JPH02232601A - Lens material consisting of high-refractive index resin - Google Patents

Abstract

PURPOSE:To obtain the material having a high refractive index and small sp. gr. by forming the material of a copolymer formed by polymerizing 10 to 80wt.% styrene deriv. and 20 to 90wt.% copolymerizable monomer copolymerizable with the styrene deriv. CONSTITUTION:This material consists of the copolymer obtd. by copolymerizing 10 to 80wt.% styrene deriv. expressed by formula I or formula II and 20 to 90wt.% copolymerizable monomer copolymerizable with the styrene deriv.. (In the formulas, X and Y denote halogen atoms exclusive of a fluorine atom, methoxy group or methylthio group; p and q denote 0 to 5 integer; n denotes 1 to 3 integer). Di-substitution product or tri-substitution product with which the value of the number n of the substitution atomic group having one or two arom. rings is 2 or 3 is also useful as the styrene deriv.. The material having the small sp. gr. while having the high refractive index is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a high refractive index resin lens material, and more particularly to a high refractive index resin lens material having a high refractive index and a low specific gravity.

[Conventional technology]

Generally, spectacle lenses and contact lenses are used for vision correction, but among these, spectacle lenses are lightweight, easy to process, and inorganic glass lenses.
Lenses made of synthetic resin are widely used because they have useful advantages such as stability and dyeability.

Such resin lenses are required to have various properties, among which a high refractive index and low light dispersion are fundamentally important.

In particular, by using a resin lens material with a high refractive index, it is not only easy to design a lens with the required characteristics, but also the thickness of the peripheral edge of the lens (so-called edge thickness) can be substantially reduced. This is extremely preferable since weight reduction is also achieved at the same time.

Currently, the most popular resin material for eyeglass lenses is polydiethylene glycol bisallyl carbonate. However, this lens material has a low refractive index (nf > 1 at a temperature of 20°C).
, around 50.

Under these circumstances, research on polymers or copolymers suitable as high refractive index resin lens materials has been conducted in many fields, and some of them are being put into practical use. A typical example is a dimethacrylate or diacrylate copolymer in which a halogen-substituted aromatic ring is bonded to a methacroyloxy group or an acroyloxy group via an alwylene glycol group, as disclosed in Japanese Patent Publication No. 5g-14449. Polymers have been proposed.

However, in order to achieve a high refractive index, conventionally known polymers used as resin lens materials are said to contain a large amount of bromine atoms (mainly bromine atoms). The specific gravity of the polymer becomes considerably large, and as a result, the light weight, which is the greatest feature of resin lens materials, is lost, and in the end, the advantage of a high refractive index is greatly diminished.

[Problem to be solved by the invention]

The present invention was made based on the above circumstances, and an object of the present invention is to provide a high refractive index resin lens material that has a high refractive index and a low specific gravity.

[Means to solve problems]

The high refractive index resin lens material of the present invention has the following structural formula (I
) or styrene derivative 10 represented by structural formula (II)
It is characterized by consisting of a copolymer obtained by polymerizing ~80% by weight and 20~90% by weight of a copolymerizable monomer copolymerizable with the styrene derivative.

Structural formula (I) Structural formula (n) <<In each formula, X and Y represent a 7% rogen atom other than a fluorine atom, a methoxy group, or a methylthio group, and p and q
represents an integer of 0 to 5, and n represents an integer of 1 to 3. >> The present invention will be specifically explained below.

In the present invention, the above structural formula (I) or structural formula (n
) and a copolymerizable monomer copolymerizable with the styrene derivative are polymerized in a specific range of ratios, and the resulting copolymer is used as a resin lens material.

The method for obtaining the above-mentioned specific styrene derivatives is not particularly limited, but generally uses relatively inexpensive black-mouth methylstyrene and a phenol derivative, and involves dehydrochlorination or dechlorination. The styrene derivative can advantageously be produced by a coupling reaction. Chloromethylstyrene, which is used as a raw material in this method, has three types of isomers; among these, the meta and para isomers are easily available, but of course the ortho isomer may also be used, and a single isomer is also available. It may consist of isomers or a mixture of each isomer.

The styrene derivative used in the present invention has the above structural formula (I
) and structural formula (II), it is a compound in which 1 to 3 hydrogen atoms excluding aromatic atoms in the styrene molecule are substituted with a substituent atomic group having 1 or 2 aromatic rings; One or two members of the substituent group can support substituents X and/or Y.

The substituents X and Y in the aromatic ring of the substituted atomic group of this styrene derivative are halogen atoms other than fluorine atoms, that is, halogen atoms such as chlorine atom, bromine atom, or iodine atom, or methoxy group (-0 C H3) or methylthio group (- S C Hs). The numbers p and q of these substituents are assumed to be integers from O to 5, but if the substituent is a halogen atom and the styrene derivative has a large number, the resulting copolymer will have a higher refractive index. Become something. However, since the specific gravity increases at the same time, the values of p and q may be appropriately selected depending on the intended use of the lens finally obtained. In particular, styrene derivatives having a p value of 1 to 3 are preferred because the resulting copolymer has a good balance between refractive index and specific gravity.

Furthermore, as styrene derivatives, disubstituted or trisubstituted compounds in which the number n of substituent atomic groups having one or two aromatic rings is 2 or 3 are also useful in the present invention.

Specific examples of the styrene derivative represented by structural formula (I) include 0-phenoxymethylstyrene, m-phenoxymethylstyrene, p-phenoxymethylstyrene,
3.4-diphenoxymethylstyrene, O-(2,4.
6-}ribromophenoxymethyl)styrene, m~(2
, 4. 6-tribromophenoxymethyl) styrene, p-(2.4.6- } IJbromophenoxymethyl) styrene, 3.4-di(2.4.6-tribromophenoxymethyl) styrene , m-(2-methylthiophenoxymethyl)styrene, p-(2-methoxyphenoxymethyl)styrene, and the like.

Specific examples of the styrene derivative represented by the structural formula (Il) include m-(4-phenylphenoxymethyl)styrene, p-(4-7phenylphenoxymethyl)styrene, 3,4-di( 4-7phenylphenoxymethyl)styrene, m-(2-phenylphenoxymethyl)styrene, p-(2-phenylphenoxymethyl)styrene, 3
．． 4-di<2-phenylphenoxymethyl>styrene,
m-(4-(4-promophenyl)phenoxymethyl]
Styrene, p-(4-(4-promophenyl)phenoxymethyl)styrene, rn-(2-phenyl-4-bromophenoxymethyl)styrene, p-(2-phenyl-4-bromophenoxymethyl)styrene, etc. be able to.

The styrene derivatives used in the present invention are not limited to those exemplified above.

Moreover, not only one type of styrene derivative but two or more types can also be used.

The above styrene derivative is copolymerized with a copolymerizable monomer that can be copolymerized with the styrene derivative.

By appropriately selecting the type and proportion of this copolymerizable monomer, it is possible to obtain a copolymer having various performances required for lenses.

However, in order to make the copolymer that will be criticized have a sufficiently high refractive index, the copolymerizable monomer must have a high refractive index with nW of 1.53 or more when polymerized alone. It is preferable to use one or more monomeric compounds that give a polymer having the following properties.

Specific examples of the above-mentioned copolymerizable monomer include the following.

(I) Alkyl (meth)acrylates such as methyl acrylate, methyl methacrylate, naphthyl acrylate, naphthyl methacrylate, phenyl acrylate, phenyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, ethylene Glycol dimethacrylate, tribromophenyl acrylate, tribromophenyl methacrylate,
2.2-bis-(4-methacryloxyethoxy-3.5
-dibromophenyl)propane, 2,2-bis-(4-
Methacryloxy-3,5-dibromophenyl)propane, 2,2-bis(4-acryloxy-3t5-dibromophenyl)propane, 2,2-bis-(4-methacryloxyphenyl)propane, 2,2-bis -(4-acryloxyethoxyphenyl)propane, others.

(2) Aromatic vinyl compounds such as styrene, α-methylstyrene, divinylbenzene, vinylnaphthalene, m-diisopropenylbenzene, 2-imbrobenylnaphthalene, and others.

(3) Allyl compounds such as triallyl isocyanurate, diallyl phthalate, and others.

The above-mentioned monomers are examples of monomers used as copolymerizable monomers in the present invention, and the present invention is not limited thereto.

It is also extremely useful to use these copolymerizable monomers singly or in combination of two or more. Since the styrene derivative used in the present invention is a compound having only one polymerizable ethylenically unsaturated bond in its molecule, the copolymerizable monomer is a polymerizable ethylenically unsaturated bond. When a polyfunctional monomer having two or more saturated bonds is used, a three-dimensional network structure is formed because the polyfunctional monomer acts as a so-called crosslinking agent, and the resulting copolymer has excellent solvent resistance. Becomes excellent in sex.

According to the present invention, the styrene derivative is used in an amount ranging from 10 to 80% by weight based on the total monomers used in the polymerization reaction. If the proportion of this styrene derivative is less than 10% by weight, the resulting copolymer will not have a sufficiently high refractive index. Furthermore, if this proportion exceeds 80% by weight, the resulting copolymer will have poor solvent resistance. Since the above-mentioned styrene derivative is often solid, considering the ease of polymerization reaction, its usage ratio is 13 to 75% by weight of the total monomer.
It is particularly preferable that

On the other hand, the proportion of the copolymerizable monomer copolymerized with the above styrene derivative is 20 to 90% by weight, particularly preferably 25% by weight, depending on the type of monomer actually used and the properties required of the resulting copolymer. -87% by weight.

The above-mentioned styrene derivative and copolymerizable monomer can be polymerized using a common radical polymerization initiator. The polymerization method may be one used in ordinary radical polymerization reactions. However, if the copolymerizable monomer is a polyfunctional monomer, the resulting copolymer will have a crosslinked structure, so it is practically impossible to process it by melting or dissolving it. It is possible. Therefore, in this case, the cast polymerization method (
It is generally preferred to utilize a cast polymerization method.

In the case of the cast polymerization method, molds or molds made of glass, plastic, metal, etc., are plate-shaped, lens-shaped, cylindrical, prismatic, conical, spherical, or otherwise designed according to the purpose. A monomer mixture of the above styrene derivative and copolymerizable monomer in a predetermined ratio is mixed and injected into the mold along with a radical polymerization initiator and various additives added as necessary. By raising the temperature and polymerizing this, a molded product made of the desired copolymer can be obtained. Alternatively, cast polymerization can be performed by performing a certain degree of polymerization of the monomer mixture using a separate container, and then injecting the resulting brevolimer or syrup into a mold to complete the polymerization.

In the above, the monomer mixture and the polymerization initiator may be mixed in their entire amounts at once, or may be added to the reaction system in stages.

The additives used include colorants, ultraviolet absorbers, antioxidants, heat stabilizers, and others.

The resulting copolymer is heated to complete any incomplete polymerization or to improve its hardness, or annealed to remove distortion caused by cast polymerization. Needless to say, processing can be performed.

The molded copolymer obtained as described above can be provided as the desired resin lens as it is, but it is also possible to obtain the desired resin lens by further cutting and polishing the copolymer. Can be done. Furthermore, if necessary, dyeing, surface polishing, and antistatic treatment are applied to the molded product or copolymer to further improve the various properties required as a lens, and to increase the surface hardness. Of course, it is also possible to perform secondary processing such as an inorganic or organic hard coat or a non-reflective coat that is commonly applied to optical materials.

〔effect〕

As described above, the high refractive index resin lens material of the present invention comprises a specific styrene derivative represented by the structural formula (I) or the structural formula (■), and a copolymerizable monomer copolymerizable with the styrene derivative. Since it is made of a copolymer obtained by polymerizing and in a specific ratio, it has a high refractive index and a low specific gravity, as will be clear from the description of the examples below.

〔Example〕

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

Example 1 30 parts by weight of p-(4-phenylphenoxymethyl)styrene represented by the following structural formula, 60 parts by weight of styrene, and 10 parts by weight of divinylbenzene were mixed and dissolved, and this monomer mixture was polymerized. A mixture containing 1.0 parts by weight of lauroyl peroxide as an initiator was poured into a mold made of glass, and the reaction temperature was varied at 60°C for 15 hours, at 80°C for 2 hours, and at 100°C for 1 hour. Polymerization is carried out, whereby a center thickness of the copolymer of 1,5 a+m, -t. oo
I made a geobutter lens. This lens was almost colorless and had good transparency.

This lens was completely insoluble in common organic solvents such as methanol, ethanol, acetone, and toluene, and was recognized to have a sufficient crosslinked structure.

The refractive index and Abpe number at 20°C of the copolymer of this lens were measured using an Appe refractometer, and the specific gravity was measured using an automatic hydrometer "Densimeter D-SJ (manufactured by Toyo Seiki Q@).The results are as follows. It is as follows.

Refractive index: 1.613 Abpe's number: 29.4 Specific gravity: 1.08 From the above, it is clear that this resin lens material has a high refractive index and a very small specific gravity.

Comparative Example 1 2.2-bis(4-methacryloxyethoxy-3,5-
30 parts by weight of dibromophenyl)broban and 6 parts of styrene.
A lens was produced by polymerization in the same manner as in Example 1, except that a monomer mixture consisting of 0 parts by weight and 10 parts by weight of divinylbenzene was used.

The same measurements as in Example 1 were performed on the copolymer of this lens. The results are as follows.

Refractive index Abpe number ratio Gravity Example 2 Structural formula below 1. 596 30.2 1.21 50 parts by weight of p-(2.4.6-tribromophenoxymethyl)styrene, 40 parts by weight of styrene, and 10 parts by weight of divinylbenzene were mixed, and this monomer was mixed. A polymer mixture containing 1.0 parts by weight of lauroyl peroxide as a polymerization initiator was poured into a mold made of glass, and heated at 50°C for 2 hours and at 60°C for 15 hours.
Polymerization was carried out by changing the reaction temperature to 80° C. for 2 hours and 100° C. for 1 hour, thereby producing a copolymer lens having a center thickness of 1.5+ nm and −3.00 diopter. This lens was almost colorless and had good transparency.

This lens was completely insoluble in common organic solvents such as methanol, ethanol, acetone, and toluene, and was recognized to have a sufficient crosslinked structure.

The same measurements as in Example 1 were performed on the copolymer of this lens. The results are as follows.

Refractive index 1.619 Abpe number 30.6 Specific gravity 1.33 Comparative example 2 Methacryloxy-
2.4.6-}A monomer mixture having the same composition as in Example 2 was obtained, except that 50 parts by weight of ribromobenzene was used, and polymerization was carried out in the same manner as in Example 1, except that this was used. A lens was created.

The same measurements as in Example 1 were performed on the copolymer of this lens. The results are as follows.

Refractive index 1. 609 Heat Number 30.0 Specific Gravity 1.43 Example 3 m-(4-methylthiophenoxymethyl)styrene shown by the following structural formula and m-(4-methylthiophenoxymethyl)styrene shown by the following structural formula were mixed at a weight ratio of 3=7. 23.3 parts by weight of a mixed monomer consisting of 30 MMB of 2,2-bis(4-methacryloythethiophenyl)propane, 36.7 parts by weight of α-methylstyrene, and 10 parts by weight of divinylbenzene.
parts by weight, and polymerization was carried out in the same manner as in Example 1 except that this monomer mixture was used to obtain a center thickness of 1.5a+a+
, -2.00 diopter lenses were prepared. This lens was almost colorless and had good transparency.

This lens was completely insoluble in common organic solvents such as methanol, ethanol, acetone, and toluene, and was recognized to have a sufficient crosslinked structure.

The same measurements as in Example 1 were performed on the copolymer of this lens. The result is the following tofuri.

Refractive index: 1.594 Afbe number: 34.2 Specific gravity: 1.07 Example 4 p-(2-phenyl-4-promophenoxymethyl) represented by the following structural formula 40 parts by weight of styrene, 20 parts by weight of α-methylstyrene, 25 parts by weight of diallylphthalate, and 15 parts by weight of divinylbenzene are uniformly mixed, and impropenyl peroxydicarbonate is added to this monomer mixture as a polymerization initiator. 0.5 parts by weight and 0.5 parts by weight of lauroyl peroxide were poured into a mold made of glass, and heated at 50°C for 5 hours, at 60°C for 17 hours, at 80°C for 2 hours, and at 100°C. Polymerization was carried out for 1 hour and at varying reaction temperatures to give a center thickness of I.5+nm, -2.50
A diopter lens was made. This lens was almost colorless and had good transparency.

This lens was completely insoluble in common organic solvents such as methanol, ethanol, acetone, and toluene, and was recognized to have a sufficient crosslinked structure.

The same measurements as in Example 1 were performed on the copolymer of this lens. The results are as follows.

Refractive index 1.615 Appe number 30.2 Ratio Weight 1.24

Claims (1)

[Claims] 1) 10 to 80% by weight of a styrene derivative represented by the following structural formula (I) or (II) and 20 to 90% by weight of a copolymerizable monomer copolymerizable with the styrene derivative. %
A high refractive index resin lens material comprising a copolymer obtained by polymerizing. Structural formula (I) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ Structural formula (II) ▲ Contains numerical formulas, chemical formulas, tables, etc. ▼ (In each formula, X and Y are halogen atoms other than fluorine atoms, methoxy groups, or methylthio p and q are integers of 0 to 5, and n is an integer of 1 to 3.) 2) The styrene derivative has the structural formula (I) or the structural formula (
The high refractive index resin lens material according to claim 1, which is a compound having a p value of 1 to 3 in II).