JPH01103616A - 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, the present invention 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. In particular, for eyeglass lenses, it is desirable that the lenses be light so that the weight of the whole eyeglass does not have a large effect on both the physiology and the optics of the eyeglass, 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 the weight to half that of inorganic glass, it has a refractive index of 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, when producing a wide variety of products such as eyeglass 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 method is also desired.

To solve these problems, we have developed a high refractive index plastic that is made from urethane resin, which is obtained by addition polymerizing the reaction product of an isocyanate compound and an unsaturated compound containing a hydroxyl group, and has excellent heat resistance and impact resistance. Method for obtaining lenses (Japanese Patent Application Laid-open No. 136602/1983)
, a method of 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 has been proposed (Japanese Unexamined Patent Publication No. 87129/1983).

[Problem that the invention seeks to solve]

However, the former method requires high refractive index and heat resistance.
Although a plastic lens with excellent impact resistance can be obtained, the polymerization process after injection into the lens mold takes a long time of 20 to 50 hours, resulting in extremely low productivity.Also, the urethane resin used as the raw material is solid or solid at room temperature. It is a high viscosity liquid,
The problem is that the workability of cast polymerization is poor. Furthermore, there is another problem in that the resulting lens becomes yellow due to elimination of methylene hydrogen at the 2-position of the urethane bond.

In addition, although the latter method improves productivity because it can be cured in a short time of about 30 seconds to 1 minute, it has disadvantages such as the resulting lenses are yellow-colored and have poor impact resistance and abrasion resistance. have. Furthermore, when trying to manufacture a thick lens with a thickness of about 15 m/m, there is a problem that the deep hardening property is insufficient.

[Means for solving problems]

In view of the above problems with VC, the present inventors provide a high refractive index plastic lens with excellent heat resistance, yellow curvature resistance, translucency, impact resistance, abrasion resistance, and dyeability with good productivity. As a result of intensive study on this matter, we have arrived at the present invention.

That is, the gist of the present invention is that (A) general formula [l
] 40 to 90 parts of urethane poly(meth)acrylate obtained by reacting a polyisocyanate represented by the formula with a hydroxyl group-containing (meth)acrylate, (wherein R, R, or R is a hydrogen atom or a methyl group, and n is an integer of 1 to 3.) (B) 10 to 601 parts of a radically monomerizable vinyl monomer having a boiling point of 100°C or higher, and (C) an i1 initiator to (A
), 0.0 per 100 parts by weight of the total amount of components (B)
1 to 5 parts by weight, and the refractive index of the polymer obtained by polymerizing the composition is 1.52 or more.

The urethane poly(meth)acrylate (A) used in the present invention is a main component of the plastic lens material of the present invention, and provides molded lenses with good yellowing resistance, impact resistance, abrasion resistance, and dyeing resistance. It can be produced by carrying out an addition reaction between a polyisocyanate compound represented by the general formula [I] and a (meth)acrylate monomer containing a hydroxyl group.

Specific examples of the polyisocyanate compound represented by the general formula [I] include m-tetramethylxylene diisocyanate, p-tetramethylxylene diisocyanate, and the like.

In the present invention, depending on the purpose, two or more incyanate groups may be present in the molecule obtained by reacting the polyisocyanate with a compound having at least two or more active hydrogen atoms such as an amino group, a hydroxyl group, a carboxyl group, or water. It is also possible to add a compound having the above diisocyanate compounds, or trimers to pentamers of the diisocyanate compounds.

Hydroxyl group-containing (
As the meth)acrylate, 2-hydroxyethyl (
meth)acrylate, 2-hydroxypropyl(meth)
acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and monoepoxy compounds such as butylglycidyl ether, 2-ethylhexylglycidyl ether, phenylglycidyl ether, glycidyl'methacrylate, and (meth)acrylate. Examples include addition reaction products with acrylic acid, and (meth)acrylic acid monoesters of polyethylene glycol or polypropylene glycol.

The addition reaction between a polyisocyanate and a hydroxyl group-containing (meth)acrylate can be carried out using a known method, for example, by heating a mixture of a hydroxyl group-containing (meth)acrylate and a catalyst, such as diptylthine dilaurate, at 50°C to 90°C in the presence of an incyanate compound. It can be produced by dropping under certain conditions.

In the present invention, urethane poly(meth)acrylate (4) can be used alone or in a mixture of two or more, but the viscosity of the monomer mixture, the refractive index of the resulting plastic lens material, And m-tetramethylxylene diisocyanate and 2
- Reaction products with hydroxyglobil methacrylate are preferred.

Radical monomerizable vinyl monomer (B) used in the present invention
is not particularly limited and may be arbitrarily selected depending on the purpose. Specific examples include methyl methacrylate, ethyl (meth)acrylate, (meth)acrylic acid n
-Butyl, l-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate ,
Benzyl (meth)acrylate, Phenyl (meth)acrylate, Phenoxyethyl (meth)acrylate, Phenoxypropyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, (Meth) ) 2-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenylglycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate,
Mono(meth)acrylic compounds such as phenyl cellosolve (meth)acrylate, N-vinyl-2-pyrrolidone (meth)acrylate, dicyclopentenyl (meth)acrylate, biphenyl (meth)acrylate, dicyclopentenyl (meth)acrylate, etc. , styrene, vinyltoluene, chlorostyrene, divinylbenzene, 1-vinylnaphthalene, 2-vinylnaphthalene, etc., nohinyl compounds, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol;
- di(meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, polyprolene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, diglopylene glyc; - di(meth)acrylate , polyethylene glycol di(meth)acrylate, 1,3-phthylene gelicol (meth)acrylate, trimethylolpropane tri(meth)acrylate,
Neopentyl glycol diacrylate, hexamethelene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, Trimethylolpropane triethoxy (meth)acrylate, trimethylpropane triethoxy (meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(
meth) acryloxyethyl isocyanurate, 2,2'
-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2.2'-bis(4-(meth)acryloxypentaethoxy-phenyl)propane, 2.2'-
Examples include polyfunctional (meth)acryloyl group-containing compounds such as bis(4-(meth)acryloxyethoxy-3,5-dibromphenyl)propane.

In addition, allyl compounds such as diethylene glycol bisallyl carbonate, diallyl phthalate, dimethallyl phthalate, and allyl methacrylate can also be used.

These radically polymerizable vinyl monomers can be used alone or in a mixture of 2'#i or more. (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyl (meth)
Preference is given to using acrylates, biphenyl (meth)acrylate, dimethallyl phthalate, diallyl phthalate, di(meth)allyl biphenylate. These can be used alone or in combination.

The polymerization initiator (C) used in the present invention releases an energy active source, that is, a radical species, to initiate polymerization using heat or light.

Among the initiators (C), specific examples of thermally active radical polymerization initiators include benzoyl peroxide, diisopropylperoxyperponate, t-butylperoxy-isobutyrate, t-butylperoxy-2-ethylhexano ate, cumene hydroperoxide, azobisisobutyronitrile, and other organic peroxides.

Further, as specific examples of the photopolymerization initiator, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
Hydroxycyclohexylphenylketone, methylphenylglyoxylate, acetophenone, benzophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-(4-(methylthio)phenyl-2-
Morpholino-1-propanone, benzyl, benzoin methyl ether, benzoin ethyl ether, 2-chlorothioxanthone, inpropylthioxanthone,
2,4.6-)limethylpenzoyldiphenylphosphine oxide and the like.

Among these, in order to obtain a lens material with good productivity, which is the effect of the present invention, as a radical polymerization initiator, a photopolymerization initiator that can be cured in a short time and saves energy is preferable, and among them, 2-hydroxy-2-methyl -1-phenylpropan-1-one, hydroxycyclohexylphenyl ketone, methylphenylglyoxylate, 2°4.6
By using -17 methylbenzoyl diphenylphosphin oxide, a transparent cured product with almost no yellowing can be obtained, and it also has excellent deep curability, so it is particularly preferred.

Among the above-mentioned photoinitiators, 2,4.6-)limethylbenzoyldiphenylphosphine oxide has a sensitive wavelength of active energy rays of 370 to 390 n+n, which is the sensitive wavelength of ordinary ultraviolet-activated photoinitiators. 33
Since it is on the longer wavelength side than 0 to 360 nm, it has particularly excellent deep curability.

In this case, it is preferable that the amount of 2,4.6-)limethylbenzoyldiphenylphosphine oxide is as small as possible.
When using 0.01 to 0.05 parts by weight per 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 combination to improve its weather resistance, but in this case also the above 2,4゜6-) IJ methyl pen The use of soil diphenylphosphine oxide is particularly preferable because it has a different sensitive wavelength from that of the ultraviolet absorber, and therefore can be manufactured using inexpensive high-pressure mercury lamp equipment.

The glasstic lens material of the present invention includes 40 to 90 parts by weight of the above-mentioned urethane poly(meth)acrylate (A) and a radically polymerizable kj = monomer (B) having a boiling point of 100°C or higher.
After pouring into the mold a monomer mixture consisting of 10 to 60 parts by weight, 100 parts by weight of the polymerization initiator (C) and 100 parts by weight of the polymerization initiator (C), the mixture was heated in a hot air stove. Alternatively, it can be produced by irradiating ultraviolet rays and polymerizing and curing in the presence of a photopolymerization initiator. If the mixing ratio of each component is less than 40 parts by weight, urethane poly(meth)acrylate (A) 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 decrease. descend. In addition, the blending ratio of the radically polymerizable vinyl monomer (B) is 10
]! If the amount is less than 60 parts by weight, the dilution effect will not be sufficient (the viscosity of the monomer mixture will increase, and the workability of casting will decrease; if it exceeds 60 parts by weight, the abrasion resistance of the resulting plastic lens material will decrease). , which is not preferable because impact resistance decreases.

Moreover, the polymerization initiator (C) is a monomer mixture (4) + (B) 1
If the amount is less than 0.01 parts by weight, the curability will not be sufficient, and if it exceeds 5 parts by weight, no significant improvement in curing performance can be expected, which is undesirable 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.

Furthermore, in the present invention, in addition to the above-mentioned polymerization curing method using ultraviolet irradiation, it is also possible to apply a known polymerization curing method using irradiation with X-rays, electron beams, visible light, and the like.

In carrying out the present invention, various ultraviolet curable monomers, oligomers, and other copolymerizable monomers, triphenylphosphine, etc. may be used during polymerization to the extent that the effects of the present invention are not impaired. Anti-tarnishing agents, ultraviolet absorbers, bluing dyes, etc. may be added.

〔Example〕

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

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

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

(2) Lead-silver hardness: Measured according to JIS-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 D1003-6
Measured according to 1.

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

Q...Easy to inject X...Difficult to inject (5) Workability: Lenses were processed using an eyeglass lens beading machine and judged visually.

O...edges are not chipped and smooth A cut surface was obtained.

×・・・Smooth cutting surface cannot be obtained. won.

(6) Impact resistance: A lens with a center wall thickness of 2u was tested in accordance with FDA standards.

O... Particularly excellent ○... Excellent The dispersion liquid was heated to 80 °C, and the lenses were immersed in the dye bath for 5 minutes, and the dyeing properties were compared with lenses made from a homopolymer of diethylene glycol bisallyl carbonate that were similarly dyed. Judging visually.

Q...Stainability is the same or Are better.

×: Poor staining properties.

Example 1 Production of urethane dimethacrylate> 244 parts of tetramethylxylene diisocyanate and 063 parts of hydroquinone monomethyl ether were placed in a three-necked flask.
302 parts of 2-hydroxypropyl methacrylate and 0.0 parts of diptyltin dilaurate while stirring at 60°C.
The mixture with 3 parts was added dropwise over a period of 3 hours. After the dropwise addition was completed, the reaction was further continued at 70°C for 8 hours to obtain urethane dimethacrylate.

Production of plastic lens material> 40 parts of benzyl methacrylate and 0.2 parts of methylphenylglyoxylate were mixed with 60 parts of the above urethane dimethacrylate, and after stirring well at room temperature, the monomer mixture was molded into a mold with a diameter of 70 m. /m, for finished products with an internal capacity of 20M and for semi-finished products with an internal capacity of 80M. UV rays were irradiated for 30 seconds at a distance of 10 cm from the lamp.

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 sn were obtained using a mold made of flat glass, and the characteristics of these cured products were evaluated.

The results are shown in Table 1.

Example 2 In Example 1, methylphenylglyoxy L'-)0
．． Instead of 2 parts, 2 parts of t-butylperoxyisobutyrate was used and polymerization and curing was carried out at 70°C for 2 hours and at 100°C for 3 hours to obtain a lens molded product and a cured plate. The evaluation results are shown in Table 1.

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.

The abbreviations of the monomers in Table 1 are as follows.

UDMI: ) Urethane dimethacrylate obtained by reacting dimethylxylene p-diisocyanate with 2-hydroxypropyl methacrylate UDM2: ) Urethane dimethacrylate obtained by reacting dimethylxylene p-diisocyanate with 2-hydroxypropyl methacrylate Methacrylate UDM3: Urethane dimethacrylate obtained by reacting xylylene diisocyanate and 2-hydroxypropyl methacrylate UDAI:) Urethane diacrylate obtained by reacting rimetherxylene m-diisocyanate and 2-hydroxypropyl acrylate BzMA: Pen dil methacrylate THFM: tetrahydrofurfuryl methacrylate BphMA: biphenyl methacrylate 2 bars = phenyl methacrylate MMA: methyl methacrylate MA: methyl acrylate TGA: tetraethylene glycol diacrylate TBM: 2.2'-bis(4-methacryloxyethoxy-3, 5-dibromphenyl) propane DGB diethylene glycol bisallyl carbonate Oll: methylphenyl glyoxylate H1l: t-
Buter peroxyimputylate 012: 2-Hydroxy-2-methyl-1-phenylpropan-1-one O13: Hydroxycyclohexylphenyl ketone H12 Nidiisopropyl peroxyver carbonate 014: Benzophenone Ot 5: 2,4. 6-) Limethylbenzoyldiphenyl 7-osphine oxide [Effects of the invention] As detailed above, the material of the present invention has excellent heat resistance, yellowing resistance, translucency, impact resistance, abrasion resistance, and stainability. It can be seen that it is suitable as a plastic lens because of its excellent and high refractive index.

Patent applicant Mitsubishi Rayon Co., Ltd. Agent Patent attorney Toshio Yoshizawa

Claims (1)

[Claims] (A) 40 to 90 parts by weight of urethane poly(meth)acrylate obtained by reacting a polyisocyanate represented by the following general formula [I] with a hydroxyl group-containing (meth)acrylate ▲ Numerical formula, chemical formula , tables, etc. ▼ [ I ] (In the formula, R_1, R_2 or R_3 represent a hydrogen atom or a methyl group, and n represents an integer from 1 to 3.) (B) Possible for radical polymerization with a boiling point of 100°C or higher The total amount of components (A) and (B) is 100 to 60 parts by weight of vinyl monomer and (C) polymerization initiator.
A plastic lens material comprising 0.01 to 5 parts by weight based on the weight of the composition, and having a refractive index of 1.52 or more of a polymer obtained by polymerizing the composition.