JPH02150410A - Resin material having high refractive index - Google Patents

Abstract

PURPOSE:To obtain the title material consisting of a copolymer obtained by copolymerizing a monomer obtained by reacting an unsaturated isocyanate compound with an active hydrogen compound with a copolymerizable monomer and suitable as a material for plastic lens. CONSTITUTION:The aimed material consisting of a copolymer obtained by copolymerizing (A) 15-80 pts.wt. monomer obtained by reacting an unsaturated isocyanate compound (e.g. methacryloylethyl isocyanate) expressed by the formula (X is H or methyl; n is 0-2) with active hydrogen compound (e.g. ortho- phenylphenol) having at least one aromatic group and at least one kind of hydroxyl group, thiol group and amino group with (B) 20-85 pts.wt. monomer (e.g. styrene) copolymerizable with the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a high refractive index resin material, and particularly to a high refractive index resin material suitable as a material for a plastic lens.

[Background of the invention]

Traditionally, inorganic glass lenses have been widely used in optical equipment, but recently lenses made of synthetic resin have become more popular.
Due to its light weight, high impact resistance, good processability, and other features, it has begun to be widely used together with inorganic glass lenses.

On the other hand, there are various requirements regarding the physical properties of lenses, and among them, there is an extremely high requirement that the material have a high refractive index. This is because a material with a high refractive index allows lenses with equivalent performance to be manufactured with a smaller 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, the significance of making a lens with a high refractive index is extremely significant, and there is a strong desire to provide a resin material having a high refractive index.

However, considering transparency, lightness, etc., which are important characteristics of lenses, no satisfactory resin material has yet been provided. To be more specific, the currently most popular materials for eyeglass resin lenses are diethylene glycol bisallyl carbonate resin and polymethyl methacrylate51, both of which have a refractive index of 1. It is low, around 50.

On the other hand, as a resin material with a relatively high refractive index, the refractive index is n
It is known that there is polystyrene with d=1.59, which can be used as a copolymer component of resin materials for lenses. In terms of refractive index, it is desirable to have a refractive index as high as or higher than that of polystyrene.

[Conventional technology]

From the above background, high refractive index tit
Considerations are being made to obtain fatty materials.

Further, it is generally known that polymers of compounds having aromatic groups have a high refractive index.

[Problem to be solved by the invention]

However, while polymers into which halogen atoms have been introduced have a refractive index that increases according to the content of halogen atoms, their specific gravity also increases according to the content of halogen atoms, and as a result, the maximum The light weight, which should be a feature of the lens, is lost, and as a result, the advantage of having a large refractive index is greatly diminished.

In addition, it is usually difficult to introduce radically polymerizable functional groups into compounds that have aromatic groups, and for this reason, it is difficult to actually produce resin materials that have the desired high refractive index and low specific gravity. was difficult.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and provide a high refractive index resin material that has a high refractive index, a low specific gravity, and can be manufactured advantageously.

[Means to solve the problem]

The high refractive index resin material of the present invention contains an unsaturated incyanate compound represented by the following structural formula (I), which has at least one aromatic group and at least one of a hydroxyl group, a thiol group, and an amide group. Monomers obtained by reacting with active hydrogen compounds (hereinafter referred to as "specific monomers")
part by weight and 20 to 85 parts by weight of a monomer copolymerizable with this specific monomer (hereinafter referred to as "copolymerizable monomer"). shall be.

Structural formula (I) (X represents a hydrogen atom or a methyl group, and n is an integer of 0 to 2.) [Effect] The high refractive index resin material according to the present invention has a specific monomer and a copolymerizable monomer. The specific polymer has an aromatic group and a radically polymerizable functional group, so the copolymer has a small specific gravity and has a small amount of aromatic groups. Therefore, it has a high refractive index.

In other words, the reaction to obtain a specific monomer with an unsaturated isoneanate compound and an active hydrogen compound is not easily affected by the type and number of aromatic groups possessed by the active hydrogen compound. A variety of active hydrogen compounds can be used with n, thus e.g.
A copolymer having a sufficiently high refractive index of 1.58 or more and a small specific gravity can be obtained.

Furthermore, since the reaction between the unsaturated incyanate compound and the active hydrogen compound is carried out with high efficiency without producing any by-products, the reaction product can be used as a copolymerizable monomer as a specific monomer without purification. The specific monomer can be subjected to a copolymerization reaction with a copolymerizable monomer, and due to the radically polymerizable functional group of the specific monomer, it can be easily copolymerized with a copolymerizable monomer. Therefore, the desired high refractive index resin material can be produced very advantageously.

The present invention will be specifically explained below.

In the present invention, a specific monomer is used as a copolymer component, and this specific monomer is a specific unsaturated incyanate compound represented by the above formula (I), a specific active hydrogen compound, are combined by a urethanization reaction.

In the general formula (I) representing the above-mentioned unsaturated incyanate compound, the value of n is 0 to 2, and the larger the value of n, the higher the stability of the unsaturated incyanate compound and the easier it is to handle. This is advantageous in this respect. However, on the other hand, the refractive index of the copolymer finally obtained decreases, so the value of n may be selected depending on the required properties. Specifically, n-1 unsaturated incyanate compounds are particularly useful from the viewpoint of handling and the ability to obtain copolymers with a relatively high refractive index.

Examples of the unsaturated incyanate compound used in the present invention include methacryloyl ethyl isocyanate, acryloyl ethyl isocyanate, methacryloyl isocyanate, acryloyl isocyanate, methacryloyl ethoxyethyl isocyanate, and acryloyl ethoxyethyl isocyanate.

The active hydrogen compound reacted with the above unsaturated incyanate compound has at least one aromatic group and at least one of a hydroxyl group, a thiol group, and an amine group. The hydroxyl group, thiol group, or amino group may contain not only one but two or more of these groups, or may contain one or more of each of two or more groups. When an active hydrogen compound containing multiple of these groups is used, one molecule thereof reacts with two or more molecules of the unsaturated incyanate compound, and the resulting specific monomer is a polyfunctional monomer. This is preferable because the copolymer finally obtained has a three-dimensional structure and therefore has excellent durability and impact resistance.

Typical active hydrogen compounds used in the present invention include (I) formula Z'(Y'), (M), or (2) formula Z'(Y'), -R-Z"(Y ”), ·(M)q.

Here, Zl and Z2 represent an aromatic group having an aromatic skeleton. Examples of this aromatic skeleton include, but are not limited to, the following.

Yl and Y2 are substituents on the aromatic groups Z' and Z2, and represent a halogen atom, an alkyl group, an alkoxy group, a thioalkoxy group, etc., and p and p'
is the number of the substituents Y' and Y2, and represents an integer of 0 to 5.

M is the formula +0CH2CH2 OH.

(-OCH, CH2-wheel SHS+0CH2CH2~NH
2, -R'-OH, -R'-3H or -R'-NH2
represents an active hydrogen-containing substituent represented by (where m is an integer of 0 to 2, R1 is an alkylene group having 2 or more carbon atoms), and q is the number of the active hydrogen-containing substituent M, 1
Represents an integer from ~3.

R is a segment that connects aromatic groups, and R2
, 10 + cH2CH20bR'-fOcH2CH2 sho 0 or -R''-0-fcH,cH20 shoR'-+OCH,CH
, square 0-R' (wherein, R2 is an alkylene group having 3 or more carbon atoms, r and S are integers of 0 to 2, and R3 is an alkylene group having 2 or more carbon atoms).

It has at least one aromatic group as described above, and at least one of a hydroxyl group, a thiol group, and an amino group.
The active hydrocarbon compound having the species is reacted with and bonded to the unsaturated isonanate compound represented by formula (I) above.

This reaction is generally called a urethanization reaction, and it can be carried out in an organic solvent that is inert to the reaction, and the specific monomer can be obtained by removing the organic solvent after the reaction is complete. . Further, when the mixture of the unsaturated incyanate compound and the active water compound is liquid, the reaction can be carried out without using such an organic solvent. Furthermore, this urethanization reaction can also be carried out in a copolymerizable monomer to be combined with the specific monomer that is the reaction product. In this case, the reaction solution obtained can be used as it is as a direct raw material for the high refractive index resin material of the present invention, so this reaction means is extremely useful.

In order to advance this urethanization reaction, it is sufficient to simply heat the reaction mixture to a high temperature. However, in order to shorten the reaction time, the reaction is usually carried out under heating using a suitable reaction catalyst. Examples of such reaction catalysts include dirobetiltin dilaurate, stannath octoate, dimethyltin dichloride, and ferric chloride.

The specific monomer obtained by the above urethanization reaction is
Copolymerized with a copolymerizable monomer. Not only one kind of this copolymerizable monomer but also two or more kinds can be used. As the copolymerizable monomer, it is preferable to use one that provides a liquid mixture at room temperature when the specific monomer is mixed with the copolymerizable monomer.

The reason for this is that the specific monomer resulting from the urethanization reaction may become a viscous liquid or solid. That is, even in such a case, by using a suitable monomer as described above as a copolymerizable monomer, the monomer composition to be subjected to the polymerization reaction becomes a low-viscosity liquid, and the polymerization process can be easily performed. This is because it becomes possible to easily perform the following steps. From this point of view, the monomer actually used as the copolymerizable monomer is preferably a liquid substance with low viscosity.

It is also preferable in that by selecting the type of copolymerizable monomer, it is possible to obtain properties suitable for the intended use in the final copolymer.

Specific examples of the copolymerizable monomer used in the present invention include aromatic vinyl compounds such as styrene, α-methylstyrene, p-chlorostyrene, p-bromostyrene, chloromethylstyrene, divinylbenzene, diallyl Phthalate, diallyl isophthalate, diethylene glycol bisallyl carbonate, allyl compounds such as allylphenol, methyl methacrylate, n-
Various acrylates such as butyl acrylate, diethylene glycol dimethacrylate), 1,3-butanediol diacrylate, phenyl methacrylate, 2,2-bis(4-methacrylate, nyl)propane, and 2,46-dribromophenyl methacrylate. Examples include, but are not limited to, methacrylates and methacrylates.

In the present invention, the ratio of the specific monomer to the copolymerizable monomer can be changed depending on the intended use of the high refractive index resin material, but the specific monomer is 15 to 80% by weight. parts, and the copolymerizable monomer is used in a ratio of 2a to 85 parts by weight. When the proportion of the specific monomer is less than 15 parts by weight, it is difficult to obtain a high refractive index and low specific gravity in the final copolymer. In order to increase the refractive index and reduce the specific gravity of the copolymer, it is advantageous to have a large proportion of the specific monomer, and from this point of view, the proportion of the specific monomer is preferably 20 parts by weight or more. . however,
In practice, specific monomers are often obtained as viscous liquids or solids, and therefore, in order to facilitate the polymerization process,
The proportion of the specific monomer is 30 parts by weight or less, thereby making it possible to easily produce a copolymer having a refractive index n of 1.58 or more.

The method for copolymerizing the above specific monomer with the copolymerizable monomer may include suspension polymerization, emulsion polymerization, or cast polymerization, depending on the use of the final copolymer. A known method is employed. When the specific monomer or copolymerizable monomer is a difunctional or higher-functional monomer, the copolymer formed has a crosslinked structure, which results in poor FTR4S resistance. Although it is preferable in this case, it becomes difficult to mold it afterwards.Therefore, in this case, a cast polymerization method is used.

In the case of the cast polymerization method, molds or molds made of glass, plastic, gold, etc., are plate-shaped, lens-shaped, cylindrical, prismatic, conical, spherical, or otherwise designed according to the purpose. A frame (mold) is prepared, and a mixture of a specific monomer and 9 copolymerizable types in a predetermined ratio is mixed and injected into it together with a radical polymerization initiator and various additives added as necessary. A molded product can be obtained by raising the temperature and polymerizing this. Here, as additives, colorants, ultraviolet absorbers, antioxidants, heat stabilizers, and others are used.

In addition, when both the specific monomer and the copolymerizable monomer are monofunctional, emulsion polymerization or suspension polymerization is preferably used, and the resulting copolymer is further processed as necessary. molded into shape.

The copolymer obtained by the above method may be used as it is as a material for the desired product, such as a lens material, or the copolymer may be further cut and polished to form the desired high refractive index resin material. is also possible. Furthermore, if necessary, the molded product or copolymer may be dyed, surface polished, or antistatic treated to further improve its properties, and in order to increase surface hardness, inorganic or organic Of course, it is also possible to perform secondary processing such as a hard coat or a non-reflective coat that is applied to ordinary optical materials.

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

Example 1 Methacryloylethyl isocyanate represented by the structural formula % Formula % 23.
85 g and 26.15 g of ortho-phenylphenol.
was placed in 200 g of acetone, 0.01 g of di-n-butyltin dilaurate was added thereto, and the mixture was reacted with stirring at 60° C. for 2 hours. After the reaction, acetone was removed using an evaporator, thereby obtaining a viscous, colorless and transparent specific monomer with a yield of approximately 100%.

50 parts by weight of this specific monomer, 20 parts by weight of styrene,
20 parts by weight of α-methylstyrene and 4 parts by weight of divinylben
0 parts by weight and 1 part by weight of lauroyl peroxide was added thereto to obtain a monomer composition, which was poured into a glass mold and heated at 60°C for 16 hours and at 80°C for 5 hours. A polymerization reaction was further carried out at 100° C. for 3 hours to obtain a colorless and transparent copolymer.

The refractive index of this copolymer was measured using an Atsube refractometer, and found to be n d = 1.595.

Further, the specific gravity of this polymer was extremely small at 1.12.

Comparative Example 1 Example 1: methacryloyl ethyl isocyanate and n-butyl alcohol, which is an aliphatic alcohol, in equimolar amounts
A urethanized monomer was obtained by reacting in the same manner as above.

50 parts by weight of this monomer, 20 parts by weight of styrene, and α-
20 parts by weight of methylstyrene and 10 parts by weight of divinylbenzene were mixed, and a polymerization reaction was carried out according to the method of Example 1 to obtain a copolymer.

This copolymer had a low refractive index of n=1.551.

From the above, it is clear that the copolymer obtained in Example 1 has a higher refractive index than the copolymer of Comparative Example 1 because it contains an aromatic group.

Example 2 21.22 parts by weight of methacryloylethyl isocyanate, 43.78 parts by weight of 1-(4-phenylphenoxy)-2-hydroxy-3-phenoxypropane represented by the structural formula,
30 parts by weight of phenyl methacrylate and 5 parts by weight of divinylbenzene were mixed, 0.01 part by weight of di-n-butyltin dilaure was added thereto, and a urethanization reaction was carried out at 60°C for 2 hours to obtain a specified A mixture of a monomer and a copolymerizable monomer was obtained.

After cooling this mixture to room temperature, 1 part by weight of lauroyl peroxide was added thereto, the mixture was stirred and poured into a glass mold, and a polymerization reaction was carried out under the same conditions as in Example 1, resulting in a colorless and transparent product. A molded copolymer was obtained.

This copolymer had a refractive index of n = 1.597 and a specific gravity of 1.13, and was a copolymer having a high refractive index and a small specific gravity.

Comparative Example 2 65 parts by weight of tetrabromobisphenol A bis(2-methacryloxyethyl) ether represented by the structural formula (%), 30 parts by weight of phenyl methacrylate, and 5 parts by weight of divinylbenzene were mixed, and this was carried out. A copolymer was obtained by carrying out the urethanization reaction treatment and polymerization treatment in the same manner as in Example 2.

This copolymer has a refractive index of n=1.597 and Example 2
However, the specific gravity was 1.54, which was considerably larger than that of the copolymer of Example 2.

Example 3 28.6 parts by weight of methacryloylethyl isocyanate, 26.4 parts by weight of α-aminonaphthalene, 10 parts by weight of bisphenol A bis(2-methacryloxyethyl) ether represented by the structural formula (%), and 2 , 10 parts by weight of 4,6-tribromophenyl methacrylate and 25 parts by weight of α-methylstyrene were mixed, 0.01 part by weight of dilobtiltin dilaurate was added thereto, and the urethanization reaction was carried out at 60°C for 2 hours. A mixture of the specific monomer and the copolymerizable monomer was obtained.

After cooling this mixture to room temperature, 1 part by weight of lauroyl peroxide was added thereto, the mixture was stirred and poured into a glass mold, and a polymerization reaction was carried out under the same conditions as in Example 1. A transparent plate-shaped molded copolymer was obtained.

This copolymer has a refractive index of nd=1.607 and a specific gravity of 1.
．． 19, and was a copolymer with a high refractive index and low specific gravity.

Comparative Example 3 10 parts by weight of bisphenol A bis(2-methacryloxyethyl) ether, 65 parts by weight of 2.4.6-)dibromophenyl methacrylate, and 25 parts by weight of α-methylstyrene.
parts by weight were mixed, and this was subjected to urethanization reaction treatment and polymerization treatment in the same manner as in Example 3 to obtain a copolymer.

This copolymer had a refractive index of n,=1.612 and was obtained in Example 3.
Although the specific gravity was slightly higher than that of the copolymer of Example 3, the specific gravity was l,49, which was significantly larger than that of the copolymer of Example 3.

Example 4 Acryloyl ethyl isocyanate represented by the structural formula % formula % 15.4
parts by weight and tetrabromobisphenol Δbis(2-hydroxyethyl)ether ((CHs)2C(C-H2
34.6 parts by weight of Br20CzH-OH)z> were placed in 200 g of acetone, 0.01 parts by weight of di-n-butyltin dilaurate was added thereto, and the mixture was reacted with stirring at 60° C. for 2 hours. After the reaction was completed, most of the acetone was removed by an evaporator, and then dried at 50° C. for 16 hours using a vacuum dryer, thereby obtaining a specific monomer that was a solid bifunctional monomer.

50 parts by weight of this specific monomer and 30 parts by weight of p-chlorostyrene
parts by weight and 20 parts by weight of α-methylstyrene,
1 part by weight of lauroyl peroxide was added to this to obtain a monomer composition, which was poured into a glass mold,
A polymerization reaction was carried out under the same conditions as in Example 1 to obtain a colorless and transparent plate-shaped molded copolymer.

This copolymer has a refractive index of nd=1.606 and a specific gravity of 1.
．． 27, and was a copolymer with a high refractive index and low specific gravity.

Example 5 11.61 monomers of methacryloyl isocyanate represented by the structural formula % formula % and 3 parts of 1-(2-phenylphenoxy)-2-hydroxy-3-(4-methylthiophenoxy)propane represented by the structural formula
8.4 ffiffi parts, 2,4.6-) 10 parts by weight of ribcumophenyl methacrylate, 30 parts by weight of p-chlorostyrene, and 10 parts by weight of divinylbenzene were mixed, and di-n-butyltin dilaurate was added to the mixture. 0.01 part by weight was added and the urethanization reaction was carried out at 60°C for 2 hours.
A mixture of a specific monomer and a copolymerizable monomer was obtained.

After cooling this mixture to room temperature, add 1 layer of lauroyl peroxide to it. The mixture was poured into a glass mold, and a polymerization reaction was carried out under the same conditions as in Example 1 to obtain a slightly yellow transparent plate-shaped copolymer.

This copolymer has a refractive index of n=1.613 and a specific gravity of 1.
．． 21, and was a copolymer with a high refractive index and low specific gravity.

Example 6 1 part of 23.5 ml of methacryloylethylisonane) and 4,4°-thiodiphenol<(HOC,H,)2S
) 16.5 parts by weight, 15 parts by weight of 2,4.6-tribromophenyl methacrylate, and 10 parts by weight of α-methylstyrene.
15 parts by weight of divinylbenzene and 20 parts by weight of p-chlorostyrene were added and mixed, and 0. Add 1 part by weight of fl and heat at 60°C.
The urethane reaction was carried out for 2 hours to obtain a mixture of the specific monomer and the copolymerizable monomer.

After cooling this mixture to room temperature, 1 part of lauroyl peroxide was added thereto, the mixture was stirred and poured into a glass mold, and a polymerization reaction was carried out under the same conditions as in Example 1. A transparent plate-shaped molded copolymer was obtained.

This copolymer had a refractive index of n = 1.596 and a specific gravity of 1.22, and was a copolymer having a high refractive index and a small specific gravity.

Example 7 27.1 parts by weight of methacryloylethyl isocyanate and 27.1 parts by weight of 2-naphthalenethiol (C+.H,S H).
9 parts by weight of divinylbenzene, 10 parts by weight of 2,4.6-)ribromophenyl methacrylate, 20 parts by weight of α-methylstyrene, and 15 parts by weight of divinylbenzene.
- 0.01 part by weight of 6
A urethane reaction was carried out at 0° C. for 24 hours to obtain a mixture of the specific monomer and the copolymerizable monomer.

After cooling this mixture to room temperature, 1 part by weight of lauroyl peroxide was added thereto, the mixture was stirred and poured into a glass mold, and a polymerization reaction was carried out under the same conditions as in Example 1. A transparent plate-shaped molded copolymer was obtained.

This copolymer had a refractive index of n d = 1.620 and a specific gravity of 1.19, and was a copolymer having a high refractive index and a small specific gravity.

Claims (1)

[Scope of Claims] 1) An unsaturated isocyanate compound represented by the following structural formula (I) is combined with an active hydrogen compound having at least one aromatic group and at least one of a hydroxyl group, a thiol group, and an amino group. Monomers 15-8 obtained by reaction
0 parts by weight and 20 to 8 monomers copolymerizable with this monomer
A high refractive index resin material comprising a copolymer obtained by copolymerizing 5 parts by weight. Structural formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (X represents a hydrogen atom or a methyl group, and n is an integer from 0 to 2.) 2) In structural formula (I), when n=1 The high refractive index resin material according to claim 1. 3) The high refractive index resin material according to claim 1, which has a refractive index n_d of 1.58 or more.