JPS6234101A - Plastic lens having high refractive index - Google Patents

Abstract

PURPOSE:To obtain a high refractive index, satisfactory formability and heat resistance by using a resin contg. specified two kinds of monomers as essential components and having a three-dimensional structure. CONSTITUTION:A plastic lens is made of a resin contg. a monomer represented by formula I (where X is halogen other than F and m=1-5) and a monomer represented by formula II (where R is H or methyl, X is halogen other than F, Y is a group represented by formula III, m=3-5 and n=0-5) as essential components and having a three-dimensional structure. A residue of a multifunctional vinyl compound represented by formula IV (where each of R1 and R2 is H or methyl, X is halogen other than F, A is -SO4- or the like, m=0-2 and n=0-1) or formula V is preferably used as a compound having a three-dimensional structure in the resin. It is preferable that the resin is composed essentially of 20-85pts.wt. monomer represented by the formula I, 5-70pts.wt. monomer represented by the formula II and 10-60pts.wt. units having a three-dimensional cross-linkable structure. Since the monomers represented by the formulae I, II are used by large amounts, a lens having a high refractive index of >=1.63 is obtd. and the thickness of the peripheral part of the lens can be reduced. Since the multifunctional monomer is used, the degree of cross-linking is increased and superior heat and shock resistances and workability are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a plastic lens with a high refractive index and excellent transparency and heat resistance.

[Conventional technique N・↑j] Plastic lenses have been widely used in optical products in recent years because they are superior to glass lenses in terms of lightness, workability, impact resistance, dyeability, etc. In particular, there is a particularly high demand for lightweight lenses for eyeglass lenses, and currently about 40% of lenses are replaced by plastic.

Conventionally, dielene glycol bisallyl carbonate resin (CR-1) is used as a resin for eyeglass plastic lenses.
39) and polymethyl methacrylate (PMM
A) is mainly used.

In particular, since it has a diethylene glycol bisallyl carbonate crosslinked structure, it has high surface hardness and excellent processability, and is most commonly used today as a lens for eyeglasses for vision correction.

Furthermore, as prior art to the present application, Japanese Patent Publication No. 58-14449
Publication No. 60-1 7081, Japanese Patent Application Publication No. 1983
JP-A-13747, JP-A-56-3-6601, JP-A-60-69114, etc.

[Problems to be Solved by the Invention] However, diethylene glycol bisallyl carbonate resin has a refractive index of 1.49 to 1.50, which is lower than the refractive index of ordinary glass lenses (1.5 to 1.6). For,
When a lens is made of this resin, the outer periphery of the lens is thicker than that of glass, resulting in poor visibility. This is particularly noticeable when the power of the lens increases.

In addition, PMMA has the same problems as the diethylene glycol bisallyl carbonate resin mentioned above, and since it is a two-dimensional polymer and thermoplastic, it has poor processability and is only used in some sunglasses and safety glasses. .

On the other hand, in the prior art, resins with a fairly high refractive index (II,) of around 1.60 are obtained, and diethylene glycol bisallyl carbonate resin and PPMA
This has almost solved the drawback that the outer peripheral part of the lens is thick. However, the medium to high refractive index is still insufficient compared to lath lenses (refractive index = 1.6 to 1.8), and further improvements have been desired.

To show a concrete comparison with the prior art, for example,
In Example 1 of Publication No. 8-1 4449, it is described that a copolymer of dimethacrylate of a tetrabromosphenol A derivative and crossstyrene has a maximum refractive index of 1.608.

Furthermore, in Example 3 of JP-A-60-69114, it is described that a copolymer of dimethacrylate of tetrabromobisphenol Ag4 and methacrylate of a nuclear halogen-substituted phenol derivative has a maximum refractive index (IIo) of 1.608. has been done. However, all resins have a refractive index of 1.63 or less.

In view of the above drawbacks, the present invention has a refractive index (IID) of 1.63.
The object of the present invention is to provide a plastic lens that has extremely high properties as described above and also has excellent polymerization properties and heat resistance.

[Means for solving problems] In order to achieve the above object, the present invention has the following configuration.

``A high refractive index plastic lens comprising a resin having repeating structural units represented by general formulas I and II as a main component and having a three-dimensional crosslinked structure.

General formula I (In the formula, × represents a halogen atom excluding fluorine, m = an integer of 1 to 5.) General formula ■ (In the formula, R is hydrogen or a methyl group, X is a halogen atom excluding fluorine, Y is from OC82CH2-1) one or more repeated units, m = 3 to 5, n
= represents an integer from Q to 2. ) In the present invention, preferably, the main components are styrene substituted with a nuclear halogen and (meth)acrylate of a phenol derivative substituted with a nuclear halogen, and the copolymerization component is a di( It has a copolymer structure obtained by reacting one or more monomers selected from methacrylate, di(meth)acrylate of 2,2-bisphenolpropane (hereinafter abbreviated as bisphenol A) derivative, and divinylbenzene. Required with plastic lenses.

In the present invention, the nuclear halogen-substituted styrene residue is 20 to
A range of 85 strain opening is possible, but preferably 30-8
0 unit is part. If it is less than 20 parts by weight, it is difficult to obtain a high refractive index of 1.63 or more, while if it exceeds 85 parts by weight, crosslinking will be insufficient and the processability of the lens will tend to deteriorate.

The (meth)acrylate residue of the nuclear halogen-substituted phenol derivative can range from 5 to 70 parts by weight, and from 20 to 6 parts by weight.
0 parts by weight is preferred. Although a high refractive index lens of the order of 1.63 can be obtained even with a resin having no (meth)acrylate residue of a nuclear halogen-substituted phenol derivative, the Abbe number tends to be low, so 5 parts by weight or more is preferable.

On the other hand, if the amount exceeds 70 parts by weight, the solubility will be insufficient and it will be difficult to put it into practical use.

Residues of polyfunctional monomers required as crosslinking agents, i.e., di(meth)acrylate residues of bisphenol S derivatives, di(meth)acrylates of bisphenol A derivatives, divinylbenzene residues, alone or in a mixture thereof, in the amount can range from 10 to 60 parts by weight, preferably from 15 to 50 parts by weight. If the amount is less than 10 parts, crosslinking will be insufficient and it will be difficult to obtain lenses with excellent heat resistance and impact resistance.

On the other hand, if the amount exceeds 60 parts by weight, in systems containing residues of di(meth)acrylate of bisphenol S derivatives and di(meth)acrylate of bisphenol A derivatives, each monomer becomes insufficiently dissolved, making practical use impossible. It can be difficult.

The composition and ratio of each component constituting the copolymer of the present invention are determined by FT-IR, NMR, GL, GC-MS, and HPLC.
It can be easily confirmed using ordinary analytical procedures such as elemental analysis.

The nuclear halogen-substituted styrene residue constituting the present invention can be achieved by polymerizing using the following monomers. For example, monobrostyrene, dibrostyrene, tribrostyrene, monochlorostyrene, dichlorostyrene, trichlorostyrene, monoiodostyrene,
Short styrene, etc., and mixtures thereof.

Particularly preferred among these are monobrom styrene, dibrom styrene, dichlorostyrene, and mixtures thereof.

Of the nuclear halogen substituted phenol derivatives constituting the present invention (
The meth)acrylate residue can be obtained by polymerizing using the monomer m described below. For example, 3-tribromophenoxy-2-hydroxypropyl (meth)
Acrylate, 3-pentabromophenoxy-2-hydroxypropyl (meth)acrylate, 3-trichlorophenoxy-2-hydroxypropyl (meth)acrylate, pentachlorophenoxy-2-hydroxypropyl (meth)acrylate, tribromophenoxy (meth) Acrylate, tribromophenoxyethyl (meth)
Acryle-1~, pentabromophenoxy (meth)acrylate, pentabromophenoxyethyl (meth)acrylate, trichlorophenoxy (meth)acrylate, trichlorophenoxyethyl (meth)acrylate,
Pentachlorophenoxyethyl (meth)acrylate-1~
, pentachlorophenoxyethyl (meth)acrylate, etc., and mixtures thereof.

Particularly preferred among these are tribromophenoxyethyl (meth)acrylate, pentabromophenoxyethyl (meth)acrylate, and 3-dribromophenoxy 2-hydroxypropyl (meth)acrylate.

The di(meth)acrylate residue of the bisphenol S derivative, which is a preferred constituent of the present invention, can be coupled by combining the following monomers. For example, 2,2-bis(14-acryloyloxyethoxy-
3,5-dibromophenyl)sulfone, 2,2-bis(
4-methacryloyloxyethoxy-3,5-dibromophenyl) sulfone, 2,2-bis(4-acryloyloxyjethoxy-3,5-dibromophenyl) sulfone, 2,2-bis(4-methacryloyloxyjethoxy- 3,5-dibromophenyl) sulfone, 2,2-bis(4-acryloyloxyethoxy-+3,5-dichlorophenyl) sulfone, 2゜2-bis(4-methacryloyloxyethoxy-3,5-dichlorophenyl) sulfone etc., and mixtures thereof.Particularly preferred among these are 2,2-bis(4-acryloyloxy-1-x-3,5-dibromophenyl)sulfone, 2,2-bis(4- methacryloyloxyethoxy-3,5-dibromophenyl) sulfone.

Bisphenol A, a preferred component constituting the present invention
The di(meth)acrylate residue of the derivative can be achieved by polymerization using the following monomers.

For example, 2,2-bis(4-acryloyloxyethoxy-3,5-dibromophenyl)propane, 2,2-bis(4-methacryloyloxyethoxy-3,5-dibromophenyl)propane, 2,2-bis(4-methacryloyloxyethoxy-3,5-dibromophenyl)propane, (4-acryloyloxyjethoxy-3,5-dibromophenyl)
Propane, 2,2-bis(4-methacryloyloxyjetoxy-3,5-dichlorophenyl)propane, 2,
2-bis(4-methacryloyloxyjetoxy-3,
5-dichlorophenyl)propane, and mixtures thereof. Among these, 2.
2-bis(4-acryloyloxyethoxy-3,5-
dibromophenyl)propane, 2,2-bis(4-methacryloyloxyethoxy-3,5-dibromophenyl)propane, and 2,2-bis(4-acryloyloxyethoxy-3,5-dibromophenyl)propane.

Divinylbenzene residue, which is a preferred constituent of the present invention, can be obtained by combining divinylbenzene monomer.

In the present invention, it is possible to use a monomer copolymerizable with the above-mentioned monomers in an amount of 20 parts by weight or less. Since the resin for plastic lenses of the present invention frequently uses halogen-substituted styrene and (meth)acrylate of halogen-substituted phenol derivatives as its constituent components, a lens with a very high refractive index of about 1.63 or more can be obtained. Further, it has a feature that the refractive index can be adjusted by appropriately selecting copolymer components.

Of course, the lens resin of the present invention has a high degree of crosslinking due to the combined use of a polyfunctional monomer, and also has excellent heat resistance, impact resistance, and processability.

The method of manufacturing a plastic lens of the present invention is carried out by a casting method. That is, by mixing the nuclear halogen-exchanged styrene and the halogen-exchanged phenol derivative (meth)acrylate, and then mixing the crosslinking agent component, for example, bisphenol S derivative di(meth)acrylate-1, divinylbenzene. j Add one or more aromatic monomers and mix and dissolve.

Melting is possible at temperatures ranging from warm and humid to 80'C.

After dissolving, a radical polymerization initiator and various additives are added and mixed. Various known radical polymerization initiators can be used. For example, cyisopropylperoxydicarbonate, t-butylperoxypivalate,
Filter with t-butylperoxyisobutylene-1., t-butylperoxyisopropyl carbonate, etc. Preferred are t-butylperoxyisobutyrate and t-butylperoxyisopropyl carbonate.

The amount used can range from 0.09005 to 3% by weight, but is preferably from 0.01 to 0.1ffiffi%.

Types of additives include ultraviolet absorbers, antioxidants, deodorizers, aromatic additives, etc., and any known additives can be used. As a result of examining various additives, the present inventors found that Tinuvin 328 (trade name, Jiha Geigy Co., Ltd.) was used as an ultraviolet absorber.
Irganox 1076 (trade name, Ciba Kaigy Co., Ltd.) as an antioxidant in the range of 1 to 1.0 ffiffi%.
It has been found that addition in the range of 1.0% by weight is good.

After various additives are added and mixed and dissolved, the monomer mixture is passed through a membrane filter, and dissolved gases such as air are then vacuum-degassed, and the monomer mixture is injected into a mold. The mold consists of two glass plates that form the concave and convex surfaces of the lens, and a polyethylene gasket 1 that holds them.

After pouring it into the mold, heat it in a pot and cover it. Polymerization step A1 is a polymerization process in which the frame used (this varies depending on the type of agent II, polymerization initiator, etc., but generally the temperature range is from 40'C to 120'C is gradually brought to ambient temperature over 15 to 40 hours). For example, in the case of bisphenol S di(meth)acrylate, polymerization is carried out at 60'C for 20 hours, at 70°C for 5 hours,
Polymerization is carried out at 100'C for 10 hours, and the mold is released after cooling slowly.

The plastic lens of the present invention can be subjected to known surface modifications such as hard coating, antireflection, anti-snow protection, improved abrasion resistance, and improved chemical resistance.

[Example] Next, the present invention will be illustrated by examples. Various physical properties of the polymers obtained in the Examples were measured by the following test methods.

(1) Using the refractive index and Atsbe number Pulfrich refractive index, the wavelength is 58 at a temperature of 20'C.
Measurements were taken at the D line for 9.3 people, the E line for 546.1 people, and the underlined line A'↑ for 486.1 people.

(2) Color tone The color tone of the lens molded product was visually determined.

(3) Bending rigidity: Based on JIS K 7203. However, the shape of the test piece is 30mm x 10mi x 3mm, and the distance between the fulcrums is 2.
2TrlrrI.

(4) Post-processable molded lenses are polished, dyed, hard coated, anti-reflective,
Appearance A5 and optical stability of lens when anti-fogging property etc. are applied Example 1 50 parts by weight of dibromustyrene, 1 to 20 parts by weight of phenoxyethyl acrylate on pentapro, 2,2-bis( 4-
After dissolving 30 parts by weight of acryloyloxyethoxy-3.5 dibromophenyl) sulfone at 50'C, 0.03% by weight of t-butylperoxyisopropyl carbonate as a polymerization initiator was added and mixed well. Zarani, ultraviolet absorber Dinuvin 328 (Ciba-Geigi brand name) 0.3% by weight, antioxidant Irganox 1076
(Ciba Geigy Co., Ltd. trade name) 0.3% by weight was added and sufficiently dissolved and mixed. Furthermore, ultraviolet absorber Tinuhin 328 (product name of Ciba Geigy Co., Ltd.) 0.3%, antioxidant Irganox 1076 (product name of Ciba Geigy Co., Ltd.) 0.3%,
was added and thoroughly dissolved and mixed.

After passing through the solution, dissolved air was removed by vacuum degassing. The mold was poured using a syringe into a mold opened with a glass mold for lens molding having a diameter of 80 mm and a polyester-lined gasket.

The polymerization was first solidified at 60'C for 20 hours, then completed at 70'C for 5 hours and at 100'C for 10 hours. After the polymerization was completed, the polymer was gradually cooled and taken out from the mold. Table 1 shows various physical properties of the obtained polymer. The jq Radar lens is strong and rigid, has a high refractive index nD of 1.66, and has an Atsbe number of 30.

Example 2 2,2-bis(4-acryloyloxyethoxy-3,5-dibromophenyl)sulfone used in Example 1 was replaced with 2,2-bis(4-acryloyloxyethoxy-3,5-dibromophenyl). Polymerization was carried out using the same composition, additives, and operating method as in Example 1, except that phenyl)propane was used. Table 1 shows the physical properties of the obtained polymer.

Examples 3 and 4, Comparative Examples 1 and 2 Lenses with different compositions were produced by the same method as in Example 1, and the results are shown in Table 1. As is clear from Table 1, the lens according to the present invention had a very high refractive index and also had excellent performance in casting workability, heat resistance, and post-processability.

[Advantageous Effects of the Invention 1] The plastic lens of the present invention has the following characteristics compared to conventional plastic lenses.

■ Due to its ultra-high refractive index, the thickness of the outer periphery of the lens can be made much thinner.

■ Lenses with excellent heat resistance and processability (7).

(2) Since 7JO is added to the di(meth)acrylate compound of the nuclear halogen-substituted phenol derivative, and )) modified cedar halogen-substituted soot-styrene is used as an essential component, the workability is good.

Claims (5)

[Claims] (1) A high refractive index plastic lens comprising a resin having repeating structural units represented by general formulas I and II as a main component and having a three-dimensional crosslinked structure. General formula I ▲Mathematical formulas, chemical formulas, tables, etc.▼・・・(I) (In the formula, X represents a halogen atom excluding fluorine, m = an integer from 1 to 5.) General formula II ▲Mathematical formulas, chemical formulas , tables, etc. ▼...(II) (In the formula, R is hydrogen or methyl group, X is a halogen atom excluding fluorine, Y is -O-CH_2-CH_2-, ▲ Numerical formula, chemical formula, table, etc. There are ▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ One or more types of repeating units selected from m = 3 to 5, n =
Represents an integer from 0 to 2. ) (2) A high refractive index plastic lens according to claim (1), wherein the compound having a three-dimensional crosslinked structure is a compound having a residue of a polyfunctional vinyl compound. (3) A high refractive index plastic lens according to claim (2), wherein the residue of the polyfunctional vinyl compound is represented by the general formula III. General formula III ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) (In the formula, R_1 and R_2 are hydrogen or methyl groups, X is a halogen atom excluding fluorine, A is ▲mathematical formulas, chemical formulas, tables, etc. There are ▼ or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼,
Represents an integer of m=0 to 2 and n=0 to 1. (4) A high refractive index plastic lens according to claim (2), wherein the residue of the polyfunctional vinyl compound is represented by the general formula IV. General formula IV ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(IV) (5) 20 to 85 parts by weight of general formula (I), general formula (II)
) and 10 to 60 parts by weight of a unit having a three-dimensional crosslinked structure, the high refractive index plastic lens according to claim 1.