase the copper ion concentration in the optical member. Therefore, the present inventors selected various phosphate ester compounds to which copper ions coordinate, and conducted studies to increase the copper ion content while considering moldability, stability, and the like as an optical component. Optical materials and optical members described in gazettes have been obtained.

By the way, among optical members, particularly, an optical filter is particularly desired to be light and light when applied to an imaging unit or a window provided in a small device such as a portable device. Further improvement in environmental stability such as heat resistance and copper ion concentration is desired. In addition, high translucency in the visible region is also important for application to the imaging unit, etc., so that it is molded into a plate-like or sheet-like member such as a filter. It is considered that a translucent resin is essential.

Therefore, the present inventors have focused on the optical material containing the above-mentioned conventional phosphate ester compound, copper ions and a translucent resin, with an emphasis on the viewpoints of further stability and an increase in the concentration of copper ions, and repeated studies. Have been.

As a result, among the phosphate ester compounds disclosed in the above-mentioned publications, the so-called non-polymerizable phosphoric acid ester compound (non-polymeric phosphoric acid ester compound) having no polymerizable functional group was used together with copper ions. When the concentration was increased, in some cases, a phenomenon called so-called bleed, in which dissolved substances precipitated on the material surface when left in a high-temperature, high-humidity environment for a long time, was observed. In this case, depending on the degree of bleeding, the stability and high near-infrared light absorption characteristics of the optical material may be impaired.

On the other hand, such a phenomenon was not observed when a so-called polymerizable phosphate compound having a polymerizable functional group (polymerizable phosphate compound) was used. However, non-polymeric phosphate compounds are often more useful than polymeric phosphate compounds from the viewpoints of moldability in post-processing and mold releasability during polymerization.

Accordingly, the present invention has been made in view of such circumstances, and provides an optical material having excellent absorption characteristics of specific wavelength light and moldability, and capable of maintaining high stability for a long time even in a high-temperature, high-humidity environment. The purpose is to do.

In order to solve the above-mentioned problems, an optical material according to the present invention is characterized in that a non-polymerizable ester phosphate compound and a copper ion are represented by the following formula (1) and a first monomer represented by the following formula (1). A second monomer represented;

And is contained in a resin having the following components.

In the formula, Y ¹ and Y ² represent a hydrogen atom or a methyl group, which may be the same or different, and Z ¹ is a methyl group or a carbon atom bonded to an oxygen atom of a (meth) acrylic acid skeleton Represents an organic group having ² to 20 carbon atoms and being primary, and Z ² represents an organic group in which the carbon atom bonded to the oxygen atom of the (meth) acrylic acid skeleton is non-primary. Show.

In the present invention, “the resin containing the first monomer and the second monomer as constituents” specifically means the first monomer and the second monomer. (Polymerization method, form, etc.), a copolymer of the first monomer and the second monomer, and a first monomer and a second monomer And polymer blends of each homopolymer.

In the optical material having such a configuration, since copper ions are contained in the resin containing the first and second monomers, which are both acryl-based resins having excellent translucency, as components. Excellent in visible light transmittance and near infrared light absorption. In addition, since a non-polymeric phosphate compound is used as the ester phosphate compound, it has excellent moldability and mold releasability during mold polymerization! / Puru.

Further, when a resin containing such a first monomer and a second monomer as components is used as a resin, the above-described conventional problem is caused despite the fact that a non-polymerized phosphate compound is contained. It was confirmed that bleeding, which is a point, was effectively suppressed. On the other hand, when the resin consisting of the first monomer is used alone, the bleeding is not eliminated, and when the resin consisting of the second monomer is used alone, the non-polymerized phosphate ester is not used. It was confirmed that the copper complex of the compound was hardly dissolved in the resin in + minutes.

Here, the present inventors have closely monitored the bleed phenomenon, which is the conventional problem described above, and found that the bleeding optical material includes the above-mentioned Japanese Patent Application Laid-Open No. 2000-154504. It was found that whitening due to the influence of air moisture did not occur as pointed out in the above. In addition, an investigation of the precipitates revealed that it appears to contain not a copper phosphate but a phosphate ester compound and copper. In general, bleeding on the surface of a material often results from hydrolysis of a dissolved component to lower the molecular weight. When the whitening phenomenon described above occurs, precipitation of copper phosphate, which is a hydrolysis product, is usually observed in the material. From these results, it is thought that the mechanism causing the bleeding phenomenon in question is not exactly the same as that caused by normal hydrolysis, and also different from the mechanism of the bleaching phenomenon, but details are not yet clear. .

On the other hand, in the optical material of the present invention, the bleeding is suppressed by using the first monomer and the second monomer as the constituent components of the resin. The resulting resin is not particularly superior in compatibility with the copper phosphate compound as compared to the resin comprising the first monomer.

Therefore, it is unlikely that the compatibility with the resin greatly contributes to the elimination of bleed. In this connection, focusing on the influence of polarity, bipolar (meth) acrylic acid esters were used alone or in combination with the first monomer in the acrylic resin. No improvement was observed.

Focusing on the water absorption of the resin itself, some resins composed of the second monomer have extremely low water absorption (hygroscopicity) by themselves. As described above, it is highly likely that the precipitate is not produced by hydrolysis, so it is possible, but low water absorption is a major factor in eliminating bleed. It is considered difficult at present.

Furthermore, the resin composed of the second monomer is generally hydrophobic, but in terms of the constituent elements and molecular form, the resin composed of the first monomer has substantially the same hydrophobicity. I can say. However, as described above, no improvement in bleeding is observed with the resin comprising the first monomer alone.

From these, the detailed mechanism by which bleed is significantly improved (eliminated) only when the first monomer and the second monomer are used in combination is unknown at this time. However, translucent Although it is common to use an acrylic resin from the viewpoint, bleeding is eliminated only when using a resin in which the second monomer and the first monomer are used in combination among the acrylic resins. Obtaining stable optical materials with excellent environmental resistance is hard to imagine from conventional common sense.

In the second monomer, Z ² in the formula (2) has 3 to 10 carbon atoms, and the carbon atom bonded to the oxygen atom of the (meth) acrylic acid skeleton is secondary or tertiary. It is preferred that This not only significantly improves the moisture resistance of the optical material, but also significantly improves the solubility of the copper complex of the phosphate compound.

More specifically, Z ² in equation (2) is

Is preferable.

In the formula, Z ²¹ and Z ^{22 each} represent a C to C ₈ hydrocarbon group, and z ²³ , z ²⁴ , and z ²

⁵ represents a C Cs hydrocarbon group. Specifically, a substituted or unsubstituted isopropynole group, a tertiary butyl group, a secondary butyl group, a 1-ethylpropyl group, a tert-pentyl group, a 1-methylbutyl group, and a 1-ethylbutyl group are more preferable. Alternatively, it is also preferable that the second monomer is a substituted or unsubstituted cyclic hydrocarbon group having 3 to 30 carbon atoms and Z ² in the formula (2). Z ² may be a condensed ring group or a non-condensed ring group. In this case, the moisture resistance of the optical material can be significantly improved as compared with the case where Z ² is a substituted or unsubstituted secondary or tertiary hydrocarbon group.

Specifically, Z ² in the formula (2) is a substituted or unsubstituted cyclohexyl group, a pentyl group at a mouth, a cyclobutyl group, a heptinole group at a mouth mouth, a cyclooctyl group, a methylhexene group at a methyl mouth mouth, a trimethylcycline Hexyl group, decahydronaphthyl group, Or, it is a Nantyl group.

On the other hand, it is more preferable that Z ² in the formula (2) is a bridge. In this case, the moisture resistance of the optical material is further improved.

Specifically, Z ² in the formula (2) is a norpolnyl (pol) group, an isopol dinole group, a norbornylmethyl group, a dicyclopentyl group, a dicyclopentyl group, a phentyl group, an adamantyl group, a tetracycloyl group [4.4. 0 ² ' ⁵ .

A dodecinole group, a tricyclo [5.2.1.0 ² · ⁶ ] decal 8-yl group, and a tricyclo [5.2.1.0 ² ′ ⁶ ] deca 8-methyl group are preferred.

Here, there is an example in which a compound having a borneol skeleton such as a pornyl group is used to increase TG while being a nonpolar substance. TG tends to increase with an increase in polarity. However, in general, when steric hindrance is large (bulky) and the movement of a ring in a molecule is restricted, TG acts to increase TG only by its steric effect. However, the considerable causal relationship between the bleed prevention effect of the present invention and such a three-dimensional effect is unclear at present.

Alternatively, even when Z ² in the formula (2) is a group having 6 to 30 carbon atoms and having a substituted or unsubstituted aromatic ring, the moisture resistance of the optical material is further improved, which is preferable. It is. Z ² may be a condensed ring group or a non-condensed ring group.

Specifically, Z ² in the formula (2) is a substituted or unsubstituted aryl group. More specifically, Z ² in the formula (2) is a substituted or unsubstituted phenyl group or a naphthyl group. Alternatively, an anthryl group is preferable.

More specifically, it is preferred that the first monomer is methyl (meth) acrylate.

The meaning of `` meta '' above and in parentheses above is used for convenience to simplify the description when it is necessary to describe both acrylic acid or its derivatives, and methacrylic acid or its derivatives. This is a description method used in the present specification. In addition, it is useful that the mass mixing ratio of the first monomer to the second monomer in the resin component is 20:80 to 90:10. If the mixing ratio of the first monomer is less than 20% by mass (the mixing ratio of the second monomer is more than 80% by mass / ₀ ), the copper complex of the phosphoric acid ester compound is contained in the resin. Tends to be difficult to dissolve. On the other hand, if the mixing ratio of the first monomer is more than 90% by mass (the mixing ratio of the second monomer is less than 10% by mass), the moisture resistance tends to be not sufficiently improved.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, preferred embodiments of the optical material according to the present invention will be described.

The optical material of the present invention contains copper ions. Specific examples of copper salts for supplying copper ions include copper acetate, copper acetate monohydrate, copper formate, copper stearate, copper benzoate, copper ethyl acetate, copper pyrophosphate, copper naphthenate, Copper salt anhydrides, hydrates or hydrates of organic acids such as copper citrate, or copper salt anhydrides, hydrates or hydrates of inorganic acids such as copper chloride, copper sulfate, copper nitrate, and basic copper carbonate Hydrate or copper hydroxide. Of these, copper acetate, copper acetate monohydrate, copper benzoate, copper hydroxide, and basic copper carbonate are preferably used.

Further, metal ions other than copper ions (hereinafter, referred to as “other metal ions”) may be included. Such other metal ions are not particularly limited, and include ions of alkali metals, alkaline earth metals, transition metals, and the like. More specifically, sodium, potassium, calcium, iron, manganese , Magnesium, nickel and the like.

<Non-polymerized phosphate compound>

Examples of the non-polymerizable phosphate compound contained in the optical material of the present invention include those represented by the following formula (5). (Five)

• Here, in the formula, R represents an organic group having no polymerizable functional group. Examples of such an organic group include a substituted or unsubstituted alkyl group, an oxyalkyl group, a polyoxyalkyl group, a group represented by any of the following formulas (6) to (12), and a polymerizable group such as an aryl group. Those having no functional group are mentioned. Further, n is 1 or 2, and when n is 1, R may be the same or different.

R 12

R 22

-(CHCH ₂ 0) _m -R 11

(6) (CH ₂ CHO) _m -R 12 (7)

(11) — (

0

^{_{- (R 32 -0) k -R}} 41 -C-0-R 52 (12) In the formula (6) ~ (1 2) , 1¾ 11 ~1 17 is Arukiru group having 1 to 20 carbon atoms, Represents an aryl or aralkyl group having 6 to 20 carbon atoms (wherein a hydrogen atom bonded to a carbon atom constituting an aromatic ring is at least one substituted by an alkyl group having 1 to 6 carbon atoms or halogen) which may also be), R ²¹ ~: ²⁵ is a hydrogen atom or a carbon atoms represents 1-4 alkyl group (and伹, R ^23, R ^24, when R ²⁵ are all hydrogen atoms Except), R ^{3 1} and R ^{3 2} represents an alkylene group having 1 to 6 carbon atoms, R ^{4 1} represents an alkylene group having 1 to 1 0 carbon atoms, R ^{5 1} and R ^{5 2} is carbon The number represents an alkyl group of 1 to 20, m represents an integer of 1 to 6, and k represents an integer of 0 to 5.

Examples of the cyclic organic group include a substituted or unsubstituted cycloalkyl group, an aryl group, and an aralkyl group that do not have a polymerizable functional group. Examples of the aryl group include a substituted or unsubstituted phenyl group, a naphthyl group and an anthryl group having no polymerizable functional group. Further, those substituents include those in which at least one hydrogen atom bonded to a carbon atom constituting an aromatic ring is substituted with a halogen atom or a non-polymerizable functional group having 1 to 40 carbon atoms. Can be exemplified. More specifically, among the esterified phosphate compounds specifically described in the above publications or pamphlets, non-polymerizable compounds (containing no polymerizable functional group) can be used. Further, these non-polymeric phosphate compounds can be produced by the method described in the publication or pamphlet. By using such a non-polymeric phosphate compound, it is possible to obtain an optical material having excellent moldability and releasability when performing a polymerization treatment using MONORED (mold).

The first monomer used in the optical material of the present invention is an acrylic resin represented by the above formula (1), wherein the organic group Z ¹ bonded to the (meth) acrylic acid skeleton is a methyl group, Is a primary one in which the carbon atom bonded to the oxygen atom of the (meth) acrylic acid skeleton has 2 to 20 carbon atoms.

Examples of the first monomer include, but are not particularly limited to, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-putinole (meth) acrylate, Isoptyl (meth) acrylate, n-hexyl (meta) acrylate, neopentyl (meth) acrylate, isopentyl (meth) acrylate, n-octyl (meth) acrylate, benzyl (meth) acrylate, phenoxyshetyl (meta) ) Atarilate, glycidyl (meta) Tarylate, 2-hydroxyl (meth) atalylate, 2-hydroxypropyl (meth) atalylate, methoxypolyethylene glycolone (meth) atalylate, 2-ethylhexyl (meth) atalylate, isodecyl (meth) Atarilate, isostearyl (meth) atalylate and the like can be mentioned, and these can be used alone or in combination of two or more. Among them, methyl (meth) acrylate is more preferable from the viewpoints of translucency and industrial availability, and methyl methacrylate is particularly preferable in that it has a high affinity for a non-polymerized ester phosphate compound.

The second monomer constituting the resin used in the optical material of the present invention is an acrylic resin monomer represented by the above formula (2), and is an organic group bonded to the (meth) acrylic acid skeleton. Z ² has a non-primary carbon atom bonded to the oxygen atom of the (meth) acrylic acid skeleton.

As described above, by using a resin in which the second monomer and the first monomer are used in combination, it is possible to mold an optical material containing a non-polymerized phosphate compound and a high concentration of copper ion. Even when the body is left in a high-temperature, high-humidity environment for a long time, bleeding can be sufficiently suppressed. Further, since the moisture resistance is improved in this way, it is possible to prevent a so-called whitening phenomenon from occurring.

Further, Equation (2) that of secondary or tertiary chain hydrocarbon group of Z ² force carbon number is 3-2 0 and a substituted or unsubstituted in, for example, Z ² is a substituted or unsubstituted chain It is preferable that the carbon atom bonded to the oxygen atom of the (meth) acrylic acid skeleton does not form a ring even if it has a cyclic hydrocarbon group or a ring. The use of such a ^second monomer having Z ² can significantly improve the solubility of the copper complex of the phosphate compound. In this case, if the carbon number of Z ² exceeds 20, the compatibility tends to be insufficient.

More specifically, Z ² is a substituted or unsubstituted isopropyl group, tertiary butyl group, secondary butyl group, 1-ethylpropyl group-tertiary pentyl group, 1 More preferably, it is a monomethylbutyl group or a monoethylbutyl group. Among them, those in which Z ² is an isopropyl group or a tertiary butyl group, that is, the second monomer is, for example, isopropyl methacrylate or (14) represented by the following formula (13) or (14), respectively. Particularly preferred is tert-butyl methacrylate or the like.

Some of such second monomers are commercially available, such as tertiary butyl methacrylate.For example, various alcohols are reacted with (meth) acrylic acid chloride in the presence of triethylamine. Can be obtained by

Alternatively, it is preferable that Z ² in the formula (2) is a substituted or unsubstituted cyclic hydrocarbon group having 3 to 30 carbon atoms and Z ² is a condensed ring group or a non-condensed ring group. (That is, it may be a multi-membered ring or a polycyclic ring). This has the advantage that the moisture resistance of the optical material can be further improved as compared with the case where Z ² is a substituted or unsubstituted secondary or tertiary hydrocarbon group. If the number of carbon atoms exceeds 30, the compatibility becomes insufficient and the resin body may become cloudy.

Specifically, for example, Z ² is a substituted or unsubstituted cyclohexyl group, cyclopentyl group, cyclobutyl group, cycloheptyl group, cyclooctyl group, methylcyclohexyl group, trimethylcyclohexyl group, decahydronaphthyl group And a cycloalkyl group such as a nantyl group. Among these, from the viewpoint of thermal and hydrolytic stability, Z ² is a cyclohexyl group, that is, the second monomer is, for example, cyclohexyl represented by the following formula (15). Particularly preferred is methacrylate.

Such a second monomer may be a commercially available product such as cyclohexyl methacrylate, etc. For example, the second monomer can be produced by the following method. That is, it can be obtained by reacting various alcohols with (meth) acrylic acid chloride in the presence of triethylamine. To give an example, 2-decahydronaphthyl (meth) tarylate is obtained by reacting 2-decahydronaphthol with a (meth) acrylic acid methacrylate in the presence of triethylamine, extracting with an organic solvent such as ether, and then depressurizing. It can be obtained by distillation.

Alternatively, it is more preferable that Z ² in the formula (2) is a bridging body, that is, the second monomer is a bridging compound. By using such a second monomer, the moisture resistance of the optical material can be further improved.

Specifically, as Z ² in the formula (2), a norpoluel (bonyl) group, an isobonolenyl group, a norbornylmethyl group, a dicyclopentenetinole group, a dicyclopentanyl group, a phentyl group, an adamantyl group, a tetracyclo [4.4 . 0 2,5. 17,10] Dodeshinore group, tricyclo [5.2.1.0 ² ^'6] dec-one 8-I group, tricyclo [5.2.1.0 ^2. ^6] Deka

8-methyl group. Among these, those in which Z ² has a norbornyl group or an isobolur group, that is, the second monomer is, for example, isobornyl methacrylate represented by the following formula (16) Is particularly preferred.

Some of such second monomers can be obtained as a commercial product such as isopolnyl methacrylate, etc., for example, as described above, various alcohols can be obtained in the presence of triethylamine. It can also be obtained by reacting with (meth) acrylic acid chloride.

Further, Z ² in the formula (2) may be a group having 6 to 30 carbon atoms and having a substituted or unsubstituted aromatic ring, and may be a condensed ring group or a non-condensed ring group. Good. Also in this case, the moisture resistance of the optical material can be improved as in the case of the alicyclic group represented by the formula (3) such that Z ² is a cyclohexyl group or the like. Specifically, Z ² in the formula (2) is a substituted or unsubstituted aryl group, and more specifically, Z ² in the formula (2) is a substituted or unsubstituted phenyl group, a naphthyl group, Examples include an anthryl group, a phenanthryl group, and a phenaleryl group.

Such a second monomer is synthesized by, for example, a condensation reaction between (meth) acrylic acid and phenol as described in JP-A-63-57554 for fuel methacrylate. It is possible.

The amount of the second monomer used in the present invention is not particularly limited, but may vary depending on the type of the first monomer and / or the type of the second monomer. It is useful that the mass mixing ratio of the body and the second monomer is from 20:80 to 90:10.

If the mixing ratio of the first monomer is less than 20% by mass (the mixing ratio of the second monomer is more than 80% by mass), the copper complex of the phosphate ester compound dissolves in the resin. It tends to be difficult. On the other hand, when the mixing ratio of the first monomer is more than 90% by mass (the mixing ratio of the second monomer is less than 10% by mass), the moisture resistance tends to be not sufficiently improved. Therefore, by setting such a suitable mixing ratio, the concentration of copper ions can be sufficiently and surely increased, and a more stable optical material having excellent moisture resistance can be easily realized.

The optical material of the present invention having such a configuration is capable of absorbing the above-described specific wavelength light. Excellent characteristics such as yield characteristics, moldability, and stability in high temperature and high humidity environments can be achieved, so it can be used as various functional materials in various forms (use forms) or in combination with various functional materials Thus, it can be suitably used for various applications.

Examples of such a form include a coat shape, a sheet shape, a disk shape, a fiber shape, a film shape, a prism shape, a lens shape, a columnar shape, a plate shape, a film shape, and the like. It can be used in the form of an adhesive, an adhesive, or a molded article.

In addition, various functional materials include coating materials (agents), hard coat materials (agents), bandpass functional materials such as low-pass filters, diffraction grating materials, electromagnetic wave shielding materials for EMI removal, birefringent plates, coloring agents, Light stabilizer, antioxidant, ultraviolet absorber, crystal, antistatic agent, heat stabilizer, release agent, polymerization regulator, other optical materials, antireflective material (antireflective coating material), depolarizing plate, conductive A composite functional material combined with a layer or the like can be given. Various applications include CCD lid materials, PDP front panel and other display front panels, display front filters, goggles, lenses such as glasses, optical fibers, optical switches, optical filters, optical low-pass filters, and visibility correction. Examples include filters, photometric filters, imaging filters, window materials, agricultural covering materials, lighting equipment, and the like.

(Example)

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

(1) Production of phosphate compound: 90.1 _g of 1-methoxy-2-propanol was dissolved in 18 Om1 of toluene, and cooled to 5 ° C or lower. 4 g was added little by little, and the whole amount was added by stirring, and then stirring was continued for 15 hours. Then, the mixture was stirred and mixed at 60 ° C for 8 hours, and after adding 7 ml of water, the temperature was raised to 100 ° C and the 3B temple was agitated. After completion of the reaction, toluene and unreacted 1-methoxy-2-propanol were distilled off under reduced pressure to obtain 124 g of a slightly yellow viscous oily phosphate compound. Was analyzed by gas chromatography da rough the Re this methylated with trimethylsilyl agent, phosphoric acid ester compound represented by the following formula (1 7) (mono ester component) is 61.8 mass ^_0/0, the following formula 32.8% by mass of the phosphate compound (diester component) represented by (18), and 2.4% by mass of the phosphoric acid component. /. It was confirmed that the mixture was included.

CH ₃

O— CH— CH ₂ — O—— CH ₃ O-C— C-O— CH ₃

IHH ₂

0 = P-OH Π7) 0 = P— OH (18)

H OH O— C-C—— O-CH ₃

IH ₂

CH ₃

(2) Production of phosphate ester copper compound: phosphate ester compound obtained in (1) above

(Mixture) After 100 g of toluene was dissolved in 30 Oml of toluene, 90 g of copper acetate monohydrate was added thereto, and the mixture was dehydrated and refluxed. After dehydration, residual acetic acid and toluene were removed from the reaction solution under reduced pressure to obtain a blue-green powder of a copper phosphate compound (copper salt).

(3) Preparation of a monomer solution: 18.75 g of the phosphoric acid ester copper compound obtained in (2) above was treated with methyl methacrylate (hereinafter referred to as “MMA”) as a first monomer and a second monomer. With the monomers of the acrylic resin represented by the formulas (14), (15) and (16) (hereinafter referred to as “α”, “”, and “γ”, respectively) After dissolving and mixing in the above mixture, 0.2 g of -methylstyrene was added, and the mixture was stirred at room temperature for 48 hours to obtain a monomer solution as a specific composition.

The total amount of the first monomer and the second monomer was 81.25 g, and the mixing ratio of both was changed. At this time, the solubility of the copper phosphate compound at room temperature was sufficient. (4) Assembly of glass mold for polymerization: Two glass mold plates with a diameter of 8 O mm were prepared. An annular soft PVC packing is placed on one peripheral edge of this glass mold plate, and the other glass mold plate is placed on top of it and placed in opposition, and both glass mold plates are clamped from outside. Hold down and hold to assemble a glass mold (mold) for polymerization.

(5) Production of resin plate molding: To each of the monomer solutions prepared in (1) above, 1.O g of t-butyl peroxydecaneate was added, and the mixture was filtered through a membrane filter. It was injected into the glass mold for polymerization assembled in (2) above.

Then, each of them is housed in an open, and at a constant temperature of 40 ° C for 3 hours,

Temperature rise from 400 ° C to 100 ° C for 2 hours, constant temperature of 100 ° C for 2 hours, temperature decrease from 100 ° C to 70 ° C for 2 hours Polymerization solidification was performed under control. After completion of the polymerization, the glass mold for polymerization was removed from the open, and the clamp and the glass mold plate were removed to obtain each of 2 mm thick transparent blue resin plates as the optical material of the present invention.

A resin plate was manufactured in the same manner as in Example 1, except that the resin composed of MMA as the first monomer was used alone as the resin component.

A resin plate was manufactured in the same manner as in Example 1 except that the resin consisting of the second monomer, 0 and γ, was used alone as the resin component.

The moisture resistance test was performed on the resin plates obtained in Examples 1 to 3 and Comparative Example 1. In addition, in Comparative Example 2, the copper complex was not sufficiently dissolved, and the resin body became cloudy, so this test was not performed.

First, release each resin plate for 250 hours in an environment with an ambient temperature of 60 ° C and a relative humidity of 90%. After the placement, bleeding and turbidity were visually observed. Spectrophotometry was performed using a spectrophotometer “u400” (manufactured by Hitachi, Ltd.). Table 1 shows some of the results.

The legend in the table indicates that no turbidity or bleeding occurred at the time of 1000 hours and no deterioration of the spectroscopic characteristics was indicated as 'A'. A sample that did not cause any deterioration in spectral characteristics was denoted as “Β”, and a sample in which neither turbidity nor bleeding occurred and the spectral characteristics did not deteriorate after 300 hours was denoted as “C”. In the case where the second monomer is 0% by mass (that is, the resin plate of Comparative Example 1),

Since bleeding occurred at the lapse of 100 hours, it was set to 'D' in the table.

The resin plate that showed good results in the moisture resistance test (marked Α or 中 in Table 1) was visually observed after standing at 800 ° C in a dry environment for 100 hours. Bleeding and turbidity were observed. Spectrophotometry was performed using the above spectrophotometer “U-400”. As a result, no abnormality such as turbidity or bleeding was observed in any of the resin plates subjected to the test.

Comparative Example 1 Examples 1 to 3 Mixing ratio of second monomer

0 1 0 3 0 5 0 7 5 (% by mass in total resin) β

C B A C

(Example 2) Second

Single 本 D C Aor Β A C

(Example 3)

Type of

C Β A B

(Example 1) Remarks: Legends A to D in the table show the evaluation for moisture resistance.

(4) Other performance comparisons

Of the resin plate of Comparative Example 1 (using MMA alone) and the resin plate of Example 1 having a mass mixing ratio of MMA to H, β, and γ of 50:50, phosphate ester copper compound Table 2 shows the solubility of the product and the moisture resistance and heat resistance when the concentration of the copper phosphate ester compound in the resin plate is 18.875 mass%.

Table 2

A resin plate was prepared in the same manner as in Example 1 except that the monomers represented by the following formulas (19) to (21) (Comparative Examples 3, 4, and 5) were used as the second monomer. Was made.

The monomers of the formulas (19) to (21) are respectively a bifunctional (meth) acrylate and a (meth) acrylate having Z ² in the second monomer being a lower alkyl, It belongs to fluorinated (meta) acrylate. When these resin plates were subjected to the same moisture resistance test as above, whitening or bleeding occurred in all the resin plates within 100 hours.

Industrial applicability

As described above, according to the optical material of the present invention, the resin containing the first monomer and the second monomer as host components for the non-polymerized phosphate compound and the copper ion host resin. By using, it is possible to achieve excellent absorption characteristics of specific wavelength light unique to copper ions and moldability, and to maintain high stability for a long time even in a high-temperature and high-humidity environment.

Claims

The scope of the claims

1. A non-polymerized phosphate compound and a copper ion are a first monomer represented by the following formula (1) and a second monomer represented by the following formula (2);

(Wherein Y ¹ and Y ² represent a hydrogen atom or a methyl group and may be the same or different, and Z ¹ is a methyl group or a carbon atom bonded to an oxygen atom of a (meth) acrylic acid skeleton Represents an organic group having 2 to 20 carbon atoms and being primary, and Z ² represents

(Meth) An organic group in which the carbon atom bonded to the oxygen atom in the acrylic acid skeleton is non-primary. ),

An optical material which is contained in a resin having the following components.

2. The method according to claim 1, wherein Z ² in the formula (2) has 3 to 20 carbon atoms and the carbon atom bonded to the oxygen atom of the (meth) acrylic acid skeleton is secondary or tertiary. Optical material.

3. Z ² in the formula (2) is a substituted or unsubstituted group represented by the following formula (3) or the following formula (4);

The optical material according to claim 2, wherein (Z ²¹ and Z ²² each represent a hydrocarbon group of Ci Cs, and z ²³ , z ²⁴ , and z ^{25 each} represent a C to C ₅ hydrocarbon group). .

4. The optical material according to claim 1, wherein Z ² in the formula (2) is a substituted or unsubstituted cyclic hydrocarbon group having 3 to 30 carbon atoms.

5. In the above formula (2), Z ² represents a substituted or unsubstituted cyclohexyl group, cyclopentyl / le group, cyclobutyl group, cycloheptinole group, cyclooctynole group, methylhexyl group, or trimethylcyclyl group. 5. The optical material according to claim 4, which is a xyl group, a decahydronaphthyl group, or a natyl group.

6. The optical material according to claim 4, wherein Z ² in the formula (2) is a bridge body.

7. In the above formula (2), Z ² represents a norbornoleninole group, an isopolnyl group, a norvolenolemethinole group, a dicyclopentenetinole group, a dicyclopentael group, a phentyl group, an adamantyl group, a tetracyclo [4.4.0 ² ^'5. 17.10] dodecyl group, a tricyclo [5. 2.1.0 ^{^2'6]} Deka 8 I group, tricyclo [5.2.1.0 ^2' ^6] the optical material according to claim 6 wherein the Deka 8-methyl group .

8. The optical material according to claim 4, wherein Z ² in the formula (2) is a group having 6 to 30 carbon atoms and having a substituted or unsubstituted aromatic ring.

9. The optical material according to claim 8, wherein Z ² in the formula (2) is a substituted or unsubstituted phenyl group, a naphthyl group, or an anthryl group.

10. The optical material according to any one of claims 1 to 9, wherein the first monomer is methyl (meth) acrylate.

1 1. The optical mixing according to any one of claims 1 to 10, wherein a mass mixing ratio of the first monomer and the second monomer in the resin is 20:80 to 90:10. material.