JP2609487B2 - Phosphite compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymerizable monomer,
In particular, the present invention relates to a novel phosphite compound which is useful as an optical material and is useful for paints, inks, adhesives and the like.

[0002]

2. Description of the Related Art At present, as an optical material widely used, there is a resin obtained by casting polymerization of diethylene glycol bisallyl carbonate. However, this resin has a refractive index (n _D ) of 1.50, which is smaller than that of an inorganic lens, and it is necessary to increase the center thickness, edge thickness, and curvature of the lens in order to obtain optical characteristics equivalent to those of an inorganic lens. Therefore, it is inevitable that the entire body becomes thick. Therefore, introduction of halogen atoms other than fluorine, aromatic rings and sulfur atoms into the molecular structure of the resin, that is, the molecular structure of the monomer, has been studied as a means for increasing the refractive index of the resin (Japanese Unexamined Patent Publication No.
Nos. 1-86701, 63-45081, and 63-130614).

[0003]

The resin obtained from the above-mentioned monomer has a considerably higher refractive index than conventional lens materials. However, these materials are not well-balanced in terms of optical properties such as specific gravity, transparency, and weather resistance, and are not always satisfactory as lens materials.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a compound having a phosphite ester skeleton is a novel polymerizable monomer capable of achieving the above-mentioned object. And came to propose the present invention.

That is, the present invention provides the following formula (1)

[0006]

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[0007] [where, A _{1 is, - (X 1 -R 3)} k - or _{-R 4 - (X 1 -R 3} ) k - ( where, X ₁ is oxygen atom or a sulfur atom, R ₃ and R ₄ are the same or different alkylene group, phenylene group, toluene-α-
A diyl group or a xylene-α, α′-diyl group;
k is an integer of 0 or more. ) And Y ₁ and Y ₂ are
The same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups or alkylthio groups, respectively;
R ₁ is an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aralkylthio group,

[0008]

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Or

[0010]

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[0011] {where, A _{2 is, - (X 2 -R 5)} m -, - R 6
-(X ₂ -R ₅ ) _m -or -X ₃ -R _6- (X ₂ -R ₅ ) _m- , and A ₃ is -X _3- (R ₅ -X ₂ ) _m -or -X ₃ -R ₆
— (X ₂ —R ₅ ) _m — (where X ₂ and X ₃ are each an oxygen atom or a sulfur atom, and R ₅ and R ₆ are the same or different alkylene group, phenylene group, toluene-α, respectively) -Diyl group or xylene-α, α'-diyl group, m is an integer of 0 or more.), And Y ₃ and Y ₄ are the same or different hydrogen atom, halogen atom, alkyl group, It is an alkoxy group or an alkylthio group, and R ₇ is a hydrogen atom or a methyl group. ｝
R ₂ represents an alkyl group, an aryl group, an aralkyl group or

[0012]

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[0013] {where, A _{4 is, -X 5 - (R 7 -X} 4) n - or _{-X 5 -R 8 - (X 4} -R 7) n - ( where, X ₄ and X ₅
Is an oxygen atom or a sulfur atom, respectively, and R ₇ and R ₈ are the same or different alkylene group, phenylene group, toluene-α-diyl group or xylene-
α, α'-diyl group, and n is an integer of 0 or more. ), And R ₁₀ is a hydrogen atom or a methyl group. ｝. A phosphite compound represented by the formula:

In the general formula (1) of the present invention, Y ₁ ,
As the halogen atoms represented by Y ₂ , Y ₃ and Y ₄ , chlorine, bromine and iodine halogen atoms are preferably used.

The alkyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ in the general formula (1) is not particularly limited, but is generally a linear or branched alkyl group having 1 to 4 carbon atoms. Are preferred. Specific examples of the alkyl group generally preferably used include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a t-butyl group.

Further, in the general formula (1), Y ₁ , Y ₂ ,
The alkoxy groups represented by Y ₃ and Y ₄ are not particularly limited, but generally include a group containing a linear or branched alkyl group having 1 to 4 carbon atoms. Specific examples of the alkoxy group generally preferably used include a methoxy group,
Examples include an ethoxy group, an n-propoxy group, and t-butoxy.

Further, in the general formula (1), Y ₁ , Y ₂ ,
Alkylthio group represented by Y ₃ and Y ₄ are not particularly limited, it is generally preferred group containing a linear or branched alkyl group having 1 to 4 carbon atoms. Specific examples of the alkylthio group generally preferably used include a methylthio group, an ethylthio group, an n-propylthio group, a t-butylthio group and the like.

In the present invention, from the viewpoint of a high refractive index, Y ₁ , Y ₂ , Y ₃ and Y ₄ in the general formula (1) are preferably a halogen atom and an alkylthio group, and more preferably an alkylthio group in view of the specific gravity. .

Further, R ₃ , R ₄ , R in the general formula (1)
_5, although the alkylene group is not particularly limited represented by R _6, R ₇ and R _8, with 2-6 range carbon atoms to decrease the refractive index with an increase in the number of carbon atoms, in particular 2 to 4 It is preferable to select within the range.

Further, R ₃ , R ₄ ,
R ₅ , R ₆ , R ₇ and R ₈ are a phenylene group, a toluene-α-diyl group

[0021]

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And a xylene-α, α'-diyl group

[0023]

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It may be

Further, k, m and n in the general formula (1)
May be an integer of 0 or more. However, if k, m and n are too large, a problem arises that heat resistance of the obtained resin is impaired.
The range of ~ 2 is preferred. When k, m and n are 0,-(X ₁ -R ₃ ) _k -,-(R ₅ -X ₂ ) _m -,-(X ₂ -R ₅ ) _{m
-, - (X 4 -R 7} ) n - and _{- (R 7 -X 4) n} - represents a bond.

X ₁ , X ₂ , X ₃ , X _{4 in the} general formula (1)
And X ₅ may be an oxygen atom or a sulfur atom,
Sulfur atoms are particularly preferred for obtaining a high refractive index in the obtained resin.

Further, R ₁ and R _{2 in the} general formula (1)
As the alkyl group represented by, the groups already described for Y ₁ , Y ₂ , Y ₃ and Y ₄ can be employed. Also, R ₁ and R ₂
The aryl group represented by is not particularly limited to the number of carbon atoms, but is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a tolyl group, and a xylyl group. The aralkyl group represented by R ₁ and R ₂ is not particularly limited to the number of carbon atoms, but is preferably an aralkyl group having 7 to 10 carbon atoms such as a benzyl group, a phenethyl group, a phenylpropyl group, and a phenylbutyl group.

Further, the alkoxy group and the alkylthio group represented by R ₁ in the general formula (1) are the same as those described above for Y ₁ ,
The groups described for Y ₂ , Y ₃ and Y ₄ can be employed. The arylthio group represented by R ₁ is not particularly limited in the number of carbon atoms, but may have 6 to 6 carbon atoms such as a phenylthio group, a naphthylthio group, a phenanthrylthio group, an anthrylthio group, a tolylthio group or a xylylthio group. Fourteen arylthio groups are preferred. The aralkylthio group represented by R ₁ is not particularly limited to the number of carbon atoms, but includes an aralkylthio group having 7 to 10 carbon atoms such as a benzylthio group, a phenethylthio group, a phenylpropylthio group, and a phenylbutylthio group. Groups are preferred.

The structure of the compound represented by formula (1) of the present invention can be confirmed by the following means.

[0030] (i) an infrared absorption spectrum (IR) absorption based on C-H bond around 3150～2800Cm ^-1 by measuring, based on the unsaturated hydrocarbon group of the terminal in the vicinity of 1650～1600Cm ^-1 absorption Can be observed.

(B) ¹ H-nuclear magnetic resonance spectrum ( ¹ H
-NMR), it is possible to know the bonding mode of the hydrogen atoms present in the compound of the present invention represented by the general formula (1).

(C) By elemental analysis, the weight percentages of carbon, hydrogen, sulfur, phosphorus and halogen are determined, and the weight percentage of oxygen is calculated by subtracting the sum of the recognized weight percentages of each element from 100. Therefore, the composition formula of the compound can be determined.

The phosphite compound represented by the general formula (1) may be obtained by any method, but a typical production method is described below.

General formula (2)

[0035]

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And / or general formula (3)

[0037]

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[0038] {where, A _{1 is, - (X 1 -R 3)} k - or _{-R 4 - (X 1 -R 3} ) k - ( where, X ₁ is oxygen atom or a sulfur atom, R ₃ and R ₄ are the same or different alkylene group, phenylene group, toluene-α-
A diyl group or a xylene-α, α′-diyl group;
k is an integer of 0 or more. ) And Y ₁ and Y ₂ are
The same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups or alkylthio groups, respectively;
X is a halogen atom. And a compound represented by the following formula (4) Wherein R ₁ is an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aralkylthio group,

[0039]

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Or

[0041]

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[0042] {where, A _{2 is, - (X 2 -R 5)} m -, - R 6
-(X ₂ -R ₅ ) _m -or -X ₃ -R _6- (X ₂ -R ₅ ) _m- , and A ₃ is -X _3- (R ₅ -X ₂ ) _m -or -X ₃ -R ₆
— (X ₂ —R ₅ ) _m — (where X ₂ and X ₃ are each an oxygen atom or a sulfur atom, and R ₅ and R ₆ are the same or different alkylene group, phenylene group, toluene-α, respectively) -Diyl group or xylene-α, α'-diyl group, m is an integer of 0 or more.), And Y ₃
And Y ₄ are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups or alkylthio groups, respectively, and R ₇ is a hydrogen atom or a methyl group. And R ₂ is an alkyl group, an aryl group, an aralkyl group or

[0043]

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[0044] {where, A _{4 is, -X 5 - (R 7 -X} 4) n - or _{-X 5 -R 8 - (X 4} -R 7) n - ( where, X ₄ and X ₅
Is an oxygen atom or a sulfur atom, respectively, and R ₇ and R ₈ are the same or different alkylene group, phenylene group, toluene-α-diyl group or xylene-
α, α'-diyl group, and n is an integer of 0 or more. ), And R ₁₀ is a hydrogen atom or a methyl group. ｝ And Z is a halogen atom. And a halogenated phosphorus compound represented by the formula

The charged molar ratio of the compounds represented by the general formulas (2), (3) and (4) may be appropriately determined as necessary. (4)
Are generally reacted in stoichiometric amounts, ie, equimolar.

In the above reaction, it is generally preferable to use an organic solvent. Examples of the solvent suitably used include aliphatic or aromatic hydrocarbons such as hexane, heptane, petroleum ether, benzene, and toluene;
Ethers such as diethyl ether, tetrahydrofuran, and dioxane;

The temperature in the above reaction varies depending on the type of the raw material and the type of the solvent, but is generally preferably from -50 to 50 ° C. The reaction time also varies depending on the type of the raw material, but it is usually sufficient to select from a range of 5 minutes to 24 hours, preferably 30 minutes to 12 hours. It is preferable to carry out stirring during the reaction.

The method for isolating and purifying the desired product from the reaction system, that is, the compound represented by the general formula (1) is not particularly limited, and a known method can be employed.

The compound of the present invention represented by the general formula (1) gives a resin having a high refractive index, a low specific gravity and excellent transparency.

When an optical material, particularly a lens material, is obtained by using the phosphite compound of the present invention, if the compound represented by the general formula (1) is monofunctional, it may be a radically copolymerizable polyfunctional compound. It is preferable to copolymerize with the unsaturated monomer. Examples of the polyfunctional unsaturated monomer are as follows. In addition, acrylate and methacrylate are collectively referred to as (meth) acrylate. Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, thioglycol di (meth)
Di (meth) acrylate such as acrylate; divinylbenzene, 2,5-divinylpyridine and the like.

Further, from the viewpoint of obtaining a polymer having a high refractive index, it is preferable to use a polyfunctional unsaturated monomer having a refractive index of the homopolymer of 1.55 or more. Specific examples of such polyfunctional unsaturated monomers include bisphenol A, bisphenol S, 2,2 ', 6,6'-tetrachlorobisphenol A, 2,2', 6,6'-tetra Bis β-methallyl carbonate, diacrylate or dimethacrylate of bisphenols such as chlorobisphenol S, 2,2 ′, 6,6′-tetrabromobisphenol A or 2,2 ′, 6,6′-tetrabromobisphenol S Bisβ- such as bishydroxyethyl tetrachlorophthalate, bishydroxyethyl tetrachloroisophthalate, bishydroxyethyl tetrachloroterephthalate, bishydroxyethyl tetrabromophthalate or bishydroxyethyl tetrabromoterephthalate; Methallylka -Carbonate, diacrylate or dimethacrylate;
Examples thereof include divinylbenzene and 2,5-divinylpyridine.

On the other hand, it is not always necessary to use a monofunctional unsaturated monomer capable of being radically copolymerized together with the above-mentioned polyfunctional unsaturated monomer. The monofunctional unsaturated monomer has a homopolymer having a refractive index of 1.5 from the viewpoint of obtaining a polymer having a high refractive index.
It is good to use 5 or more monomers.

The details are as follows. Phenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate,
Trichlorophenyl (meth) acrylate, monobromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, pentabromophenyl (meth) acrylate,
Monochlorophenoxyethyl (meth) acrylate, dichlorophenoxyethyl (meth) acrylate, trichlorophenoxyethyl (meth) acrylate, monobromophenoxyethyl (meth) acrylate, dibromophenoxyethyl (meth) acrylate, tribromophenoxyethyl (meth) acrylate, Pentabromophenoxyethyl (meth) acrylate, phenylthio (meth) acrylate, benzylthio (meth) acrylate, benzylthioethylthio (meth) acrylate, styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, iodostyrene, methylstyrene, Methoxystyrene, 2-vinylthiophene, vinylnaphthalene, N-vinylcarbazole, benzyl (meth) acrylate Ethyl vinyl benzene. These monomers can be used alone or in combination of two or more.

In the present invention, when an optical material, particularly a lens material, is obtained, the composition ratio of the monomer is such that when the compound represented by the general formula (1) is a monofunctional compound, the proportion of the monomer in the total monomer is 30-90% by weight, especially 40-80% by weight
In the case of a polyfunctional compound, it is preferably used in a proportion of 10 to 100% by weight, particularly 40 to 100% by weight, based on all monomers.

On the other hand, when the compound represented by the above general formula (1) is a monofunctional compound, the amount of the radically copolymerizable polyfunctional unsaturated monomer used is the proportion of the total monomer. Is preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight. When the compound represented by the general formula (1) is a polyfunctional compound, it is 0 to 90% by weight in the total monomer.
In particular, the range of 0 to 60% by weight is preferable.

Further, when the compound occupied by the general formula (1) is a monofunctional compound, the amount of the monofunctional unsaturated monomer capable of undergoing radical copolymerization is occupied in all monomers. The proportion is preferably from 0 to 40% by weight, particularly preferably from 0 to 20% by weight. When the compound occupied by the general formula (1) is a polyfunctional compound, it is 0 to 90% by weight in all monomers. % By weight, especially in the range of 0 to 60% by weight.

The polymerization method for obtaining a high refractive index resin using the monomer composition is not particularly limited, and a known casting polymerization method can be employed. The polymerization can be started by using a radical polymerization initiator such as various peroxides or azo compounds, or by irradiating ultraviolet rays, α-rays, β-rays, γ-rays or the like, or a combination of both. To illustrate a typical polymerization method,
The monomer composition containing the radical polymerization initiator may be injected between the molds held by the elastomer gasket or the spacer, cured in an air furnace, and then removed.

The radical polymerization initiator is not particularly limited and known ones can be used. Typical examples thereof include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide. And peroxyesters such as t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate and t-butylperoxybenzoate; Percarbonates such as diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate and di-sec-butylperoxydicarbonate; and azo compounds such as azobisisobutyronitrile. The amount of the radical polymerization initiator used depends on the polymerization conditions, the type of the initiator, and the composition of the monomer composition, and cannot be unconditionally limited, but is generally, based on 100 parts by weight of the monomer composition. It is preferably used in the range of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight.

Among the polymerization conditions, particularly the temperature affects the properties of the obtained high refractive index resin. Since this temperature condition is affected by the type and amount of the initiator and the type of the monomer composition, it cannot be unconditionally limited, but generally, the polymerization is started at a relatively low temperature and the temperature is slowly increased. It is preferable to perform a so-called tapered two-stage polymerization in which the polymerization is performed at a high temperature when the polymerization is completed. Since the polymerization time also varies depending on various factors similarly to the temperature, it is preferable to determine an optimum time in advance according to these conditions, but in general, the conditions are selected so that the polymerization is completed in 2 to 40 hours. Is preferred.

Of course, at the time of the polymerization, a releasing agent, an ultraviolet absorber, an antioxidant, a coloring inhibitor, an antistatic agent, various stabilizers such as fluorescent dyes, dyes, pigments, and fragrances, and additives are optionally used. Can be selected and used.

Further, the high refractive index resin obtained by the above method can be subjected to the following treatment depending on the use. That is, dyeing using a dye such as a disperse dye, silane coupling agent and silicon, zirconia, antimony,
A hard coating agent containing a sol of an oxide such as aluminum as a main component, a hard coating agent containing an organic polymer as a main component, SiO ₂ , Ti
Processing such as anti-reflection processing and anti-static processing by vapor deposition of a thin film of a metal oxide such as O ₂ or ZrO or application of a thin film of an organic polymer, and secondary processing can also be performed.

[0062]

The phosphite compound of the present invention has a high refractive index and a small specific gravity, and is useful as a monomer which gives a resin excellent in transparency, weather resistance and the like. Therefore, a homopolymer of the phosphite compound of the present invention or a high refractive index resin obtained by copolymerization of the compound with an unsaturated monomer is useful as an organic glass, for example, an eyeglass lens, an optical device Ideal for optical lenses such as lenses, prisms,
It can be suitably used for applications such as optical disk substrates and optical fibers.

[0063]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

The physical properties of the phosphite compound and the high refractive index resin obtained in the examples were measured by the following test methods.

(1) IR spectrum Measured by the KBr method using a DIGILAB FIS-7 manufactured by BIO-RAD and a Fourier transform infrared spectrophotometer.

(2) ¹ H-NMR spectrum PMX-60SI type (60 MHz) manufactured by JEOL Ltd.
The use, samples were diluted CDCL _3, were measured using tetramethylsilane as an internal standard.

(3) Refractive index The refractive index at 20 ° C. was measured using an Abbe refractometer manufactured by Atago Co., Ltd. Bromonaphthalene or methylene iodide was used as the contact solution.

The refractive index of the phosphite compound was determined by extrapolating the compound dissolved in a liquid unsaturated monomer.

(4) Appearance The appearance was measured visually.

(5) Weather Resistance A sample and a polystyrene were placed in a long life xenon fade meter (FAC-25AX-HC type) manufactured by Suga Test Instruments Co., Ltd. and exposed to xenon light for 100 hours. A sample having a lower degree of coloring than the sample was evaluated as ○, an equivalent sample was evaluated as Δ, and a sample with higher coloration was evaluated as ×.

The unsaturated monomers used in the following examples are represented by the following symbols. Here, [] indicates the refractive index of the homopolymer.

St: styrene [1.590] ClSt: chlorostyrene (a mixture of o and m forms)
[1.610] DVB: divinylbenzene [1.615] Example 1 10.0 g (0.062 mol) of chlorophosphinic acid dimethylthioester was charged into a 500 ml three-necked flask equipped with a thermometer, a dropping funnel and a mechanical stirrer.
It was dissolved in 200 ml of diethyl ether and cooled to 0 ° C.
While stirring, a solution of 4-vinylphenylmagnesium chloride in diethyl ether (0.837 mol / l) 74.
1 ml was slowly added dropwise. At this time, the reaction temperature was maintained at 0 to 5 ° C., and the mixture was further stirred at 20 ° C. for 2 hours after completion of the dropwise addition. Thereafter, the reaction mixture was poured into water, and the organic layer was washed with diluted hydrochloric acid and a diluted aqueous solution of sodium carbonate, and then washed with water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure.
Evaporation gave a white solid. This was recrystallized from toluene to obtain 8.6 g of colorless needle-like crystals (yield 61).
%). FIG. 1 shows an IR chart of this.
Absorption at 3150-2800 cm ^-1 based on CH bond, 1
At 640 cm ^-1 , absorption based on the CH ₂ ＣＨCH group was observed. FIG. 2 shows a chart of ¹ H-NMR (in CDCl ₃ solvent, based on tetramethylsilane, ppm) of this product. A signal (a) derived from a vinyl proton was observed at δ5 to 7 ppm, a signal (b) derived from a phenyl group of a styryl group was observed at 7 to 8 ppm, and a signal (c) derived from a methylthio group was observed at 3.1 ppm.

[0073]

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Further, the elemental analysis values (calculated values in parentheses) are as follows: C: 52.53% (52.60%), H: 5.5.
76% (5.74%), S: 28.15% (28.09
%) And P: 13.56% (13.56%), which were in good agreement with the calculated values. The refractive index was found by extrapolation to be n _D = 1.676.

Example 2 10.0 g (0.062 mol) of chlorophosphinic acid dimethylthioester was placed in a 500 ml three-necked flask equipped with a thermometer, a dropping funnel and a mechanical stirrer, dissolved in 200 ml of tetrahydrofuran, and cooled to 0 ° C.
While stirring, a solution of 4-vinylbenzylmagnesium chloride in tetrahydrofuran (0.765 mol / l) 8
1.0 ml was slowly added dropwise. At this time, the reaction temperature is 0 to 5
C., and the mixture was further stirred at 20.degree. C. for 2 hours after completion of the dropwise addition. Thereafter, the reaction mixture was poured into water, and the organic layer was washed with diluted hydrochloric acid and a diluted aqueous solution of sodium carbonate, and then washed with water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a white solid. This was recrystallized from toluene to obtain 7.9 g of colorless needle-like crystals (yield 53%). In this IR chart, 315
Absorption based on C—H bond at 0-2800 cm ⁻¹ , 1640
An absorption based on the CH ₂ ＣＨCH group was observed at cm ⁻¹ . In addition, according to ¹ H-NMR (based on tetramethylsilane in ppm in CDCl ₃ solvent, ppm), the signal (a) derived from a vinyl proton was found at δ5 to 7 ppm, and the signal derived from a phenyl group of styryl group was found at 7 to 8 ppm ( b) 3.7-3.
A signal (c) derived from methylene of benzyl group at 8 ppm
Further, a signal (d) derived from a methylthio group was observed at 3.1 ppm.

[0076]

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Further, the elemental analysis values (calculated values in parentheses) are as follows: C: 54.44% (54.51%), H: 6.
26% (6.24%), S: 26.81% (26.47
%) And P: 12.49% (12.78%), which agreed well with the calculated values. The refractive index was found by extrapolation to be n _D = 1.662.

Examples 3 to 62 The phosphite compounds shown in Table 1 were synthesized in the same manner as described in detail in Examples 1 and 2 using various raw materials. Table 1 also shows the properties, elemental analysis results, and refractive index of the obtained phosphite compound.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

[Table 3]

[0082]

[Table 4]

[0083]

[Table 5]

[0084]

[Table 6]

[0085]

[Table 7]

[0086]

[Table 8]

[0087]

[Table 9]

[0088]

[Table 10]

[0089]

[Table 11]

Example 63 To 100 parts by weight of a mixture of 50 parts by weight of the phosphite compound synthesized in Example 1 and 50 parts by weight of divinylbenzene as an unsaturated monomer, was added t-butyl par as a radical polymerization initiator. One part by weight of oxy-2-ethylene hexanate was added and mixed well. This mixture was poured into a mold composed of a gasket composed of a glass plate and an ethylene-vinyl acetate copolymer, and cast polymerization was performed. In the polymerization, the temperature was gradually increased from 30 ° C. to 90 ° C. over 18 hours using an air furnace, and the temperature was maintained at 90 ° C. for 2 hours. After the completion of the polymerization, the mold was taken out of the air furnace, and after standing to cool, the polymer was removed from the glass of the mold.

The obtained polymer was colorless and transparent, had a refractive index (n _D ²⁰ ) of 1.663 and a specific gravity of 1.29, and had a weather resistance of Δ.

Example 64 Example 63 was repeated except that a composition comprising a phosphite compound shown in Table 2 and a monomer copolymerizable therewith was used.
Was performed in the same manner as described above. The physical properties of the obtained polymer were measured and are shown in Table 2.

[0093]

[Table 12]

[0094]

[Table 13]

[0095]

[Table 14]

[0096]

[Table 15]

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum chart of the phosphite compound of the present invention obtained in Example 1.

FIG. 2 is a ¹ H-nuclear magnetic resonance spectrum chart of the phosphite compound of the present invention obtained in Example 1.

Claims (1)

(57) [Claims] [Claim 1] The following formula (1) [Where, A _{1 is, - (X 1 -R 3)} k - or -R ₄ - (X ₁ -
R ₃ ) _k- (where X ₁ is an oxygen atom or a sulfur atom, and R ₃ and R ₄ are the same or different alkylene group, phenylene group, toluene-α-diyl group or xylene-α, α Y ₁ and Y ₂ are respectively the same or different hydrogen atom, halogen atom, alkyl group, alkoxy group or alkylthio group, and R 1 ₁ is an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aralkylthio group, Or ｛Wherein A ₂ is-(X ₂ -R ₅ ) _m- , -R _6- (X ₂ -R ₅ )
_m - or _{-X 3 -R 6 - (X 2} -R 5) m - and is, A
₃ is -X _3- (R ₅ -X ₂ ) _m -or -X ₃ -R _6- (X _2-
R ₅ ) _m — (where X ₂ and X ₃ are an oxygen atom or a sulfur atom, respectively, and R ₅ and R ₆ are the same or different alkylene group, phenylene group, toluene-
It is an α-diyl group or a xylene-α, α′-diyl group, and m is an integer of 0 or more. ) And Y ₃ and Y ₄
Is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group of the same or different kind, and R ₇ is a hydrogen atom or a methyl group. And R ₂ is an alkyl group, an aryl group, an aralkyl group or ｛Wherein A ₄ is -X _5- (R ₇ -X ₄ ) _n -or -X _{5-
R 8 - (X 4 -R 7} ) n - ( where, X ₄ and X ₅ are each oxygen atom or a sulfur atom, R ₇ and R ₈ are each the same or different alkylene group, a phenylene group,
It is a toluene-α-diyl group or a xylene-α, α′-diyl group, and n is an integer of 0 or more. ) And R
₁₀ is a hydrogen atom or a methyl group. ｝. ]
A phosphite compound represented by the formula: