JPH03145601A - Plastic lens material - Google Patents

Abstract

PURPOSE:To obtain the plastic lens which has a high refractive index and can reduce the thickness of the lens by using a specific compd. as the essential monomer component of a polymer. CONSTITUTION:This plastic lens material consists of the polymer composed of the compd. expressed by formula I as the essential monomer component. (In the formula I, n is 1 to 5 integer). Namely, a trithiocyanurate ring which enhances the refractive index and improves heat resistance is introduced into this monomer. Thus, the lens which is colorless and transparent, has the high refractive index and low dispersion, has excellent impact resistance, weatherability and heat resistance and is free from optical distorions is obtd.. The circumferential thickness of the lens is reduced and the lens which is lessened in double refractions and chromatic aberrations is obtd. in the case of using this lens material particularly as a concave lens for glasses.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The plastic lens material of the present invention has a high fil! Refractive index,
J3 has low dispersion and excellent optical properties, and is particularly preferably used for eyeglass lenses and camera lenses.

1. Prior Art] Plastic lenses are lighter than glass lenses, are less likely to break, and are easier to dye, so in recent years they have begun to be used for eyeglass lenses, camera lenses, and optical elements. As the plastic lens 011, L polyethylene glycol bisallyl carbonate (CR39) is generally used. However, the refractive index (no) of this material is 1.5.
0, so the glass lens for glasses (no −= 1
．． In order to obtain an optical f1 equivalent to 52), it was necessary to increase the thickness of the lens.

Therefore, when this lens is used for eyeglasses, the thickness of the lens becomes thick and aesthetics deteriorate, which is not preferable. In particular, in the case of a concave lens, the thickness around the lens becomes thick, causing birefringence and chromatic aberration, which is not desirable.

Therefore, there has been a demand for plastic lenses (material A) with a high refractive index that can reduce the thickness of the lens while taking advantage of the characteristics of a plastic lens with light specific gravity.

As a plastic lens material that provides a high refractive index, Japanese Patent Application Laid-Open No. 62-276501 discloses a material that has a refractive index (no) of 163 or more by introducing a pnotalene ring. In addition, Japanese Patent Application Laid-Open No. 1982 gg2o January discloses a material with a refraction "*(no) of 1.60 or more by introducing brominated biphenyl into the carbamate bond. -26
No. 62Ha discloses a material whose refractive index (no) becomes 158 or more by introducing a bond into S-carbame-1.

Furthermore, by introducing a bromide suphenol A skeleton into JP-A No. 62-34101, the refractive index (no) was increased to 160.
The following materials are disclosed.

[Problem to be Solved by the Invention 1] However, the plus book lens material described in the above-mentioned Japanese Patent Application Laid-Open No. 62-276501@ is brittle and has poor 11+j impact resistance. It has the disadvantage that mechanical strength is not satisfied.

JP-A-61-88201, JP-A-64-
Although the plastic lens material described in Publication No. 26622 solves this problem of poor impact resistance P, it is a material that tends to polymerize non-uniformly and cause striae during the production of Bunszig lenses. . Moreover, there is a drawback that optical distortion occurs due to the striae.

In particular, the plastic lens material described in JP-A-61-88201 has the drawback of poor weather resistance and a tendency to yellow when used for a long period of time. Also, the time It(164-26
The plastic lens material described in Publication No. 622 has poor heat resistance, and when a hard coat layer for antireflection is applied to the lens, the surface scratches due to heat are reduced and the scratches are reduced.
-There is a drawback that the layer is prone to cracking.

Furthermore, the plus book lens material described in the above-mentioned Japanese Patent Application Laid-Open No. 62-34101q also has the drawback of poor weather resistance and yellowing when used for a long period of time.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a high refractive index, but dispersive plastic lens material which eliminates the above-mentioned drawbacks of conventional plastic lens materials.

"F stage for solving the problem" The present invention has been made to achieve the above object, and the plastic lens material of the present invention has the following general formula r
It is characterized by consisting of a polymer containing the compound represented by I 11 as an essential monomer component. .

(In the formula, n is a stroke number of 1 to 5.) That is, the above monomer providing the plastic lens material of the present invention is characterized in that a trithiocyanurate ring is introduced that increases the refractive index and improves the heat resistance. There is.

Furthermore, it has a styrene skeleton with a high refractive index as a polymerization functional group, and by introducing 3 moles of it into the molecule, the resulting polymer has a high refractive index, high strength, and high heat resistance, making it 4T. It is said that

Next, the reason why n is limited to 1 to 5 in general formula [I] will be described. This is because when n is O, the dispersion of the obtained polymer becomes large, and the Abbe number (v0) becomes 30 or less, making it unsuitable for use as an optical lens. Also, n
is 6 or more, which is not preferable because the mechanical strength and heat resistance of the polymer decrease. Therefore, n is limited to an integer from 1 to 5.

And, as the seven pieces represented by the general formula [TI,
Examples include 1-lith styrylmethyl]thiA cyanurate, 1-lith styrylethyl 1-thia cyanurate, 1-lith stilbemple thiocyanurate, and the like.

The present invention will be explained in more detail below.

The plastic lens material provided by the present invention has the general formula [
, I ] may be used, but if necessary, it may be made of a polymer obtained by using other radically polymerizable heptamers as a copolymerization component. There may be.

The preferable amount of heptamine represented by the general formula "1" is 50 to 100% by weight. The reason is that monomer h1 is 5
This is because if it is less than 0%, the effect of increasing the refractive index, heat resistance, and strength will be small.

The monomer used as a copolymerization component is a +11-functional heptad-1 polyfunctional monomer. A chromomonomer or the like can be used in addition, and it is desirable that the refractive index of the homopolymer thereof is 148 or more. Specifically, methyl methacrylate-1-, butyl methacrylate, cyclohe4-syl methacrylate-1-, 4-t-butyl methacrylate, cyclohe-1-syl methacrylate-1, 2,3-dibromo-10-vinyl methacrylate,
1, phenyl acrylate 1-, nononyl methacrylate
1~, benzyl acrylate, benzyl methacrylate, chlorinyl acrylate-1~, riE'' Lophenyl methacrylate, pro-phenylacrylate, B``1 Mophenyl methacrylate, trichlorophenyl acrylate, 1~RIK1'' Lophenyl methacrylate-1 ~, triproyl acrylate 1-11 ~ ribromofer methacrylate, 2-methacryloyloxymethacrylate, 3-methacryloyloxymethacrylate, 2-(2-methacryloyl 4diethyl)thionene , bromo-2-methacryloyloxymethyldiophene, dibu]] 2-methacryloyl A, trib D 1: 2-methacryloyl 1-dimethyldiophene, 2-1-licyclo[5,
2,1,0" 63-3 Dehir A xyedyl methacrylate-1~, 2-1-Lisif ITI [5,2,1,02=6
1-3-decerthiotinal methacrylate, 2-1~licyclo[5,2°1.02=6]-]3,4-dichlorodecylbu=onipurmethacrylate=1~2-1~licyclo[5,2°1.02=6]-] 5,2゜1.02゜613.4-Dibromodesilube A, monofunctional acrylic acid varnish I and methacrylic acid esters such as delmethacrylate; ~Rimethylene glycol dimethacrylate, De1~Rimethylene glycol dimethacrylate-1~, Heki4
Tsumeburenguri 1-rudimethacrylate-1, dieboulenguli=]-rudimethacrylate-1-11~lyethylene glycol dimethacrylate-1~, te~laedylene glycol dimethacrylate-1~, trimethylolpropane 1
〜Reacryl 1〜, Trinoalolpropane 1〜Remethacrylate, 2,2-bis(4-7cri1]Iluo↑
Schifinyl)propane, 2,2-bis-(4-methacryloyloxy7T-nyl)propane, 2,2-bis-(4
-Methacryloyloxy]-21-Sif1nyl)pan, bis(4-methacryloyloxy]-1-gysyphenyl)sulfone, 2,2-his-(3,5-dibu1]- 4-Methacryloyl A-1~xinoenyl> propane, 2,5-bismethacryloyl[1yl'A-1 cymedyldiophene, 2,5-bismethacryloyl[cymedyl]3,4-dibroE''fonoJ Polyfunctional acrylic esters and methacrylic esters such as Noblue 2-chloroacrylate-1, methyl 2-bromoacrylate-1~, Schiff'] xyl-2-chloroacrylate cyclohexyl-2-bromoacrylate i~, 2- Tricyclo[5,2,1°02°6]-3-deceloxyethyl-2-chloroacryle-1-,2-1helicyclo[5
, 2, 1゜θ''' Tsumugi-→]-3-dehirch Aniblue 2-chloroacryle-1-12-1~licyclo[5,2,1,02'6L-
2-halogenoacrylic acid esters such as 3,4-dibromodecyldioedyl 2-chloro7crylyl 1.: mebrodioacrylate-1~, methylthiomethacrylate-1~,
Butylthioacryle-1-, Butylthioacryle-1-
,) J, Nistyl and thiomethacrylic acid esters such as phenylthiomethacrylate, penzylbuoacrylate, benzylthiomethacrylate-1, etc. Unsaturated di-1-lyl such as lyl; allyl benzoate, diallyl phthalate, diethylene glyc]-rubisallyl carbon-1-, 2,2-bis-(4-allyl Axycarbonyloxyethoni-1 di-3 ,5-dibuIcomophenyl)propane, 2,2-bis-(4allyloxy-
Allyl carbonate, allyl carbonate, and allyl ethers such as 3,5-dibroseptaphenyl)bu[]pan;
Vinyl aromatics such as styrene, chlorostyrene, bromostyrene, dichlorostyrene, dibrostyrene, methylstyrene, divinylbenzene, etc.; 4-bo-1 diacrylate, Evo↑cymethacrylate 1~, polyJ syl acrylate 1~ , polyethral methacrylate, polyurethane acrylate-1-, polyurethane methacrylate, and the like. Lenses made from the plastic lens material of the present invention! FJ construction is
001 to 10 parts by weight of a polymerization initiator was added to the monomer composition represented by the general formula [1] or a monomer composition mixed with other radically polymerizable ZE I monomers as necessary, and the polymerization initiator was uniformly dissolved. Thereafter, the predetermined shape is poured into a glass mold and polymerization is carried out by heating or irradiating ultraviolet rays.The polymerization initiator is not particularly limited as long as it generates radicals when heated or irradiated with ultraviolet rays. When radical polymerization is carried out by heating, azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, etc. are used, and the polymerization temperature is 0 to 15.
Preferably, the temperature is 0°C and the polymerization time is 05 to 72 hours. In addition, when polymerization is carried out by ultraviolet irradiation,
Nylpropan-1-one, benzophenone, Michlerke 1-1-one, 2-chlorothioxanthone, 2-isobropyrthi-1-zanthone, benzoin, penzoin isobutyl ether, benzyl, penzyl dimedyl ketal, hydro'-dicyclo-1- Sylph [Nilke 1 Hen, etc.] is used, the illumination intensity is preferably 0.1 to 100 mW/cffl, and the irradiation time is preferably 1 minute to 10 hours.

Furthermore, the plastic lens material according to the present invention may contain known additives such as ultraviolet absorbers, antioxidants, drip-proofing agents, colorants, etc.

Example 1 The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

(Evaluation of physical properties) Physical properties of the polymers obtained in Examples and Comparative Examples were evaluated as follows.

Refractive index evaluation (no) and Atsube number <ν0> were measured at 20° C. using an Atsube refractometer 31 manufactured by Atago Co., Ltd.

Weather resistance: I put the lens in a weather meter equipped with a Nanshine carbon arc lamp, took it out after 200 hours, and compared the hue with the lens before the test.

The evaluation standard M was rated as no change (○), slight yellowing (△), and yellowing (x).

Endurance! A lens with an impact center thickness of 2M was tested according to the 1-DA standard. Those that passed were marked as ○, and those that did not pass as ×.
Measurement was carried out at -1-M under a load of gr, and evaluation was made based on the peak temperature of the obtained chart.

Visual observation was performed using the optical strain Schlieren method. Those without distortion were rated O, and those with distortion were rated ×.

(Example 1) A mixture of 1 to 100 parts by weight of sudyryl methyl] dioshyamerate (S 3 TC-11 and 5 parts by weight of azobis dimeburubare F) 2 to 5 parts by weight was assembled using two glass molds for lens molding. Pour into a lens mold, and
10 hours at 0°C, then 5 hours at 60°C, then 120
'C'c It was heated for 3 hours to polymerize and obtain a plastic lens. Table 1 shows the physical properties of the obtained lens (polymer).

From Table 1, the lens of Example 1 is colorless and transparent, has a very high refractive index (no) of 1.68, and has an Atsube number (ν0
) was also as high as 28 (low dispersion), and had excellent weather resistance, impact resistance, and heat resistance (130° C.), and no optical distortion.

(Examples 2 to 7) Example 1 except that the seven-mer composition shown in Table 1 was used.
A lens (polymer) was obtained by performing the same operation as above. These physical properties are summarized in Table 1 together with Example 1.

From Table 1, the lenses of Examples 2 to 7 are colorless and transparent;
The refractive index (no) is high at 1.59 to 1.65, and the Atsbe number (νD) is also high (low dispersion) at 30 to 36. To 105・1
50° C.) and had no optical distortion.

Comparative Example 1 1-43.511 parts of xylylene diisocyanate, 1-43.511 parts of pentachloride: j1 to Fugis (1-mercap to 1-propylene)! i6. ! A mixture of the proposed part and 1-0.05 parts by weight of dizobletin dilaure was injected into a lens mold assembled by two glass molds for lens molding, and heated at 60°C for 10 hours, then at 180°C. The mixture was heated for 5 hours and further heated at 120° C. for 3 hours to polymerize. Table 1 shows the physical properties of the polished lens (polymer).

From Table 1, although the lens of this comparative example was colorless and transparent and had excellent impact resistance against harmful substances, the heat resistance temperature was low at 86°C, and optical distortion was also observed.

Comparative Example 2.3 A lens (polymer) was obtained in the same manner as in Example 1, except that the Nanatsuma 1 #4 precept shown in Table 1 was used. These physical properties are shown in Table 1 together with Comparative Example 1.

From Table 1, although the lens of Comparative Example 2 had no optical distortion and had excellent impact resistance, it was pale yellow and had poor weather resistance. Further, although the lens of Comparative Example 3 was colorless and transparent and had no optical distortion, it was inferior in weather resistance and impact resistance.

(Margin below) The abbreviations in Table 1 mean the following substances.

1) 5TC-1; Compound 5TC-2+, where n=1 in general formula [I]; Compound 5TC-3, where n=2r in general formula [il; Compound 5TC-, where n=3 in general formula [I] 4.Compound 2) which is n・-4 in the general formula CI] BzHA; benzyl methacrylate-1-31C
HPH; D--cyclohexylphinyl methacrylate 4) VT; vinyl diophene 5) TCDH^; bisacryloxymethyltricyclo[5,2,1,02°6]decane 6) DVB; divinylbenzene 7) HPS
;Metakurihafu 1suru ricylate 8) XDf
;xylylene diisocyanate 9) PTHP
; Pentaerythritolte 1-Rakis (to Mercap 1-Propione-1) 79 10) Br4 BPADH; 111 PIN: Polyisopropenylnaphthalene 12) V-64i; Azobisdimethylvaleroni 1-Ryl 13) DBTDL; Sibutyl tin zilla Ure-1-14) Br3 PH8; 2, 4, 6-
Tripro ℃ x Nyl methacrylate 15) LPO, lauroyl peroxide [Effects of the invention] As invented above, the plastic lens material according to the present invention is colorless and transparent, has a high refractive index, low dispersion, and has impact resistance and weather resistance. A lens with excellent properties and heat resistance and no optical distortion can be obtained.

In particular, when used as a concave lens for eyeglasses, the thickness around the lens can be made thinner and the lens has less birefringence and chromatic aberration.

Claims (1)

[Claims] A plastic lens material comprising a polymer containing a compound represented by the following general formula [I] as an essential monomer component. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, n is an integer from 1 to 5.)