JP2813535B2 - Optical material and method for manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical plastic material using a novel reactive oligomer and a method for producing the same. The optical material of the present invention has a high refractive index and low dispersion, and has excellent optical characteristics. Therefore, it is preferably used for optical lenses such as camera lenses, spectacle lenses, contact lenses, and intraocular lenses, prisms, filters, optical fibers, optical disk substrates, and the like.

[0002]

2. Description of the Related Art Compared with glass, plastic is lightweight, hard to break, and easily dyed. Practical plastic materials include poly (diethylene glycol bisallyl carbonate) (C) which is a general-purpose plastic material.
R-39), polymethyl methacrylate and polycarbonate. Recently, polyurethanes obtained from pentaerythritol tetrakis (mercaptopropionate) and diisocyanate compounds, polyurethanes obtained from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and diisocyanate compounds, Polymers and the like obtained using 5-dimercaptomethyl-1,4-dithiane have been developed. These polymers are described in JP-A-63-46213, JP-A-2-270859, and JP-A-3-236386.
Nos. 4,028,045 and 5,985, respectively.

[0003]

In general, transparent glass and polymers have a lower Abbe number (in other words, a higher dispersion) as the refractive index increases, and vice versa (Hans U. Simlock et al., Supra). Ange Hante Hemy, International Edition, Advanced Materials, 28
Vol., August / September, 1122, 1989). Therefore,
It is generally considered that it is extremely difficult to synthesize a polymer having simultaneously increased refractive index and Abbe number. On the other hand, research and development have been conducted to synthesize a polymer having simultaneously increased refractive index and Abbe number.
Polymers described in JP-A-6213 and JP-A-2-270859 were obtained. However, the refractive index and Abbe number of these polymers were still not high enough to be applicable to many optical designs.

Further, 2,5-dimercaptomethyl-1,4-dithiane (hereinafter abbreviated as DMMD) described in JP-A-3-236386 has a refractive index and an Abbe number. At the same time, it was a material (refractive index 1.646, Abbe number 35.2) higher than the conventional one. A polymer obtained using this compound has a higher refractive index and Abbe number than a polymer using a conventional polythiol compound. However, particularly in the field of spectacle lenses, it is desired to provide an optical material having a higher refractive index, and at that time, it is required that the Abbe number is about the same as the conventional one.

Accordingly, an object of the present invention is to provide an optical material having a higher refractive index and an Abbe number that can be maintained at least as high as that of a conventional product, and a method for producing the same.

[0006]

SUMMARY OF THE INVENTION The present invention provides a method of formula 1 wherein
n is an integer from 2 to 20), and is a polyaddition product containing one or more kinds of repeating units represented by the following formula (1):

[0007]

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The present invention further relates to (A) one or more reactive oligomers represented by Formula 2 (where n is an integer from 2 to 20), and (B) one molecule of the reactive oligomer. Compounds having two or more vinyl groups, compounds having two or more iso (thio) cyanate groups in one molecule, and one or more vinyl and one or more iso (thio) cyanate groups in one molecule One or two selected from the group consisting of compounds having
The present invention relates to a method for producing the optical material, wherein a polyaddition reaction with a seed or more is performed.

[0009]

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Hereinafter, the present invention will be described in detail. The optical material of the present invention is a polyadduct containing one or more of the repeating units represented by the above formula 1. Preferably, the optical material of the present invention is a polyadduct containing two or more of the repeating units represented by the above formula (1). In addition, from the viewpoint that the Abbe number can be maintained as high as the conventional product and has a higher refractive index, n in the formula is preferably in the range of 2 to 10, more preferably in the range of 2 to 5. Something is appropriate. Further, the polyadduct of the present invention suitably contains 20 to 50 mol% of one or more kinds of the repeating units represented by the formula 1.

The optical material of the present invention can be obtained using the reactive oligomer represented by the above formula (2) as a raw material. In this reactive oligomer, the degree of polymerization n is 20 or less. this is,
This is because when the degree of polymerization increases, the oligomer becomes cloudy, and as a result, the optical material of the present invention also tends to cloud. The reactive oligomer having a degree of polymerization n of 20 or less is colorless and transparent.
Further, the optical material of the present invention can be obtained by using a reactive composition containing two or more of the above reactive oligomers.

The reactive oligomer used in the present invention is:
It is an oxidation product originally obtained by oxidizing the 2,5-dimercaptomethyl-1,4-dithiane (DMMD) as described below. However, usually,
Oxidation products obtained by oxidizing DMMD include reactive oligomers of different types having different degrees of polymerization n. Therefore, it is usually appropriate to prepare the optical material of the present invention using an oxidation product containing a plurality of the reactive oligomers described above. However, if necessary, each reactive oligomer can be separated from the oxidation product and used. For this separation, a conventional method, for example, a method such as chromatography or molecular distillation can be used. The oxidation product may contain unreacted DMMD, and as a result, the optical material of the present invention may contain a repeating unit in which n is 1 in the above formula 1.

The production of the reactive oligomer used in the present invention can be carried out by oxidizing DMMD as shown in the following scheme. When DMMD is oxidized, only the mercapto group of DMMD is oxidized, disulfide bonds are generated between the molecules, and the molecules are sequentially condensed and oligomerized. However, this oxidation is performed under the condition that a disulfide bond is generated, but sulfur of the 1,4-dithiane ring in DMMD is not oxidized to generate sulfone or sulfoxide (see the following formula).

[0014]

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Examples of the oxidizing agent used for the oxidation include air (oxygen), hydrogen peroxide, halogen, hypohalous acid, methyl sulfoxide, manganese oxide (I
V) Iron (III) chloride, potassium hexacyanoferrate (III), nitric oxide, sulfuryl chloride, pyridine-N-
Oxide, N-nitroso-N-methyltoluene-p-
Examples include sulfonamide, flavin, and sulfur using butylamine as a catalyst. When air (oxygen) is used as the oxidizing agent, the reaction solution is made alkaline or Cu (I
It is preferable to use I), Fe (III), or a cobalt complex as a catalyst since the oxidation reaction rate tends to increase. By using these oxidizing agents, an oxidizing reaction in which only disulfide bonds are generated can be performed.

When DMMD is oxidized, the degree of polymerization increases as the reaction proceeds, and the oxidation product is not an oligomer having a single degree of polymerization but a mixture of oligomers having different degrees of polymerization. When the oxidation reaction proceeds to some extent, a polymer having a high degree of polymerization is precipitated, and the obtained oxidation product becomes cloudy. When the cloudy oxidation product undergoes a polyaddition reaction with an isocyanate, the resulting polyadduct also becomes cloudy. Cloudy polyadducts are not suitable as optical materials. Therefore, in the present invention, a colorless and transparent reactive oligomer having a polymerization degree n of 20 or less is used. The oxidation reaction conditions for controlling the polymerization degree n of the reactive oligomer to 20 or less may be appropriately adjusted according to the oxidizing agent used, the reaction temperature and time. For example, when oxidizing with air (oxygen) in the presence of an Fe (III) catalyst, a reactive oligomer having a polymerization degree n of 20 or less can be obtained by setting the reaction temperature to room temperature and the reaction time to 20 hours or less. In the case of oxidation with methyl sulfoxide, the colorless and transparent polymerization degree n is 2 by setting the reaction temperature to 80 ° C. and the reaction time to 8 hours or less.
Zero or less reactive oligomers are obtained.

The reactive oligomer has a higher refractive index and a lower Abbe number as the degree of polymerization n is larger. Therefore, reactive oligomers having different degrees of polymerization n can be appropriately used according to the refractive index and Abbe number required for the optical material of the present invention. Similarly, when a mixture of reactive oligomers is used, the type (degree of polymerization) and content of the reactive oligomers in the mixture are appropriately determined according to the refractive index and Abbe number required for the optical material of the present invention. Can be selected. As described above, in order to obtain a reactive oligomer having a desired refractive index and Abbe number, an oxidizing agent, an oxidation reaction temperature and a time may be appropriately adjusted.

The polyadduct, which is an optical material of the present invention, is obtained by polyaddition of a monomer having an iso (thio) cyanate group or a vinyl group, in which the reactive oligomer undergoes an addition reaction with mercapto groups at both ends. can get. That is, the component A containing the reactive oligomer described above, a compound having two or more vinyl groups in one molecule, a compound having two or more iso (thio) isocyanate groups in one molecule, and a compound having one or more iso (thio) isocyanate groups in one molecule. The polyadduct of the present invention can be obtained by subjecting a compound having at least one vinyl group and at least one iso (thio) cyanate group to a polyaddition reaction with at least one component B. it can.

The component A has a mercapto group and / or a hydroxy group in one molecule and a mercapto group in one molecule in addition to the reactive oligomer in order to appropriately improve the physical properties of the polyadduct. It may contain a compound (component C) in which the total number of groups and hydroxy groups is 2 or more. Specific examples of these compounds include trimethylolpropane, 1,2
-Ethanedithiol, 1,3-propanedithiol, tetrakis (mercaptomethyl) methane, pentaerythritol tetrakis (mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), 2-mercaptoethanol, 2,3-dimercaptopropanol, 1 , 2-Dihydroxy-3-mercaptopropane, 4-mercaptophenol, 1, n-benzenedithiol (n = 2,3,4), 1,3,5-benzenetrithiol, 1, n-bis (mercaptomethyl)
Benzene (n = 2,3,4), 1,3,5-tris (mercaptomethyl) benzene, toluene-3,4-dithiol, bis (4-hydroxyphenyl) sulfide and the like can be mentioned.

On the other hand, the vinyl group-containing compound used for the component B includes divinylbenzene, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and at least two or more compounds per molecule. (Meth) acryloxy group-containing urethane-modified (meth) acrylate, epoxy-modified (meth) acrylate, polyester-modified (meth) acrylate and the like. The above (meth) acrylate means both acrylate and methacrylate, and the (meth) acryloxy group means both acryloxy and methacryloxy groups.

The compounds containing an isothiocyanate group used for the component B are specifically xylylenediiso (thio) cyanate, 3,3'-dichlorodiphenyl-4,4'-diiso (thio) cyanate, 4,4 ' -Diphenylmethanediiso (thio) cyanate, isophoronediiso (thio) cyanate, 2,2 ', 5,5'-tetrachlorodiphenyl4,4'-diiso (thio) cyanate, tolylenediiso (thio) cyanate and the like. Can be

Specific examples of the compound containing a vinyl group and an iso (thio) cyanate group used in the component B include 2
-(Meth) acryloxyethyl iso (thio) cyanate, (meth) acryloyliso (thio) cyanate and the like.

A component and B component, or A component and B component and C
The components are (vinyl group + iso (thio) cyanate group) /
The value of (mercapto group + hydroxy group) is 0.5 to 3.0.
It is appropriate that the mixture is uniformly mixed so as to fall within the range described above to obtain a polymerization raw material mixture. However, when a vinyl group is contained in the component B, it is preferable that all of the polymerization functional groups of the component A or the components A and C are mercapto groups. In addition, a catalyst can be used for this polyaddition reaction. Therefore, the above-mentioned catalyst can be further appropriately added to the above-mentioned polymerization material mixture. Examples of the catalyst include an organic peroxide, an azo compound, and a basic compound in the reaction between a mercapto group and a vinyl group. In the reaction between a mercapto group or a hydroxy group and an isothiocyanate group, an organic tin compound or an amine compound is mentioned as an example of the catalyst. Further, in order to improve the light fastness of the obtained polyadduct, an ultraviolet absorber, an antioxidant, an anti-coloring agent and the like may be appropriately added to the polymerization raw material mixture.

The polymerization raw material mixture containing the component A, the component B, the additives and the catalyst, and if necessary, the component C is poured into a container having an appropriate shape and heated to obtain a polyadduct. . The container may be subjected to a release treatment, or a release agent may be previously mixed into the polymerization raw material mixture so that the polymer can be easily taken out of the container. The polymerization temperature is -20 to 1
It is appropriate that the temperature is in the range of 50 ° C. and the polymerization time is in the range of 0.5 to 72 hours. The thus obtained polyaddition product is particularly preferable as an optical product such as a plastic lens, a camera lens, an eyeglass lens, a contact lens, an optical lens such as an intraocular lens, a prism, a filter, an optical fiber, and an optical disk substrate. Used.

[0025]

The present invention will be further described with reference to the following examples.
In addition, the measurement of various physical properties in an Example was performed by the following methods. [Measurement of Visible Light Transmittance (T%)] Using a spectrometer UV-330 manufactured by Hitachi, Ltd., the transmittance of a sample having both sides polished and having a thickness of 1 mm was measured in the range of 450 to 900 mm. [Measurement of Refractive Index (n _D ) and Abbe Number (ν _D )] Measured at 20 ° C. using an Abbe refractometer 3T manufactured by Atago. Diiodomethane was used as the contact liquid between the sample and the prism. [Heat Resistance] While applying a load of 10 gf with a 0.5 mmφ pin using a TMA device manufactured by Rigaku Corporation, the temperature was raised at 10 ° C./min, and the thermal deformation onset temperature was read from the obtained chart to evaluate.

Reference Example 1 (Synthesis of Reactive Oligomer 1 (When Oxidized with Methyl Sulfoxide) 45.17 g (0.147 mol) of DMMD
86 g (0.587 mol) of methyl sulfoxide was added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling the reaction mixture, the same amount of water as methyl sulfoxide was added, and the mixture was extracted with chloroform. The extract was washed with water, dried over magnesium sulfate, and chloroform was removed under reduced pressure to obtain a mixture of reactive oligomers (yield: about 90%). _{n D / ν D = 1.680 /} 34.3; 1 H-NMR (CDC1 3) δ1.59-1.65
(M, 100H), δ 2.80-3.20 (m, 10.
2H); IR (liquid film method) 2901, 2543, 1406, 131
1,1259,1228,1210,1181,90
7,694 cm ^-1 ; Raman 500, 540, 630, 720, 790, 14
From the ratio of the area of the chart obtained by 00,2550,2900 cm ^-1 GPC analysis, the obtained mixture of reactive oligomers was 6.54% in DMM.
D, 29.9% dimer, 26.4% trimer, 17.
It contained 7% tetramer and 19.5% of an oligomer mixture having a degree of polymerization of 5 or more.

Reference Example 2 (Synthesis of reactive oligomer 2 (Fe (III) catalyst,
460m for 97.54g (0.46mol) DMMD
of methanol, and 124.11 g (0.1.
46 mol) of ferric chloride hexahydrate methanol (3
20 ml) solution was added quickly and stirred at room temperature. 4
After stirring for an hour, the precipitate was taken out by decantation, dissolved in chloroform, and the solution was washed with water and dried over magnesium sulfate. Chloroform was removed under reduced pressure to obtain a mixture of reactive oligomers (yield about 90%).
%). From the ratio of the area of the chart obtained by n _D / ν _D = 1.665 / 35.0 GPC analysis, the obtained reactive oligomer mixture was 3.64% DMM.
D, 58.5% dimer, 26.5% trimer, 8.5
It contained 2% tetramer and 2.84% oligomer mixture having a degree of polymerization of 5 or more.

Comparative Reference Example 1 The refractive index of DMMD described in JP-A-3-236386 was 1.646, and the Abbe number was 35.2.

Example 1 (Synthesis of Polyadduct) A mixture of the reactive oligomers obtained in Reference Example 1 (NMR
3.74 g of average molecular weight (374.35) determined from (10)
^-2 mol), 1.94 g (10 ^-2 mol) of 1,3-bis (isocyanatomethyl) cyclohexane and 3.0 mg (10 ^-5 mol) of dibutyltin dichloride were uniformly mixed. Next, the mixture was degassed under vacuum, and then poured into a glass container.
After heating for 120 hours at 120 ° C., a polymer was obtained.
The resulting polymer is hard and has a visible light transmittance (45
0-900 nm) is 87-92%, the refractive index (n _D ) is 1.645, the Abbe number (ν _D ) is 37.0, and the heat resistance is 1
14 ° C. ¹ H-NMR (in DMSO-d ₆₎ δ0.4-1.8
(M, 1.00H), δ 2.75-3.40 (m, 2.
33H); IR (KBr) 3307,2914,1653,150
0, 1404, 1191 cm ^-1 ; weight average molecular weight (polystyrene conversion) 15400

Examples 2 to 10 Using the raw materials shown in Table 1, the same operation as in Example 1 was performed to obtain polyadducts. Table 1 shows the physical properties of these polyadducts.
Shown in From Table 1, the polyadducts of Examples 2 to 10 are colorless and transparent due to the high visible light transmittance, and have a refractive index (n _D ).
Is 1.630 to 1.677, and the Abbe number (ν _D ) is 34.
2 to 41.0, and heat resistance was 109 to 129 ° C.

Comparative Example 1 4.88 g (10 ^-2 mol) of pentaerythritol tetrakis (mercaptopropionate), 3.76 g (2 × 10 ^-2 ) of m-xylylene diisocyanate and 6.1 mg of dibutyltin dichloride (2 × The mixture of ^10-5 ) was uniformly stirred. After degassing the obtained mixture under vacuum, it was poured into a glass container and heated at 50 ° C. for 10 hours, at 60 ° C. for 5 hours, and at 120 ° C. for 3 hours to obtain a polymer. Table 1 shows the physical properties of the obtained polymer. From Table 1, the polymer obtained in this application comparative example was colorless and transparent, but had a refractive index (n _D ) of 1.59 and a heat resistance of 86 ° C. Inferior to any of the polymers obtained.

Comparative Examples 2 and 3 Using the raw material compositions shown in Table 1, the same operation as in Comparative Example 1 was performed to obtain a polymer. Table 1 shows the physical properties of these polymers.
Shown in From Table 1, the polymer of Comparative Example 2 has a relatively high refractive index (n _D ) of 1.670, but is yellow, has an Abbe number (ν _D ) of 28, and a heat resistance of 94 ° C. 3
Two properties were inferior to any of the polymers obtained in the previous examples. The polymer obtained in Comparative Example 3 was colorless and transparent, had an Abbe number (ν _D ) of 52, had a relatively high heat resistance of 101 ° C., but had a refractive index (n _D ) of 1.530. It was lower than any of the polymers obtained in the examples.

[0033]

[Table 1]

RO-1: Reactive oligomer mixture obtained in Reference Example 1 RO-2: Reactive oligomer mixture obtained in Reference Example 2 HXDI: 1,3-bis (isocyanate) Methyl) cyclohexane XDI: m-xylylene diisocyanate DIH: 1,6-diisocyanatohexane 4-MP: 4-mercaptophenol PETMA: pentaerythritol tetrakis (mercaptoacetate) IPDI: isophorone diisocyanate TDI: toluene diisocyanate EDT: ethanedithiol EDMA: Ethylene glycol dimethacrylate MEI: 2-methacryloxyel isocyanate DBTDC: Dibutyltin dichloride DBTDL: Dibutyltin dilaurate ADVN: Azobisdimethylvaleronitrile 1,3,5-TMB: 1,3,5- tri mercaptobenzene DAPE: di arylidene pentaerythritol PETMP: pentaerythritol tetrakis (mercaptopropionate)

FIG. 1 shows the relationship between the refractive index of the polymer obtained in the above example and the Abbe number by black circles (●). For comparison, the relationship between the refractive index of the polymer for lenses described in JP-A-63-46213 and the Abbe number is shown by a square (□), and the refractive index of the polymer for lenses described in JP-A-2-270859 is disclosed. And the relationship between the Abbe number and the white circle (○).
The relationship between the refractive index of the polymer for lenses described in JP-A-36386 and the Abbe number is indicated by a triangle (△). As is clear from FIG. 1, the optical material of the present invention exhibits higher refractive index and lower dispersion (high Abbe number) than the conventional polymer.

[0036]

The optical material of the present invention has a high refractive index and Abbe number and is excellent in heat resistance. Therefore, it is preferably used for optical products such as camera lenses, spectacle lenses, contact lenses, and intraocular lenses, and optical products such as prisms, filters, optical fibers, and optical disc substrates.

[Brief description of the drawings]

FIG. 1 shows the relationship between the refractive index and Abbe number of various polymers.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G02B 6/00 391 G02B 6/00 391 G02C 7/02 G02C 7/02 7/04 7/04

Claims (6)

(57) [Claims] 1. An optical material comprising a polyadduct containing one or more kinds of repeating units represented by Formula 1 (where n is an integer from 2 to 20). Embedded image 2. The polyadduct contains 20 to 50 mol% of one or more of the repeating units represented by the formula 1.
The optical material as described. 3. (A component) Formula 2 (where n is 2 to 20)
And (B component) a compound having two or more vinyl groups in one molecule, and two or more iso (thio) groups in one molecule. A) a polyaddition reaction between a compound having a cyanate group and one or more compounds selected from the group consisting of one or more vinyl groups and one or more compounds having one or more iso (thio) cyanate groups in one molecule; The method for producing an optical material according to claim 1, wherein: Embedded image 4. (A component) Formula 2 (where n is 2 to 20)
One or two or more reactive oligomers represented by the following formula (C): a mercapto group in one molecule;
A compound having a hydroxy group or both thereof and having a total number of mercapto groups and hydroxy groups of 2 or more in one molecule; a compound (B) having two or more vinyl groups in one molecule; One or two selected from the group consisting of a compound having two or more iso (thio) cyanate groups, and a compound having one or more vinyl groups and one or more iso (thio) cyanate groups in one molecule. The method for producing an optical material according to claim 1, wherein a polyaddition reaction is performed with at least a seed. Embedded image 5. The sum of the total number of vinyl groups and iso (thio) cyanate groups contained in the compound (B) with respect to the total number of mercapto groups and hydroxy groups contained in the compound (A) and the compound (C). 5. The production method according to claim 4, wherein the raw materials for the polyaddition reaction are adjusted so that the ratio [vinyl group + iso (thio) cyanate group] / [mercapto group + hydroxy group] is in the range of 0.5 to 3.0. 6. An optical product using the optical material according to claim 1 or 2, or an optical material manufactured by the manufacturing method according to any one of claims 3 to 5.