JPH0525240A - Composition for plastic lens - Google Patents

Abstract

PURPOSE:To obtain a composition which can provide a lens having a high refractive index and being excellent in impact resistance, heat resistance, surface hardness and chemical resistance by mixing a mixture of a specified polyisocyanate with a specified polythiol compound with a compound having a radical-polymerizable double bond. CONSTITUTION:A composition for plastic lenses comprising 10-70 pts.wt. composition prepared by mixing at least one alicyclic or aromatic polyisocyanate compound having at least two isocyanate groups in the molecule with at least one polythiol compound having at least two thiol groups in the molecule at an NCO/SH molar ratio of 0.5-2.0 and 90-30 pts.wt. at least one compound having at least one radical-polymerizable double bond in the molecule. This composition can be cured within several minutes to tens of minutes by irradiating it with ultraviolet rays in the presence of an actinic radiation-sensitive free-radical source as a polymerization initiator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a monomer composition which is excellent in heat resistance, surface hardness, chemical resistance and transparency and which can provide a plastic lens having a high refractive index.

[0002]

2. Description of the Related Art Plastic lenses are widely used in optical products because of their characteristics such as easy molding and light weight. Above all, since transparent plastics used as eyeglass lenses are required to have heat resistance and chemical resistance, they are not thermoplastics such as polymethylmethacrylate and polystyrene, but thermosetting plastics such as polydiethylene glycol bisallyl carbonate (CR-39). Has been used. However, in recent years, since CR-39 has a low refractive index, many attempts have been made to develop a new transparent plastic having a high refractive index.

In order to obtain a plastic lens having a high refractive index, it is common to introduce a halogen atom except fluorine, an aromatic group and a sulfur atom into the molecular structure. Japanese Patent Application Laid-Open No. 60-199016 and Japanese Patent Application Laid-Open No. 6-199016 disclose attempts to increase the refractive index by introducing sulfur atoms.
3-130614 and Japanese Patent Laid-Open No. 64-26622.

[0004]

However, with these compositions, it is possible to obtain a plastic lens having a high refractive index, a low dispersibility and an excellent impact resistance, but the polymer has a thiocarbamic acid bond as the cross-linking structure. Therefore, the heat resistance becomes insufficient. Further, the reaction between the thiol and the isocyanate is a thermal addition reaction, and it takes 10 to 20 hours, which is also inferior in terms of productivity.

The present invention has been made in the background described above, and an object thereof is to obtain a plastic lens having a high refractive index and excellent impact resistance, heat resistance, surface hardness, and chemical resistance. To provide a composition capable of

[0006]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to solve the above problems, polyisocyanate and a polythiol compound were selected as components having a high refractive index, low dispersibility and excellent impact resistance. Obtained from the obtained thiourethane polymer and a compound having at least one radically polymerizable and unsaturated double bond in the molecule, which is represented by (meth) acrylate as a component excellent in heat resistance, surface hardness and chemical resistance. It has been found that a plastic lens having a high refractive index, low dispersibility, and excellent impact resistance, heat resistance, surface hardness, and chemical resistance can be obtained by combining a crosslinked polymer, and the present invention has been completed.

That is, the plastic lens composition of the present invention comprises (A) at least one alicyclic or aromatic polyisocyanate compound having at least two isocyanate groups in the molecule and at least two in the molecule. A composition in which at least one polythiol compound having a thiol group is mixed so that the ratio of -NCO group / -SH group is 0.5 to 2.0 molar ratio, 10 to 70 parts by weight, and (B) molecule. At least one compound having at least one radically polymerizable unsaturated double bond, 30 to 90
It is characterized by being composed of parts by weight.

The composition for plastic lenses of the present invention comprises
An active energy ray-sensitive radical source is used as a polymerization initiator, and it is cured in a few minutes to several tens of minutes by irradiation with general ultraviolet rays, so that a plastic lens can be efficiently obtained. In this case, the compound having a radically polymerizable unsaturated double bond is polymerized and cured, or at the same time, the addition reaction between the polyisocyanate and the polythiol proceeds. When the polymerization is incomplete only by irradiation with active energy rays, heating may be performed thereafter.

Explaining each component, of the component (A), specific examples of the alicyclic or aromatic polyisocyanate compound having at least two isocyanate groups in the molecule include isophorone diisocyanate and dicyclohexylmethane-4. , 4'-diisocyanate, m-
Xylylene diisocyanate, p-xylylene diisocyanate, 1,3-bis (α, α dimethylisocyanate methyl) benzene, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, Examples thereof include polymethylene polyphenyl polyisocyanate and 2,6-naphthalene diisocyanate.

Specific examples of the polythiol compound having at least two thiol groups in the molecule include di (2-mercaptoethyl) ether, ethylene glycol dithioglycolate, propylene glycol dithioglycolate, diethylene glycol dithioglycolate, Dipropylene glycol dithioglycolate, 1,
4-butanediol dithioglycolate, 1,4-butanediol dithiopropionate, trimethylolpropane tris (thioglycolate), trimethylolpropane tris (β-thiopropionate), pentaerythritol tetrakis (thioglycolate) , Pentaerythritol tetrakis (β-thiopropionate), dipentaerythritol pentakis (β-thiopropionate), 1,2-benzenedithiol, 1,4-benzenedithiol, 4-tert-butyl-1,2. -Benzenedithiol, 4,4'-thiodi-benzenethiol and the like.

The above-mentioned at least one kind of polyisocyanate compound and at least one kind of polythiol compound are mixed so that the ratio of --NCO group /-SH group is 0.5 to 2.0 molar ratio. After mixing the compound having at least one radically polymerizable unsaturated double bond in the molecule with the polyisocyanate compound, an appropriate amount of the polythiol compound may be mixed, or after mixing the radically polymerizable compound and the polythiol compound, You may mix a polyisocyanate compound.

The mixing ratio of the component (A) is 10 to 70 parts by weight, preferably 20 to 50 parts by weight. (A)
If the amount of the component exceeds 70 parts by weight, the heat resistance and surface hardness of the plastic lens are lowered, and if it is less than 10 parts by weight, sufficient impact resistance cannot be obtained. The compound having at least one radically polymerizable unsaturated double bond in the molecule of the component (B) is a methacryl group, an acryl group, an allyl group, a methallyl group, a vinyl group as the radically polymerizable unsaturated double bond. Etc. These radically polymerizable groups are preferably bonded to the main skeleton of an aliphatic, alicyclic or aromatic group through an ester bond or an ether bond, but urethane (meth) acrylate, epoxy (meth) acrylate and the like are also used. It is possible.

As the component (B), it is preferable to use a compound having two or more radically polymerizable unsaturated double bonds and a compound having one radically polymerizable unsaturated double bond in combination. The compound having two or more radically polymerizable unsaturated double bonds may be an ester type monomer as shown in the following specific examples, but is an adduct of m-xylylene diisocyanate and 2-hydroxypropyl methacrylate. Some urethane (meth) acrylate,
It is particularly preferable to use an epoxy (meth) acrylate obtained from bisphenol A type diglycidyl ether and acrylic acid.

Specific examples of the ester type monomer include:
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate Pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, -n-hexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl (meth) acrylate, Allyl (meth) acrylate,
Methallyl (meth) acrylate, glycidyl (meth) acrylate, -N, N-dimethylaminoethyl (meth) acrylate, -N, N-diethylaminoethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate , (Meth) acrylic acid dibromopropyl, (meth) acrylic acid vinyl-2-pyrrolidone, (meth) acrylic acid polyethylene glycol monoalkyl ether, (meth) acrylic acid polypropylene glycol monoalkyl ether,
2-Hydroxyethyl (meth) acrylate, (meth)
2-Hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phosphoethyl (meth) acrylate, cyclohexylphenyl- (meth) acrylate
(Meth) acrylate, isobonyl (meth) acrylate, (meth) acrylic acid-adamantyl benzyl- (meth) acrylate, (meth) acrylic acid-tricyclo (5,2,1,02.6) decan-8-ylphenoxy Ethyl- (meth) acrylate, phenoxy-2-methylethyl- (meth) acrylate, 3-phenoxy-2-
Hydroxypropyl- (meth) acrylate, phenyl-di (oxyethyl)-(meth) acrylate, phenyl-tri (oxyethyl)-(meth) acrylate, phenyl-di (2-methyloxyethyl)-(meth) acrylate, phenyl- Tri (2-methyloxyethyl)
-(Meth) acrylate, phenoxybutyl- (meth)
Acrylate, phenyl-di (oxybutyl)-(meth) acrylate, phenyl-tri (oxybutyl)-
(Meth) acrylate, 2-phenylphenyl- (meth) acrylate, 4-phenylphenyl- (meth) acrylate, 4-phenylphenoxyethyl- (meth)
Acrylate, 2-phenylphenyl-2-methyloxyethyl- (meth) acrylate, 4-phenylphenyl-2-methyloxypropyl- (meth) acrylate, 4-phenylphenyl-2-hydroxyoxypropyl- (meth) acrylate, 2-naphthyl- (meta)
Acrylate, 1-naphthyl- (meth) acrylate,
1-naphthyloxyethyl- (meth) acrylate, 2
-Naphthyloxyethyl- (meth) acrylate, 1-
Naphthyl-di (oxyethyl)-(meth) acrylate, 2-naphthyl-di (oxyethyl)-(meth) acrylate, 1-naphthyl-2-methyloxyethyl-
(Meth) acrylate, 2-naphthyl-2-methyloxyethyl- (meth) acrylate, 1-naphthyl-2-
Hydroxypropyl- (meth) acrylate, 2-naphthyl-2-hydroxyoxypropyl- (meth) acrylate, 2-bromophenyl- (meth) acrylate,
4-bromophenyl- (meth) acrylate, 2-bromophenyl- (meth) acrylate, 4-bromophenyl- (meth) acrylate, 2,4-dibromophenyl- (meth) acrylate, 2,4,6-tribromo Phenyl- (meth) acrylate, 2,3,4,5,6-pentabromophenyl- (meth) acrylate, 2,4-
Dibromophenoxyethyl- (meth) acrylate,
2,4,6-tribromophenyl-di (oxyethyl)
-(Meth) acrylate, 2,4,6-tribromophenyl-2-methyloxyethyl- (meth) acrylate, 2-bromobenzyl- (meth) acrylate, 4-
Bromobenzyl- (meth) acrylate, 2,4-dibromobenzyl- (meth) acrylate, 2,4,6-tribromobenzyl- (meth) acrylate, 2,3,3
4,5,6-pentabromobenzyl- (meth) acrylate, 2-chlorophenyl- (meth) acrylate,
2,4-dichlorophenyl- (meth) acrylate,
2,4,6-Trichlorophenyl- (meth) acrylate, 2,3,4,5,6-pentachlorophenyl- (meth) acrylate, 2,4-dichlorophenyloxyethyl- (meth) acrylate, 2,4,6 -Trichlorophenyloxyethyl- (meth) acrylate, 2,
4,6-Trichlorophenyl-di (oxyethyl)-
(Meth) acrylate, 2,4,6-trichlorophenoxy-2-methyloxyethyl- (meth) acrylate, 2,4,6-tribromophenyl-2-hydroxyoxypropyl- (meth) acrylate, 2,3,3 4,
5,6-Pentabromophenyl-2-hydroxyoxypropyl- (meth) acrylate, 2-phenyl-4-
Bromophenyl- (meth) acrylate, 2- (4-bromophenyl) -4,6-dibromophenyl- (meth)
Acrylate, 2- (4-chlorophenyl) 4,6-dichlorophenyl- (meth) acrylate, 2-phenyl-4-bromophenyloxyethyl- (meth) acrylate, 2- (4-bromophenyl) -4,6-dibromo Phenyloxyethyl- (meth) acrylate, 2-
(2,4,6-tribromophenyl) -4,6-dibromophenyl- (meth) acrylate, 2- (2,4-dibromophenyl) -4,6-dibromophenyloxyethyl- (meth) acrylate, 1 -(4-chloronaphthyl) -oxyethyl- (meth) acrylate, 2- (4
-Chloronaphthyl) -oxyethyl- (meth) acrylate, 1- (4-bromonaphthyl) -oxyethyl-
(Meth) acrylate, 2- (4-bromonaphthyl)-
Oxyethyl- (meth) acrylate, 1- [3- (2
-Bromonaphthyl)]-2-humanroxypropyl- (meth) acrylate, 2- [3- (2-bromonaphthyl)]-2-hydroxyoxypropyl- (meth) acrylate and other mono (meth) acrylate compounds; ethylene Glycol-di (meth) acrylate, diethylene glycol-di (meth) acrylate, triethylene glycol-di (meth) acrylate, tetraethylene glycol-di (meth) acrylate, pentaethylene glycol-di (meth) acrylate, nonaethylene glycol- A di (meth) acrylate compound of polyethylene glycol such as di (meth) acrylate; propylene glycol-di (meth) acrylate, dipropylene glycol-di (meth) acrylate, tripropylene glycol-di (meth) acrylate Rate, tetrapropylene glycol-di (meth) acrylate, nonapropylene glycol-di (meth) acrylate and other polypropylene glycol di (meth) acrylate compounds; butylene glycol-di (meth) acrylate, dibutylene glycol-di (meth) Di (meth) acrylate compound of polybutylene glycol such as acrylate, tributylene glycol-di (meth) acrylate, tetrabutylene glycol-di (meth) acrylate, nonabutylene glycol-di (meth) acrylate; 1,3-butylene glycol -Di (meth) acrylate, 1,6-hexamethylene-di (meth) acrylate, 1,14-tetradecamethylene-di (meth) acrylate, neopentyl glycol-di (meth) acrylate, Di (meth) acrylate compound of caprolactone adduct of neopentyl glycol roxipivalate, neopentyl glycol adipate-di (meth) acrylate, dicyclopentenyl-di (meth) acrylate, dicyclopentenyl-di (meth) acrylate, 2- (2-hydroxy-
1,1-dimethyl) -5-hydroxy (meth) acrylate, trimethylolpropane-tri (meth) acrylate, ditrimethylolpropane-tetra (meth) acrylate, pentaerythritol-tri (meth) acrylate, dipentaerythritol-penta ( (Meth) acrylate, dipentaerythritol-hexa (meth) acrylate, di (meth) acryloyloxyethyl isocyanurate, tris (meth) acryloyloxyethyl isocyanurate, 2,2-bis (4- (meth) acryloyloxyphenyl)- Propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) -propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) -propane, 2,
2-bis (4- (meth) acryloyloxyethoxy-
3,5-dibromophenyl) -propane, 2,2-bis (4- (meth) acryloyloxydiethoxy-3,5
-Dibromophenyl) -propane, 2,2-bis (4-
(Meth) acryloyl pentaethoxyphenyl-3,5
-Dibromophenyl) -propane, 2,2-bis (4-
(Meth) acryloyloxyethoxy-3-phenylphenyl) -propane, bis (4- (meth) acryloyloxyethoxyphenyl) -sulfone, bis (4-
(Meth) acryloyloxydiethoxyphenyl) -sulfone, bis (4- (meth) acryloyloxypentaethoxyphenyl) -sulfone, bis (4- (meth) acryloyloxyethoxy-3-phenylphenyl) -sulfone, bis (4 -(Meth) acryloyloxyethoxy 3,5-dimethylphenyl) -sulfone, bis (4- (meth) acryloyloxyphenyl)
-Sulfide, bis (4- (meth) acryloyloxydiethoxyphenyl) -sulfide, bis (4- (meth) acryloylpentaethoxyphenyl) -sulfide, di ((meth) acryloyloxyethoxy) phosphate, tri ((meth ) Acryloyloxyethoxy) phosphate, 2,4-di (meth) acryloxynaphthalene, 2,6-di (meth) acryloxynaphthalene, 1,7-di (meth) acryloxynaphthalene, etc. Acrylate compounds; styrene, chlorostyrene, bromostyrene, divinylbenzene, 1
Vinyl compounds such as vinylbenzene, 1-vinylnaphthalene, 2-vinylnaphthalene and N-vinylpyrrolidone;
Allyl compounds such as diethylene glycol bisallyl carbonate, trimethylolpropane diallyl, dimethallyl phthalate and diallyl phthalate; and (meth) acrylic acid and metal salts such as barium, lead, antimony, titanium, tin and zinc. These are used alone or as a mixture of two or more.

The blending ratio of the component (B) is 30 to 90 parts by weight, preferably 50 to 80 parts by weight. (B)
If the amount of the component exceeds 90 parts by weight, the impact resistance of the plastic lens decreases, and if it is less than 30 parts by weight, sufficient heat resistance and surface hardness cannot be obtained.

The plastic lens composition of the present invention may contain various additives such as an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a bluing agent and a pigment, if necessary. ..

Polymerization initiators used for curing the plastic lens composition of the present invention include di-n-butyltin dilaurate and tri-n-butyl acetate for the addition reaction of polyisocyanate and polythiol. Organotin compounds such as tin and tributyltin chloride, benzoyl peroxide for the polymerization of the radically polymerizable compound as the component (B),
Organic peroxides such as t-butylperoxyisobutyrate and t-butylperoxy-2-ethylhexanoate,
Azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile), 2-hydroxy-2-methyl-1-phenylpropan-1-one, methyl Phenylglyoxylate,
Examples include photopolymerization initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide. These are used alone or in a mixture of two or more. The mixing ratio of this polymerization initiator is 100 parts by weight of the entire composition,
It is preferable to use 0.001 to 0.1 part by weight of the organotin compound for the addition reaction and 0.005 to 5 parts by weight of the initiator for the radical polymerization.

The polymerization and curing method is carried out, for example, by injecting the composition of the present invention containing a polymerization initiator into a mold made of two glass plates, which are mirror-polished, through a gasket made of ethylene-vinyl acetate copolymer, It is carried out by irradiating active energy rays from one side or both sides of the mold or by heat treatment. Further, irradiation and heating may be combined.
Here, the mold includes glass and glass, glass and plastic, glass and metal, or a combination thereof. Further, as the gasket, in addition to the thermoplastic resin as described above, two molds may be fixed with an adhesive tape made of polyester or the like.

[0019]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples. The abbreviations of the monomers are as follows. XDI: m-xylylene diisocyanate IPDI: isophorone diisocyanate TDI: 2,6-tolylene diisocyanate PETP: pentaerythritol tetrakis (β-thiopropionate) TPTP: trimethylolpropane tris (β-thiopropionate) TBT: 4 , 4′-Thiodi-benzenethiol UM1: 2,6-tolylene diisocyanate and urethane dimethacrylate obtained by reacting 2-hydroxypropyl methacrylate UM2: 1,3-bis (α, α-dimethylisocyanatomethyl) benzene And urethane diacrylate obtained by reacting 2-hydroxyethyl acrylate PM: phenyl methacrylate TCM: tricyclo (5,2,1,02.6) decane-
8-yl methacrylate BPM: biphenyl methacrylate CR39: diethylene glycol bisallyl carbonate

[Example 1] XDI 17 parts, PETP
23 parts, UM1 40 parts, PM 20 parts, 2, 4, 6
-Trimethylbenzoyldiphenylphosphine oxide 0.03 part, t-butylperoxy oxyisobutyrate 0.1 part, tributyltin chloride 0.05 part, 2-hydroxybenzophenone 0.1 part were mixed and stirred well at room temperature. Then, it pressure-reduced to 50 mmHg and deaerated for 10 minutes.

This composition is mirror-finished and has a diameter of 70 mm.
Combine the two pieces of glass to a thickness of 2 mm,
It was poured into a mold surrounded by a polyvinyl chloride gasket. Then, the both sides of the mold were irradiated with 10 J / cm @ 2 of ultraviolet rays from a high pressure mercury lamp of 2 kW and then heated at 120 DEG C. for 2 hours. After that, remove the lens from the mold, 110 ℃
It was annealed by heating for 1 hour. The flat plate thus prepared was evaluated by the following evaluation method, and the results are shown in Table 1. Visible light transmittance (%): measured according to ASTM D-1003. Refractive index: Measured with an Abbe refractometer at a D line of 589.3 nm. Surface hardness: Rockwell hardness; JIS K7202
Was measured according to. Heat resistance: Tg at a load of 10 g as measured by TMA
showed that. Impact resistance: A lens having a thickness of 1.5 mm was subjected to a falling ball test in accordance with FDA standards. However, the maximum weight of the steel ball when the steel ball was dropped from a height of 127 cm was shown.

[Examples 2 to 5] Lenses were manufactured and evaluated in the same manner as in Example 1 except that the monomers were used in the proportions shown in Table 1. The results are also shown in Table 1.

[Comparative Example 1] 100 g of CR-39 (diethylene glycol bisallyl carbonate) and 3 g of diisopropyl peroxypercarbonate were mixed and stirred well, and then poured into the same mold as used in Example 1 and 4
5 ° C for 10 hours, 60 ° C for 3 hours, 80 ° C for 3 hours, 9
Molded by holding at 5 ° C. for 6 hours. The lens was removed from the mold and heated at 120 ° C. for 1 hour to be annealed. The flat plate thus manufactured was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 42 g of m-xylylene diisocyanate, 58 g of pentaerythritol tetrakis (β thiopropionate), 0.05 g of tributyltin chloride.
Were mixed and well stirred, and then the mixture was poured into the same mold as used in Example 1, and the mixture was heated at 45 ° C. for 5 hours and at 50 ° C. for 3 hours.
Molding was carried out by holding at 3 ° C for 3 hours and at 95 ° C for 6 hours. The lens was removed from the mold and heated at 120 ° C. for 1 hour to be annealed. Example 1 of the flat plate thus prepared
Evaluation was conducted in the same manner as above, and the results are shown in Table 1.

[Comparative Examples 3 to 5] Flat plates were prepared and evaluated in the same manner as in Example 1 except that the monomers were used in the proportions shown in Table 1. The results are also shown in Table 1.

[0026]

Industrial Applicability As described above, the composition for plastic lenses of the present invention is cured in a few minutes to several tens of minutes by irradiating a general ultraviolet ray, so that it has good productivity and high refractive index. Low dispersion, and impact resistance,
It is possible to obtain a plastic lens having excellent heat resistance, surface hardness, and chemical resistance.

[Table 1]

Claims (1)

Claims: (A) At least one alicyclic or aromatic polyisocyanate compound having at least two isocyanate groups in the molecule and at least two thiol groups in the molecule. At least one of the polythiol compounds having a ratio of -NCO group / -SH group of 0.5 to
Compositions mixed to have a 2.0 molar ratio, 10-70
Parts by weight, (B) at least one compound having at least one radically polymerizable unsaturated double bond in the molecule, 3
A composition for a plastic lens comprising 0 to 90 parts by weight.