JPS598710A - Resin for high refractive index lens having excellent light resistance - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a lens resin having a high refractive index and excellent light resistance.

Compared to inorganic glass lenses, plastic lenses are lighter, more difficult to break, and can be dyed, so in recent years they have become popular for use in eyeglass lenses, camera lenses, and optical elements. As a resin currently widely used for this purpose, there is a resin obtained by cast polymerization of diethylene glycol bisallyl carbonate (hereinafter referred to as CR-39). However, the refractive index (ηd) of this lens resin is 1.50, which is smaller than that of a glass lens (ηd approximately 1.52), and in order to obtain the same optical characteristics as a glass lens, the central thickness of the lens must be , edge thickness, and curvature must be increased, making it inevitable that the overall wall thickness will become thicker. For this reason, a lens resin with a higher refractive index is desired. However, polycarbonate (ηd 1.58 to 1.59) and polystyrene (ηd 1.58 to 1.60) are already known as materials having a relatively high refractive index.

However, since these resins are structurally two-dimensional polymers and thermoplastic, they are unsuitable for cast polymerization, which is suitable for producing a wide variety of products such as eyeglass lenses. Furthermore, post-processing after molding, especially so-called beading, is difficult for these resins, and the scope of use of these resins is currently limited to a small number of products such as safety glasses.

Therefore, like CR-39, cast polymerization is possible and
There is a strong demand for lens resins that have a higher refractive index than resins using 39-39 and form a three-dimensional crosslinked structure after polymerization, so that they do not clog the grinding wheel during grinding with a diamond grinding wheel. . Various researches have already been conducted on resins that meet these aspirations, and CR-39 and C
A resin copolymerized with a second monomer having a higher refractive index than R-39 has been proposed.
53, JP 53-7787, JP 54-77686
, Japanese Patent Publication No. 56-36601). However, since these resins use CR-39 as the main component, the refractive index of the resin obtained by polymerization is naturally limited. It is difficult to obtain resins that do not discolor upon exposure to ultraviolet light over time.

Therefore, in order to obtain a resin with a higher refractive index, CR
There is a strong demand for difunctional monomers that provide a refractive index higher than -39. However, the homopolymers of bifunctional monomers proposed to date generally have extremely low impact resistance.

Improvements have been made by blending and copolymerizing a large amount of halogen-substituted styrenes as the second monomer. Therefore, the resulting polymerized resin has a high refractive index, for example 1.
Although these resins can be obtained, they tend to be colored during polymerization or turn yellow when the polymerized resin is exposed to ultraviolet rays for a long period of time, and these resins naturally have limitations in their practical use.

In view of this situation, the present inventor () conducted intensive research in order to solve the drawbacks of lens resins, and as a result, developed bisallyl carbonate, a novel difunctional monomer. Alternatively, a resin obtained by copolymerizing bis β-methyl carbonate and a second monomer whose homopolymer has a refractive index of 1.55 or more has a high refractive index and is three-dimensionally crosslinked. Because of its structure, it has excellent processability such as beading, and furthermore, it has been found that yellowing due to long-term exposure to ultraviolet rays is extremely small, and light resistance can be greatly improved, leading to the present invention. Ta.

That is, the present invention relates to the general formula (I) 0) (where,
, R represents hydrogen or a methyl group) and the first monomer of bisallyl carbonate-1 or bisβ-methylallyl carbonate-1, and as a homopolymer. having a refractive index of 1.55 or more, which is capable of radical polymerization and has an aromatic ring, and which is obtained by copolymerizing the main component with a second monomer of L, which has a high refractive index and excellent light resistance. The present invention provides resins for lenses.

A novel bisallyl carbonate or bisβ- represented by the general formula (■) as the first monomer in the present invention
Methyl allyl carbonate is produced by heating an aromatic compound having two hydroxyl groups or its nuclear-substituted derivative with ethylene oxide under pressure using triethylamine as a catalyst. It can be obtained by obtaining a nuclear substituted product thereof, which is further reacted with allyl chloroforme-1 or β-methylallyl chloroformate. [1,4-bis(hydroxyethoxy)benzenebisallyl carbonate-1-11,4-bis(hydroxyethoxy)benzenebisβ-dimensional methylallyl carbonate, 2,3,5,6-tetrachloro -1,11-bis(human oxyethoxyethoxy)benzene bisallyl carbonate, 2,3,5.6-tetrachloro-1,4-bis(
hydroxyethoxy)benzene bisβ-methylallyl carbonate, 2,3.5.6-tetrabromo-1,4-
Bis(hydroxyethoxy)benzene bisallyl carbonate, 2.3.5.6=tetrabromo-1,4-bis(hydroxyethoxy)benzene bisβ-methylallyl carbonate, 1,3-bis(hydrokine ethoxy) Benzene bisallyl carbonate, 1,3-bis(hydroxyethoxy)benzene bisβ-methylallyltono-bonate, 2,4,5.6-tetrachloro-1,3-bis(hydroquine ethoxy/)benzene bisallyl carbonate, 2.4.5.6-Tetrachloro-1,3-bis(hydroquinetoquine)benzenebisβ-methylallyl force
Soilnate, 2,4,5.6-chitrafuromor 1.3
-His(Hitoaki/Kotoki/)be/senhis allyl carbonate, 2,4,5.6-tetrabromo-1,:3 his(hydroxyethoxy)benzenebisβ-methylallyl carbonate, 1,5-bis (Hydroxyethoxy)
Naphthalenepisallylnonobone-1.,1,5-bis(hydroxyethokino)naphthalenebisβ-methylallylcarbonate 1-11. ．． 6-bis(hydroxyethoxy)naphthalenebisallyl carbonate, 1,6-bis(hydroxyethoxy)naphthalenebisβ-methylallyl carbonate, 7-his(hydroxyethoxy)
Naphthalene bisallyl carbonate, 1,7-bis(hydroquinethoxy)naphthalenebisβ-methylallyl carbonate, 2,6-his(hydroxyethoxy)naphthalenebisallyl carbonate, 2,6-bis(hydroxyethoxy)naphthalenebisβ- Methylallyl carbonate, 2.7-bis(hydroxyethoxy)naphthalenebisallyl carbonate, 2. h-bis(hydroxyethoxy)naphthalenebisβ-methylallyl carbonate, 4.41-bis(hydrokinethoxy)dinoenylbropa/bis-7” for IJ carbone, 1.=
1'-bis(hydroquinethoxy)diphenylpropane bisβ-methylallyl carbonate, 3.3', 5.5
'-Tetrachloro-4,41-bis(hydrokine ethoxy(diphenylpropane bisallyl carbonate, 3
,3',5,5'-tetrachloro~4,. 1 l
, -His(hydroxyethoxy)diphenylpropane bisβ-methylallyl carbonate, a, 3'.

5.5'--tetrabromo-4,417bis(hydroxyethoxy)diphenylpropane bisallyl carbonate, 3+ 1 + 5, 51-tetrabromo-4,4
1-bis(hydroquinethoxy)diphenylpropanebisβ-methylalicica-bone 1-14.4'-bis(
hydroxyethoxy)cyphenylsulfone bisallyl carbonate, i, -), 4,4'-bis(hydroquinethoxy)diphenylsulfone bisβ-methyl carbonate, 3.3', 5.5'-tetrachloro -4,41
-bis(hydroquinethoxy)diphenylsulfonebisallyl carbonate, 3.3',5.51-tetrachloro-4゜41-his(hydroxyethoxy/)diphenylsulfonebisβ-methylallylcarbonate, 3
,3゜5.51-tetrabromo-4,41-bis(hydrokine ethoxy)diphenylsulfone bisallyl carbonate, 3.3',5.5'-tetrabromo-4,41
-bis(hydroxyethoxy)diphenylsulfonebisβ-methylallyl carbonate. If the first monomer represented by the general formula (I) is homopolymerized by itself, the impact resistance is extremely low. It is necessary to use a monomer.

That is, the second monomer in the present invention is a radically polymerizable monofunctional monomer having an aromatic ring, and has a homopolymer refractive index of 1.55 or more. Any monomer that satisfies this requirement can be used, but the general formula (
The light resistance of the resin obtained by non-polymerization with the first monoband represented by i), that is, the resin that causes extreme coloring due to long-term exposure to ultraviolet rays, is undesirable. Representative monomers suitable for general use include phenyl acrylate, phenyl methacrylate, nuclear chlorine-substituted noenyl acrylate=-1-, Nishi phenyl methacrylate, benzyl acrylate, benzyl methacrylate-1, nuclear u substituted benzyl acrylate, nuclear chlorine substituted benzyl methacrylate, nuclear central bamboo substituted benzyl acrylate, nuclear bromine substituted benzyl methacrylate-1
・Acrylates and methacrylates such as α-naphthyl acrylate, α-naphthyl methacrylate l/-1-1 β-naphthyl acrylate, β-nanothyl methacrylate, styrenes such as styrene, nuclear chlorine-substituted styrene, nuclear bromine-substituted styrene, 1- Vinyl naphthalene/, 2-
There are vinylnaphthalene orders such as vinylnaphthalene. Among these, the present invention has particularly excellent j-light resistance (
-7 To prepare the resin, phenyl methacrylate, nuclear halogen-substituted methacrylate-1, benzyl methacrylate,
For nuclear halogen substitution/dyl methacrylate], it is desirable to use.

In the general formula (1), the first monomer, bisallyl, is represented by -1, '+, and 2 is b. Although it cannot be limited, the number of the first single M unit is 5 to 80.
It is used in a weight range of 10 to 70% by weight.

When 5% by weight is unvortexed, the surface hardness decreases significantly, and when it exceeds 80% by weight, the impact resistance decreases, which is not good for Hf.

In addition, as a second monomer, especially for styrenes and vinyl phthalenes (in case of This is undesirable because the rate of yellowing increases due to long-term exposure to ultraviolet rays.

In addition, in order to obtain the resin for lenses of the present invention, the radical initiators used during polymerization are particularly limited. Peroxides such as carbonate, di-20ethylhexylcarbonate, tertiarybutylperoxycarbonate, etc. and 0.0I~S azobisisobutyronitrile natonoazo compounds Used at a rate of 5% of market weight.

I') (IC) The resin for lenses in the present invention is prepared by combining one or more first monomers of bisallyl carbonate and bisβ-methylallyl carbonate represented by the general formula (1). A mixture of a radically polymerizable monomer having an aromatic ring and a radical initiator is used in the known casting polymerization method, i.e., a gasket or spacer is assembled with a glass or metal mold. This can be done by injecting it into a mold and polymerizing and curing it by heating or irradiating it with ultraviolet rays.At this time, the mixture before polymerization is preliminarily added with an ultraviolet absorber, an antioxidant, a color inhibitor, and a silicone. Additives such as light dyeing may be added as necessary.

Therefore, the reused resin for lenses of the present invention has a high refractive index and is excellent in workability such as beading, and furthermore, it is a resin that does not significantly improve yellowing caused by ultraviolet rays over a long period of time, It can be used for ophthalmic lenses, camera lenses, and optical elements.

Examples are shown below. Note that in the examples, parts indicate weight, and % indicates weight (4%).The refractive index of the lens resin obtained in the examples and the test method for yellowing due to exposure to ultraviolet rays are as follows. Test method/1 = yo) j-.

Refractive index: 611] determined at 20°C using an Asobe refractometer
−.

Ultraviolet ray resistance test: A weather meter (WE-SUN-DC-1 model manufactured by Toyo Rika Co., Ltd.) equipped with a Zanshine Ka-Bon arc lamp was equipped with a 5nO. After 1000 and 1500 hours, the lens was taken out and the hue was compared with the lens before testing using a weatherometer.

The evaluation criteria are 0: No discoloration, △: Slightly yellow, ×; Yellow and 17.

Synthesis Example 1 1,4-bis(hydroxyethogycy)benzene 19,8
1 part was dissolved in 50 parts of chloroborum, 24.2 parts of triethylamine was added thereto, and 25 parts of allyl chloroformate was added dropwise at 5 to 10 DEG C. over 2 hours while stirring.

Next, after heating at 45 to 50°C for 3 hours, the reaction solution was poured into a separating roller and washed with dilute hydrochloric acid and water. The pale yellow organic layer obtained was dried over calcium chloride, and then It was treated with activated carbon and concentrated under reduced pressure to obtain a white solid.This was recrystallized from benzene to form white flaky crystals of 1,4-bis(hydroxyethoxy)benzene bisallyl carbonate (hereinafter referred to as Compound A). ) 22.5
Department? It's 1.

Melting point 93-95°C C (%) )-1 (%) Elemental analysis value 59.56 6.38 Calculated value 5
9. nl 6.05 (as Cps 8220g) N M RδCDC ('34.15 (41-1, t),
4.41~4.68 (411゜), 5.20~5.4
0 (41-1, m), 5.75-6.15 (21-1
, m), 6.85 (41!, s) Synthesis row 2 1.5-bis(hydroxyethoxy)naphthalene 24.
Dissolved in 8 parts 50 parts of yakloform, 19 parts of pyridine
．． Add 5 parts of β-methylallyl chloroformate while keeping the temperature between 5 and 108C while stirring.
The mixture was added dropwise over 2 hours. After heating at 55-60°C for 3 hours, the reaction solution was poured into a liquid separation solution, washed with dilute hydrochloric acid and then with water, and the pale yellow organic layer obtained was dried over calcium chloride and then washed with activated carbon. Workup and concentration in vacuo gave a white solid.

This was recrystallized from toluene to obtain white amorphous crystals, 1,5-bis(hydroxyethoxy/)naphthalenebisβ.
-Methyl allyl carbonate (hereinafter referred to as compound B)
Obtained 32 copies.

Melting point 112-115°C Calculated value 64.85 6.35 (as C2<1-'280g) NMRδCDC1337,35(6+l,m),4.8
5 (4H, d), 4, 58-4, 38 (8H, m)
, 3.90 (411, s), 1.65 (6H, s) Synthesis Example 3 Synthesis Example 101.4 Instead of 19.8 parts of bis(hydrokine ethoxy)benzene and 50 parts of chloroform, 3.3'
, 5,5'-tetrabromo-4,41-bis(hydrogyneetogine)diphenylpropane 63 parts and 150 parts of chloroform were used in the same manner as in Synthesis Example 1.
3, 3+, 5, 5'- which is a white amorphous crystal
Tetrabromo-4,4'-bis(hydroxyethoxy)
Diphenylpropane bisallyl carbonate-1 (hereinafter referred to as
58 parts (referred to as Compound C) were obtained.

Melting point 76-78°C C (%) 1 (%) Br (%) Elemental analysis value 40.59 3.35 40.3
7 Calculated value 40.53 3.53 39.95
(as C27H28B'40g) NMRδcDc
e, 1. ．． 60 (6H, s), 4.20-4.30
(4H.

+), 4.48-4.68 (8N, m), 5.20-6
．． 40 (41-1, m), 5.70-6.15 (21 (
, m), 7.30 (4H,s) Synthesis Example 4 3.
, :3', 5,51-tetrachloro-4,41
-bis(hydroquino-l-xy)diphenylsulfone 4
Synthesis Example 1 was repeated except that 7.6 parts and 150 parts of chloroform were used to prepare 3, which is a white amorphous crystal.
43 parts of 3','5,5'-tetrachloro-4,41-bis(hydroxy/'ethoxy)cyphenylsulfone bisallyl carbonate-1- (hereinafter referred to as compound 2) were obtained.

Melting point 58-61°C C (%) l-1 (%>cec%) S (%
) Elemental analysis value 44.1.3 3.32 21. R3
5, Old calculation value 44.73 3.44 22.01
C98 (C241-49°Cl!40+o as S)
NMr(δCI)C131,60(6H,S), 4.2
5-4.35 (4F!.

t), 4.4Fi to 4.6R (FtH, m), 5.20
~5.40 (4N, m), 5.70 ~ 6.15 (2H,
m), 7.25 (4N, s) Example 1 A mixture of 50 parts of phenyl methacrylate, 50 parts of compound A, and 1.7 parts of benzoyl peroxide was mixed into a glass mold for lens molding and a polyethylene gasket. Pour into a mold and heat at 60°C for 24 hours, and then incubate for 1 hour.
Copolymerization was carried out by holding at 00°C for 2 hours. Next, the resin was removed from the mold, the refractive index was measured, and the UV resistance was tested. (2) As a result, the refractive index of the obtained colorless and transparent lens was 1.565, and the results of the ultraviolet resistance test were also excellent.

Examples 2 to 12 Lenses were prepared by copolymerizing monomers of various compositions in the same manner as in Example 1, and the results are compared in Table 1. Shown together with Examples 1-5.

/ Compounds indicated by the abbreviations in the body composition column of Table 1 above are shown in 17 words.

PIMA: phenyl methacrylate p-MtPJ
MA: n-methoxyphenyl methacrylate o-Ce5Vo-chlorostyrene p -B rP IMA: p-phyllomophenyl methacrylate o -ClBMA: o-chlorobenzyl methacrylate-1 Br5t: Bromostyrene (〇One 70
(weight%, p 30% by weight) Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1) General formula (I) (I) n (where X is hydrogen, chlorine or bromine, n is an integer from 1 to 4, and A is an impropenyl group or a sulfone group),
R represents hydrogen or a methyl group) and one or more types of bisallyl carbonate or bisβ-methylallyl carbonate, and a refractive index of 1.5 as a homopolymer.
A resin for lenses having a high refractive index and excellent light resistance, which is obtained by copolymerizing one or more monofunctional monomers having an aromatic ring in a radical polymerization reaction.