JPS61296301A - Lens material - Google Patents

Abstract

PURPOSE:To improve a non-color characteristic, transparency and solvent resistance by consisting a titled material of a specific monomer, crosslinking agent monomer copolymerizable with said monomer and ethylenic unsatd. monomer. CONSTITUTION:This material is constituted of 20-97wt% the monomer (I) expressed by the formula (1), 0-40wt% crosslinking agent monomer (II) having >=2 functional groups copolymerizable with said monomer and 0-40wt% ethylenic unsatd. monomer (III) copolymerizable with said monomers [where the compsn. of the copolymer is based on the total weight of the monomers (I)-(III).] The crosslinking agent monomer (II) is exemplified by multifunctional methacrylate and multifunctional acrylate, more specifically mono- and diethylene glycol di(meth)acrylate, etc. The monomer (III) is exemplified by (meth)acryloxyethoxy-2,4,6-tribromobenzene, etc. The lens material having the excellent non-color characteristic, transparency and solvent resistance and the extremely good balance is thus obtd.

Description

BACKGROUND OF THE INVENTION TECHNICAL FIELD The present invention relates to lens materials. More specifically, the present invention provides a copolymer with a refractive index of 7.60 comprising an acrylic or methacrylic acid amide of a halogen-substituted aniline derivative and a crosslinking agent having two or more functional groups as essential components.
The above is related to lens materials having an Abbe number of 27 or more.

Conventionally, various inorganic glass lenses have been used in optical equipment, but synthetic resin lenses are preferred due to their light weight, processability, stability, dyeability, mass productivity, and low cost. It is beginning to be widely used.

Among the various physical properties required of a lens, high refractive index and low dispersion are extremely important. Having a high refractive index means, for example, a microscope, a camera,
This has the advantage of not only making the lens system, which occupies an important position in optical instruments such as telescopes and spectacle lenses, compact and lightweight, but also suppressing aberrations such as one spherical surface.

On the other hand, it goes without saying that low dispersion is extremely important in terms of reducing chromatic aberration.

However, in general, even in synthetic resin lenses, high refractive index lenses tend to have high dispersion, and low refractive index lenses tend to have low dispersion, similar to inorganic glass lenses.

For example, diethylene glycol bisallyl carbonate resin (hereinafter referred to as CR-39) is currently the most popular lens material for synthetic resin lenses for eyeglasses.
Although R-39 has a high Atsbe number of C 60 (that is, low dispersion), its refractive index is nD=i,t.

This is extremely low. Polymethyl methacrylate, which is partially used as a lens material, has a high Atsube number of ν=bo, similar to CR-39, but its refractive index is nD=/,
! 9 is low. Polystyrene (nD=l, tde, ν=3o, q) and polycarbonate (n2°=/, tata, ν=kode, ri), which are said to have relatively high refractive index and low dispersion.
is unsatisfactory in other physical properties required as a lens material. For example, polystyrene lacks surface hardness and solvent resistance, and polycarbonate lacks surface hardness and impact resistance.

Furthermore, polycarbonate is improved as a synthetic resin lens with a high refractive index and low dispersion (Japanese Patent Application Laid-Open No. 1983-Zari 7!).
λ Publication) and aromatic polyester (Japanese Unexamined Patent Publication No. 1987-1-71)
013,3) has also been proposed, but as far as the present inventors know, it is still not satisfactory in terms of the other physical properties mentioned above. Polynaphthyl methacrylate, which has a high refractive index (
nD = /, A4C) and polyvinylnaphthalene (n
D=/, t, g) have low Abbe numbers of ν=2 and ν=J, respectively, and there are many problems with each material.

Recently, high refractive index copolymers containing halogen-substituted aromatic acrylic esters or methacrylic esters as components have been known (JP-A-53-77gg, JP-A-33-77t). No., JP-A No. 1973-1/2/G), these copolymers do not mention the Atsube number,
The chemicals used are also limited to chlorine and bromine.

For this reason, there has been a demand for synthetic resin lenses with a well-balanced refractive index, Abbe's number, solvent resistance, etc.

Summary The present invention aims to solve the above-mentioned problems, and attempts to achieve this object by using a crosslinked coelectric material of acrylic acid amide or methacrylic acid amide of halogen-substituted aniline.

That is, the lens material according to the present invention having a refractive index nD = /, AO or more and an Atsubbe number ν = 27 or more contains 27 to 97% by weight of monomer (I) represented by the following formula (1), and copolymerized therewith. Possible crosslinker monomers with one or more functional groups (II
) and 3 to 60% by weight of an ethylenically unsaturated monomer (I[)o-1io copolymerizable with these (however, copolymerizable The composition of the combination is based on the total amount of monomers (I) to (I). In the present invention, by using acrylic acid amide or methacrylic acid amide of halogen-substituted aniline as a monomer of the polymer for lens materials, this polymer has an extremely high refractive index of nD=/, 60 or more, and is also heat-resistant. The number is also relatively low dispersion with ν = richness or more, and it is colorless.
It is an extremely well-balanced lens material with excellent transparency and solvent resistance, and it solves the problems of the conventional lens materials described above.

It was first discovered by the present inventors that the copolymer of the present invention has such excellent properties as a lens material. This property indicates that this copolymer has the formula (1)
This is thought to be caused by the fact that it is a monomer and a copolymer with a crosslinking agent.

DETAILED DESCRIPTION OF THE INVENTION Copolymer The copolymer constituting the synthetic resin lens material of the present invention consists of specific copolymer components.

The lens material of the present invention is characterized by the use of a copolymer containing acrylic acid amide or methacrylic acid amide represented by the following formula (1) as a component.

(In the formula, X is H, CH3Y is C1, Br or I, and m is an integer from / to j) These acrylamides or methacrylic amides disclosed in the present invention are free from halogen by containing halogen. It is possible for the resulting polymer to have both a higher refractive index and a relatively high Akbe number compared to the substituted product. Generally speaking, in the order of C1, Br, and I, and the higher the content, the higher the refractive index of the produced polymer, but the higher the halogen content, the higher the melting point. ) When synthesizing acrylic acid amide or methacrylic acid amide, there are drawbacks such as the lack of a good solvent for halogen-substituted aniline. Therefore, the value of m indicating the number of halogens is preferably 1 to 3.

Of course, even if m is 0, the produced polymer has a high melting point, but it can be used depending on the purpose and is within the scope of the present invention. Note that the plurality of halogens when m is greater than or equal to 0 do not have to be the same.

An amide bond produces a higher refractive index than a general ester bond, and therefore, in this respect, monomer (I) has a higher refractive index than a halogen-substituted phenol acrylic ester or methacrylic ester. It gives a high refractive index.

As the monomer (I) represented by formula (1), for example, 0
-Iodophenyl (meth)acrylamide, m+iodophenyl (meth)acrylamide, p-iodophenyl (meth)acrylamide, Ko, Hiroshi, 6-dryodophenyl (meth)acrylamide, p-promophenyl/L/
(meth)acrylamide, O-promophenyl (meth)
Acrylamide, m-promophenyl (meth)acrylamide, 2.4t.

A-) Libromophenyl (meth)acrylamide, 0-
Chlorophenyl (meth)acrylamide, m-chlorophenylacrylamide, p-chlorophenyl (meth)acrylamide 1.1,4t, A-trichlorophenyl (
meth)acrylamide, 3-dichlorophenyl(meth)acrylamide, λ.

Examples include dacibromophenyl (meth)acrylamide. Of course, it is not limited to these. In addition, (meth)acrylamide here means either acrylamide or methacrylamide.

These can be used alone or in combination.

By using the above monomer (I) as a component of the copolymer,
A copolymer with a high refractive index and low dispersion can be obtained. However, a homopolymer containing only monomer (I) is unsuitable as a lens material.

This is because a homopolymer of only this monomer is relatively easily attacked by organic solvents and lacks solvent resistance.

In the present invention, in order to increase the solvent resistance, heat resistance, and surface hardness of the homopolymer of monomer (I) of formula (1), two or more functional groups copolymerizable with the homopolymer A three-dimensional crosslinked structure is formed by introducing a specific amount of a crosslinking monomer (If) having the following.

Specific examples of the crosslinking monomer (If) include polyfunctional methacrylic ester and polyfunctional acrylic ester crosslinking monomers. Specific examples of these include mono- and diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate,
(meth)acrylic acid esters of aliphatic polyhydric alcohols such as trimethylolpropane tri- or di(meth)acrylate; di(meth)acrylic acid esters of various aromatic polyhydric alcohols such as catechol, resorcinol, hydroquinone, and various dihydroxynaphthalenes; There are acid esters, etc.

As another example of the crosslinking monomer, aromatic divinyl compounds represented by divinylbenzene are also suitable. but,
Particularly when a high refractive index is desired, the aromatic divinyl compound preferably has a norogen-substituted aromatic ring. Examples of the bifunctional crosslinking agent having a -rogen-substituted aromatic ring include co,corbis(4=-(meth)acryloxyethoxy-3,!-dihalophenyl)propane, co,corbis[ter(meth)acryloxy poly(dyltetra)ethoxy)-3,r-dihalophenyl]furopane, cot-biscq-cmeta)acryloxy-1
3゜5-dihalophenyl]propa7,! , 2-bis[dararyloxy S, S-dihalophenyl]propane, 2-bis[! -(meth)acryloxypropoxy-3
, r-dihalophenyl]furopane, 1,2,2-bis[cou(meth)acryloxypoly(dyltetra)propoxy-3,j-dihalophenyl]furopane, and mixtures thereof. These halogen-containing crosslinking monomers may be used alone or in combination, and since they all have a high refractive index, a crosslinked copolymer can be produced without lowering the refractive index of the copolymer.

The ratio of monomer (1) to monomer (II) is
) is in the range of 97% by weight of monomer (I)J and 60% by weight of monomer (I[)j, based on the total amount of monomer (I)J. If monomer (I) is less than this range, a lens material with high refractive index/low dispersion cannot be obtained, whereas if it is more than this range, the resulting copolymer will have poor solvent resistance. .

Monomer (3) The copolymer according to the present invention preferably contains a small amount of the above-mentioned two monomers (both in SO weight %).However, as long as the purpose of the present invention is not unduly hindered, this copolymer is an ethylenically unsaturated monomer (i) that can be copolymerized with these two monomers.
) may be further copolymerized. The amount of ethylenically unsaturated monomer is preferably such that it accounts for o-'m% by weight of the copolymer, preferably from 0 to 30% by weight.

Specific examples of the monomer (3) include (meth)acryloxyethoxy-! , Hiroshi, A-) Ribromobenzene, (meth)acryloxypoly(di-tet:y degree) ethoxyl, 5-meth(acrylate) such as q,6-dribromobenzene, methyl methacrylate, naphthyl methacrylate, naphthyl acrylate Examples include various alkyl (meth)acrylates such as styrene, various aromatic vinyl compounds such as α-methylstyrene, and the like. The amount (and type) of such comonomers should be selected within a range that does not excessively impair the high refractive index, low dispersion, transparency, and solvent resistance that are the characteristics of the copolymer of the present invention. Should.

Polymerization The polymerization of the above-mentioned multimonomers proceeds with a conventional radical polymerization initiator. The polymerization method may also be one commonly used for normal radical polymerization. However, since the resulting copolymer is crosslinked and treatment involving melting or dissolution is virtually impossible, cast polymerization is generally preferred from the viewpoint of use in plastic lenses.

Cast polymerization is a well-known technique. Note: As the polymerization container, plate-shaped, lens-shaped, cylindrical, prismatic, conical, spherical, or other molds or molds designed according to the purpose are used. The material may be any suitable material such as inorganic glass, plastic, or metal. Polymerization can be carried out by heating a mixture of monomers and a polymerization initiator charged in such a container as necessary, or by pre-polymerization obtained by carrying out a certain degree of polymerization in a separate container. The polymerization can also be carried out by charging the polymer or syrup into a polymerization container to complete the polymerization.

The required monomers and polymerization initiator may be mixed in their entire amounts at once, or may be mixed in stages. In addition, this mixture may contain antistatic agents,
It may also contain colorants, fillers, ultraviolet absorbers, heat stabilizers, antioxidants and other auxiliary materials.

Another specific example of the polymerization method of the present invention is a method in which a mixture of required monomers and a polymerization initiator or a prepolymer is suspended in water to carry out polymerization, that is, suspension polymerization. This method is suitable for obtaining spherical lenses of various particle sizes. The suspension polymerization method is also a well-known technique, and the present invention may be appropriately carried out according to well-known knowledge.

The resulting copolymer is heated to complete any polymerization that may or may not have been completed or to increase its hardness.
Alternatively, it goes without saying that post-treatments such as annealing can be carried out to remove distortions incorporated by cast polymerization.

Lens The lens according to the present invention is essentially the same as conventional synthetic resin lenses except that the lens material is the crosslinked copolymer of the present invention. Therefore, if the present copolymer is directly obtained as a lens by a cast polymerization method, or if it is cut out from a plate material or other material, and if necessary, surface polishing, antistatic treatment, and other post-treatments are performed, the present invention can be achieved. A lens is obtained that has the inherent properties of the polymer. Furthermore, to increase the surface hardness, it is of course possible to coat the surface with an inorganic material by vapor deposition or the like, or to coat the surface with an organic code agent by dipping or the like.

Experimental Examples Example 1 O-iodophenylmethacrylamide mpR'C and co-
Corbis (4-methacryloxyethoxy-3゜terdibromophenyl)propane and a polymerization initiator and a mixture of !; Bulk polymerization was carried out in a glass ampoule in which parts by weight were added and purged with nitrogen.6
16 hours at 0℃, 1 hour at go℃, 7 hours at 100℃,
The polymerization was completed by heating at 40° C. for 30 minutes.

The copolymer thus obtained was an almost colorless and transparent three-dimensional crosslinked product, and was completely insoluble in solvents such as tetrahydrofuran, acetone, methanol, benzene, and chloroform, and had extremely high solvent resistance. . When this copolymer was measured using an Atsube refractometer at 3°C, the refractive index and Atsube number were as follows.

Refractive index nD=/,/, 36 Abbe's number ν=276g As described above, the lens material of this example had a high refractive index and Abbe's number, and was also useful as it had excellent solvent resistance and transparency.

Example: O-iodophenylmethacrylamide J'M parts, cross-linking agent monomers: 3177730 parts by weight of U,2-bis[dermethacryloxyethoxy-3,5-dibromophenyl] and methacryloxyethoxyl l''j rottrib. After adding parts by weight of lauroyl peroxide/ON as a polymerization initiator to a mixture of parts by weight of lomobenzene, bulk polymerization was carried out under the same polymerization conditions as in Example.

The obtained bulk polymer was transparent and completely insoluble in various solvents as in Examples.

Its optical properties are as follows.

np = /, 6.20 ν =, 27.6 Example 3 Using m-iodophenylmethacrylamide instead of 0-iodophenylmethacrylamide in Example 1,
Also, instead of lauroyl peroxide as a polymerization initiator, tert-butylcumyl peroxide was used at 0.0%. Polymerization was carried out under the following polymerization conditions using the same parts by weight.

The bulk polymer obtained at 710°C for 76 hours and at 130°C for 7 hours was transparent and completely insoluble in various solvents as in Example.

Its optical properties are as follows.

nD = 76 = 30 7 Example d Polymerization was carried out under the same conditions as in Example/, except that 0-bromophenyl methacrylamide was used in place of 0-iodophenyl methacrylamide. The obtained bulk polymer was transparent and, as in Example 1, completely insoluble in various solvents.

Its optical properties are as follows.

nD=/, l, /7 C=-93 Example! In Example 2, core 3-dichlorophenylmethacrylamide was used instead of O-iodophenylmethacrylamide, and polymerization was carried out under the same conditions. The obtained bulk polymer was transparent and completely insoluble in the respective solvents as in Example 1. Its optical properties are as follows.

nD=/, &07 C=379

Claims (1)

[Claims] Monomer (I) 20 to 97 represented by the following formula (1)
3 to 60% by weight of crosslinking monomer (II) having two or more functional groups copolymerizable with this and 0 to 40% of ethylenically unsaturated monomer (III) copolymerizable with these.
% by weight, with a refractive index n^2^0_D=1.60 or more and an Abbe number ν=27.
The above lens materials (however, the composition of the copolymer is monomer (
It is based on the total amount of I) to (III). ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (In the formula, X is H or CH_3, Y is Cl, Br or I, and m is an integer from 1 to 5)