JPS6051706A - Resin for high refractive index plastic lens - Google Patents

Abstract

PURPOSE:A resin for tough plastic lenses having a refractive index >=1.55, comprising a polymer obtained by the vinyl polymerization of a specified urethanized (meth)acryl monomer. CONSTITUTION:A urethanized (meth)acryl monomer is synthesized by reacting the OH groups of a (meth)acryl monomer of the formula (wherein R1 and R2 are each H or methyl, m+n=0-4, and X is Cl, I, or Br) with the NCO groups of a polyisocyanate. This monomer is vinyl-polymerized to obtain the purpose resin. Although the above monomer can be vinyl-polymerized alone to obtain a resin for high-refractive index lenses, the urethanized (meth)acrylic monomer (a first vinyl monomer) may be copolymerized with another vinyl monomer having an aromatic ring in the molecule (a second vinyl monomer).

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a resin for high refractive index plastic lenses.

[Prior art]

Plastic lenses are easier to make than glass lenses.
Furthermore, since it is lightweight and has good impact resistance, it has the advantage of being highly safe when used in eyeglass lenses. Conventional resins for plastic lenses include acrylic resin, polycarbonate resin, allyl diglycol carbonate resin, and polystyrene resin. Of these, plastic lenses are widely used for vision correction glasses.

This is diethylene glycol bisallyl carbonate, which is a thermosetting resin. This resin has a number of advantages, including excellent impact resistance, the fact that the lens power does not change significantly with changes in temperature, and good machinability and processability.

Cicacia diethylene glycol bisallyl carbonate has a refractive index of 1.50, and when a lens is made from this resin, it has the disadvantage that the end thickness of the lens is larger than that of a glass lens. This is particularly noticeable when the lens power increases.

In order to improve this drawback, various resins for glass lenses have been proposed in recent years.

For example, Japanese Patent Publication No. 58-17527 describes that a copolymer of dimethacrylate and 1-fulstyrene having lj bisphenol groups has a refractive index of 1.591. The publication describes that a copolymer of dimethacrylate and chlorostyrene having a tetrabromobisphenol group has a refractive index of 1.603.

However, although these resins have a very high refractive index, they have the disadvantage of poor toughness and weakness against impact.

On the other hand, a method is also known in which a polyurethane is mixed or copolymerized to impart toughness and an appropriately high refractive index to the resin.

For example, US p 4,360,653 describes that copolymers of polyol (allyl carbonate) and terminal acrylate polyurethanes have strength, impact resistance and optical clarity, and EPC publication 59561
Publication A discloses that a reaction product of hydroxyacrylate-1 and xylene diisocyanate has a refractive index of 1.55 or more, but these resins do not have a refractive index high enough to make corrective lenses.

[Purpose of the invention]

The object of the present invention is 1.55 or more, preferably 1.60 or more.
- The object of the present invention is to capture a strong plastic lens resin that has a high refractive index.

[Structure of the invention]

The present invention deals with urethanization (
It is a high strength 1 (refractive index lens resin) characterized by being made of a polymer obtained by vinyl polymerizing meth)acrylic monomer.

Here, "I+R2 is hydrogen 1-take methyl group 1m and n are integers whose total is O to 4, and x (6 represents chlorine, iodine or bromine.

Acrylic monomer used in the present invention (
The following can be mentioned for binding (referred to as component a).

2-(4-Hydroxyethogine-3,5-dibromphenyl) 2-(4-acryloxyethoxy-3,5-dibromphenyl)propane.

2-(4-hydroxyethoxy-6,5-dibromphenyl)-2-(4-methacryloxyethoxy-6,5-
dibromophenyl) propane.

2-(4-Hydroxyethoxy-6,5-dibromphenyl')-2-(4-7ri!JnlC3.5=sifuromphenyl)furopane.

2-(4-hydroxyethoxy-ro, 5-dibromphenyl)-2-(4-methacryloxy-ro.

5-dibromphenyl)furopane.

2-(4-hydroxy-6,5-dibromphenyl)-
2-(4-acryloquine-6,5-dibromphenyl)
propane.

2-(4-hydroxy-ro,5-dibromphenyl)
2 (4-methacryloxy-6,5-dibromphenyl)propane.

2-(4-hydroxyjethoxy-3,5-dibromphenyl)-2-(4-acryloxyjethoxy-6,5
-dibromphenyl)propane.

2-(4-Hydroxyjethoxy-6,5-dibromphenyl)-2-(4-hydroxydiethoxy-3,
5-cyfuromphenyl) furono(n), etc.

Among the above compounds, one is particularly favorable, 2-(4-hydroxyethoxy-ro,5-dibromphenyl)-2-(
4-Acryloxyethoxy-ro,5-dibromphenyl)propane, 2-(4,-hydroxyethoxy-6,5
-dibromphenyl) 2 (4-acryloxy-ro,
5-dibromphenyl)propane, 2(4-hydroxyethoxy6,5-dibromphenyl L-2-(4-
tsucryloxyethoxy-5,5-dibromphenyl and mixtures thereof.

The following polyfunctional incyanates (referred to as component b) can be used.

As a diisocyanate.

Hexamethylene diisocyanate.

Inphorone diisocyanate.

2.2.4-Trimethylhexamethylene diisocyanate.

Dicyclohexylmethane-1-.

Lysine diisocyanate methyl ester xylylene diisocyanate.

Bis(incyanatomethyl)cyclohexane.

Tolylene diisocyanate.

4,4'-diphenylmethaneisocyao, -1.

Dust, and multifunctional warehouse ti isocia λ・-1
・As for closing.

Piunt reaction product of hexamethylene diisocyanate-1.

A reaction adduct of hexamethylene diisocyanate and 1.1-tumethylolpropane.

2-ethyl incyanate- natehexanoate.

1, 6. 1 1-Undecane triincyanate.

A reaction adduct of inphorone diisocyanate and trimethylolpropane.

A reaction adduct of xylylene diisocyanate and trimethylolpropane.

Reaction of bis(incyanatomethyl)cyclohexane with trimethylolpropane 21 adas.

There is.

Among the above-mentioned incyane-1.compounds, particularly preferred are xylylene diisocyanate, inphoroncyisocyanate-1., bis(incyanate methyl)cyclohexane, and the like.

The present invention combines the (meth)acrylic monomer represented by the above general formula = (a) with the OH group and the above-mentioned polyfunctional incyanate (b).
) to synthesize a urethanized (meth)acrylic monomer.

111 of this urethanized (meth)acrylic monomer.

Although it is possible to independently polymerize vinyl and create a resin for plastic lenses with a high refractive index, the present invention is further capable of producing resin for plastic lenses.

The urethanized (meth)acrylic monomer (first vinyl monomer) described in Section 2 can be copolymerized with another vinyl monomer (second vinyl monomer) having an aromatic ring in the molecule.

The purpose of the second vinyl monomer is to improve various performances required of the lens by copolymerizing with the first vinyl monomer. The second vinyl monomer is preferably one whose homopolymer has a refractive index of 1.55 or more, and particularly preferably one having a nuclear or rogen-substituted aromatic ring. Specific examples are as follows.

Styrene, divinylbenzene, chlorostyrene.

Dichlorostyrene, bromostyrene, dichlorostyrene, iodonutyrene, phenyl (meth)acrylate, monochlorophenyl (meth)acrylate, dichlorophenyl (meth)acrylate.

Trichlorophenyl (meth)acrylate, monobromphenyl (meth)acrylate, dibromphenyl (meth)acrylate, tribromophenyl (meth)acrylate, pendabromphenyl (meth)acrylate,
Monobromphenoxyethyl (meth)acrylate, dichlorophenoxyethyl (meth)acrylate, trichlorophenoxyethyl (meth)acrylate, monobromphenoxyethyl (meth)acrylate, dibromphenoxyethyl (meth)acrylate, tribromphenoxyethyl (meth)acrylate ) acrylate.

Pentabromphenoxyethyl (meth)acryle'-)
+ N-vinylcarbazole, 2,2-bis(4-methacryloxyethoxy-6,5-dibromphenyl)propane, 2,2-bis(4-acrylogyethoxy-5.
5--) fromophenyl)propane.

2 + (4-methacryloxy-ro,5-sidaromphenyl)-2-('!-hydroxy-ro,5-dibromphenyl)furopane, sialicinclay+-r sibril infucray 1-,l-lylyl trime Lite-1.

Benzyl acrylic +. □ - 1. etc.

Among the two vinyl monomers, styrene, chlorstyrene, bromustyrene, cyfuromstyrene, tribromophenyl methacrylate-1-, l-IJ fluorophenoxyethyl methacrylate-1, divinylbenzene and tora Particularly suitable are mixtures of the following.

The amounts of component (a) and component (b) used are such that the molar ratio of NCO groups in component (b) to OH groups in component 0 is 95 to 20.
It is possible to select within the range, but preferably NC010
H=0.5-15. Outside this range, the mechanical and thermal properties of the lens deteriorate.

It is easy to have poor cutting and polishing properties.

The second vinyl monomer having an aromatic ring in the molecule can be used in an amount of 0 to 70% by weight based on the total weight, but it is preferable to use an appropriate amount depending on the reactivity and physical properties.

For example, if the weight ratio exceeds 70, the mechanical properties and machinability become poor.

In the present invention, in addition to the first vinyl monomer and the second vinyl monomer, other polymerizable monomers or compounds containing hydroxyl groups that do not contain vinyl groups are copolymerized in a proportion of 20% by weight or less.

Alternatively, other polymers of up to 20% by weight may be mixed.

A method for producing a plastic lens using the resin for plastic lenses of the present invention can be carried out by a known cast polymerization method. Specifically, the A and B components of the present invention were mixed, 2 a normal polymerization initiator was added, the reaction was allowed to proceed to some extent (preliminary (iifi polymerization)), and dissolved gases such as air were degassed in vacuum. Afterwards, it is poured into a mold and heated to polymerize.

The heating temperature is initially a relatively low temperature (e.g. 40-50'
c)), and as the reaction progresses, the temperature is increased by 1.
At about 10'O, raise it twice and slowly rise τJJJ1
Single polymerization is preferable in terms of reducing distortion of the lens.

Various known polymerization initiators can be used, but the polymerization initiator should be selected depending on the desired reaction temperature. For example, 1,1-azobiscyclohexane carbonate, diisopropyl peroxycarbonate, i,i'-azopiscyclohexane nitrate, di-tθrt-butyl peroxide, and the like are suitable.

The plastic lens containing the resin of the present invention as a resin component has the following advantages compared to commercially available plastic lenses. The time is right.

A strong plastic lens with a high refractive index can be obtained.

Excellent impact resistance.

Shrinkage rate during molding polymerization is relatively small.

(Tsuku) Each of the acrylic monomer, incyanate compound and aromatic vinyl monomer can be selected as appropriate.

This allows the optical characteristics to be adjusted freely.

Excellent bending elasticity.

Plastic lenses containing the resin of the present invention can be subjected to known physical or chemical methods to achieve surface modification such as antireflection, high hardness, abrasion resistance, improved chemical resistance, and antifogging properties. Is possible.

In particular, anti-reflection treatment is applied by forming two layers of coatings with different refractive indexes on the surface, coating of polysiloxane, silica sol, etc. is applied to form a highly hard coating on the surface, and this is dyed to create fashionable products. 2) Forming a metal film on the surface by means such as vapor deposition to give a mirror effect, and forming a hygroscopic film on the surface to prevent fogging can be conveniently carried out.

During the polymerization, (1 type agent, ultraviolet absorber, antioxidant, 2 coloring inhibitor, antistatic agent, fluorescent dye stain).

Additives such as various stabilizers can be selected and used as necessary.

In order to explain the present invention more specifically, Examples and corresponding comparative examples are shown below. From these results, it is clear from these results that the use of a urethanized polyfunctional block with a halogen-substituted core or an acrylate can increase the refractive index, rigidity, and impact resistance. It will be understood that it is effective for "direction". Of course, the present invention is not limited to these examples.

In addition, in Examples and Comparative Examples, various physical properties were measured by the following test methods.

Measurement method: Refractive index and Atsube number: 20°C using Atsube refractometer
Measured at.

Wavelength 1d: 5892.9ALv'D line Use the value at .

Color tone: The color tone of the flat plate or lens molded product was judged with the naked eye.

Impact strength: Measured using a die-stat tester. Thickness of test piece: 2.7 to 5011I [11° width 10mm Rigidity: in accordance with ASTM D747.

Test piece 30 m+n x 1 n mm x I bending deflection: According to ASTM-D770.

Test piece: 80 runs x 10 mm x filtration Cutting and polishing properties: Cutting properties and polishing properties were compared with the lens of Comparative Example 2.

Example 1 11.5 parts by weight of 2-isocyanate ethyl-2,6-diiso/anetohexanoate and 2-(4-acryloxyethoxy-6,5-dibromophenyl)-2(
4-hydroxyethoxy-6,5-dibromophenyl)
To 885 parts by weight of propane were added parts by weight of dibutyltin dilaurate o, ooi as a sealed C00H reaction catalyst and parts of dibutyltin dilaurate 01 as a polymerization initiator.

Mix well. This liquid mixture had a high viscosity and was difficult to mix uniformly, so it was diluted with a dimethylformamide solvent and mixed uniformly, and then the solvent was completely removed.

This mixture was heated to 50°C to reduce the viscosity, and the diameter was 100°C.
The mixture was poured into a mold formed with a glass plate of 1.0 mm in diameter and a polyethylene gasket I, and cast polymerization was performed.

Initially, the NC010H reaction was completed by heating at 60°C for 5 hours, then the temperature was raised to 80°C, and polymerization was carried out over 30 hours while increasing the temperature stepwise from 80°C at 12 [1'ci]. Ta.

After the polymerization was completed, the dipolymer was gradually cooled and released from the mold. Various physical properties of the polymer were measured and shown in Table 1. ?
The iJ resin was tough, colorless and transparent, and had a high refractive index nD of 161 (and Abbe number 34).

Example 2 2-incyanate ethyl-2,6-diiso/anetohexanoate 69 overlapping part 2-(4-acryloxyethoxy-6,5-dibromophenyl), -2-(4-hydroxyethoxy- 3,5-
To a mixture of 53.1 parts by weight of dibromophenylfurono(n) and 40.0 parts by weight of chlorostyrene, 1 o ppm of dibutyltin dilaurate was added as an NC○-OH reaction catalyst, and the mixture was heated at 50°C for 2 hours. The mixture was cooled to 100 mL, and 0.1% diisopropyl barosedicarbonate was added as a radical polymerization initiator.This prepared solution had a low viscosity and could be easily poured into a lens mold.

After heating this solution at 60°C for 10 hours to solidify it,
Cast polymerization was performed by continuing heating at 4o'c for 5 hours, at 50'q for 5 hours, at 60'c for 6 hours, at 80°G for 6 hours, and at 100°C for 10 hours. Table 1 shows the physical properties of the obtained cured resin. The molded product was strong and rigid, had a high refractive index nD of 161, and an Abbe number of 66.

Examples 6 to 7 Lenses were produced using the same method as in Example 2 with two different compositions, and the results are shown in Table 1. High refractive index, surface 1
It has excellent mechanical properties such as impact resistance.

Claims (1)

[Scope of Claims] It is characterized by being composed of a polymer obtained by vinyl polymerizing a urethanized (meth)acrylic monomer obtained by reacting a (meth)acrylic monomer represented by the following general formula with a polyfunctional incyanate. Resin for high refractive index lenses. Here, Rj + R2 represents hydrogen or a methyl group, 9m and n are integers whose total is O to 4, and X represents chlorine, iodine or bromine.