JPS6267501A - Copolymer for optical use - Google Patents

Abstract

PURPOSE:To obtain a plastic base material for lens having high refractive index and superior characteristics by using, as principal components, a specified first monomer comprising an ester deriv. of p-hydroxy benzoic acid, and at least one kind of radically polymerizable second monomers which may produce homopolymers having >=1.55 refractive index. CONSTITUTION:A plastic base material consists, as principal components, of at least one kind of the first monomer expressed by the formula, and at least one kind of radically polymerizable second monomers which produce homopolymers having >=1.55 refractive index. In the formula, R1 is H or CH3, and R2 is 2-6C alkylene which may contain an 0 atom in the C-C bond. The copolymer has >=1.55 refractive index, and is superior in the castability, mold releasability, impact resistance, workability, dyeability, heat resistance, surface hardness, solvent resistance, chemical resistance, weather resistance, light resis tance, ultraviolet rays absorbing property, sweat resistance, and in the adhesion to antireflection film and hard coat silicone film, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a lens copolymer useful for plastic lenses, and more particularly to a lens copolymer having a high refractive index and excellent mechanical properties.

(Adventures of the Invention) Recently, plastic lenses have been preferred instead of glass lenses for eyeglass lenses. Plastic lenses are lightweight, safe (impact resistance), easy to work with, and have advantages that glass lenses do not have.
It has advantages such as dyeability, and until now it has been used as a plastic material, for example, polymethyl methacrylate, polydiethylene glycol bisallyl carbonate (so-called C
R-39 resin), polycarbonate, polystyrene, etc. are used. Among them, CR-39 resin is superior to other plastics in all characteristics, and almost 100% of corrective eyeglass lenses are made of CR-39 resin.

However, the only drawback of this CR-39 resin is its low refractive index, n, -1,49 (glass is
1.53). Therefore, concave lenses for nearsightedness have significantly thicker edges than glass lenses, while convex lenses for farsightedness or presbyopia have thicker centers, and in both cases, the curvature becomes steeper, which is disliked by eyeglass wearers. is inviting.

On the other hand, polystyrene has a relatively high refractive index of 1.59, but is difficult to use because it has low surface hardness, poor heat resistance, solvent resistance, and weather resistance, and poor dyeability. A method of copolymerizing styrene with methyl methacrylate or acrylonitrile to improve surface hardness, weather resistance, etc. to some extent is already known, but heat resistance, solvent resistance, etc. are hardly improved, and the refractive index is It decreases as the proportion of the two components increases. Furthermore, although plastics such as polyvinylnaphthalene, polyvinylcarbazole, and polynatallylate have high refractive indexes, they are extremely discolored and have extremely poor impact resistance, weather resistance, etc., so that they cannot be used as lenses at all.

(Object of the invention) Therefore, the present invention has a high refractive index of 1.55 or more,
and cast moldability, mold releasability, impact resistance, processability, dyeability,
Heat resistance, surface hardness, solvent resistance, chemical resistance, weather resistance, light resistance, ultraviolet absorption, sweat resistance, adhesion of antireflection coatings (inorganic dielectric multilayer or single layer coatings) and silicone hard coat coatings. Our objective is to provide plastic materials for lenses with excellent properties.

(Summary of the Invention) As a result of extensive research, the present inventors have discovered that a copolymer having the composition shown below is optimal for the intended material, and has accomplished the present invention.

That is, the present invention provides one ship type I: (in the formula, R is H or CH, one group, and R2 is C-
2 to 6 carbon atoms in which an oxygen atom may intervene in the C bond
is an alkylene group. ), the refractive index of the ester derivative and homopolymer of parahydroxybenzoic acid, which is one or more first monomers, is 1.
．． Provided is a copolymer for a lens having a refractive index of 1.55 or more, the main component of which is one or more radically polymerizable second monomers having a refractive index of 55 or more.

Further, the present invention provides a lens made of the above copolymer.

The first monomer represented by the general formula I used as the main component in the present invention is a new compound that has not been reported in literature, patents, etc., for example, the general formula 1 mole of a diester of glycol hydroxybenzoic acid represented by the general formula (1): R.

A dehydrohalogenation reaction is carried out with 2 moles of methacrylic acid or acrylic acid halide represented by CHt-C-(nee It can be obtained by

The starting material, the compound of general formula (2), is known and may be available as a commercial product, but if it is not available, (a) 2 moles of parahydroxybenzoic acid or its derivative and 1 mole of glycol are esterified. or else (b) 2 moles of an alkali salt of barahydroxybenzoic acid with the general formula rV: x, pg
Synthesize the compound of the general formula (■) by carrying out a dehalogenating alkali reaction with 1 mol of α,ω-dihalogenated alkane represented by can do.

In addition, the first monomer of the general formula (2) is prepared by adding 2 moles of an alkali salt of parahydroxybenzoic acid to the first monomer of the general formula (2): L Rt
By performing a dehalogenating alkali reaction with 1 mole of α,ω-dihalogenated alkane represented by It can be synthesized by carrying out a dehydrohalogenation reaction with 2 moles of methacrylic acid or acrylic acid halide.

The first monomer represented by formula I may be used alone or in combination of two or more.

The first monomer is used in an amount that accounts for 3 to 80 weight percent of the total monomer mixture, particularly preferably in an amount that accounts for 5 to 40 weight percent. This is because when the amount of the first AI used is less than 3% by weight, no improvement is seen in surface hardness, solvent resistance, heat resistance, coatability, processability, etc. If it exceeds the range, the surface hardness will increase significantly, but the impact resistance and workability will be extremely reduced, which is not preferable.

On the other hand, as the radically polymerizable second monomer whose homopolymer has a refractive index of 1.55 or more, any monomer may be used as long as it is colorless and transparent and satisfies the above requirements, such as the following: used.

(1) Halogen-substituted or unsubstituted styrene or its derivative (2) Halogen-substituted or unsubstituted phenyl ester of methacrylic acid or acrylic acid (1 = 4 halogens may be substituted, and types of halogen include chlorine, (3) Halogen substitution of methacrylic acid or acrylic acid or tA benzyl ester (1 to 4 halogens may be substituted, and the type of halogen is chlorine, bromine or iodine) ) (4) o-phthalic acid diallyl ester (benzene nucleus may be substituted with halogen) (5) unsaturated epoxy resin (bisphenol A type) (6) 2-methacryloyloxy or 2- Phenyl ester or benzyl ester of acryloyloxybenzoic acid (The benzene nucleus and phenyl or benzyl nucleus of benzoic acid may be substituted with 1 to 4 halogen atoms, and the types of halogen include chlorine, bromine, or iodine. Any of these monomers may be used.) From the purpose of the present invention, it is particularly preferable to use the monomer (6).

In addition to the above monomers, α-naphthyl methacrylate, β
- Second monomers such as naphthyl methacrylates such as naphthyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, vinylnaphthalenes such as 1-vinylnaphthalene and 2-vinylnaphthalene, 4-vinylbiphenyl, divinylbenzene, vinyl phenyl sulfide, etc. is available.

The second monomer may be used alone or in a mixture of two or more types.The amount to be used varies depending on the type and amount of the first monomer to be copolymerized, so it cannot be determined uniquely. However, for the purpose of the present invention, a range of 20 to 97% by weight is preferably used. If the amount of the monomer used is less than 200% by weight, the crosslinking density will increase and the impact resistance of the resulting copolymer will decrease, while if it exceeds 97% by weight, surface hardness, solvent resistance, etc. will decrease. No improvement seen and not desirable.

In the present invention, it is possible to easily obtain the desired copolymer for lenses with a high refractive index by copolymerizing only the first monomer and the second monomer; , refractive index 1.5 to improve impact resistance, weather resistance, etc.
It is also possible to copolymerize 0 to 67% by weight of a radically polymerizable third monomer having no groove. Generally, as the refractive index of a copolymer increases, its impact resistance rapidly decreases. In order to improve this decrease in impact resistance, butyl (meth)
It is desirable to copolymerize acrylate, (meth)acrylic acid alkyl esters such as β-hydroxylethyl methacrylate, and to improve dyeability and weather resistance, diethylene glycol bisallyl carbonate,
It is preferable to copolymerize methyl methacrylate or the like.

In order to polymerize the copolymer for lenses according to the present invention, the monomer mixture is heated together with an initiator if necessary. In addition to or in place of heating, radiation such as ultraviolet rays, T-rays, X-rays, and electron beams may be irradiated.

As the initiator, common radical initiators such as benzoyl peroxide, diisopropyl peroxydicarbonate, and azobisisobutyronitrile can be used.

In the case of polymerization, it is preferable to carry out polymerization and molding at the same time, and the mixture of the monomer mixture and the radical initiator is poured into a mold assembled with a mold (made of glass or metal) and a gasket. , polymerization and curing using means such as heating or radiation irradiation.

Of course, it is also possible to adopt a method of curing by irradiating with radiation without using any agent.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. In addition, in the example,
All percentages and parts are by weight unless otherwise specified.

Reference Example 1 (First unit) IMBP combination) 11
MBP: 1,3-bis[(4'-methacryloyloxy)benzoyloxyfupropane 166g of rose hydroxybenzoic acid about 4oo117!
of methanol, and to this solution was added, without stirring, 71 g of potassium hydroxide dissolved in about 300 mL of methanol. The resulting mixed solution was heated to 60°C to completely dissolve the solid content (potassium salt), then cooled to room temperature, and the resulting precipitate was filtered and dried to yield 194 g.
A parahydroxybenzoic acid potassium salt (having the above structural formula) was obtained. Yield: 92% A solution of 176 g of potassium parahydroxybenzoate dissolved in 500 ml of dimethylformamide was charged into a flask equipped with a stirrer, thermometer, condenser, dropping funnel, and nitrogen introduction tube, and refluxed while flowing nitrogen gas. When 101 g of 1,3-dibromopropane was added dropwise under these conditions and reacted for 3 hours, potassium bromide was precipitated.

After cooling the resulting reaction mixture, potassium bromide was filtered off, and the filtrate was concentrated by heating. The concentrated solution was dropped into water, the resulting precipitate was filtered off, and the resulting solid was dried, then dissolved in a mixed solvent of methanol/water and recrystallized.

The obtained crystals were filtered and dried to obtain 100 g of product. Yield: 63% (3) Synthesis of the final target product: 32 g of the product from (2) above was dissolved in about 200 mff of tetrahydrofuran and cooled to 0°C. This solution is 0
An aqueous solution containing 28 g of methacrylic acid chloride followed by 115 g of sodium hydroxide while being maintained at
001111 was added dropwise over a total of 1 hour. After the dropwise addition was completed, the temperature was returned to room temperature and the reaction was allowed to proceed for 3 hours.

When the reaction product was allowed to stand still, it separated into two layers, a solvent layer and an aqueous layer, so the aqueous layer was removed and the solvent layer was concentrated. The obtained concentrate was dropped into a dilute NaOH aqueous solution, and the generated precipitate was filtered off, washed with water, and dried. The obtained solid was recrystallized twice with ethanol, filtered, and dried to obtain 13 g of white powder. Yield: 2
8% (4) Melting point of target product: 97-102'C (5) Actual elemental analysis value of target product: C25,3; H2S,6; 07.8 Theoretical: C25; H24; 6) NMR chart of target product: Figure 1, reference 3''LL
"Synthesis of Group I BH, which is the first monomer) 11 BE: 1.
2-bis[(4'-methacryloyloxy)benzoyloxy]ethane 149 g of the product synthesized in Section (1) of Reference Example 1 was
+si! This solution was charged into a flask equipped with a stirrer, a thermometer, a condenser, a dropping funnel, and a nitrogen inlet tube, and 41 g of 1,2-dichloroethane was added under reflux conditions while flowing nitrogen gas. When the mixture was reacted dropwise for 3 hours, potassium chloride was precipitated.

After cooling the resulting reaction mixture, potassium chloride was filtered off, and the filtrate was concentrated by heating. The concentrated solution was dropped into water, the resulting precipitate was filtered off, and the resulting solid was dried, then dissolved in a mixed solvent of methanol/water and recrystallized.

The resulting crystals were filtered off and dried to yield 52 g of product. Yield: 41% (2) Synthesis of final target product: 45 g of the product obtained in the previous section (1) was dissolved in about 400 mff of tetrahydrofuran and cooled to 0°C. This nong nong &
While maintaining the temperature at 0°C, 48 g of methacrylic acid chloride and then approximately 1201w6 of an aqueous solution containing 25 g of sodium hydroxide were added dropwise over a total of 1 hour. After the dropwise addition was completed, the temperature was returned to room temperature and the reaction was allowed to proceed for 3 hours.

When the reaction product was allowed to stand still, it separated into two layers, a solvent layer and an aqueous layer, so the aqueous layer was removed and the solvent layer was concentrated. The obtained concentrate was dropped into a dilute ill Na OIt aqueous solution, and the generated precipitate was filtered off, washed with water, and dried. The obtained solid was recrystallized twice with ethanol, filtered, and dried to obtain 19 g of white powder. Yield: 2
8% (3) Melting point of target product = 105-109.5°C (4)
Elemental analysis value of target product Actual value: C24,2; H21,5; 07.9 Theoretical value: C24; H22; 08 (5) NMR chart of target product: Figure 2 (Example 1)
) 11 parts BP 10 parts, 5-promo 1-phenyloxocarbonyl-2-methacryloyloxyhenzene 30
parts, 60 parts of styrene and benzoyl peroxide
A 0.2 part mixture was poured into a mold consisting of a glass mold for lens molding with a diameter of 65 mm and a polyethylene gasket, and kept in a hot air oven at 50° C. for 16 hours. Furthermore, after holding at 100° C. for 4 hours, the lens-shaped copolymer was taken out from the mold.

(Examples 2 to 10 and Comparative Examples 1 to 5) Lens-shaped copolymers having various compositions were polymerized using the same method as in Example 1. Note that, unlike in Example 1, a polymerization method using continuous temperature elevation was employed in some cases.

(Measurement of physical properties) The refractive index, surface hardness, color, impact resistance, solvent resistance, heat resistance, processability, and coatability of the (co)polymers polymerized in Examples and Comparative Examples were measured.

Each physical property was measured as follows.

Refractive index: Measured using an Atsube refractometer.

Surface hardness: Pencil hardness was measured according to JIS (K'5400).

Color: Observed and evaluated with the naked eye.

Heat resistance: After being left in hot air drying at 120℃ for 3 hours,
The lens was taken out, and if no lens coloration or surface distortion was observed with the naked eye, it was judged to have passed.

Solvent resistance: Lenses were immersed in methyl alcohol, acetone, benzene, and toluene at room temperature for 7 days, and those with no clouding on the surface in any of the solvents were evaluated as passing.

Workability: Lenses were processed using an eyeglass lens polishing machine, and those with no chipped edges and a smooth cut surface were considered acceptable.

Impact resistance: Lenses with a center wall thickness of 2111 were tested according to FDA specifications.

Coating property: Lenses on which 1 μm of 5iOz was deposited were immersed in warm water at 80° C. for 24 hours, and those with no peeling of the SiO□ film were passed.

Among the above measurements, solvent resistance, heat resistance, workability, impact resistance, and coatability were evaluated in the following three stages.

○ Excellent; △ Fair; × Poor In addition, the abbreviations in the monomer composition column represent the following meanings.

HMBP: 1.3-bis[(4'-methacryloyloxy)benzoyloxy]propane HABP: 1. 3-bis[(4'-acryloyloxy)benzoyloxy]propane H? IBE: 1. 2-bis[(4'-methacryloyloxy)benzoyloxylaethane IIABE: It 2-bis[(4'-acryloyloxy)benzoyloxylaethane HMBB: 1. 4-bis[(4'-methacryloyloxy)benzoyloxycobutane HABB: 1,4-bis[(4'-acryloyloxy)henzoyloxy]butane H BO: 1,5-bis[(4'-methacryloyl) Oxy)benzoyloxy]-3-oxopenkungu' [Raw St: Styrene o -C3t: Orthochlorstyrene Ph? IA
: Phenyl methacrylate B, MPhS: 5-bromo-1-phenyloxycarbonyl-2-methacryloyloxybenzene B, APhS: 5-bromo-1-phenyloxycarbonyl-2-acryloyloxyhenzene HMPhS: 1-phenyloxycarbonyl- 2
- Methacryloyloxyhensen third monomer CR-397 diethylene glycol bisallyl carbonate MM8: Methyl methacrylate (effects of the invention) As described above, the copolymer according to the present invention has a high refractive index of 1.55 or more. and cast moldability, mold releasability, impact resistance, processability, dyeability, heat resistance, surface hardness, solvent resistance, chemical resistance, weather resistance, light resistance, ultraviolet absorption, sweat resistance, It has excellent adhesion to anti-reflection films (inorganic dielectric multi-layer or single-layer films) and silicone hard coat films. Therefore, this copolymer is useful in lenses, especially ophthalmic lenses.

[Brief explanation of drawings]

1 and 2 are NMR charts.

Claims (1)

[Claims] General formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is H or CH_3 group, R_2 is
2 carbon atoms in which an oxygen atom may intervene in the C-C bond
-6 alkylene group. ), the refractive index of the ester derivative and homopolymer of parahydroxybenzoic acid, which is one or more first monomers, is 1.
．． A copolymer for lenses having a refractive index of 1.55 or more and containing as a main component one or more radically polymerizable second monomers having a refractive index of 55 or more.