JPH01309001A - Plastic lens material - 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] [Field of Industrial Application] The present invention relates to a plastic lens material,
More specifically, < relates to a high refractive index plastic lens material that is three-dimensionally crosslinked and has excellent impact resistance, abrasion resistance, and dyeability.

[Conventional technology]

Plastic lenses are becoming widely used in optical products due to their ease of molding and light weight. Particularly in eyeglass lenses, the weight of the entire eyeglass has a large effect on both the physiology and the optics of the eyeglass, so it is desired that the lens be light, and in recent years, resins made of polydiethylene glycol bisallyl carbonate have become the mainstream for plastic eyeglass lenses.

However, although this plastic eyeglass lens can reduce its weight to half that of inorganic glass, its refractive index is only 1.
Since the refractive index is as low as 49 to 1.50, the center thickness, scorch thickness, and curvature tend to be large compared to inorganic glass, and a plastic lens with a high refractive index is desired.

In addition, in the case of producing a wide variety of products such as eye bell lenses, the cast polymerization method is used, which requires polymerization time of 10 hours or more to obtain lenses, which is a less productive method. A manufacturing method is also desired.

In order to solve these problems, we are using a urethane resin that has a high refractive index and excellent heat resistance and impact resistance as a material that is obtained by addition polymerizing the reaction product of an isocyanate compound and an unsaturated compound containing a hydroxyl group. A method for obtaining a plastic lens (Japanese Patent Application Laid-Open No. 57-156602), a method for obtaining a lens by adding a photosensitizer to epoxy di(meth)acrylate, injecting it into a lens mold, and polymerizing and curing it with ultraviolet rays (Japanese Patent Application Laid-Open No. 156602). Publication No. 59-87129) and the like have been proposed.

[Problem that the invention seeks to solve]

However, the former method requires high refractive index and heat resistance.
Although plastic lenses with excellent impact resistance can be obtained, the polymerization process after injection into the lens mold requires a long time of 20 to 50 hours, resulting in extremely low productivity.Also, these urethane resins are solid or highly resistant at room temperature. It is a viscous liquid and has the problem of poor workability in cast polymerization.

In addition, although the latter method improves productivity because it can be cured in a short time of about 60 seconds to 1 minute, it has the disadvantage that the resulting lenses have poor impact resistance and abrasion resistance. . Furthermore, when attempting to manufacture a thick lens with a thickness of approximately 15 m/m, there is a problem that the deep hardening property is insufficient, and the desired performance cannot be obtained.

[Means for solving problems]

In view of the above-mentioned problems, the present inventors have conducted intensive studies to provide high-refractive-index plastic lenses with excellent translucency, impact resistance, abrasion resistance, and dyeability with good productivity, and have developed the present invention. It's arrived.

That is, the present invention provides (40 to 90 parts by weight of urethane poly(meth)acrylate having two or more (meth)acryloyl groups in one molecule,
represents a hydrogen atom or a methyl group, and m or n represents an integer of 0 or 1 or more. ) At least one monomer represented by 1
0 to 60 parts by weight of (M.

(B) Based on 100 parts by weight of the total amount of components (LO1-5
The plastic lens material is comprised of parts by weight and has a refractive index of 1.53 or more.

The first component of the present invention, urethane poly(meth)acrylate (Al) having two or more 7 (meth)acryloyloxy groups in one molecule, is the main component of the plastic lens material of the present invention, and is molded. The lens has good impact resistance and abrasion resistance.

It provides a dyeing function and can be produced by addition reaction between a compound having two or more isocyanate groups in the molecule and a (meth)acrylate monomer containing a hydroxyl group.

Isocyanate compounds having two or more isocyanate groups in the molecule include aliphatic, aromatic or alicyclic isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate. , tolylene diisocyanate, quinrylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, dicyclohexylmethane diisocyanate, biphenyl diisocyanate, naphthalene diisocyanate, etc., and these isocyanates and active hydrogen atoms such as amino groups, hydroxyl groups, carboxyl groups, and water. Compounds having two or more isocyanate groups in the molecule obtained by reaction with a compound having at least two of these, or trimers to pentamers of the diisocyanate compounds mentioned above can be used.

As the hydroxyl group-containing (meth)acrylate to be reacted with the isocyanate compound, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl/L/
(meth)acrylate, 2-hydroxybuty V(meth)
acrylates, 4-hydroquinbuty/I/(meth)acrylates, and monoepoxy compounds such as butyl glycidyl V diμ ether A/, 2-ethyl V hexyl glycidyl ether, Feni M glycidyl ether, glycidyl methacrylate and (meth)acrylic acid. and (meth)acrylic acid monoesters of polyethylene glycol or polypropylene glycol.

The addition reaction between the isocyanate and the hydroxyethyl-containing O(meth)acrylate can be carried out by a known method, for example, by reacting a hydroxyl group-containing (meth)acrylate in the presence of an isocyanate compound, for example, by adding a mixture with dibutyltin silacrate at 50°C. It can be produced by dropping it under conditions of ~90°C. Among the urethane poly(meth)acrylates thus obtained, in order to obtain a plastic lens material with a high refractive index, cyclohexane diisocyanate,
isophorone diisocyanate, quinrylene diisocyanate, diphenylmethane diisocyanate), m-phenylene diisocyanate, naphthalene diisocyanate,
Biphenyl diisocyanate and the like are preferred. In particular, due to the viscosity of the monomer mixture and the refractive index of the resulting plastic lens material, as well as its good deep curing properties when using photoactive species such as ultraviolet rays as a polymerization initiator, , 2-hydroxypropyl methacrylate is preferred. These urethane poly(meth)acrylates (A) can be used alone or in combination of two or more.

The monomer (E) represented by the general formula (1), which is the second component of the present invention, serves as a reactive diluent for the urethane poly(meth)acrylate (A), which is the main component. .

Specific examples of the monomer include phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate,
Examples include phenyl acrylate, benzyl methacrylate, and phenoxy7-ethyl methacrylate. These monomers can be used alone or in combination of two or more.

The third component of the present invention is a polymerization initiator (C1) that generates an energy active source of free radicals (C1 is a polymerization initiator that releases an energy active source, that is, a radical species, by heat or light to initiate polymerization. be.

Specific examples of thermally active radical polymerization initiators among initiators (at) include benzylic peroxide, diisopropyl baroxycarbonate, t-butyperoxyisobutyrate, t-butylperoxy-2 -Organic peroxides such as ethylhexanoate, cumene hydroperoxide, and azobisisobutyronitrile.

Further, specific examples of the photopolymerization initiator include 2-hydroxy V+ 2-methyl-1-phenylated propan-1-one, hydroxycyclohexyl phenyl ketone, methylphenylated glyoxylated F1-setophenone benzophenone, λ2- dimethoxy 2-phenylacetophenone,
2-)4-ru(4-(methylthio)phenyl2-
Examples include morpholino-1-propanone, benzyl, benzoin methyl ether, benzoin ethyl ether, 2-chlorothioxanthone, isopropylthioxanthone, and 2.4.6-drimethylbenzoyldiphenylphosphine oxide.

Among these, in order to obtain a lens material with good productivity, which is the effect of the present invention, photopolymerization initiators that can be cured in a short time and with energy saving are preferable as radical polymerization initiators, and among them, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, hydroxyl chlorohexylphenyl ketone, methylphenylglyoxylate, 2, 4.
6-) By using lymethylpenzoyldiphenylphosphine oxide, a transparent cured product with almost no yellowing can be obtained.

It also has excellent deep hardening properties and is particularly preferred.

Among the photopolymerization initiators mentioned above, 2.4.6-) IJ
Methylpenzoyl diphenylphosphine oxide has a sensitive wavelength of active energy rays of 370 to 390 nm, which is 35 nm, which is the sensitive wavelength of ordinary UV-active photoinitiators.
Since it is on the longer wavelength side than 0 to 360 nm, it has particularly excellent deep curability.

In this case, the smaller the amount of 2.4.6-drimethylbenzoyldiphenylphosphine oxide, the better.
When using [L01 to 0.05 parts by weight for 00 parts by weight,
A transparent cured product without yellowing is obtained.

In addition, when producing a molded product by cast polymerization, a UV absorber is often used in order to improve its weather resistance, but in this case also the above-mentioned 2.4°6-drimethylbenzoyl diphthalate is used. The use of enylphosphine oxide is particularly preferable because it has a different sensitive wavelength from that of the ultraviolet absorber, and therefore can be manufactured using safe high-pressure mercury lamp equipment.

The plastic lens material of the present invention contains 40 to 90 parts by weight of the above-mentioned urethane poly(meth)acrylate (A), 110 to 60 parts by weight of the monomer represented by the pattern [I], (
A) + Polymerization initiator (for 100 M parts of component B)
C) It can be produced by injecting a monomer mixture consisting of 001 to 5M parts into a mold and then heating it in a hot air oven or irradiating it with ultraviolet rays in the presence of a photopolymerization initiator to polymerize and harden it.

If the proportion of each component is less than 40 parts by weight, the urethane poly(meth)acrylate will not cure sufficiently, and if it exceeds 90 parts by weight, the viscosity of the monomer mixture will increase and the workability of cast polymerization will deteriorate. In addition, if the blending ratio of monomer (B) represented by pattern hole (1) is less than 10 parts by weight, the dilution effect will not be sufficient, the viscosity of the monomer mixture will increase, and the workability of cast polymerization will decrease. If the amount exceeds 60 parts by weight, the abrasion resistance and impact resistance of the obtained plastic lens material will decrease.

Moreover, the polymerization initiator (0) is a monomer mixture (~+(B) 1
00 parts by weight, if it is less than 101 parts by weight, curing will not be sufficient, and if it exceeds 5 parts by weight, no significant improvement in curing performance can be expected, which is not preferable from a cost standpoint.

In order to polymerize and cure the monomer mixture by irradiating ultraviolet rays, ultraviolet rays with a wavelength of 2000 to 8000 A are preferable.
Normal atmosphere is sufficient for the irradiation atmosphere. Further, as a light source, a known chemical lamp, xenon lamp, low pressure mercury lamp, high pressure mercury lamp, etc. can be used.

Further, in the present invention, in addition to the above-mentioned polymerization curing method using ultraviolet irradiation, the known XM, 1B! It is also possible to apply a polymerization curing method using irradiation with rays, visible light, or the like.

In carrying out the present invention, various ultraviolet curable monomers, oligomers, other co-M gold fm-h monomers, triphenylphosphine, etc. may be used during polymerization to the extent that the effects of the present invention are not impaired. Antioxidants, UV absorbers,
You can also add blueing dye etc.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples. In the examples, "parts" indicate "parts by weight."

In addition, the physical property evaluation in this example was measured according to the method described below.

(1) Refractive index: Measured using an Atsube refractometer.

(2) Pencil hardness: Measured according to J1 day-5400. In the case of photocuring, the surface irradiated with light was the front surface, and the opposite side was the back surface.

(3) Visible light transmittance: ASTM Dl 003
-61.

(4) Injection workability: The degree of difficulty in injecting the mixed composition into the mold using a syringe at room temperature was determined.

○...Easy to inject ×...Difficult to inject (5) Workability: The lens was processed using a spectacle lens polishing machine and judged visually.

○...Smooth cut with no chipped edges A ground surface was obtained.

×・・・Smooth surface cut minor surface cannot be obtained It was.

(61 Impact Resistance - A lens with a center wall thickness of 2 mm was tested in accordance with FDA standards.

◎... Particularly excellent ○... Excellent The dyeing property was compared with that of a lens made from a single combination of diethylene glyco-V bisallyl carbonate and a lens made from a single type combination of diethylene glyco-V bisallyl carbonate by heating the solution to 80°C and fiffing the lens for 5 minutes in a dye bath with was determined visually.

○...Staining properties are the same, and the color is superior. It is.

×: Poor staining properties.

Example 1 (Production of urethane dimethacrylate) In a three-necked flask, xylylene diiso V ane zss part,
Add 2 parts of hydroquinone monomethyV ether α, and add 60
A mixture of 310 parts of 2-hydroxypropyl methacrylate and 5 parts of diptyltin dilaurate α was added dropwise to the mixture over 3 hours while stirring at a temperature of 0.degree. After dropping, further heat to 70℃
The reaction was continued for 3 hours to obtain urethane diacrylate.

(Manufacture of plastic lens material) 50 parts of benzyl methacrylate and 2 parts of methylphenylglyoxylate were mixed with 70 parts of the above urethane dimethacrylate, and after stirring well at room temperature, this monomer mixture was mixed with a diameter of 70.1111%. It was injected into a mold consisting of glass for lens molding and a gasket made of polyethylene-vinyl acetate copolymer for finished products with an internal capacity of 20 m and for semi-finished products with an internal capacity of 80 m, and a lamp was made using a 6 KW Takatakagi mercury lamp. Ultraviolet rays were irradiated for 30 seconds at a distance of 10 cm+m.

After demolding from the glass mold, the lens was held at 110° C. for 1 hour to remove internal distortion of the lens. At the same time, flat plates with a thickness of 2 mm were obtained using a mold made of flat glass, and the physical properties of these plates were evaluated regarding their hardening properties.

The results are shown in Table 1.

Example 2 In Example 1, polymerization was carried out at 70°C for 2 hours and at 100°C for 3 hours using 2 parts of methylphenylglyoxylate (instead of 2 parts of L, t-butylperoxyisobutyrate). By curing, a Lanes molded product and a flat cured product were obtained.The evaluation results are shown in Table 1, I/c.

Examples 3 to 9, Comparative Examples 1 to 5 Lenses were manufactured in the same manner as in Example 1 using the monomers shown in Table 1. The results are also listed in Table 1.

However, in Comparative Example 1.2, 3 parts of diisopropyl peroxy percarbonate and 2 parts of CL were used to heat polymerize and cure. The abbreviations of the monomers in Table 1 are as follows.

Ul) Ml: Urethane dimethacrylate obtained by reacting xylylene diisocyanate and 2-hydroxypropyl methacrylate UDM2: Urethane dimethacrylate obtained by reacting isophorone diisocyanate and 2-hydroxyethyl methacrylate UDM5 Nidiphenylmethane diisocyanate and 2 - Urethane dimethacrylate obtained by reacting hydroxyethyl methacrylate UDAl: Urethane diacrylate obtained by reacting xylylene diisocyanate and 2-hydroxyprobyl acrylate BzM: Penzyl methacrylate PM: Phenyl methacrylate V-t PPM: phenoxyethyl methacrylate DGB diethylene glycol bisallyl carbonate MMA: methyl methacrylate 1! iM1: Epoxy dimethacrylate consisting of bisphenol A type jepoxy and methacrylic acid 011: Methylphenyl glyochinate H11: t-
Butyl peroxyisobutyrate 012: 2-Hydroxy-2-methyl-1-phenylpropan-1-one 013: Hydroxycyclohexylphenyl ketone H12 diisopropyl baroxybar carbonate o14: Benzophenone 015: λ4,6-) Methylpenzoyl diphenylphosphine oxide [Effects of the Invention] As detailed above, the material of the present invention has excellent translucency, impact resistance, abrasion resistance, and dyeability, and has a high refractive index, so it can be used for plastic lenses. It can be seen that it is suitable as a material for industrial use.

Patent applicant: Mitsubishi Rayon Co., Ltd. Agent: Patent Attorney: Toshio Sawa

Claims (1)

[Scope of Claims] (A) 40 to 90 parts by weight of urethane poly(meth)acrylate having two or more (meth)acryloyl groups in one molecule, (B) General formula [I] ▲ Numerical formula, chemical formula, table, etc. ▼[I] (In the formula, R_1 and R_2 are hydrogen atoms or methyl groups, m
Alternatively, n represents an integer of 0 or 1 or more. 10 to 60 parts by weight of at least one monomer represented by (A) and (C) at least one polymerization initiator that generates a free radical energy active source in a total amount of components (A) and (B) of 10 to 60 parts by weight.
A plastic lens material comprising 0.01 to 5 parts by weight relative to 0 parts by weight, and wherein the refractive index of the polymer of the composition is 1.53 or more.