JP2764450B2 - Curable composition and plastic lens comprising the cured product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a curable composition which is easy to mold and gives a cured product having a relatively high refractive index and excellent heat resistance and impact resistance, and the curability. The present invention relates to a plastic lens made of a cured product of the composition.

[Prior art] As a resin for optical materials, for example, a resin for a vision correcting lens, polydiethylene glycol bisallyl carbonate (CR-39) developed by PPG (US) in 1942 is manufactured using surface polishing, easy molding, It has been used as a mainstream resin from the viewpoint of balance between dyeing properties and other physical properties.

However, CR-39 has a low refractive index of 1.498, and has the disadvantage that the lens cannot be made thinner when strong correction is required.

In order to solve this drawback, various resins for high refractive lenses have been proposed, and some of them have been put to practical use. In particular, JP-A-57-54
Since the publication of Japanese Patent Publication No. 901, the number of patent applications for high-refractive index resins has increased sharply, indicating that active research and development are being conducted mainly by chemical-related material manufacturers.

For example, an example of a tetrabromophenyl methacrylate / divinylbenzene system disclosed in JP-A-61-73101,
Examples of halogenated bisphenol S dimethacrylate system disclosed in JP-A-62-73201, examples of tetrabromobisphenol A dimethacrylate / styrene system disclosed in JP-A-57-54901, and examples of tetrabromobisphenol A disclosed in JP-A-60-103302. Examples of diallyl carbonate-based resins have been proposed.However, these resins have problems such as a decrease in weather resistance due to contained halogen and an increase in specific gravity, and in a system having a vinyl group and a methacryloyl group, It is difficult to control the copolymerizability, and there may be cases where uneven polymerization or whitening occurs, and there is a disadvantage that the flexibility of blending is generally low.

In the example of benzyl fumarate / diallyl isophthalate disclosed in JP-A-61-34007, a medium-to-high refractive index lens using a non-halogen system has been proposed, but the balance between heat resistance and impact resistance is proposed. Inferior to CR-39 in point.

Furthermore, in the examples of the system using thiourethane disclosed in JP-A-60-199016 and JP-A-60-217229, although the impact resistance is improved, the heat resistance is low, and the reaction control and demolding are extremely difficult. And the disadvantage that the surface accuracy of the cured product is low.

[Problems to be Solved by the Invention] The present invention overcomes the above-mentioned drawbacks of the conventional resin for optical materials, has a relatively high refractive index, and has impact resistance, heat resistance,
Excellent physical properties such as low specific gravity, less production trouble,
An object of the present invention is to provide a curable composition that can form a cured product extremely easily, and a plastic lens made of a cured product of the curable composition.

[Means for Solving the Problems] According to the present invention, a novel curable composition capable of achieving the above object and a plastic lens comprising a cured product of the curable composition are provided. That is, the present invention has a structure of the general formula (I), wherein CH ₂ CHCHCH ₂ O (COArCOORO) _n COArCOOCH ₂ CH ＝ CH ₂ (I) (wherein, R has 2 to 20 carbon atoms) A divalent hydrocarbon residue, Ar is a 1,2-, 1,3- or 1,4-phenylene group, and n is 1
Represents a number from ~ 100. However, this excludes the case where Ar is only a 1,4-phenylene group. And at least 10% by weight of a diallyl phthalate oligomer having an unsaturation of 20 to 100 as expressed by an iodine value measured by the Wijs method, from a vinyl monomer capable of copolymerizing the oligomer and a radical polymerization initiator. It is a curable composition characterized by becoming. Further, the present invention relates to the diallyl phthalate-based oligomer represented by the general formula (I).
A curable composition which is an oligomer in which part or all of a divalent hydrocarbon residue having 2 to 20 carbon atoms represented by the formula is substituted by a polyol residue having 3 or more carbon atoms and 3 or more hydroxyl groups. And a plastic lens comprising a cured product of the curable composition.

For the oligomer represented by the general formula (I), several synthesis methods can be considered. For example, a method in which a diallyl phthalate and a diol are reacted while distilling off allyl alcohol in the presence of a transesterification catalyst, or dimethyl phthalate , Or diethyl phthalates, and diol and allyl alcohol are reacted in the presence of a transesterification catalyst while distilling off methanol or ethanol.

Further, when a part or all of R represented by the general formula (I) is a trivalent or higher polyol, the polyol corresponding to diallyl phthalate, diallyl isophthalate and diallyl terephthalate alone or as a mixture may be mixed with the diol or alone. Or by heating the oligomer of general formula (I) and the corresponding polyol in the presence of a transesterification catalyst.

Of course, it may be synthesized by a method more than this.

In this case, when Ar in the general formula (I) is a 1,2-substituted phenylene group (phthalate), the price is the lowest and the cured product has excellent mechanical properties. It is also suitable for use as a hydrophilic composition, but is not particularly suitable for use as a high-grade optical material because it tends to be colored.

A cured product obtained from a 1,3-substituted phenylene group (isophthalate) derivative has good chromatic aberration and is suitable as a high-grade optical material or a plastic lens.

A cured product obtained from a derivative of a 1,4-substituted phenylene group (terephthalate) has excellent heat resistance and excellent optical properties, and thus is preferable as an optical material used at high temperatures.

In this case, the diol to be reacted is 0.99 mol or less with respect to 1 mol of the phenylene group, 0.5 mol or less with trivalent polyol, preferably 0.33 mol or less with 0.1 mol of tetravalent polyol.
33 mol or less, preferably 0.25 mol or less may be used.

In general, the mechanical properties are improved by bringing the diol closer to 1 mol, but the viscosity of the oligomer increases, so that it must be appropriately selected according to the purpose. Further, a polyol having a valency of 3 or more improves mechanical properties such as flexural strength. However, caution is required because the viscosity is increased and the danger of gelation is increased.

As such a diol having 2 to 20 carbon atoms, ethyl glycol, 1,2-propylene glycol,
1,4-butanediol, 1,6-hexanediol, 1,4-
Cyclohexane dimethanol, 1,3-butanediol,
Examples thereof include diols containing a resin group or an aromatic ring such as neopentyl glycol, 1,3-cyclohexanediol, p-xylene glycol, and styrene glycol. At this time, in consideration of solubility with other polymerizable monomers, a diol having a side chain is preferable to a linear α, ω-diol, and such a diol is preferably 1,2-propylene glycol. , 1,3-butanediol, neopentyl glycol,
2,3-butanediol, 1,4-pentanediol, 1,3-
Pentanediol, 1,2-pentanediol, 2,3-pentanediol, 2,4-basediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, 1,2-hexane Diol, 2,3-hexanediol,
2,4-hexanediol, 2,5-hexanediol, 3,4
-Hexanediol and the like.

Examples of the polyol having 3 or more carbon atoms and 3 or more hydroxyl groups include resinous trihydric alcohols such as glycerin and trimethylolpropane; and aliphatic tetrahydric alcohols such as pentaneerythritol and sorbitol. Generally, when the carbon chain of the glycol is long, the impact resistance is improved, and when the carbon chain is short, the refractive index tends to be high.

The diallyl phthalate oligomer obtained in this manner cannot be cured if the degree of unsaturation represented by the iodine value measured by the Wijs method is lower than 20, but takes a very long time to cure. Will be. Conversely, if it exceeds 100, the impact resistance will be inferior, so it is not a critical value, but for general use, this range is a well-balanced range and can be widely used.

A diallyl phthalate-based oligomer having the structure of general formula (I) or a part of a divalent hydrocarbon residue represented by R in the structural formula derived from a trivalent or higher polyol;
Oligomers substituted with a valent hydrocarbon residue have the property of mixing well with many organic compounds, and have the characteristics of having extremely high impact strength and heat resistance when cured alone.

Therefore, the impact resistance of the cured product obtained by curing the composition by mixing the diallyl phthalate-based oligomer with another vinyl-based monomer copolymerizable with this oligomer at a mixing ratio according to the purpose of use is improved. The heat resistance can be improved.

The use amount of the diallyl phthalate oligomer used to achieve the object of the present invention is in the range of 10 to 90% by weight, preferably 20 to 90% by weight. When the amount of the diallyl phthalate oligomer is less than 10% by weight,
Sufficient curing cannot be expected in any of the impact resistance and heat resistance of the cured product obtained by curing.

The vinyl monomer copolymerizable with the diallyl phthalate oligomer represented by the general formula (I) and which can be copolymerized with the oligomer may be monofunctional or polyfunctional, and is compatible with the oligomer. There are no special restrictions. In addition, two or more copolymerizable vinyl monomers can be used as a mixture, and the mixing ratio is not limited, and an arbitrary ratio can be selected.

Examples of such a vinyl monomer include unsaturated aliphatic esters, aromatic vinyl compounds, unsaturated fatty acids and derivatives thereof, unsaturated dibasic acids and derivatives thereof, and vinyl cyanide compounds such as (meth) acrylonitrile. Is mentioned.

As unsaturated fatty acid esters, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate Alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, (iso) bornyl (meth) acrylate, adamantyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, fluoro Phenyl (meth) acrylate, chlorophenyl (meth) acrylate, bromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, methoxyphenyl (meth) acrylate Acrylic acid aromatic ester such as cyanophenyl (meth) acrylate, biphenyl (meth) acrylate, bromobenzyl (meth) acrylate, fluoromethyl (meth) acrylate, chloromethyl (meth) acrylate, bromoethyl (meth) acrylate, trichloromethyl (Meth) acrylate,
In addition to haloalkyl (meth) acrylates, 2-hydroxyethyl (meth) acrylates, polyethylene glycol (meth) acrylates, etc., and (meth) acrylates such as glycidyl (meth) acrylates and alkylamino (meth) acrylates is there. Also, α-
Α-substituted acrylates such as fluoroacrylates and α-cyanoacrylates.

As the aromatic vinyl compound, styrene or α-
Examples include α-substituted styrene such as methyl styrene, α-ethyl styrene, α-chloro styrene, etc., nuclear-substituted styrene such as fluorostyrene, chlorostyrene, bromostyrene, chloromethyl styrene and methoxy styrene, and diallyl phthalate.

As unsaturated fatty acids and derivatives thereof, (meth) acrylamide, N, N-dimethyl (meth) acrylamide,
There are (meth) acrylamides such as N, N-diethyl (meth) acrylamide and (meth) acrylic acid.

Examples of unsaturated dibasic acids and derivatives thereof include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, and N-carboxy. Examples include N-substituted maleimides such as phenylmaleimide, maleic acid, maleic anhydride, fumaric acid, and the like.

In addition to the above monofunctional vinyl monomers, the compound represented by the general formula (I)
Examples of the vinyl monomer copolymerizable with the diallyl phthalate oligomer represented by formula (1) include a crosslinkable polyfunctional monomer. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3-butylene glycol Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5
-Pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol hydroxyvivalate di (meth) acrylate, oligoester di (meth) acrylate Acrylate, polybutadiene di (meth) acrylate, 2,2-bis (4-
(Meth) acryloyloxyphenyl) propane, 2,2
-Bis (4- (ω- (meth)) acryloyloxypolyethoxy) phenyl) propane, 2,2-bis (4- (ω
-(Meth) acryloyloxypolyethoxy) dibromophenyl) propane, 2,2-bis (4- (ω- (meth)
Di (meth) acrylates such as acryloyloxypolypropoxy) phenyl) propane and bis (4- (ω- (meth) acryloyloxypolyethoxy) phenyl) methane, diallyl phthalate, diallyl isophthalate,
Bifunctional crosslinkable monomers such as diallyl terephthalate, diallyl carbonate, diethylene glycol diallyl carbonate, divinylbenzene, N, N'-m-phenylenebismaleimide, trimethylolethanetri (meth) acrylate, trimethylolpropanetri (meth) acrylate Trifunctional crosslinkable monomers such as pentaneerythritol tri (meth) acrylate, tri (meth) allyl isocyanurate, triallyl trimellitate, diallyl chlorendate, tetrafunctional such as pentaneerythritol tetra (meth) acrylate Crosslinkable monomers and the like.

The curable composition of the present invention can be cured by radical polymerization.

The radical polymerization initiator used for curing is heat,
Any radical polymerization initiator can be used as long as it can generate radicals by microwaves, infrared rays or ultraviolet rays, and can be appropriately selected according to the purpose and use of the curable composition.

Examples of radical polymerization initiators that can be used for polymerization by heat, microwaves, and infrared rays include 2,2'-azobisisobutyronitrile, 2,2'-azobisisovaleronitrile, and 2,2'-azobis-2. Azo compounds such as 1,4-dimethylvaleronitrile, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, ketone peroxides such as acetylacetone peroxide, isobutyryl peroxide,
2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, lauroyl peroxide, p-
Diacyl peroxides such as chlorobenzoyl peroxide, hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide, t-butyl peroxide, dicumyl Dialkyl peroxides such as peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, tris (t-butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 2,2 -Peroxyketals such as di (t-butylperoxy) butane, t-butylperoxybivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t
-Butyl peroxyhexahydroterephthalate, di-
t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxytrimethyladipate, etc. Percarbonates such as alkyl peresters, diisopropyl peroxy dicarbonate, di-sec-butyl peroxy dicarbonate, and t-butyl peroxy isopropyl carbonate are exemplified.

Examples of the radical polymerization initiator that can be used in the polymerization by ultraviolet rays include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, and 4′-isopropyl-2-hydroxy-
2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 4,4'-bis (diethylamine) benzophenone, benzophenone, methyl (o-benzoyl) benzoate, 1-phenyl-1,2-propanedione-2 -(O-ethoxycarbonyl) oxime, 1
-Phenyl-1,2-propanedione-2- (o-benzoyl) oxime, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl, benzyl methyl ketal, benzyl diethyl ketal And carbonyl compounds such as diacetyl, anthraquinone or thioxanthone derivatives such as methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone; and sulfur compounds such as diphenyldisulfide and dithiocarbamate.

The amount of the radical polymerization initiator to be used cannot be unconditionally determined because it varies depending on the type of the radical polymerization initiator, the type of the charged monomer and the composition ratio, but is usually in the range of 0.001 to 20 mol% based on the monomer component. Preferably it is in the range of 0.01 to 10 mol%. 0.001 of radical polymerization initiator used
If the amount is less than mol%, the polymerization takes a long time, and if the amount exceeds 20 mol%, it is not economical, and in some cases, foams during the polymerization or the molecular weight of the cured product obtained by the polymerization becomes extremely small. Not preferred.

The curable composition of the present invention may be polymerized and cured as it is, or, depending on the purpose, may be preliminarily polymerized and then polymerized and cured to adjust the viscosity or reduce the shrinkage during polymerization.

The polymerization temperature and the polymerization time during the curing of the curable composition cannot be specified unconditionally because they vary depending on the type of the radical polymerization initiator used and the amount used, but the polymerization temperature is usually in the range of 0 to 200 ° C. Preferably, the polymerization time is usually in the range of 0.5 to 50 hours.

The curable composition of the present invention is not only excellent in moldability, but the cured product obtained by curing the curable composition has a relatively high refractive index, and is excellent in heat resistance and impact resistance. Therefore, it is extremely useful in industrial fields such as optical materials, coating materials, sealing materials, paints, and adhesives, particularly in the field of optical materials.

For the production of the plastic lens of the present invention, for example, the curable composition is injected into a lens mold assembled from a glass mold and a gasket, heated, irradiated with ultraviolet rays or other active energy rays, and cured to remove. It can be easily done by typing.

The plastic lens of the present invention, eyeglasses, sunglasses,
It is suitably used for optical microscopes, telescopes, cameras and the like.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

The physical properties of the cured products obtained in Examples and Comparative Examples were measured by the following methods.

(1) Refractive index The refractive index at 20 ° C. was measured using an Abbe refractometer (3L type manufactured by Shimadzu Corporation).

(2) Glass transition temperature (Tg) Using a dynamic viscoelasticity measurement device (Ryovibron DDV-II-EP manufactured by Orientec), the peak (inflection point) of tan δ was read to obtain a sample (thickness of 0.1). mm).

(3) Impact resistance Using a 2D lens with a center thickness of 1.2 mm, a 16.3 g steel ball was dropped naturally from a height of 127 cm according to the FDA standard, and a steel ball drop test was performed. Those that were cracked or cracked were marked as x.

(4) Water absorption The percentage of weight increase when a sample dried under reduced pressure at 50 ° C for 5 days using a test piece of JIS-K-7209 for 2 hours in water at 100 ° C is shown based on the dry weight. Was.

(5) Moldability When a thick lens having a border thickness of 25 mm was molded, the reaction was so severe that the lens could not be molded due to runaway and the lens which was extremely difficult to remove was designated as x.

<< Method for producing diallyl phthalate oligomer >> (Synthesis Example 1) 400 g of diallyl terephthalate (DAT) and diallyl isophthalate (D) were placed in a three-necked flask equipped with a distillation apparatus.
200 g of IP), 109.8 g (0.44 times mol) of 1,3-butanediol and 0.3 g of dibutyltin oxide were charged and heated to 180 ° C. under a nitrogen stream to distill off allyl alcohol generated. When about 120 g of allyl alcohol was distilled off, the pressure in the reaction system was reduced to 50 mmHg, and the distillation rate of allyl alcohol was stopped. After the theoretical amount of allyl alcohol had distilled off, heating was continued for an additional hour. After that, reduce the pressure,
After distilling off unreacted DAT and DIP, it was measured by GPC and Mn = 103
570 g of a diallyl terephthalate-based oligomer having an iodine value of 83 and an Mw of 2360 was obtained.

 This oligomer (A) was used in Examples 1 and 2.

(Synthesis Example 2) 600 g of diallyl isophthalate and 192.7 g of a 2-mol adduct of bisphenol A ethylene oxide were used as raw materials.
580 g of diallyl isophthalate oligomer was obtained in the same manner as in Synthesis Example 1 except that (0.25 mole) was used. GPC
Mn = 1200, Mw = 2850, and the iodine value was 8
Was one.

 This oligomer (B) was used in Examples 3 and 4.

(Synthesis Example 3) A method similar to Synthesis Example 1 except that 600 g of diallyl phthalate, 46.4 g (0.25 mol) of propylene glycol, and 32.7 g (0.1 mol) of 1,1,1-trimethylolpropane were used as raw materials. As a result, 565 g of a diallyl phthalate oligomer was obtained. When measured by GPC, Mn = 1990, Mw = 3
The iodine value was 580 and the iodine value was 79. This oligomer (C) was used in Examples 5 and 6.

(Synthesis example 4) As raw materials, 300 g of diallyl isophthalate, 300 g of diallyl terephthalate and 66.3 g of pentaerythritol
520 g of diallyl terephthalate oligomer was obtained in the same manner as in Synthesis Example 1 except that (0.2 mole) was used. GPC
Mn = 1950, Mw = 3400, and the iodine value was
80. This oligomer (D) was used in Examples 7 and 8.

(Example 1) 90 g of the oligomer (A) obtained in Synthesis Example 1 above
To diethylene glycol bisallyl carbonate (CR-
39) 10 g was added and mixed, and then 4 g of diisopropyl peroxydicarbonate was dissolved as a radical polymerization initiator to obtain a curable composition. This curable composition is 50mmφ
The mixture was poured into a glass mold having a thickness of 3 mm, heated at 35 ° C. for 5 hours, heated to 80 ° C. at a rate of 10 ° C./hour, and kept at 80 ° C. for 2 hours for heat curing. After demolding, annealing was performed at 100 ° C. for 2 hours to obtain a plate-shaped cured product. The obtained cured product was a uniform, colorless and transparent resin.

 The physical properties of the cured product are shown in Table 1.

(Examples 2 to 8 and Comparative Examples 1 to 4) A cured product was obtained in the same manner as in Example 1 except that the amounts of the oligomer, monomer, and initiator were changed as shown in Table 1.

 The physical properties of the cured product are shown in Table 1.

Abbreviations Oligomer A, B, C, D ... Shown in Synthesis Examples 1, 2, 3, and 4.

CR: diethylene glycol bisallyl carbonate AB: allyl benzoate BZ: benzyl methacrylate XI: meta-xylylene diisocyanate K4: pentaerythritol tetrathioglycolate DIP: diallyl isophthalate BZF: dibenzyl fumarate IPP: diisopropyl peroxydicarbonate BL: dibutyltin Dilaurate [Effect of the Invention] The curable composition of the present invention is characterized by the fact that molding is extremely easy while having a relatively high refractive index.
Moreover, the cured product is a synthetic resin having low water absorption, high glass transition temperature, and excellent impact resistance, and having extremely well-balanced performance.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-54213 (JP, A) JP-A-2-302416 (JP, A) JP-A-58-24101 (JP, A) JP-A-60-1985 10201 (JP, A) JP-A-2-300220 (JP, A) JP-A-1-217024 (JP, A) JP-A-63-262217 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 290/00-290/06 C08G 63/21 C08G 63/47 G02B 1/04

Claims (3)

(57) [Claims] (1) having the structure of the following general formula (I), wherein CH ₂ CHCHCH ₂ O (COArCOORO) _n COArCOOCH ₂ CH ＝ CH ₂ (I) wherein R represents 2 to 20 carbon atoms; A divalent hydrocarbon residue, Ar is a 1,2-, 1,3- or 1,4-phenylene group, and n is 1
Represents a number from ~ 100. However, this excludes the case where Ar is only a 1,4-phenylene group. And at least 10% by weight of a diallyl phthalate oligomer having an unsaturation of 20 to 100 as expressed by an iodine value measured by the Wijs method, from a vinyl monomer capable of copolymerizing the oligomer and a radical polymerization initiator. A curable composition characterized by comprising: 2. The diallyl phthalate oligomer having the structure of the general formula (I) according to claim (1), wherein a part or all of a divalent hydrocarbon residue having 2 to 20 carbon atoms represented by R is present. The curable composition according to claim 1, which is an oligomer having 3 or more carbon atoms and substituted with a polyol residue having 3 or more hydroxyl groups. 3. A plastic lens comprising a cured product of the curable composition according to claim 1 or 2.