JPH01242612A - Material for plastic lens - Google Patents

Abstract

PURPOSE:To provide a lens material having high refractive index, low specific gravity, excellent impact resistance etc., by constituting the title material with a specified copolymer obtd. from an unsatd. hydroxyl compd., a hydroxylated sulfur compd., etc. CONSTITUTION:A radical-polymerizable unsatd. compd. (A) having a hydroxyl group in its molecule (e.g., 2-hydroxyethyl methacrylate) is reacted with a polyisocyanate (B) having a plurality of isocyanate groups in its molecule and a sulfur compd. (C) of the formula (wherein R<1> and R<2> are each an aliph. or arom. hydrocarbon group) having 2 hydroxyl groups in its molecule at a relative ratio of 0<a/b<=2 and 0.01<=c/b<1 (wherein a is the mole number of the hydroxyl groups in the component A; b is the mole number of the isocyanate groups in the component B; c is the mole number of the hydroxyl groups in the component C). The reaction product is polymerized with 20-70wt.% copolymerizable monomer (D) based on the whole and the obtd. copolymer is used as a plastic lens material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to plastic lens materials, and more particularly to plastic lens materials containing sulfur atoms.

[Conventional technology]

Nowadays, transparent plastic materials are lightweight,
Because it has various features that cannot be obtained with inorganic glasses, such as high impact resistance and resistance to breakage, ease of processing, and the ability to be dyed, it has begun to be used in many fields as a material for optical lenses.

In particular, as a material for eyeglass lenses for vision correction, it is lightweight,
Plastic lens materials are preferred because essential properties include high impact resistance and ease of dyeing.

Furthermore, plastic lens materials are required to have a high refractive index, and this is because plastic lens materials with a high refractive index can reduce the edges 7 of eyeglass lenses, for example. .

Conventionally, the most commonly used plastic lens material for eyeglasses is diethylene glycol bisallyl carbonate resin, but this resin has a relatively low refractive index of around 1.50, and is not necessarily satisfactory in this respect. .

On the other hand, polyurethane resins have been studied in various fields as a plastic lens material with excellent impact resistance. , U.S. Patent No. 3,90
No. 7,864, US Pat. No. 3,954,584, and others disclose lenses made of polyurethane resins.

However, these polyurethane resin lenses do not have a sufficiently high refractive index, and are not satisfactory in this respect.

Furthermore, as a polyurethane resin having a higher refractive index, one containing a halogen atom is disclosed in Japanese Patent Application Laid-Open No. 58-164.
6] Publication No. 5, Japanese Unexamined Patent Publication No. 59-133211, etc. In this way, when containing halogen atoms, especially bromine atoms and iodine atoms, the refractive index of the polymer increases depending on the content, but at the same time, the refractive index of the polymer increases depending on the content of halogen atoms. As a result, the greatest feature of plastic materials, which is their lightness, is lost, and the resulting plastic 1/ns material has the advantage of having a large refractive index greatly diminished. Become.

Furthermore, a method in which a crosslinked structure is introduced into a polymer molecule by reacting a vinyl monomer containing a hydroxyl group with an isocyanate compound has been proposed in JP-A-58-168614 and other publications.

[Problem that the invention seeks to solve]

As described above, various efforts are being made to find plastic lens materials with high refractive index and excellent impact resistance.
The current situation is that we have not yet achieved something that is fully satisfactory.

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

[Failure to solve the problem]

The plastic lens material of the present invention has the following Δ component, the following B component and the following C component, the number of moles of hydroxyl groups in the A component is a, the number of moles of isocyanate groups for Bi is b, and the number of moles of hydroxyl groups in the C component is When the number of moles is C, the ratio α=
The value of a/b is 0<α≦2.0, and the ratio β−e
A copolymer obtained by reacting at a relative ratio where the value of /b is 0.01≦β<1.0 and polymerizing with the following components at a ratio of 20 to 70% of the total weight. It is characterized by being composed of a combination.

Component A: A monomer having a radically polymerizable unsaturated group having a hydroxyl group in two molecules Component B: A polyisocyanate compound having a plurality of isocyanate groups in two molecules Component C: In a molecule represented by the following general formula (I) Sulfur compound having two hydroxyl groups General formula (I) %Formula% (R1 and R2 each represent an aliphatic or aromatic hydrocarbon group having 2 to 15 carbon atoms.) Component D: Copolymerized with the above component A Possible Monomers [Effects] The PlusDeck lens material according to the present invention has a high refractive index, excellent impact resistance, and has a small specific gravity. The reason why such an effect is obtained is that the B component, A component, and B
As a result, the copolymer obtained basically has the structure of a urethane resin with excellent impact resistance, and sulfur atoms are introduced by the C component. This is because the specific gravity can be avoided from becoming excessive, and the refractive index can be relatively high. That is, by using the C component containing a sulfur atom, the copolymer formed has a higher refractive index than a normal polyurethane polymer made of a compound having a hydroxyl group and an inesyanate compound, and ,
It has a lower specific gravity than those containing halogen atoms.

The present invention will be explained in detail below.

In the present invention, component A is composed of a monomer having a radically polymerizable unsaturated group having a hydroxyl group in the molecule, and component B has two or more isocyanate groups in the molecule.
By reacting the king with component C, which is a sulfur compound having two hydroxyl groups in the molecule represented by the general formula (I) below, at a specific relative ratio, a urethane bond can be formed by component B and component C. A urethane monomer having radical polymerizability, in which the remaining isocyanate groups of the B component and the hydroxyl groups of the A component are reacted to form a urethane bond, and the A component and the C component are bonded to the B component. is further copolymerized with a component that can be copolymerized with the urethane monomer by utilizing the radical polymerizability of the Δ component in the urethane monomer, and the resulting copolymer having urethane bonds is used as a lens material. It is something.

General formula (I) HOR'-5-R'0H (R' and R2 each represent an aliphatic or aromatic hydrocarbon group having 2 to 15 carbon atoms.) In the above, the number of moles of the isocyanate group of component B b%C When the number of moles of hydroxyl groups in the component is C, it is necessary that the value β of their ratio c/b is smaller than 1. By satisfying this condition, even if all of the hydroxyl groups of component C react with the isocyanate groups of component B,
An unreacted isocyanate group exists at the end of the molecule of the urethane compound, and component A can react and bond to this isocyanate group, thereby forming a crosslinkable polyfunctional urethane monomer. Ru.

Then, by polymerizing this urethane monomer together with component D, a plastic lens material made of the desired copolymer can be obtained.

In the present invention, specific examples of polyisocyanate compounds having a plurality of isocyanate groups used as component B include hexamethylene diisocyanate, octamethylene diisocyanate, isophorone diisocyanate), 2,2,4-trimethylhexamethylene diisocyanate, etc. , dicyclohexylmethane diisocyanate, tetramethylene diisocyanate, tolylene diisocyanate, 4,4°-diphenylmethane diisocyanate, naphthalene diisocyanate, 3.3°-dimethyl-4,4”-bisphenylene diisocyanate, metaxylylene diisocyanate, hexamethylene diisocyanate biuret reaction product, compound with trimer structure or adduct reaction product with trimethylolpropane, 3 derived from inphorone diisocyanate
Examples include, but are not limited to, functional or tetrafunctional polyisocyanate compounds, 2-isocyanate ethyl-2,6-dicyanato ethylhexanoate, and the like. Moreover, not only one kind but two or more kinds of polyisocyanate compounds can also be used.

Among the above, aliphatic isocyanate compounds or hexyl isocyanate compounds that produce polymers that are less likely to yellow than aromatic isocyanate compounds that tend to cause yellowing of the resulting copolymer due to heat or light. It is preferable to use a polyfunctional derivative of methylene diisocyanate, etc., and thereby a colorless, transparent and stable copolymer required as a plastic lens material can be obtained.

In the present invention, specific examples of the sulfur compound used as component C include 2.2''-thiodiphenolpe4.4''-thio((i-tert-butyl-m-cresol), 4,4'' Examples include, but are not limited to, "-thiodiphenol, 1,1'-thiobis(2-naphthol), etc.In addition, this sulfur compound may contain not only one type but two or more types. You can also use

In the present invention, as a specific example of a monomer having a radically polymerizable unsaturated group having a hydroxyl group and used as the component A, a hydroxyl group-containing acrylic acid J ester represented by the following general formula (ff) is used. Or methacrylic acid ester can be mentioned.

-9 formula (II) H2C=C-C-0-R'-(OH)I.

(In the formula, n!'! is an integer from l to 3, R3 represents a hydrogen atom or a methyl group, and R' represents an aliphatic or aromatic hydrocarbon group having 2 to 12 carbon atoms.) General formula Specific examples of the compound represented by (n) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroquinepropyl methacrylate, 2-hydroxy-3-phenoquinepropyl arylate, 2-Hydroquine-3-
Examples include, but are not limited to, phenoxypropyl methacrylate and 4-hydroxybutyl methacrylate.

Furthermore, examples of the monomer used as component A include monomers containing a hydroxyl group and having two or more -1- radically polymerizable unsaturated groups.

Specific examples thereof include 2-hydroxy-1-acryloxy-3-methacryloxypropane and tetramethylolmethane triacrylate.

In addition to the above, various polyols such as allyl alcohol, polyester polyols having methacrylic alcohol unsaturated groups, and polyether polyols can also be mentioned as examples of the Δ component.

In a typical method for manufacturing the plastic lens material of the present invention, the above A component, B component and C component are first mixed and reacted to form a radically polymerizable non-containing material containing sulfur atoms. A urethane monomer with saturated groups is formed. This tanning reaction can usually be carried out at a temperature ranging from room temperature to 200°C. In this urethanization reaction, in order to shorten the reaction time, a reaction catalyst used in the production of ordinary polyurethane,
For example, dibutyltin dilaurate, stannath octoate, dimethyltin dichloride, stannic chloride, and the like can be used as appropriate. Further, this urethanization reaction may be carried out in an organic solvent that is inert to the urethane bond formation reaction, and the urethane monomer can be obtained by removing the organic solvent after the reaction is completed.

In the above urethanization reaction, as mentioned above, the ratio c
/ The value β of b is smaller than 1 and 0. It is necessary that the value is 2, preferably 0.02 or more. The value of this β is 0. If it is smaller than before, the amount of C component 1 used will be extremely small, and the resulting copolymer will not be able to sufficiently exhibit high refractive index properties due to sulfur atoms. Also, A component, B
The relative proportions of the components and C component are such that the number of moles of hydroxyl groups in component A is a, and the residue α of the ratio a/b is 0<α≦2.
．． 0, preferably in the range of 0.2≦α≦1.5.

If the value of α is too large, there is a risk that the resulting copolymer will discolor, while if it is too small, the resulting copolymer may be inferior in durability.

Next, this urethane monomer is copolymerized with component D,
This forms a copolymer which is the plastic lens material of the present invention.

One of the reasons why component D is used in this way is that component A,
This is because the urethane monomer, which is a reaction product of component B and component C, may become a viscous liquid or solid. That is, even in such a case, by using component D, the monomer composition to be polymerized can be made into a low viscosity liquid, so that the polymerization process can be easily performed. Furthermore, by selecting the type of component D, it is possible to obtain properties suitable for the intended use in the resulting copolymer. From the above viewpoint, it is preferable that the monomer used as component D is a liquid substance with low viscosity.

Note that the urethanization reaction described above can be carried out in the presence of component D.

Specific examples of component D include aromatic vinyl compounds such as styrene, α-methylstyrene, chloromethylstyrene, and divinylbenzene, allyl compounds such as diallyl phthalate, diallyl isophthalate, and diethylene glycol bisallyl carbonate, methyl methacrylate, Various acrylates and methacrylates such as 2-ethylhexyl methacrylate, n-butyl acrylate, diethylene glycol dimethacrylate, 1,3-butanediol diacrylate, phenyl methacrylate, 2,2-bis(4-methacryloxyethoxyphenyl)propane Examples include, but are not limited to, the following. This D component is 1
Not only one species but also two or more species can be used.

The ratio of the urethane monomers made up of the A component, B component, and C component and the D component can be changed depending on the intended use of the plastic lens material. 1 body is 30 for the whole
The Dlii content is in the range of 20 to 70% by weight. If the proportion of the urethane monomer is less than 30% by weight, the proportion of urethane bonds will be small, making it impossible to obtain a copolymer with excellent impact resistance.

In addition, the ratio of urethane monomer to the whole is 80% by weight and 1%.
If it exceeds the viscosity of the monomer composition, the viscosity of the monomer composition may become excessively high. Direct injection becomes impossible, and the cast polymerization method, which is preferred as a method for manufacturing plastic lenses, cannot be used.

The copolymer of the urethane monomer and component D has a crosslinked structure because a considerable portion of the urethane monomer has a plurality of components A bonded to its ends.

When producing a lens using the plastic lens material of the present invention, as described above, since the copolymer has a crosslinked structure, it is almost impossible to perform melt molding. Therefore, the cast polymerization method is preferably used.

In the case of obtaining the plastic lens material of the present invention by the cast polymerization method, glass, plastic, metal, etc., which are plate-shaped, lens-shaped, cylindrical, prismatic, conical, spherical, or otherwise designed according to the purpose, can be used. A mold or mold is prepared, and urethane monomer, which is a reaction product of components A, B, and C in a predetermined ratio, and component D are mixed together with a radical polymerization initiator. The resulting monomer composition may be injected, heated and polymerized.

During polymerization, various additives can be added to the monomer composition as necessary. Here, as an additive,
Colorants, ultraviolet absorbers, antioxidants, heat stabilizers, and others are used depending on the intended use of the resulting lens.

The obtained molded product may be used as the desired lens material as it is, or it can be further ground and polished to obtain the desired lens material.

As described above, in order to obtain the plastic lens material of the present invention,
Although we have explained the case where the urethane monomer formation reaction with component A, component B, and component C is carried out prior to the copolymerization reaction with component D, it is not always essential to carry out the urethanization reaction first. isn't it. That is, first, component A and component D may be copolymerized to form a polymer, and the hydroxyl groups of component A and component B in this polymer may be reacted together with component C to form a urethane bond. .

It is also possible to polymerize component A and component D to some extent, then perform a urethane bond forming reaction, and then complete the polymerization. In these cases as well, in the finally obtained polymer, the proportions of component A, component B, component C, and component D need to be within the same range as above. Note that by performing the copolymerization reaction in advance, there is a possibility that the subsequent urethanization reaction will not proceed smoothly. In such a case, it is preferable to carry out the urethanization reaction first.

The plastic lens material of the present invention obtained as described above is dyed, surface polished, and antistatic treated as necessary to further improve its properties as a lens and improve its surface hardness. In order to increase
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 applied to ordinary lenses.

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

Example 1 20.6 g of 2-hydroxyethyl methacrylate, 29.8 g of metaxylylene diisocyanate, and 2.2'
- Thoroughly mix 9.6 g of thiodiethanol and 40 g of styrene, and add 0.0 g of dibutyltin dilaurate. old g
was added and reacted at 60° C. for 2 hours to perform a urethanization reaction. Here, α-0,505 and β=0.495.

To the obtained liquid, 1 g of lauroyl peroxide was further added to obtain a monomer composition, which was poured into a glass mold with a spherical inner surface and heated at 50°C for 2 hours.
The copolymerization reaction was carried out by changing the conditions for 10 hours at 60°C, 2 hours at 80°C, and 3 hours at 100°C, and the center thickness was 2.
A concave lens made of a transparent copolymer with a diameter of 1 m+m and 75 cm was obtained. The refractive index of this copolymer was measured using an Atsube refractometer and found to be nf-1,581.

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

Furthermore, in accordance with U.S. FDA standards, this lens was subjected to an impact resistance test using the steel ball drop method, in which a steel ball weighing 16.33 g was dropped onto a sample from a height of 127 cm, and no damage was found. It was recognized that the material had excellent impact resistance.

Further, the specific gravity of this copolymer was extremely small at 1.19.

Comparison example 1 2-b droxyethyl methacrylate-1-21.0g,
30.4 g of meta-xylylene diisocyanate, 8.6 g of diethylene glycol, and 40 g of styrene were thoroughly mixed, and urethanization reaction and polymerization were carried out in accordance with the method of Example 1 to obtain a carp with a center thickness of 2.1 g. A concave lens made of a transparent copolymer with a diameter of 75 was obtained. Here, α
=0.497, β-0,503.

The refractive index of this copolymer is nW -1,567, and the specific gravity is 1
．． It was 20.

Further, when this lens was subjected to an impact resistance test in the same manner as in Example 1, no damage was found.

From the above, the copolymer obtained in Example 1 has the same specific gravity and the same excellent impact resistance as the copolymer of Comparative Example 1 due to containing sulfur atoms. Moreover, it is clear that the refractive index is high.

Comparative Example 2 17.4 g of 2-hydroxyethyl methacrylate,
25.1 g of metaxylylene diisocyanate and 2.2
-bis(bromomethyl)-1,3-propanediol 1
7.5 g of styrene and 40 g of styrene were thoroughly mixed, and a urethanization reaction and a polymerization reaction were carried out according to the method of Example 1 to obtain a concave lens made of a transparent copolymer with a center thickness of 2.1 mm and a diameter of 75 mm+. Obtained. Here, α-0,5
00, β-0,500.

The refractive index of this copolymer was nW = 1.583, and the specific gravity was 1.40.

On the other hand, when this lens was subjected to an impact resistance test in the same manner as in Example 1, it was damaged.

From the above, the copolymer obtained in Example 1 has a refractive index equal to or higher than that of the copolymer of Comparative Example 2 containing halogen atoms, and has a lower specific gravity. It is clear that the impact resistance is also compromised.

Example 2 17.3 g of 2-hydroxyethyl meccryl, 29.6 g of inphorone diisocyanate, and 2°2'
- 8.1 g of thiodiethanol and 30 g of styrene,
Example 1
A concave lens made of a transparent copolymer having a center thickness of 2 mm and a diameter of 75 mm was obtained by carrying out a urethanization reaction and polymerization according to a method similar to the above. Here α=0.502β−0,49
It is 8.

The refractive index of this copolymer was nW = 1.581, and the specific gravity was 1.13.

Further, when this lens was subjected to an impact resistance test in the same manner as in Example 1, no crushing occurred and it was recognized that it had excellent impact resistance.

Comparative Example 3 17.6 g of 2-hydroxyethyl methacrylate, 3'0.2 g of isophorone diisocyanate, 7.2 g of diethylene glycol, 30 g of styrene, and 15 g of α-methylstyrene were thoroughly mixed, and the mixture was prepared according to Example 1. The urethanization reaction and polymerization were carried out by the following method to obtain a concave lens made of a transparent copolymer and having a center thickness of 2 mm and a diameter of 75 mm. Here, α=0.500β=0.500.

The refractive index of this copolymer is n = 1.534, and the specific gravity is 1.
．． It was 13.

On the other hand, when this lens was subjected to an impact resistance test in the same manner as in Example 1, no damage was found.

From the above, the copolymer obtained in Example 2 has a lower specific gravity and superior impact resistance than the copolymer of Comparative Example 3 due to the inclusion of sulfur atoms. However, it is clear that it also has a high refractive index.

Example 3 28.3 g of 2-hydroxy-3-phenoxypropyl acrylate and metaxylylene diine cyanide) 2
4.0 g, 7.7 g of 2.2°-thiogetanol, and 40 g of styrene were thoroughly mixed, and a thiourethane reaction and polymerization were performed by a method similar to Example 1.
A concave lens made of a transparent copolymer with a center thickness of 2.0 mm and a diameter of 80 mm was obtained. Here, α=0, 495, β=0.
It is 495.

The refractive index of this copolymer is n = 1.586, and the specific gravity is 1.
．． It was 18.

Further, when this lens was subjected to an impact resistance test in the same manner as in Example 1, no shattering occurred, and it was found that it had excellent impact resistance.

Example 4 23.2 g of 2-hydroxyethyl methacrylate, 20.1 g of hexamethylene diisocyanate, 4.
6.7 g of 4'-thiodiphenol and 50 g of styrene were thoroughly mixed, and urethanization reaction and polymerization were carried out in accordance with the method of Example 1 to obtain a material with a center thickness of 2.1 mm and a diameter of 8 mm.
A concave lens made of a 0M transparent copolymer was obtained. Here, α=0.743 and β=0.257.

The refractive index of this copolymer is n%! = 1.584, and the specific gravity was 1.15.

Further, when this lens was subjected to an impact resistance test in the same manner as in Example 1, no shattering occurred, and it was found that it had excellent impact resistance.

Comparative Example 4 2-hydroxyethyl methacrylate) 23.1 g
, 20.0 g of hexamethylene diisocyanate, 6.9 g of bisphenol A, and 50 g of styrene were thoroughly mixed, and urethanization reaction and polymerization were performed according to the method of Example 1 to obtain a material with a center thickness of 2.1 mm and a diameter of An 80 mm concave lens made of a transparent copolymer was obtained. Here, α=
0.746, β=0.254.

The refractive index of this copolymer was rl =1,562, and the specific gravity was 1.16.

Further, when an impact resistance test was conducted on this lens in the same manner as in Example 1, it was completely damaged.

From the above, the copolymer obtained in Example 4 has a higher refractive index and superior impact resistance than the copolymer of Comparative Example 4 due to the inclusion of sulfur atoms. is clear.

Example 5 8.9 g of 2-hydroxyethyl methacrylate, 15.2 g of inphorone diisocyanate, 10.9 g of 1,1-thiobis(2-naphthol), and 45 g of styrene.
and 20 g of α-methylstyrene were thoroughly mixed, and urethanization reaction and polymerization were carried out according to the method of Example I to obtain a concave lens made of a transparent copolymer with a center thickness of 2.0 mm and a diameter of 75 mm. Obtained. Here, α=0.500,
β=0.500.

This copolymer has a refractive index of nf-1,580 and a specific gravity of 1.
It was 12.

Further, when this lens was subjected to an impact resistance test in Example 17 in the same manner as in Example 1, no shattering occurred and it was found that the lens had immersed impact resistance.

Example 6 2-hydroxy-3-phenoquinepropyl acrylate)
35.8 g and 1 hexamethylene diisocyanate
3.9 g, 0.3 g of 2.2″-thiodiethanol,
Diethylene glycol dimethacrylate (note 10g and α
- 40 g of methylstyrene were sufficiently mixed, and urethanization reaction and polymerization were carried out according to the method of Example 1 to obtain a concave lens made of a transparent copolymer with a center thickness of 1.7 flI11 and a diameter of 80 mm. Here, α-0,980,
β-0,030.

This copolymer has a refractive index of nτ-1,576 and a specific gravity of 1.
It was 16.

In addition, when this lens was subjected to an impact resistance test in the same manner as in Example 1, no fracture occurred at all, indicating that it had excellent impact resistance.

Claims (1)

[Scope of Claims] 1) The following component A is combined with the following component B and component C below, the number of moles of hydroxyl groups in component A is a, the number of moles of isocyanate groups in component B is b, and the number of moles of hydroxyl groups in component C is When the number is c, the value of the ratio α=a/b is 0<α≦2.0,
And, it is obtained by reacting in a relative proportion such that the ratio β=c/b value is 0.01≦β<1, and polymerizing it with the following component D in a proportion of 20 to 70% by weight based on the whole. A plastic lens material characterized by being made of a copolymer. Component A: A monomer having a radically polymerizable unsaturated group having a hydroxyl group in the molecule Component B: A polyisocyanate compound having multiple isocyanate groups in the molecule Component C: In a molecule represented by the following general formula (I) Sulfur compound having two hydroxyl groups General formula (I) HOR^1-S-R^2OH (R^1 and R^2 each represent an aliphatic or aromatic hydrocarbon group.) Component D: The above A Monomer copolymerizable with components