JPH06324201A - Optical material - Google Patents

Abstract

PURPOSE:To obtain an optical material high in refractive index and Abbe number, low in chromatic abberation and optical strain, excellent in heat resistance and impact resistance, small in sp.gr. and capable of making the material light in weight by polymerizing a specified monomer component to obtain the material having a specified refractive index. CONSTITUTION:This material is obtained by polymerizing a monomer component contg. a compd. shown by formula I or II, and the refractive index is controlled to >=1.55. In formulas I and II, X is hydrogen atom, aryl or substituted aryl, Y is hydrogen atom, a cyano group, aryl, -OR, -SR, -OCOR, -NHCOR or -N(CH3) COR, Z is a cyano group, alkyl, aryl, aralkyl, fluoroalkyl, -COOR or -CONH2, the R in Y and Z can be the same or different, where R is alkyl, aryl, aralkyl or fluoroalkyl, and X and Y should not be hydrogen atom at the same time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical material, and more particularly to an optical material excellent in optical properties such as high refractive index, chromatic aberration and transparency and various mechanical properties.

[0002]

2. Description of the Related Art In recent years, synthetic resin materials excellent in light weight, moldability, impact resistance and dyeability have been used as lens materials instead of inorganic glass. Known examples of the synthetic resin material include polymethyl methacrylate, polydiethylene glycol bisallyl carbonate, polystyrene, and polycarbonate. The polymethyl methacrylate and polydiethylene glycol bisallyl carbonate are excellent in lightness and impact resistance, but when used as a lens because of their low refractive index of about 1.49, a lens thicker than inorganic glass is required, It has the drawback of not being suitable for higher magnification and lighter weight.
Further, the polystyrene and polycarbonate have a high refractive index of about 1.58 to 1.59, but since they are thermoplastic resins, there is a problem that optical distortion due to birefringence is likely to occur during injection molding. There are drawbacks such as lack of solvent resistance and abrasion resistance.

Therefore, recently, some technical proposals have been made to improve these conventional drawbacks with a high refractive index. For example, JP-A-1-309002 discloses a plastic lens obtained by curing a distyryl-type organic sulfur compound and a tri- or tetravalent thiol compound, and JP-A-1-315701 discloses a molecular lens. A sulfur-containing plastic lens obtained by mixing a compound having a vinyl group having a molar average of 1.3 or more and a compound having a thiol group having a molar average of 1.1 or more in a specific ratio and curing the mixture, JP-A-2-58001 proposes a high refractive index optical material obtained by reacting a dimercaptobenzene nuclear substitution product with a compound having at least two reactive unsaturated groups per molecule. There is.

[0004]

However, although the above-mentioned optical materials have a high refractive index, they have a problem in terms of chromatic aberration. Further, the thiol compound used as a raw material has a strong bad odor, and the working environment is also low. There is a problem, and the handling property is poor because the viscosity of the raw material monomer is high.

Further, the optical material obtained by polyaddition and polycondensation has a drawback that the yield is poor because it is difficult to control the polymerization reaction.

Therefore, an object of the present invention is to have a desirable refractive index, chromatic aberration, transparency, etc. for a plastic lens or other optical materials, to have various mechanical properties, and to handle it when curing it with low odor. It is to provide an optical material having excellent properties.

[0007]

According to the present invention, the following general formula 3 or 4 [wherein X represents a hydrogen atom, an aryl group or a substituted aryl group, and Y represents a hydrogen atom, a cyano group or an aryl group]. , -OR, -SR, -OCOR, indicates -NHCOR or -N (CH ₃₎ COR, Z is a cyano group, an alkyl group, an aryl group, an aralkyl group, a fluoroalkyl group,
-COOR or -CONH ₂ (wherein R in Y and Z may be the same or different and each represents an alkyl group, an aryl group, an aralkyl group or a fluoroalkyl group. Further, both X and Y are hydrogen atoms. There is no such case))] is provided by polymerizing a monomer component containing a compound represented by the formula (hereinafter referred to as compound A), and an optical material having a refractive index of 1.55 or more is provided.

[0008]

[Chemical 3]

[0009]

[Chemical 4]

The present invention will be described in detail below.

The optical material of the present invention is a material having a refractive index of 1.55 or more obtained by polymerizing a monomer component containing the compound A represented by the general formula 3 or 4. The molecular weight of the polymer obtained by polymerizing the monomer components is 10,000 to 1,000.
It is preferably about 000. When the molecular weight is less than 10,000, heat resistance is lowered, which is not preferable.

The monomer components represented by the general formulas 3 and 4 have the same chemical formula but are structural isomers. In the formula, the alkyl group and aralkyl group in Y and Z preferably have 1 to 6 carbon atoms.

As the compound A, for example, the compounds represented by the structural formulas 5 to 40 can be preferably mentioned, and they can be used alone or as a mixture in use.

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

[0020]

[Chemical 11]

[0021]

[Chemical 12]

[0022]

[Chemical 13]

[0023]

[Chemical 14]

[0024]

[Chemical 15]

[0025]

[Chemical 16]

[0026]

[Chemical 17]

[0027]

[Chemical 18]

[0028]

[Chemical 19]

[0029]

[Chemical 20]

[0030]

[Chemical 21]

[0031]

[Chemical formula 22]

[0032]

[Chemical formula 23]

[0033]

[Chemical formula 24]

[0034]

[Chemical 25]

[0035]

[Chemical formula 26]

[0036]

[Chemical 27]

[0037]

[Chemical 28]

[0038]

[Chemical 29]

[0039]

[Chemical 30]

[0040]

[Chemical 31]

[0041]

[Chemical 32]

[0042]

[Chemical 33]

[0043]

[Chemical 34]

[0044]

[Chemical 35]

[0045]

[Chemical 36]

[0046]

[Chemical 37]

[0047]

[Chemical 38]

[0048]

[Chemical Formula 39]

[0049]

[Chemical 40]

The above-mentioned compound A can be prepared by a known method. For example, in order to prepare 4-methoxy-β-cyanostyrene, 4-methoxybenzaldehyde and acetonitrile are made into a homogeneous solution, It can be obtained by a method of adding potassium hydroxide and reacting.

The content ratio of the compound A in the monomer component is in the range of 5 to 100% by weight, preferably 10 to 95% by weight. If the content is less than 5% by weight, a sufficient refractive index cannot be obtained, which is not preferable.

In the present invention, the monomer component other than the compound A may be a polymerizable monomer copolymerizable with the compound A, for example, styrene; α-methylstyrene, α-ethylstyrene, α-chlorostyrene and the like. Α-
Substituted styrene; halogen nucleus substituted styrene; alkyl nucleus substituted styrene; divinylbenzene; chloromethylstyrene; diethylene glycol bisallyl carbonate;
(Meth) acrylic acid; allyl acetate; allyl acetic acid; diallyl isophthalate; acrylonitrile; methacrylonitrile; vinyl benzoate; alkyl (meth) acrylate, alkenyl (meth) acrylate, alkoxy polyethylene glycol (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, dialkylaminoethyl (meth) acrylate, ethylene glycol bis (meth) acrylate, polyethylene glycol bis (meth) acrylate, propylene glycol bis (meth) acrylate, polypropylene glycol bis ( (Meth) acrylate, bisphenol A bis (meth) acrylate,
1, ω-alkanediol di (meth) acrylate, glycidyl (meth) acrylate, glycerol (meth)
Acrylate, dibromoneopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, dipentaerythritol (meth) acrylate, tetramethylolmethane (meth) acrylate,
2,2-bis [4- (meth) acryloxyethoxyphenyl] propane, 2,2-bis [4- (meth) acryloxydibromophenyl] propane, 2,2-bis [4-
(Meth) acryloxypolyethoxyphenyl] propane, 2,2-bis [4- (meth) acryloxypropoxyphenyl] propane, 2,2-bis [4- (meth) acryloxypolypropoxyphenyl] propane and the like ( (Meth) acrylic acid ester; fumaric acid alkyl ester;
Fumaric acid dialkyl ester; Maleic acid alkyl ester; Maleic acid dialkyl ester; Itaconic acid alkyl ester; Itaconic acid dialkyl ester; Mesaconic acid alkyl ester; Mesaconic acid dialkyl ester; Allyl glycidyl ether; Vinyl acetic acid; 2- (meth) acryloyloxyethyl Acid phosphate and the like can be mentioned, and when used, they can be used alone or as a mixture.

Further, the monomer component includes a UV absorber,
Additives such as anti-coloring agents, chain transfer agents, antioxidants, fragrances, organic dyes and inorganic pigments can be added as necessary.

The optical material of the present invention can be prepared, for example, by subjecting the monomer component containing the compound A to heat polymerization or photopolymerization in the presence of a radical polymerization initiator or a photopolymerization initiator. . As the radical polymerization initiator, an organic peroxide or an azo compound having a 10-hour half-life temperature of 160 ° C. or lower can be used, and specific examples thereof include cumyl peroxyneodecanoate, diisopropyl peroxydicarbonate, and tertiary. Butyl peroxypivalate, lauroyl peroxide, tertiary butyl peroxy 2-ethylhexanoate,
Examples thereof include benzoyl peroxide, 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane and azoisobisbutyronitrile. Examples of the photopolymerization initiator include benzoin, benzoin ethyl ether, benzoin propyl ether, benzophenone, acetophenone, Michler's ketone, azobisisobutyronitrile, azodibenzoyl and anthraquinone. The amount of the radical polymerization initiator or the photopolymerization initiator used is preferably 20 parts by weight or less, based on 100 parts by weight of all the monomer components,
It is particularly preferably 10 parts by weight or less.

To carry out the heat polymerization, for example, the monomer component and the radical polymerization initiator may be charged directly into a desired mold and polymerized by heating preferably at 0 to 200 ° C. for 1 to 48 hours. it can. At this time, the polymerization system is preferably carried out in an atmosphere of an inert gas such as nitrogen, carbon dioxide or helium. Further, before the above-mentioned polymerization, the polymerization components may be pre-polymerized, for example, at 0 to 200 ° C for 0.5 to 48 hours, then charged in a desired mold and post-polymerized. On the other hand, in order to carry out the photopolymerization, for example, a method in which the monomer component and a photopolymerization initiator are mixed, directly injected into a desired mold and irradiated with light from a mercury lamp, a halogen lamp or the like for 1 to 120 minutes to perform polymerization. Etc.

For the purpose of improving the physical properties of the obtained optical material, for example, a hard coat, a multi coat, an antireflection coat, a UV absorption coat, a plasma treatment, or the like after curing.
Surface treatment such as EB treatment, UV ozone treatment, graft polymerization and post-dyeing can also be performed.

[0057]

INDUSTRIAL APPLICABILITY The optical material of the present invention has a refractive index of 1.55 or more and a high Abbe's number, small chromatic aberration and optical distortion, and has optical transparency, heat resistance, solvent resistance and impact resistance. It has excellent properties, and it has a low specific gravity and can be made lighter. In addition, since reaction control and molding during polymerization and curing are easy, it is useful as a plastic lens such as an eyeglass lens, a camera lens, an optical material, or other optical materials.

[0058]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0059]

[Synthesis Example 1] 30 g of 4-methoxybenzaldehyde
(0.22 mol) was placed in a reaction vessel, 340 ml of acetonitrile was added to make a uniform solution, 1.44 g of potassium hydroxide was added, and the reaction was performed at 60 ° C. for 4.5 hours.
Furthermore, 0.72 g of potassium hydroxide was added and the reaction was continued for 2 hours. The obtained mixture was filtered and then concentrated to remove unreacted acetonitrile. The residue was neutralized with dilute hydrochloric acid, extracted with dichloromethane and concentrated to give crude crystals. The crude crystals were recrystallized with methanol to obtain 4-methoxy-β-cyanostyrene. Melting point is 6
It was 2 ° C. and the yield was 54%.

[0060]

Example 1 0.05 g of tertiary butyl peroxy-2-ethylhexanoate was added to and mixed with a polymerization component composed of 6 g of 4-methoxy-β-cyanostyrene and 4 g of styrene to obtain a polymerizable composition. . Then, after charging the polymerizable composition into two glass molds, the composition was placed in a constant temperature bath at 40 ° C. and heated to 70 ° C. for 12 hours, and then heated to 110 ° C. for 4 hours, Finally, it was heated at 110 ° C. for 2 hours. The obtained cured resin is taken out of the mold, and 100
Annealing treatment was performed at 2 ° C. for 2 hours to obtain a cured resin, and the refractive index, Abbe number, color and heat resistance were measured according to the following methods. The results are shown in Table 1.

Refractive Index and Abbe Number: The Abbe refractive index type (manufactured by Atago Co., Ltd.) was used, and methylene iodide was used as an intermediate solution.

B * value (yellowness): measured using Nippon Denshoku Industries Co., Ltd., trade name "Photometer Model 1001". The smaller the value, the smaller the yellowness and the better.

Heat resistance: O: No deformation or discoloration in an oil bath at 130 ° C., X: deformation or discoloration.

[0064]

Examples 2 to 10 and Comparative Examples 1 to 4 Cured resins were prepared in the same manner as in Example 1 except that the polymerization components shown in Table 1 were used, and each measurement was performed. The results of Examples are shown in Table 1, and the results of Comparative Examples are shown in Table 2.

As is clear from Tables 1 and 2, the lens according to the present invention was far superior to the conventional products in the performance required as an optical lens such as refractive index and heat resistance.

However, the abbreviations in the table indicate the following compounds.

St: Styrene CR-39: Diethylene glycol bisallyl carbonate AN: Acrylonitrile

[0068]

[Table 1]

[0069]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08F 18/02 MLF MLK 220/02 MMG 220/44 MMX 7242-4J 226/02 MNL 228/02 MNR

Claims (1)

[Claims] 1. A compound represented by the following general formula 1 or formula 2 wherein X represents a hydrogen atom, an aryl group or a substituted aryl group, and Y represents a hydrogen atom, a cyano group, an aryl group, —OR, —SR, —OC.
OR, indicates -NHCOR or -N (CH ₃₎ COR, Z
Is a cyano group, an alkyl group, an aryl group, an aralkyl group,
Represents a fluoroalkyl group, —COOR or —CONH ₂ (wherein R in Y and Z may be the same or different and represents an alkyl group, an aryl group, an aralkyl group or a fluoroalkyl group; both X and Y) Is not a hydrogen atom.)]] An optical material obtained by polymerizing a monomer component containing a compound represented by the formula, and having a refractive index of 1.55 or more. [Chemical 1] [Chemical 2]