JPH0649736B2 - Method for manufacturing high refractive index resin material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a high refractive index resin material, and particularly to a method for producing a high refractive index resin material suitable as a material for a plastic lens.

[Background of the Invention]

Inorganic glass lenses have been widely used in optical equipment, but recently, synthetic resin lenses are lightweight, have high impact resistance, good processability, and other features. It has begun to be widely used with.

On the other hand, in the case of a lens, there are various demands for its physical properties, but among them, there is a great demand for its material to have a high refractive index. This is because with a material having a high refractive index, a lens having equivalent performance can be manufactured with a small thickness. When a lens with a high refractive index is used, it is possible to make the lens system that occupies an important position in optical instruments such as a microscope, a photographic device, and a telescope compact and lightweight, and to make the spectacle lens lightweight. In addition to being able to reduce the so-called edge thickness, it is possible to obtain a great practical advantage. As described above, it is extremely significant to use a lens having a high refractive index, and it is strongly desired to provide a resin material having a high refractive index.

However, in consideration of transparency, lightness, etc., which are important characteristics of the lens, the current situation is that a satisfactory resin material has not been provided yet. Specifically, as the material of the most popular resin lens for spectacles at present, what is made of diethylene glycol bisallyl carbonate resin or polymethylmethacrylate is used, but all of them have a refractive index of about 1.50. It is low. On the other hand, as a resin material having a relatively high refractive index, the refractive index is n
It is known that there is polystyrene having _d = 1.59 and can be used as a copolymer component of a resin material 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, studies have been made on obtaining a high refractive index resin material from a polymer having a halogen atom such as a bromine atom introduced as a substituent.

Further, it is generally known that a polymer of a compound having an aromatic group has a high refractive index.

[Problems to be Solved by the Invention]

However, a polymer having a halogen atom introduced has a higher refractive index depending on the content of the halogen atom, but at the same time, has a higher specific gravity depending on the content of the halogen atom, and as a result, the maximum of the plastic material is increased. As a result, the lightness, which is a feature of the above, is impaired, and the advantage of having a large refractive index is largely diminished in the end.

In addition, it is usually difficult to introduce a radically polymerizable functional group into a compound having an aromatic group, and therefore, it is necessary to actually produce a resin material having a desired high refractive index and a small specific gravity. Was difficult.

It is an object of the present invention to solve the above problems and provide a method for producing a high-refractive-index resin material that can advantageously produce a high-refractive-index resin material having a high refractive index and a small specific gravity. And

[Means for Solving the Problems]

The method for producing a high refractive index resin material of the present invention comprises an unsaturated isocyanate compound represented by the following structural formula (I) having at least one aromatic group and at least one of a hydroxyl group, a thiol group and an amino group. 15 to 80 parts by weight of a monomer (hereinafter referred to as "specific monomer") obtained by reacting with the active hydrogen compound, and a monomer copolymerizable with this specific monomer (hereinafter referred to as "copolymerizable monomer"). 20 to 85 parts by weight).

Structural formula (I) (X represents a hydrogen atom or a methyl group, and n is an integer of 0 to 2.) [Effect] The method for producing a high refractive index resin material of the present invention is to use a specific monomer and a copolymerizable monomer. Since the specific monomer has an aromatic group and a radically polymerizable functional group, the specific monomer has a low specific gravity and a high refractive index due to the aromatic group. A copolymer can be obtained.

That is, the reaction of obtaining a specific monomer with an unsaturated isocyanate compound and an active hydrogen compound is not easily affected by the type and number of aromatic groups contained in the active hydrogen compound, and thus a preferred aromatic group or a plurality of aromatic groups can be used various active hydrogen compounds having, thus, for example n _d
Of 1.58 or more, a copolymer having a sufficiently high refractive index and a small specific gravity can be obtained.

Moreover, since the reaction between the unsaturated isocyanate compound and the active hydrogen compound is carried out with high efficiency without by-products, the reaction product is used as it is as a specific monomer without conversion to a copolymerizable monomer. It is possible to subject it to a copolymerization reaction with the body, and due to the radically polymerizable functional group of the specific monomer, it is possible to easily carry out a copolymerization reaction between this and the copolymerizable monomer. Therefore, the desired high-refractive-index resin material can be manufactured very advantageously.

Hereinafter, the present invention will be specifically described.

In the present invention, a specific monomer is used as a copolymer component, and the specific monomer includes a specific unsaturated isocyanate compound represented by the general formula (I) and a specific active hydrogen compound. , Which are bound by a urethanization reaction.

In the general formula (I) showing the unsaturated isocyanate compound, the value of n is 0 to 2, but the larger the value of n, the higher the stability of the unsaturated isocyanate compound and the easier handling. Is advantageous. However, on the other hand, the refractive index of the copolymer finally obtained is lowered, so that the value of n may be selected according to the required characteristics. Specifically, an unsaturated isocyanate compound having n = 1 is particularly useful in terms of handling and obtaining a copolymer having a relatively high refractive index.

Examples of the unsaturated isocyanate compound used in the present invention include methacryloylethyl isocyanate, acryloylethyl isocyanate, methacryloyl isocyanate, acryloyl isocyanate, methacryloylethoxyethyl isocyanate, and acryloylethoxyethyl isocyanate.

The active hydrogen compound which is reacted with the above unsaturated isocyanate compound has at least one aromatic group and at least one kind of a hydroxyl group, a thiol group and an amino group. The hydroxyl group, the thiol group, or the amino group may contain not only one kind of those groups but also two or more kinds, or may contain one or more kinds of two or more kinds each. When an active hydrogen compound containing a plurality of these groups is used, one molecule of the active hydrogen compound reacts with two or more molecules of the unsaturated isocyanate compound, and the resulting specific monomer becomes a polyfunctional monomer. It is preferable that the finally obtained copolymer has a three-dimensional structure and therefore has excellent durability and impact resistance.

Typical examples of the active hydrogen compound used in the present invention include: The compound shown by can be mentioned.

Here, Z ¹ and Z ² represent an aromatic group having an aromatic skeleton. Examples of this aromatic skeleton include: However, the present invention is not limited to these.

Y ¹ and Y ² are substituents on the aromatic groups Z ¹ and Z ² and represent a halogen atom, an alkyl group, an alkoxy group, a thioalkoxy group, and p and p ′.
Represents the number of the substituents Y ¹ and Y ² and represents an integer of 0 to 5.

M is of the formula OCH ₂ CH _{2 m} OH, OCH ₂ CH _{2 m} SH, OCH ₂ CH _{2 m} N
An active hydrogen-containing substituent represented by H ₂ , -R ¹ -OH, -R ¹ -SH or -R ¹ -NH ₂ (where m is an integer of 0 to 2 and R ¹ is an alkylene having 2 or more carbon atoms). Is a group), and q is the number of the active hydrogen-containing substituents M and is 1
Represents an integer of 3

R is a segment that binds together an aromatic _{group, -O-CH 2 CH 2 O} r R 3 OCH 2 CH 2 s O
- or ^{_{-R 2 -OCH 2 CH 2 r -R}} 3 - OCH 2 CH 2 s O-R 2 - ( wherein, ^{R 2} is an alkylene group having 3 or more carbon atoms, r and s is an integer of 0 to 2, R ³ represents an alkylene group having 2 or more carbon atoms.

At least one of the above aromatic groups and at least one of a hydroxyl group, a thiol group and an amino group
The active hydrogen compound having a seed is reacted with and bonded to the unsaturated isocyanate compound represented by the above general formula (I).

This reaction is a reaction generally called a urethanization reaction, and it may be carried out in an organic solvent inert to the reaction, and the specific monomer is obtained by removing the organic solvent after completion of the reaction. . When the mixture of the unsaturated isocyanate compound and the active hydrogen compound is liquid, the reaction can be performed without using such an organic solvent. Further, this urethanization reaction can be carried out in a copolymerizable monomer to be combined with the specific monomer as the reaction product. In this case, the obtained reaction solution can be used as it is as a direct raw material of the high refractive index resin material, and this reaction means is extremely useful.

To proceed the urethanization reaction, it is only necessary to 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 an appropriate reaction catalyst. As such a reaction catalyst, for example, n
-Butyltin dilaurate, stannas octoate, dimethyltin dichloride, stannic chloride and the like can be mentioned.

In the present invention, the specific monomer obtained by the above urethanization reaction and a copolymerizable monomer are copolymerized.
This copolymerizable monomer may be used alone or in combination of two or more. As the copolymerizable monomer, it is preferable to use one that gives a liquid mixture at a temperature when the specific monomer is mixed with the copolymerizable monomer.

The reason is that the specific monomer due to 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 the copolymerizable monomer, the monomer composition to be subjected to the polymerization reaction becomes a low-viscosity liquid, and the polymerization treatment This is because it is possible to easily perform. From this point of view, the monomer actually used as the copolymerizable monomer is preferably a liquid substance having a low viscosity. Further, it is also preferable in that it is possible to obtain the properties suitable for the intended use of the finally obtained copolymer by selecting the type of the copolymerizable monomer.

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 and divinylbenzene, diallyl. Allyl compounds such as phthalate, diallyl isophthalate, diethylene glycol bismaryl carbonate, allylphenol, methyl methacrylate, n-
Various acrylates such as butyl acrylate, diethylene glycol dimethacrylate, 1,3-butanediol diacrylate, phenyl methacrylate, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,4,6-tribromophenyl methacrylate And methacrylates can be mentioned,
It is not limited to these.

In the present invention, the ratio of the specific monomer and the copolymerizable monomer can be changed according to the intended use of the high refractive index resin material, but the specific monomer is 15 to 80 weight. Parts, the copolymerizable monomer is used in a proportion of 20 to 85 parts by weight.
When the ratio of the specific monomer is less than 15 parts by weight, it is difficult to obtain a high refractive index and a low specific gravity in the finally obtained copolymer. In order to increase the refractive index of the copolymer and reduce the specific gravity, it is advantageous that the proportion of the specific monomer is large, and from this point, the proportion of the specific monomer is preferably 20 parts by weight or more. . However, in practice, the specific monomer is often obtained as a viscous liquid or solid, and therefore the ratio of the specific monomer is set to 80 parts by weight or less in order to facilitate the polymerization treatment. Refractive index n _d
A copolymer of 1.58 or more can be easily produced.

In the present invention, as a specific method for copolymerizing the specific monomer and the copolymerizable monomer, depending on the use of the finally obtained copolymer, a suspension polymerization method, an emulsion polymerization method. Known methods such as a legal method or a cast polymerization method are adopted. When the specific monomer or the copolymerizable monomer is a bifunctional or higher functional monomer, the copolymer formed has a crosslinked structure, and excellent impact resistance is obtained. Although preferable, it is difficult to mold after that. Therefore, in this case, the cast polymerization method is used.

In the case of the cast polymerization method, a mold or a mold made of glass, plastic, metal, or the like, which is designed according to plate, lens, cylinder, prism, cone, sphere, or other purposes ( Mold) is prepared, and a mixture of a specific monomer and a copolymerizable monomer in a predetermined ratio is mixed and injected together with a radical polymerization initiator and various additives to be added if necessary, A molded product can be obtained by heating this and polymerizing it. Here, as an additive, a colorant, an ultraviolet absorber, an antioxidant, a heat stabilizer,
Others are used.

Further, when both the specific monomer and the copolymerizable monomer are monofunctional, an emulsion polymerization method or a suspension polymerization method is preferably used, and the obtained copolymer is further appropriately selected as necessary. It is molded into a shape.

The copolymer obtained by the method of the present invention may be used as it is as a material for a target product, for example, a lens material, or the copolymer is further cut and polished to obtain a target high refractive index resin material. It is also possible. Furthermore, in order to further improve various properties by subjecting the molded product or the copolymer to dyeing, surface polishing, and antistatic treatment, and to increase the surface hardness, an inorganic or organic material is used. Of course, it is also possible to carry out secondary processing such as a hard coat or a non-reflective coat which is made on a usual optical material.

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

Example 1 Structural formula Methacryloyl ethyl isocyanate 23.85
g and 26.15 g of ortho-phenylphenol were put in 200 g of acetone, 0.01 g of di-n-butyltin dilaurate was added thereto, and they were reacted at 60 ° C. for 2 hours while stirring. After the completion of the reaction, acetone was removed by an evaporator, whereby a viscous, colorless and transparent specific monomer was removed by about 10%.
Obtained in a yield of 0%.

50 parts by weight of this specific monomer, 20 parts by weight of styrene, α-
20 parts by weight of methylstyrene and 10 parts by weight of divinylbenzene were mixed, and 1 part by weight of lauroyl peroxide was added to the mixture to obtain a monomer composition, which was poured into a glass mold at 60 ° C. 16 hours, 5 hours at 80 ℃, then 100 ℃
Polymerization reaction was carried out for 3 hours to obtain a colorless and transparent copolymer.

The refractive index of this copolymer was measured by an Abbe refractometer was n d ₌ 1.595.

Moreover, the specific gravity of this polymer was 1.12, which was extremely small.

Comparative Example 1 Methacryloylethyl isocyanate and n-butyl alcohol, which is an aliphatic alcohol, are equimolar Example 1
The reaction was carried out in the same manner as in 1. to obtain a urethanized monomer.

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

This copolymer had a low refractive index of n _d = 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 by containing the aromatic group.

Example 2 21.22 parts by weight of methacryloylethyl isocyanate,
Structural formula 1- (4-phenylphenoxy) -2-hydroxy-3-phenoxypropane (43.78 parts by weight), phenyl methacrylate (30 parts by weight), and divinylbenzene (5 parts by weight) were mixed, and di-n-butyltin dilaurate was added to the mixture.
0.01 part by weight was added and urethanization reaction was carried out at 60 ° C. for 2 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 and stirred, and the mixture was poured into a glass mold and subjected to a polymerization reaction under the same conditions as in Example 1 to give a colorless and transparent product. A plate-shaped molded copolymer was obtained.

This copolymer had a refractive index of n _d = 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 Structural formula 65 parts by weight of tetrabromobisphenol A bis (2-methacryloxyethyl) ether represented by the following formula, 30 parts by weight of phenyl methacrylate, and 5 parts by weight of divinylbenzene were mixed and treated with urethane in the same manner as in Example 2. And treated by weight to obtain a copolymer.

This copolymer had a refractive index n _d = 1.597, which was similar to that of the copolymer of Example 2, but had a specific gravity of 1.54, which was considerably larger than that of the copolymer of Example 2. .

Example 3 28.6 parts by weight of methacryloyl ethyl isocyanate and α
-Aminonaphthalene 26.4 parts by weight and structural formula 10 parts by weight of bisphenol A bis (2-methacryloxyethyl) ether represented by the formula (2), 10 parts by weight of 2,4,6-tribromophenyl methacrylate and 25 parts by weight of α-methylstyrene were mixed, and di -Butyltin dilaurate (0.01 parts by weight) was added, and a urethanization reaction was carried out at 60 ° C for 2 hours to obtain a mixture of a specific monomer and a copolymerizable monomer.

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

The copolymer has a refractive index n _{d =} 1.607, a specific gravity of 1.19, was a copolymer having a small specific gravity and high refractive index.

Comparative Example 3 10 parts by weight of bisphenol A bis (2-methacryloxyethyl) ether, 65 parts by weight of 2,4,6-tribromophenyl methacrylate, and 25 parts by weight of α-methylstyrene were mixed, and this was used as an example. A urethanization reaction treatment and a weight treatment were carried out in the same manner as in 3 to obtain a copolymer.

This copolymer had a refractive index n _{d of} 1.612 and was slightly higher than that of the copolymer of Example 3, but had a specific gravity of 1.49, which was significantly higher than that of the copolymer of Example 3.

Example 4 Structural formula And acryloyl isocyanate 15.4 parts by weight shown in, tetrabromobisphenol A bis (2-hydroxyethyl) ether _{((CH 3) 2 C (} C 6 H 2 Br
₂ OC ₂ H ₄ OH) ₂ ) 34.6 parts by weight and 200 g of acetone
The mixture was placed in a flask, 0.01 part by weight of di-n-butyltin dilaurate was added thereto, and the mixture was reacted at 60 ° C for 2 hours with stirring.
After completion of the reaction, most of the acetone was removed by an evaporator, and then dried at 50 ° C. for 16 hours using a vacuum drier, whereby a specific monomer which was a solid bifunctional monomer was obtained.

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

The copolymer has a refractive index n _{d =} 1.606, a specific gravity of 1.27, was a copolymer having a small specific gravity and high refractive index.

Example 5 Structural formula 11.6 parts by weight of methacryloyl isocyanate represented by 1- (2-phenylphenoxy) -2-hydroxy-3- (4-methylthiophenoxy) propane 3 represented by
8.4 parts by weight, 2,4,6-tribromophenyl methacrylate 10 parts by weight, p-chlorostyrene 30 parts by weight,
Divinylbenzene (10 parts by weight) was mixed, and di-n-butyltin dilaurate (0.01 parts by weight) was added to the mixture, followed by urethanization reaction at 60 ° C for 2 hours to obtain a specific monomer and a copolymerizable monomer. A mixture was obtained.

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

This copolymer had a refractive index of n _d = 1.613 and a specific gravity of 1.21, and was a copolymer having a high refractive index and a small specific gravity.

Example 6 23.5 parts by weight of methacryloylethyl isocyanate,
4,4'-thiodiphenol _{((HOC 6 H 4) 2} S)
16.5 parts by weight, 2,4,6-tribromophenyl methacrylate 15 parts by weight, α-methylstyrene 10 parts by weight,
15 parts by weight of divinylbenzene and ₂₀ parts of p-chlorostyrene
Parts by weight and 0.01 parts by weight of di-n-butyltin dilaurate are added to the mixture, and urethanization reaction is performed at 60 ° C. for 2 hours to obtain a mixture of the specific monomer and the copolymerizable monomer. Obtained.

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

This copolymer had a refractive index n _d = 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 2
27.9 parts by weight of naphthalene thiol (C ₁₀ H ₇ SH) and 2,4,6-tribromophenyl methacrylate 10
Part by weight, 20 parts by weight of α-methylstyrene, and 15 parts by weight of divinylbenzene are mixed, 0.01 part by weight of di-n-butyltin dilaurate is added thereto, and urethanization reaction is performed at 60 ° C. for 24 hours to specify. A mixture of the monomer and the copolymerizable monomer was obtained.

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

This copolymer had a refractive index 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.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G02B 1/04 7132-2K

Claims (3)

[Claims] 1. An unsaturated isocyanate compound represented by the following structural formula (I) is reacted 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. Monomer 15 obtained
~ 80 parts by weight and 20 to 85 monomers copolymerizable with this monomer
A method for producing a high-refractive-index resin material, which comprises copolymerizing with parts by weight. Structural formula (I) (X represents a hydrogen atom or a methyl group, and n is an integer of 0 to 2.) 2. The method for producing a high refractive index resin material according to claim 1, wherein n = 1 in the structural formula (I). 3. The refractive index n _{d of the} obtained high refractive index resin material is
The method for producing a high-refractive-index resin material according to claim 1, which is 1.58 or more.