JPS59166550A - Copolymer composition for optical material and production thereof - Google Patents

Abstract

PURPOSE:A composition that is obtained by adding a cryptand to a copolymer from diethylene glycol bis-allyl carbonate and a specific monomer, thus being able to form lenses of high refractive index, free from change in color tone and opacification. CONSTITUTION:A cryptand is added to a copolymer made from diethylene glycol bisallyl carbonate and a monomer which is copolymerizable with the carbonate and gives a copolymer of over 1.5 refractive index. The copolymerizable monomers are selected from vinyl carbazole, styrene or styrene derivatives. The copolymer is given by effecting copolymerization of the carbonate and the monomer in the presence of the cryptand and a polymerization initiator. The amount of the comonomer is 5-60, preferably 10-50wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a transparent and high refractive index copolymer composition for optical members and a method for producing the same.

In recent years, in addition to conventional glass, as a material for optical components,
Plastic is attracting attention. This is because plastic is lighter than inorganic glass.

The reason for this is that it has excellent impact resistance and workability. For example, sunglasses, eyeglass lenses, camera lenses, magnifying glasses, Fresnel lenses.

Plastics are already being used in place of inorganic glass in polarized lenses, optical fibers, and transparent plates for splash- and dust-proof masks.

There are mainly two types of plastics currently in practical use as materials for optical members. That is, they are polymethyl methacrylate (hereinafter abbreviated as PMMA) and diethylene glycol bisallyl carbonate (hereinafter abbreviated as carbonate). PMMA has good transparency,
In addition, it is superior in terms of productivity because it can be injection molded, but its surface hardness is significantly lower than that of inorganic glass, so it is easily scratched, and the distortion that occurs during molding causes optical problems. It is not suitable for use as a precision optical material. Carbonate has many advantages over PMMA in terms of surface hardness and optical homogeneity, and is also capable of precision polishing similar to inorganic glass, making it the most widely used plastic to replace inorganic glass. .

However, such plastics generally have a low refractive index (hereinafter abbreviated as nd) of around 1.5, and have the disadvantage that, for example, lenses must be thick and thick to have the same power as inorganic glass. The latent demand for thinner lenses from consumers has not yet been satisfied.

Recently, new polymers with high refractive index have been developed for plastics as lens materials (Japanese Patent Application Laid-Open No. 55-13
747, JP-A-56-166214, JP-A-57-2312, and British Patent No. 2,076,8
No. 36), their nd shows a high refractive index of 1.55 to 1.61, but they have the drawback of being brittle compared to carbonate, which is a problem in practical use.

Currently, carbonate is the best material for plastic lenses, and various copolymers of carbonate and other monomers whose polymers exhibit a high refractive index have been proposed to increase the refractive index. There is. For example, carbonate and diallyl isophthalate (JP-A-53-7787) are known, but they have the drawback of having a different color tone from carbonate homopolymers. On the other hand, a terpolymer made by adding another monomer as a third component to carbonate and diallyl phthalate or diallyl isophthalate (Japanese Patent Publication No. 57-42841, Japanese Patent Publication No. 57
-44686, JP-A-53-7790),
Alternatively, a terpolymer consisting of carbonate and another high refractive index monomer (JP-A-57-23901) has been disclosed as an improved polymer. However, the na of such a terpolymer is 1.507 to 1.548, and the objective of increasing the refractive index is not necessarily achieved.

On the other hand, carbonate and vinyl carbazole.

Copolymers with high refractive index monomers such as vinylnaphthalene or styrene can achieve a high refractive index, but are known to be opalescent and opaque, and do not satisfy the lens properties (Japanese Patent Publication No. 57-44686 (No. Publication).

Based on the recognition of the above-mentioned problems, the present inventor has developed a copolymer with a monomer that can be copolymerized with carbonate and forms a polymer having a refractive index of 1.5 or more, which causes color tone change, Alternatively, as a result of various studies and studies on copolymer compositions for optical members with a high refractive index that do not cause opalescence, we found that by incorporating a cryptand compound in the copolymer, carbonate homopolymer The present invention was completed based on the discovery that a copolymer composition for optical members having a high refractive index can be obtained without impairing the excellent properties of the copolymer composition.

The purpose of the present invention is to create a copolymer composition for optical members with a high refractive index without impairing the excellent physical properties of carbonate polymers such as transparency, impact resistance, weather resistance, chemical resistance, coating properties, and dyeing properties. It's about providing things. Another object of the present invention is to create a high-refractive-index optical material that makes it possible to use high-refractive-index monomers that do not cause color change or opalescence and are not suitable as materials for optical members in copolymers with carbonate. An object of the present invention is to provide a copolymer composition for parts. Furthermore, another object of the present invention is to provide a method for producing the copolymer for optical members.

The present invention provides for containing a cryptand compound in a copolymer made from diethylene glycol bisallyl carbonate and a monomer that can be copolymerized with the carbonate and forms a polymer having a refractive index of 1.5 or more. A copolymer composition for optical members, in which the monomer forming the polymer having a refractive index of 1.5 or more is at least one of vinylcarbazole, styrene, and styrene derivatives, and a method for producing the copolymer. .

The carbonate used in the present invention is not limited to only monomers, but may also contain low polymers such as dimers and trimers. The cryptand compound that causes opalescence in the copolymer with the carbonate, such as monomer tri-vinylcarbazole or styrene or styrene derivative, which forms a polymer with a refractive index of 1.5 or more that can be copolymerized with the carbonate. Although the effect caused by its inclusion is significant, it is not limited to these. For example, phenyl methacrylate, diphenyl methacrylate), P-7'' romophenyl methacrylate, 〇-chlorodiphenyl methacrylate,
Pentachlorophenyl methacrylate, pentabromophenyl methacrylate, phenyl α-bromoacrylate, β-naphthyl methacrylate, p-iodostyrene methacrylate, diallylphthale F, diallyl isophthalate, diallyltetrachloroisophthalate, diallytetrabromoisophthalate, diallyl maleate ,
Triallyl cyanurate, )'l allyl isocyanurate, vinylnaphthalene, etc. may also be used.

Also, as styrene derivatives, 0-methoxystyrene, P-methoxystyrene, Ollorostyrene, 2.6-
Examples include dichlorostyrene. Such monomers are 2
It is also possible to use more than one species in combination.

The cryptand compound contained in the copolymer is known in organic chemistry as a compound exhibiting a guest-host phenomenon, and examples thereof include the following. Such cryptand compounds are commercially available from Merck & Co., USA under the trade name "Cryptofix".

The method for producing a polymer for optical members according to the present invention includes carbonate, one or more monomers that can be copolymerized with the carbonate and form a polymer having a refractive index of 1.5 or more, and cryptand. This is carried out by mixing and dissolving the compound and polymerization initiator, injecting the mixture into a mold made of, for example, a glass mold and a gasket, and curing using methods such as heating or ultraviolet irradiation. In this case, the amount of monomer that can be copolymerized with carbonate is:
Although not particularly limited since it varies depending on the desired refractive index of the copolymer, it is 5 to 60% by weight, preferably 10 to 50% by weight.

If the amount of the monomer used is less than 5% by weight, it will be difficult to increase the refractive index of the copolymer, and if it is more than 60%, the impact resistance and surface hardness will decrease, and the object of the present invention will not be achieved. .

The cryptand compound is added in an amount of 0.01 to 30% by weight, preferably 0.1 to 20% by weight, to the mixture of carbonate and a monomer capable of copolymerization (10), but depending on the composition of the monomer mixture, It is appropriately selected from within the above range depending on the composition ratio. It is preferable to add the cryptand compound to the carbonate in advance and dissolve it, and at this time, dissolution may be promoted by heating.

As a polymerization initiator, metal sodium, metal potassium,
Anionic polymerization initiators such as metallic lithium, cationic polymerization initiators such as anhydrous aluminum chloride, sulfuric chloride, titanium chloride, and boron trifluoride, and organic sensitizers such as hydrogen peroxide, benzoyl peroxide, and diisopropyl peroxydicarbonate. , azoisobutyronitrile, etc., are used in an amount of 0.1 to 10% by weight based on the mixture of monomers.

The polymerization temperature and time depend on the composition of the monomer mixture used,
Although it cannot be specified uniformly because it varies depending on the reactivity and the type and amount of polymerization initiator, it can be applied at approximately 5 to 100°C for 1 to 10 hours.
Preferably, the polymerization (11) is completed in 0 hours.

Also, photopolymerization catalysts such as benzoin, 2-methylbenzoin, benzoin methyl ether.

Benzoin propyl ether, acetoin.

Butyroin, toluoin, benzylbenzophenone, and tetramethylthiuram sulfide can be mixed in a weight ratio of 0.01 to 10 and then multiplexed by irradiation with an ultraviolet lamp, a mercury lamp, or the like. In this case, the above-mentioned polymerization initiator may be used in combination.

Such a copolymer for optical members according to the present invention has conventionally been
Significant coloration of known polymers for high refractive index lenses,
It improves the decrease in transmittance due to clouding, etc., and has the same characteristics as carbonate homopolymer in terms of impact resistance, surface hardness, and coating properties.Compared to conventional plastic lenses (nd = 1.5) Because it is thin and lightweight, it is used as an optical component, including eyeglass lenses.
The scope of use can be expanded to include camera lenses, magnifying glasses, Fresnel lenses, polarized lenses, and other various lenses and optical elements.

(12) The present invention will be explained in more detail below with reference to Examples, but these are merely examples of embodiments of the present invention, and it goes without saying that these do not limit the present invention. In addition, in the example,
Parts are parts by weight.

Example 1 To 80 parts of diethylene glycol bisallyl carbonate (Asahi Glass Co., Ltd. product), 0.2 part of a cryptand compound represented by the following structural formula ('Cryptofixna 5'': Merck Co., Ltd. product) was added and heated to 50°C. Then, 20 parts of N-vinylcarbazole was added and dissolved,
Furthermore, 1 or 2 parts of benzoyl peroxide was added, poured into a lens mold consisting of a glass mold and a gasket, and heated at 75°C.
The mixture was kept in a hot air oven for 25 hours for copolymerization. After cooling, remove the lens from the mold and insert a transparent plastic lens (1
3) Obtained. The transmittance of the obtained plastic lens was 91
% (550nm), no turbidity or striae, which are undesirable for a lens, were observed, the refractive index was measured with an Atsube refractometer, and it was nd = 1.581, and the surface hardness was J Engineering S (K 5400). It had a pencil hardness H according to the standard, and was excellent in many performances required as an optical lens.

Example 2 To 80 parts of diethylene glycol bisallyl carbonate (Asahi Glass Co., Ltd. product), 0.5 part of a cryptand compound represented by the following structural formula (1 Cryptofix + 23": Merck Co., Ltd. product) was added, and the mixture was heated to about 60°C. Dissolve while
Next, 50 parts of N-vinylcarbazole was added and dissolved,
Furthermore, 8 parts of diisopropyl peroxy (14) carbonate was added, poured into a lens mold consisting of a glass mold and a gasket, and placed in a hot air oven at 40°C for 5 minutes.
The mixture was maintained at 60°C for 6 hours and at 80°C for 15 hours for copolymerization. After cooling, the lens was taken out from the mold to obtain a transparent plastic lens. The obtained plastic lens had a transmittance of 90 cm (55' Onm), no clouding spots or striae, and a refractive index of n as measured by an Atsube refractometer.
♂'=1.611, the surface hardness was HB, and the performance as an optical lens was excellent.

Example 3 0.3 part of the same cryptand compound as in Example 1 was added to 80 parts of diethylene glycol bisallyl carbonate (Asahi Glass Co., Ltd. product) and dissolved while heating to 50°C, and then 20 parts of styrene and diisopropyl peroxide were added. 8
1, and copolymerized in the same manner as in Example 2 to obtain a plastic lens. The obtained plastic lens had a transmittance of 91%, a refractive index of 1.523, and a lead (15) flower hardness of H, and had excellent performance as an optical lens.

Example 4 A plastic lens was obtained by copolymerizing in the same manner as in Example 3 except that styrene was changed to 0-chlorostyrene. The obtained plastic lens had a transmittance of 90%, a refractive index of 1.527, and a lead hardness of ■, and its performance as an optical lens was excellent.

Comparative Examples 1 to 4 Plastic lenses were obtained by copolymerization in the same manner as in Examples 1 to 4, except that the cryptand compound was not added. The performance of the obtained plastic lens is shown in Table 1, and it was completely unsuitable for use as an optical lens.

(16) (17)

Claims (3)

[Claims] (1) Diethylene glycol bisallyl carbonate, which can be copolymerized with the carbonate, and has a refractive index of 1.
A copolymer composition for an optical member, characterized in that a copolymer comprising five or more polymer-forming monomers contains a cryptand compound. (2) The copolymer composition according to claim 1, wherein the monomer forming the polymer having a refractive index of 1.5 or more is at least one of vinylcarbazole, styrene, and styrene derivatives. thing. (3) Diethylene glycol bisallyl carbonate, which can be copolymerized with the carbonate and has a refractive index of 1
．． 1. A method for producing a copolymer for optical members, comprising copolymerizing a monomer forming a polymer of 5 or more and a cryptand compound.