JPH01209401A - plastic cleanse - 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] <Industrial Application Field> The present invention relates to a plastic lens, and more specifically, a three-dimensionally crosslinked plastic lens with excellent impact resistance, yellowing resistance, and dyeability, and a nine-high refractive index lens. This is related to wo-stic lenses.

<Conventional Technology> Plastic lenses are becoming widely used in optical products due to their ease of molding and light weight. Especially when it comes to eyeglass lenses, the weight of the whole eyeglass has a big impact on both the physiology and the optics of the eyeglass, so it is desirable that the lens be lightweight. It has become the mainstream. However, this plastic lens weighs 17% less than inorganic glass.
The refractive index of 1.49 to 2 can be reduced to
1.50, and tends to have a larger center thickness, burnt thickness, and curvature than the normally used crown glass (refractive index = 1.52), and is a plastic lens with a high refractive index equal to or higher than that of glass. 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, a plastic lens with excellent heat resistance and impact resistance is obtained using a urethane resin obtained by radical polymerization of the reaction product of an isocyanate compound and an unsaturated compound containing a hydroxy group. method (Japanese Unexamined Patent Publication No. 57-156602), a method in which a photosensitizer is added to epoxy di(meth)acrylate, the mixture is injected into a lens mold, and the lens is obtained by polymerization and curing with ultraviolet rays (Japanese Unexamined Patent Publication No. 59-87129). Public bulletins) etc. have been proposed.

When manufacturing urethane methacrylate used for the former lens material, it is preferable to use aromatic isocyanate as the raw material isocyanate in order to increase the refractive index of the lens, while for the latter epoxy di(meth)acrylate, It is said that it is better to use epoxy raw materials such as bisphenol A and bispheno-1L/F skeleton, which have a high refractive index.

<Problems to be solved by the invention> However, the weather resistance of these unsaturated group-containing urethane resins and epoxy resins, mainly yellowing due to heat treatment, ultraviolet irradiation, etc. Depends on the structure of the isocyanate compound and epoxy raw material. Weather resistance is relatively good when the main structure is an aliphatic or alicyclic structure, but as mentioned above, it is desirable for plastic lenses to have a high refractive index, so it is necessary to increase the refractive index of plastic lenses. However, these plastic lenses have the disadvantage that they yellow due to heat treatment and light irradiation. On the other hand, the former method (Japanese Unexamined Patent Publication No. 57-13660
Although a plastic lens with a high refractive index and excellent heat resistance and impact resistance can be obtained using Publication No. 2), it takes a long time of 20 to 50 hours for polymerization after injection into a lens mold, resulting in a significant drop in productivity. There is also the problem that urethane (meth)acrylate, which is a raw material, is solid or a highly viscous liquid at room temperature, and the workability of cast polymerization is poor.

In addition, in the latter method (Japanese Unexamined Patent Publication No. 59-87129), it can be cured in a short time of about 30 seconds to 1 minute.
Although productivity is improved, the impact resistance of the resulting lenses
There is a problem that not only is the abrasion resistance inferior, but also the deep curing property is inferior, so that a resin block having a maximum thickness of about 155 m, which is necessary for a lens, cannot be cured.

Means for Solving the Problems> As a result of intensive studies on the above-mentioned problems, the present inventors have developed an aliphatic or alicyclic polyisocyanate with excellent yellowing resistance and a hydroxyl group-containing (meth)acrylate. By curing a composition containing urethane poly(meth)acrylate as the main component obtained by the reaction, and in combination with Esthe A/(meth)acrylate, which has a high refractive index and has relatively excellent yellowing resistance, the surface hardness and impact resistance are improved. The inventors have discovered that it is possible to produce plastic lenses with good productivity, which are excellent in hardness, heat resistance, colorless transparency, and dyeability, and have little yellowing.

That is, the gist of the present invention is that (A) a urethane poly(
30 to 90 parts by weight of meth)acrylate, (B) general formula (
1 to 61 parts by weight of dimethacrylate represented by I), OH snow=c-coo-((!H,-OHO)-Maichi(C
H-(H,O)Ill-OC-C=CB鵞(I'1 (In the formula, R1, horse represents hydrogen or a methyl group, and m represents an integer of 0 to 5.) (In the formula, X is hydrogen, Hail methyl group, chlorine or bromine.

) (C) 9 to 69 parts by weight of a radically polymerizable vinyl monomer having a boiling point of 10° C. or higher, (D) at least one polymerization initiator in the total amount of components (A), (B), and (C1); 100 of
A plastic lens comprising a polymer obtained by physical polymerization of a composition consisting of 101 to 5 parts by weight, and having excellent yellowing resistance and a refractive index of 1.52 or more. be.

Urethane poly(meth)7 which is the first component of the present invention Ri!
J 1/-) (Al is the main component of the plastic lens of the present invention, and gives the molded lens good impact resistance, heat resistance, yellowing resistance, and stainability,
It can be produced by addition reaction between an aliphatic or alicyclic polyisocyanate compound and a hydroxyl group-containing (meth)acrylate.

Examples of these aliphatic or alicyclic isocyanate compounds include aliphatic or alicyclic isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2.2.4-trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, and dicyclohexyl. Examples include methane diisocyanate, isocyanoethyl methacrylate, propyl isocyanate, etc. Trimers to pentamers of these isocyanate compounds, and compounds having an isocyanate compound and at least two active hydrogen atoms such as an amino group, a hydroxyl group, a carboxyl group, and water. Compounds having isocyanate groups obtained by reaction with can also be used.

Hydroxyl group-containing (
As the meth)acrylate, 2-hydroxyethyl AI
(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl A/(meth)acrylate, yohyptylglycidyl ether, 2-ethylhexylglycidyl ether, phenyl Examples include monoepoxy compounds such as glycidyl ether, addition reaction products of glycidyl methacrylate and (meth)acrylic acid, and (meth)acrylic acid monoesters such as polyethylene glycol and polypropylene glycol.

The addition reaction between a polyisocyanate and a hydroxyl group-containing (meth)acrylate can be carried out by a known method, for example, by contacting a hydroxyl group-containing (meth)acrylate with a mixture of digtyltine dilaurate in the presence of an isocyanate compound at 50°C to 90°C. It can be produced by dropping it under the following conditions.

In the present invention, urethane poly(meth)acrylates can be used alone or in combination of two or more, but from the viewpoint of colorless transparency and yellowing resistance of the molded lens, hexamethylene diisocyanate and hexamethylene diisocyanate are used. is an adduct of 2,2,4-)limethylhexamethylene diisocyanate, or dicyclohexylmethane diisocyanate and 2-hydroxylthiA/(meth)acrylate, or 2-hydroxypropyl(meth)acrylate. Particular preference is given to using urethane poly(meth)acrylates.

Di(meth)acrylate (Bl) represented by general formula (I), which is the second component of the present invention, not only increases the refractive index of the lens, but also gives the lens after molding good heat resistance, impact resistance,
It has the role of imparting high rigidity. General formula (I)
The higher the content of di(meth)acrylate (B), the higher the refractive index of the lens, but on the other hand, the weather resistance of the lens decreases. When the refractive index of the polymer (0) is large, the smaller the amount of di(meth)acrylate (B) represented by the general formula (R), the better.

Specific examples of the di(meth)acrylate (B) represented by the general formula (I) include 2,2'-bis(4-(meth)
Acryloxyditoxyphenyl)propane, 2.2'-
Bis(4-(meth)acryloxyjetoxyphenyl/V
) Propane Z 2/-bis(4-(meth)acryloxypentaethoxypheni/L/)propane, 2.2'-
Bis(4-(meth)acryloxyethoxy-45-dibromphenylv)propane, 2.2'-bis(4-(meth)acryloxyjethoxy-45-dibromphenyl)propane, 2.2'-bis( 4-(meth)acryloxypentaethoxy-45-diglompheny/V)propane, 2,2'-bis(4-(meth)acryloxy-45
-Diprompheni A/) propane, Otsu2'-bis(4-
(meth)acryloxyethoxy-5-5-dichlorophenyl)propane, 2,2'-bis(4-(meth)acryloxyethoxy-5-dimethylphenyl)propane, 2
．． 2'-bis(4-(meth)acryloxyjethoxy-
45-dichlorophenyl)propane, 2,2'-bis(
Examples include 4-(meth)acryloxyjethoxy-45-dimethylpheni/l/) propane, 2,2'-bis(4-(meth)acryloxy-45-dimethylpheny/v)propane, and the refractive index and From the viewpoint of colorless transparency, 2.2'-bis(4-(meth)acryloxyjetoxyphenyl)propane and 2.2'-bis(4-(meth)acryloxyethoxy-mura-dibromphenyl)deloban are used. is particularly preferred. These di(meth)acrylates (B) represented by general formula (I) can be used alone or in combination of two or more.

The third component of the present invention, a radically polymerizable vinyl monomer with a boiling point of 100°C or higher (C+, is a diluted highly viscous urethane di(meth)acrylate (A) that is the main component of the plastic lens of the present invention). The casting workability is improved by lowering the viscosity, and the compatibility between the urethane acrylate, which is the first component, and the di(meth)acrylate (B) represented by the general formula (I), which is the second component of the present invention. In general, prescription eyeglass lenses are made by injecting a resin composition into a mold made of two pieces of molded glass and a gasket made of polyvinyl chloride, polyvinyl acetate, etc., and then polymerizing it. In order to improve workability, it is preferable that the injectable material has a low viscosity, a low boiling point, and a low odor.
bp=-78°C) has a strong odor and is highly toxic, making it unsuitable and undesirable for injection work.

Radical polymerizable vinyl monomer (at 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, (meth)
1-Butyl 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, phenoxyprobyl (meth)acrylate, (meth)acrylic acid and droxyethyl, (
Hydroxypropyl meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenylglycidyl (meth)acrylate , (meth)acrylic acid dimethylaminoethyl μ, (meth)acrylic acid phenyl cellosolve, (meth)acrylic acid N-vinyl-2-pyrrolidone,
Mono(meth)acrylic compounds such as dicyclopentenyl (meth)acrylate, N-vinyl (meth)acrylate, glycidyl (meth)acrylate (meth)acrylate, styrene, vinyltoluene, chlorostyrene, divinylbenzene, 2 - Vinyl compounds such as vinylnaphthalene, 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 -), 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(
meth)acrylate, neobentyl glycol di(meth)acrylate, hexamethylene di(meth)acrylate, pentaerythritol tri(meth)acrylate,
Examples include polyfunctional (meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(meth)acryloxyethyl isocyanurate. Others: diethylene glycol bisallyl carbonate,
Allyl compounds such as diallyl phthalate, dimethallyl phthalate, and allyl methacrylate can also be used.

These radically polymerizable vinyl monomers can be used alone or in combination of two or more types, but from the viewpoint of the refractive index of the lens after molding and colorless transparency, tetrahydrofurfuryl (meth)acrylate, Cyclohexyl (meth)acrylate, benzi A/(meth)acrylate,
Phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, piphenyl (meth)acrylate, diethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate is used. suitable. These can be used alone or in combination.

The heavy metal initiator (Dl) used in the present invention forms radical species by heat or light to initiate polymerization.

Among the initiators (D), specific examples of thermally active radical polymerization initiators include benzoyl peroxide, diisopropyl peroxyvercarbonate, t-gyl peroxy,
Isobutyrate, -butylperoxy-2-ethylhexanoate, 2.4.4-)limethylpentylperoxy-5-trimethylhexanoate, cumene hydroperoxide, azobisisobutyronitrile, etc. Examples include organic peroxides.

Specific examples of photopolymerization initiators include 2-hydroxy-2-methyA/-1-phenylpropan-1-one, hydroxycyclohexyl phenyl ketone, methylphenyl glyoxylate, acetophenone, benzophenone, and Toxyacetophenone, 2.2-dimethoxy-2-phenylacetophenone, 1-phenylacetophenone, 2-propane-dione-2-(0-ethoxycarbonyl/
%/) Oxime, 2-methyl-(4-(methylthio)phenyl)-2-morpholino-1-propanone, benzyl, benzoyl methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoisoisobutyl ether, 2-chlorothioxanthone, isopropyl Examples thereof include thioxanthone, 2,4.6-)limethylpenzoydiphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, benzoyldimethoxyphosphine oxide, and the like.

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 savings are preferred as radical polymerization initiators, and among them, 2-hydroxy-2 -Methi A/-1-phenylpropan-1-one, hydroxycyclohexylphenyl ketone, methylphenylglyoxylate, 2.
4.6-) Limethylbenzoyldiphenylphosphine oxide can be used to obtain a transparent cured product with almost no yellowing, and it also has excellent deep curability, which is particularly preferred.

In addition, to improve the weather resistance of plastic lenses,
When an ultraviolet absorber is used in combination, it is preferable to use active energy rays and an organic peroxide in combination. In this case, the ultraviolet absorber is 2-(2-hydroxy-
It is particularly preferred to use 5-methyA/phenyl)2H-benzotriazole and t-butylperoxyisobutyrate as the organic peroxide.

The plastic lens material of the present invention contains 30 to 90 parts by weight of the above-mentioned urethane poly(meth)acrylate (general formula (
Di(meth)acrylate represented by I) (B) 1~
61 parts by weight, 9 to 69 parts by weight of radically polymerizable vinyl monomer (C) with a boiling point of 100°C or higher, (Al + (B)
+ (Polymerization initiator (D) for 100 parts by weight of C1 component
α°0 After pouring a monomer mixture consisting of 1 to 5 parts by weight into a mold, it is heated in a hot air oven or with hot water, and/or irradiated with ultraviolet rays in the presence of a photopolymerization initiator to polymerize and harden. It can be manufactured easily. The mixing ratio of each component is such that if the urethane poly(meth)acrylate (A) is less than 301 parts by weight, it will not cure sufficiently, and if it exceeds 90 parts by weight, the viscosity of the monomer mixture will be high. decreases. From the viewpoint of lens molding workability and performance, 40 to 80 parts by weight is particularly preferable.

Di(meth)acrylate (B) represented by general formula (I)
If the amount is less than 9 parts by weight, not only the refractive index of the molded lens will decrease, but also the heat resistance and rigidity will decrease, and if it exceeds 61M, the weather resistance will decrease.

For these reasons, 1 to 40 parts by weight of the di(meth)acrylate (B) represented by general formula (I) is particularly preferable.

If the amount of the radically polymerizable vinyl monomer (C) exceeds 69 parts by weight, the abrasion resistance and impact resistance of the resulting plastic lens material will decrease, which is not preferable. Particularly preferred is 20 to 60 parts by weight.

The polymerization initiator (D) is a monomer mixture (A) + (B) +
(If the amount is less than 1101 parts by weight relative to 100 parts by weight of carbon, the curability will not be sufficient, and if it exceeds 5 parts by weight, no 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 irradiation with ultraviolet rays, active light having a wavelength of 200[1 to 80[10A] is preferable, and an atmosphere at normal atmospheric pressure is sufficient for the irradiation. 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 addition, when carrying out the present invention, various ultraviolet curing type upper materials may be used during polymerization to the extent that the effects of the present invention are not impaired.
, oligomers, other copolymerizable polymers, anti-yellowing agents such as triphenylphosphine, ultraviolet absorbers, bluing dyes, and the like may be added.

(Examples) Hereinafter, the present invention will be explained in more detail using examples. In the examples, "(parts)" indicates parts by weight.

Further, the physical properties in this example were measured according to the method described below.

(I) Refractive index: Measured at 589.5 nm D line using an Atsube refractometer.

(2) Pencil hardness:

Measured according to J.E. El-5400.

In the case of photocuring, the surface irradiated with light was defined as the front surface, and the opposite side was defined as the back surface.

(3) Visible light transmittance: Measured according to A8TM D1003-6t.

(4-injection workability: The degree of difficulty in injecting the monomer mixture into the mold was determined.

◯: Easy to inject ×: Difficult to inject (5) Impact resistance: A lens with a center thickness of 211111 was tested according to the PDA standard.

0; Particularly excellent. ○; Excellent.

(7) Dyeability: Sumikalon Blue-g-IPBL (Sumitomo Chemical ■#
) t S t is dispersed in 1 t of water.
Staining was carried out for 5 minutes at °C. Compared to a simultaneously dyed diethylene glycol bisallyl carbonate polymer lens,
Judging visually.

○: Excellent ×: Inferior (Example 1) (Production of urethane dimethacrylate) Hexamethylene diisocyanate 30 was placed in a three-necked flask.
Add 2 parts of hydroquinone monomethyl ether (9 parts of I), and while stirring at 60°C, add 544 parts of 2-, hydroxypropyl methacrylate and n-butyltin dilaurate [
A mixture with 4 parts of L was added dropwise over 3 hours. After the dropwise addition was completed, the reaction was continued at 70°C for another 5 hours, and 2.2'-bis(4
-methacryloxyethoxylated 5-dibromphene 1v
) Propane (manufactured by Daiichi Kogyo Seiyaku ■, GX-6094F)
20 parts, benzyl methacrylate 50 parts, 2,4.6-
) Limethylpenzoyl diphenylphosphine oxide αo s m After mixing everything and stirring well at room temperature, this monomer mixture was used for finishing molding with a diameter of 70+ m and an internal capacity of 20-m, and for semi-finish molding with an internal capacity of 80-m. The mixture was poured into a mold made of a gasket made of glass tophoryethylene-vinyl acetate copolymer, and irradiated with ultraviolet rays for 30 seconds at a distance of 101 m from the lamp using a 6KW high-pressure mercury lamp. (Integrated light amount 3000 mJ/i) Next, after being removed 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 flat glass mold, and the physical properties of these cured products were evaluated. The results are shown in Table 1.

As shown in Table 1, the obtained lens was colorless and transparent, and 1
．． It had a refractive index of 542. It also has excellent physical properties such as impact resistance, and no yellowing was observed even after a heat resistance test at 85° C. for 200 hours.

(Example 2) In Example 1, 2.4.6-) IJ methylbenzoyldiphenylphosphine oxide O, using 2 parts of t-butylperoxyisobutyrate in place of the OS part, at 70°C for 2 hours at 100°C. It was polymerized and cured at ℃ for 3 hours to obtain a lens molded product and a cured flat plate. The evaluation results are shown in Table 1.

(Examples 6 to 8. Comparative Examples 1 to 9) Lenses were manufactured in the same manner as in Example 1 using the monomers shown in Table 1. The results are also listed in the table.

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

υDME: Urethane dimethacrylate UDA2 obtained by reacting hexamethylene diisocyanate and 2-hydroxypropyl methacrylate Urethane diacrylate UDM3 obtained by reacting herring chlorohexylmethane diisocyanate and 2-hydroxypropyl acrylate: λ4,4 -) Urethane dimethacrylate obtained by reacting lymethylhexamethylene diisocyanate and 2-hydroxyethyl methacrylate UDM4: Urethane dimethacrylate obtained by reacting xylylene diisocyanate and 2-hydroxypropyl methacrylate BzMA: Benzyl methacrylate THFM: Tetofhydro 7p-furymethacrylate BphM: Biphenyl methacrylate BDM: 1,3-butylene dimethacrylate DFJM
: Diethylene glycol dimethacrylate MA : Methyl acrylate MMA : Methyl methacrylate DGB Nidiethylene glycol bisaliμ carbonate TBM : 2.2'-bis(4-(meth)acryloxyethoxy-55-dibromphenyl)propane BAM: 2.2'-bis(4-(meth)acryloquine diethoxyphenylv)propane 011:2,4.6-)limethylpenzoyldiphenylphosphine oxide 012:methylphenylglyoxylate H1l:t-
'Butyl peroxyisobutyrate 013: 2-Hydroxy-2-methyl-1-phenylpropan-1-one 014: Hydroxycyclohexylphenyl ketone 015 Nipenzophenone H12: Diisoderopyl baroxybar carbonate <Effects of the invention 〉 As detailed above, according to the present invention, it is possible to obtain a plastic that has excellent surface hardness, impact resistance, heat resistance, colorless transparency, and dyeability, and has little yellowing, and the effect is extremely large. Applicant Mitsubishi Rayon Co., Ltd. Agent Patent Attorney Toshio Yoshizawa

Claims (1)

[Scope of Claims] 1) (A) 30 to 90 parts by weight of urethane poly(meth)acrylate obtained by reacting an aliphatic or alicyclic polyisocyanate with a hydroxyl group-containing (meth)acrylate; (B) General 1 to 61 parts by weight of di(meth)acrylate represented by formula (I), ▲Mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 and R_2 are hydrogen or methyl groups, m is 0
Indicates an integer between ~5. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents hydrogen, methyl group, chlorine, bromine.) (C) 9 to 69 parts by weight of a radically polymerizable vinyl monomer with a boiling point of 100°C or higher , (D) at least one kind of polymerization initiator (A), (B),
(C) 0.01 to 100 parts by weight of the total amount of component
1. A plastic lens comprising a polymer obtained by radical polymerization of a composition comprising 5 parts by weight, and having excellent yellowing resistance and a refractive index of 1.52 or more.