JPS632001A - High refractive index resin lens and its production - Google Patents

Abstract

PURPOSE:To provide a titled lens having excellent characteristics by incorporating an urethane resin by a specific naphthalene polyol into a compsn. and incorporating the component by the naphthalene polyol at >=5wt% ratio therein. CONSTITUTION:This compsn. contains the urethane resin by the naphthalene polyol expressed by the formula and the component by the naphthalene polyol at >=5wt% ratio. This lens is formed by using the polymerizable compsn. consisting of the naphthalene polyol expressed by the formula or a mixture composed of at least >=20wt% naphthalene polyol expressed by the formula and active hydrogen compd. contg. >=2 pieces of active hydrogen, a polyisocyanate compd. and radical polymerizable monomer and bringing said compsn. into reaction and polymn. in a casting vessel.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a high refractive index resin lens and a method for manufacturing the same.

[Prior art]

Conventionally, inorganic glass lenses have been widely used in optical a2H (
However, recently, lenses made of synthetic resin have been used together with inorganic glass lenses due to their light weight, impact resistance, processability, stability, dyeability, mass productivity, and other advantageous features. It is beginning to be widely used.

On the other hand, there are various requirements regarding the physical properties of lenses, and among them, there is an extremely high demand for the material to have a high refractive index. This is because it can be manufactured with a small thickness. By using lenses with a high refractive index, lens systems that play an important role in optical instruments such as microscopes, cameras, and telescopes can be made compact and lightweight, and eyeglass lenses can also be made lightweight. Since it is possible to reduce the so-called edge thickness and reduce the so-called edge thickness, there are great practical advantages. As described above, it is of great significance to make lenses with a high refractive index, and therefore there is a strong desire to provide resin lenses made of materials with a high refractive index.

However, considering the important characteristics of lenses such as transparency and light weight, no satisfactory resin lenses have yet been provided. To be more specific, materials such as diethylene glycol bisallyl carbonate resin and polymethyl methacrylate are currently used as materials for resin lenses for eyeglasses, which are currently available at a disadvantage, but both have a refractive index of 1. It is low, around 50.

-On the other hand, urethane resins have begun to be considered as materials for resin lenses with relatively high refractive indexes, for example, in JP-A-57-
136601, West German Patent No. 2929313, US Patent No. 3907864, US Patent No. 3
No. 907,864 and others disclose lenses made of urethane resin.

However, these urethane resin lenses do not have a sufficiently high refractive index and are not necessarily satisfactory.

Furthermore, a urethane resin containing a halogen atom with a sufficiently high refractive index has been proposed in JP-A-58-164615, but this urethane resin has -
As is generally known as a problem when containing a halogenated aromatic polymer, the specific gravity is high and the weather resistance is low. Furthermore, JP-A-60-19440
In Publication No. 1, sulfur-containing urethane resins and the like are also proposed, and searches for high refractive index resin materials are being conducted in various fields.

[Summary of the invention]

The present invention was made based on the discovery that a urethane resin obtained using a specific polyol has a high refractive index and is excellent as a material for producing a low-density resin lens, and has excellent properties. The object of the present invention is to provide a high refractive index resin lens and a method for manufacturing the same.

The resin lens of the present invention is characterized in that it contains a urethane resin made of a naphthalene polyol represented by the following general formula (I), and contains a component made of the naphthalene polyol in a proportion of 5% by weight or more.

In addition, the method of the present invention includes (a) a naphthalene polyol represented by the following formula (RI) or at least 20 percent or more of a naphthalene polyol represented by the following general formula (I), and a naphthalene polyol other than the above 8 naphthalene polyionyl. A step of reacting and polymerizing a polymerizable composition consisting of a mixture with an active hydrogen compound containing two or more hydrogen atoms, (b) a polyisocyanate compound, and (c) a radically polymerizable it form in a casting container. It is characterized by including.

General formula (I) (n is an integer of 2 to 4) [Effect] According to the present invention, it contains a urethane resin made of naphthalene polyol, and contains a component made of the naphthalene polyol in a proportion of 5% by weight or more. Since it is made of polymer, it is possible to obtain a high refractive index of n'Z = 1.58 or more, and it also has high colorlessness and transparency, which are important for lenses, and has an excellent resin lens with a relatively low specific gravity. Moreover, a resin lens having such excellent properties can be manufactured very easily and reliably.

The present invention will be specifically explained below.

The resin lens according to the present invention is a specific naphthalene polyol containing two or more hydroxyl groups represented by formula (I) above, or a specific naphthalene polyol containing at least 20% by weight of the specific naphthalene polyol. A mixture of naphthalene polyol and other active hydrogen compounds (containing two or more active hydrogens) is used as a polyol material, and a polymerizable composition is obtained by using this polyol material, a polyisocyanate material, and a radically polymerizable monomer. , is produced by reacting and polymerizing this polymerizable composition in a casting container.

The naphthalene polyol used in the present invention has a plurality of hydroxyl groups as substituents on the naphthalene skeleton, and specifically, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1.5-dihydroxynaphthalene, 1
．． 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6
-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,2゜4-trihydroxynaphthalene, 1,
4.5-Trihydroxynaphthalene, 1,2.5.6
-tetrahydroxynaphthalene, and others, but are not limited to these alone, and may also be mixtures thereof.

In the present invention, the above-mentioned naphthalene polyol may be used as the entire polyol to be reacted with the polyisocyanate compound. It can also be used as a mixture with hydrogen compounds.

In this case, the active hydrogen compound is an alcoholic hydroxyl group, a carboxyl group, an amino group, an imino group, etc.
It is a compound having at least two groups containing active hydrogen atoms that are reactive with incyanate groups, and in terms of -S, polyols other than the above-mentioned naphthalene polyols can be preferably used. Various types of polyol can be used, and polyols having 2 to 4 hydroxyl groups are particularly preferred, although they are not particularly limited.

Typical polyols suitably used as active hydrogen compounds in the present invention include polyhydric alcohols, poly(oxyalkylene) diols, polyether polyols, polyester polyols, and the like. Specific examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, glycerin,
Examples include trimethylolpropane, L2.6-cyclohexandriol, bisphenol A, and the like. Of course, these are just examples, and the invention is not limited to these. Specific examples of poly(oxyalkylene) diols include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and the like. Specific examples of polyether polyols include the above-mentioned polyhydric alcohols, poly(oxyalkylene glycols), polyhydric phenols, and monoepoxides (especially ethylene oxide and propylene oxide).
Examples include compounds obtained by adding . Specific examples of polyester polyols include polyester polyols having residues of polyhydric carboxylic acids such as phthalic acid and isophthalic acid, and residues of polyhydric alcohols such as those mentioned above.Polyols of 0 or more are a mixture of two or more types. It can also be used as

Regarding the mixing ratio of the above-mentioned naphthalene polyol and the above-mentioned active hydrogen compound, it is necessary that the ratio of naphthalene polyol in the mixture is 20% or more, and if this ratio is less than 20%, The key is to obtain a resin with a high refractive index.

These naphthalene polyols or mixtures of naphthalene polyols and active hydrogen compounds become urethane resins by reacting with polyisocyanates. The polyisocyanate used here is not particularly limited, but polyisocyanates that do not have the isocyanate group directly replaced with W on the aromatic nucleus may result in the final resin lens having high transparency and yellowing. From the point that it becomes difficult,
Preferably used. Specific examples of polyisocyanates having such aromatic nuclei include xylylene diisocyanate, tetramethylxylylene diisocyanate,
Others are preferred. Polyisocyanates without aromatic nuclei include various aliphatic polyisocyanates and alicyclic polyisocyanates. Specific examples of these include hexamethylene diisocyanate, isophorone diisocyanate, and 2,2,4-trimethyl. Examples include xamethylene diisocyanate, dicyclohexylmethyl diisocyanate, bis(isocyanatemethyl)cyclohexane, etc. Of course, the polyisocyanate compounds are not limited to these, and it is of course possible to use two or more polyisocyanate compounds in combination.

A monomer composition for urethane resin is formed by naphthalene polyol or a mixture of the naphthalene polyol and an active hydrogen-containing compound and polyisocyanate, and the proportion of polyisocyanate in this composition is as follows:
It is appropriate that the equivalent ratio is within the range of 0.5 to 1.5, and particularly preferably within the range of 0.8 to 1.2.

Such monomer compositions for urethane resins are reacted to have a high molecular weight and produce urethane resins. A monomer is mixed with the monomer composition for urethane resin to form a polymerizable composition, this polymerizable composition is placed in a casting container, and the naphthalene polyol or naphthalene polyol and an active hydrogen compound are mixed. A resin lens is produced by reacting with a polyisocyanate and simultaneously radically polymerizing a radically polymerizable monomer.

It is preferable to add a radically polymerizable monomer to the monomer composition for urethane resin in this way because it can reduce the viscosity of the polymerizable composition when poured into a casting container. In addition, favorable results can be obtained in terms of mechanical properties, hardness, machinability, etc., and dyeability of the resulting lens. However, in the resin lens of the present invention, it is preferable that the urethane resin component accounts for 30% by weight or more of the total resin, and that the above-mentioned naphthalene polyol component accounts for 5% by weight or more of the total resin. It is necessary that the content is particularly preferably 6% by weight or more. If this proportion is less than 5% by weight, it becomes difficult to obtain a material with a high refractive index.

The radically polymerizable monomer that can provide a resin compatible with the above-mentioned urethane resin has a refractive index n of the resulting polymer.
Specific examples of such monomers, which preferably have a %F value of 1.55 or more, are as follows.

(a) Various acrylic esters or methacrylic esters. i.e. esters of -hydric or polyhydric alcohols with acrylic acid or methacrylic acid, such as phenyl methacrylate, acryloxyethoxybenzene, 2.
2-bis-(4-methacryloxyethoxy)phenylpropane, 2.4.6-)ribromophenyl methacrylate, and the like.

(b) Aromatic vinyl compounds such as styrene, α-methylstyrene, divinylbenzene, diisopropenylbenzene, and vinyltoluene.

(c) diallyl phthalate, allyl phenyl ether,
Various allyl compounds such as triallyl isocyanate.

The above monomers may be present in 30-7% of the total resin depending on the properties required for the final resin lens or the purpose of use.
It can be used in proportions ranging from 0% by weight.

The reaction of the monomer composition for urethane resin and the polymerization of the radically polymerizable monomer are carried out simultaneously in a casting container, thereby obtaining a resin lens with desired characteristics. Here, as the casting container, plate-shaped, cylindrical, prismatic, conical, or other molds or molds designed depending on the purpose can be used. The material may be any material selected depending on the purpose, such as inorganic glass, plastic, or metal.

Monomer compositions for urethane resins, such as naphthalene polyol alone or a mixture of naphthalene polyol and an active hydrogen compound, and a polyisocyanate compound, can be prepared as is or by causing an appropriate urethane reaction in another container in advance to have an appropriate viscosity. It may also be poured into a casting container after it has been brought to a state of liquid.

For the reaction of the monomer composition for urethane resin, it is preferable to add a polyurethane catalyst.As the polyurethane catalyst, catalysts known in the field of polyurethane chemistry can be used, and typical examples include There are three amine catalysts and organometallic compound catalysts. Specific examples of the former include triethylenediamine, triethylamine,
Examples of the latter include dibutyl metal dilaurate, stannath octoate, and other metal tin compounds. The radical polymerizable monomer is added together with a radical polymerization initiator therefor. There are no particular restrictions on the radical polymerization initiator used here, and known peroxides can be used. Although both polymerization and polymerization occur within the casting container, each monomer or composition may be added in its entirety at the same time, or may be added in stages.

As reaction and polymerization conditions, conventional conditions are selected. For example, the temperature is usually in the range from room temperature to 150°C.

Furthermore, the polymerizable composition may contain antistatic agents, colorants, fillers, ultraviolet absorbers, heat stabilizers, antioxidants, and other auxiliary materials depending on the expected use of the final resin lens. can be included. It goes without saying that the obtained resin lens can be subjected to annealing or other post-treatments in order to complete the reaction or polymerization or to remove the inherent distortion.

The resin lens according to the present invention is characterized in that its material is a polymer containing specific types of components, but other than that, it is the same as a normal resin lens. By performing additional treatments such as hard coating, hard coating, anti-reflection coating, and dyeing/light control treatment, it is possible to obtain a resin lens with the mechanical properties required for practical use.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 Styrene 40 parts by weight Benzyl methacrylate 20 parts by weight Fully purified 1,5-naphthalene diol 6.22 parts by weight Bisphenol A 15.5 parts metaxylylene diisocyanate 18.28 parts by weight di-n- dilauric acid 0.05 parts by weight or more of butyltin was placed in a container and stirred under heating until a homogeneous solution was obtained. A polymerizable composition was obtained by adding 0.5 parts by weight of lauroyl peroxide to this liquid (8).

This polymerizable composition was injected into a glass mold for lenses, and then heated at a temperature of 60°C for 2 hours, at a temperature of 65°C for 5 hours, and at a temperature of 8°C.
Heated sequentially at 0°C for 3 hours and at 100°C for 2 hours,
The reaction and polymerization were completed, and an almost colorless and strong resin lens was obtained. 1 in the resin forming this resin lens.
The content of the component due to 5-naphthalenediol is 6.22
% by weight. When the refractive index of this lens was measured using a refractometer, it was found that n'Z = 1.593. Further, the specific gravity was 1.24.

Thus, this resin lens has a high refractive index and a low specific gravity.

Example 2 Parachlorostyrene 30 parts Tribromophenyl methacrylate 20 parts 1.7-naphthalenediol 9.88 parts Bisphenol A '16', 89 parts metaxylylene diisocyanin) 23.23 parts dilaurin Acid di-n-butyltin 0.05 parts by weight or more of the substance was placed in a container and stirred under heating until a homogeneous solution was obtained. Add 0 lauroyl peroxide to this solution.
．． A polymerizable composition was obtained by adding 5 parts by weight.

This polymerizable composition was injected into a glass mold for lenses, heated at a temperature of 60°C for 2 hours, heated to a temperature of 65°C for 5 hours, and then heated to a temperature of 80°C.
C. for 3 hours and then at 100.degree. C. for 2 hours to complete the reaction and polymerization, yielding an almost colorless and strong resin lens. 1.7 in the resin forming this resin lens
- The content of the naphthalene diol component was 9.88% by weight. The refractive index of this lens was measured using an Atsube refractometer and was found to be n = 1.615. Further, the specific gravity was 1.38.

Thus, this resin lens has a high refractive index and a low specific gravity.

Claims (1)

[Scope of Claims] 1) A high refractive index product comprising a urethane resin made of a naphthalene polyol represented by the following general formula (I), and containing a component made of the naphthalene polyol in a proportion of 5% by weight or more. rate resin lens. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (n is an integer from 2 to 4) 2) (a) Naphthalene polyol represented by the following general formula (I) or at least 20% by weight of the following general formula A mixture of the naphthalene polyol represented by (I) and an active hydrogen compound containing two or more active hydrogens other than the naphthalene polyol; (b) a polyisocyanate compound; and (c) a radically polymerizable monomer. A method for producing a high refractive index resin lens, comprising the steps of reacting and polymerizing a polymerizable composition consisting of the following in a casting container. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (n is an integer of 2 to 4) 3) Claim 2, wherein the active hydrogen compound is a polyol having 2 to 4 hydroxyl groups Manufacturing method for high refractive index resin lenses.