JPH107748A - Transparent resin, its production, and plastic lend and casting monomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a transparent resin for a lens which is excellent in strengths during drilling operation and in specific gravity and dyeability by polymerizing a monomer mixture comprising a specific monomer having alkaline oxide groups, a specific polyfunctional (meth)acrylate, and another vinyl monomer. SOLUTION: This resin is obtd, by polymerizing 100 pts.wt. monomer mixture comprising 1-80 pts.wt. monomer having alkylene oxide groups and represented by formula I (wherein R1 and R4 are each independently aceyloyl or methacryloyl; R2 and R3 are each independently a 1-5C alkylene; and m and n are each an integer provided m+n is 9-50). 1-95 pts.wt. polyfunctional (mthod acrylate represented by formula II (wherein R<5> and R<6> are each independently acrylol or methacryloyl; and R7 and R8 are each independently a 1-6C monovalent hydrocarbon group), and 0-90 pts.wt. other copolymerizable vinyl monomer (pref. styrene).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent resin usable as a material for plastic lenses, a method for producing the same,
The present invention relates to a plastic lens and a monomer composition for casting.

[0002]

2. Description of the Related Art Conventionally, materials for optical lenses include acrylic resins having high transparency, diethylene glycol bisallyl carbonate resin (for example, CR-39), polystyrene, and the like.
Polycarbonate and the like are used, and among them, a lens widely used as a spectacle lens is a lens using diethylene glycol bisallyl carbonate which is a thermosetting resin. The reason is that it is excellent in transparency, low dispersibility (high Abbe number), heat resistance and impact resistance. However, a lens using diethylene glycol bisallyl carbonate has a problem that the refractive index is as low as 1.50, and the thickness of the lens is larger than that of a glass lens (particularly, it becomes more remarkable as the lens power increases). On the other hand, high-refractive thermoplastic resins include polystyrene (refractive index 1.58, Abbe number 31) and polycarbonate (refractive index 1.58, Abbe number 30). Although these have a high refractive index, they have a problem that chromatic aberration is large due to a low Abbe number, and the former has low heat resistance, and the latter has low surface hardness and is easily damaged.

[0003] JP-A-59-109002 discloses that
Polymers of 2,2-dimethyl-1,3-propanediol dimethacrylate have been proposed. This material is insufficient in strength and easily breaks when drilling, and has poor dyeability. Also, JP-A-59-109001 discloses that
A copolymer of 2,2-dimethyl-1,3-propanediol dimethacrylate / 2,2-bis (4-acryloxypolyethoxy) phenylpropane (where the total number of polyethoxy groups is 3 to 4) has been proposed. Since this material has a small number of ethoxy groups in 2,2-bis (4-acryloxypolyethoxy) phenylpropane to be copolymerized, it has little effect on improving strength and dyeability.

JP-A-4-126710 discloses a bifunctional (meth) acrylate having an alkylene oxide group / an aromatic vinyl monomer / a polymerizable monomer having a polymerizable double bond and a molecular weight of 98 or more, or Copolymers of hydrophilic oligomers have been proposed. However, this material has the disadvantage that the specific gravity is still insufficient and the hue tends to take on a yellow tint.

[0005]

As described above, hitherto, the strength, specific gravity, and dyeability when drilling are excellent,
In addition, there was no plastic lens or plastic lens resin satisfying other physical properties required for the plastic lens.

The present invention firstly provides a transparent resin which is excellent in strength, specific gravity and dyeability when drilling, a method for producing the same, and a plastic lens comprising the transparent resin. In addition to the above characteristics, a transparent resin having low dispersibility (high Abbe number), high refractive index and excellent heat resistance, a method for producing the same, and a plastic lens made of the transparent resin and a casting useful for producing the same The present invention provides a molding monomer composition.

[0007]

The transparent resin according to the present invention comprises 1 to 80 parts by weight of a monomer having an alkylene oxide group represented by the following general formula (I): II)] The polyfunctional (meth) acrylate 1 represented by
To 95 parts by weight and other copolymerizable vinyl monomers 0
It is a transparent resin obtained by polymerizing a polymerizable monomer blended so as to have a total of 100 parts by weight to 90 parts by weight.

Embedded image [However, in the general formula (I), R ₁ and R ₄ are each independently an acryloyl group or a methacryloyl group; R ₂ and R ₃ are each independently an alkylene group having 1 to 5 carbon atoms; n is an integer and is selected such that the sum of m and n is 9 to 50]

Embedded image [However, in the general formula (II), R ₅ and R ₆ are each independently an acryloyl group or a methacryloyl group, and R ₇ and R ₈ are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms. The transparent resin in the present invention preferably has a specific gravity of 1.1.
5 or less, a refractive index of 1.54 or more, and an Abbe number of 35 or more.

The transparent resin according to the present invention is produced by polymerizing a polymerizable monomer having the above composition. The plastic lens according to the present invention is made of the transparent resin described above. Further, the composition of the polymerizable monomer blended as described above is useful as a monomer composition for casting.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The monomer having an alkylene oxide group represented by the above general formula (I) has the general formula (I)
Is a compound selected so that the sum of the integers m and n is 9 to 50. If the sum of m and n is less than 9,
When drilling, the strength and dyeability tend to decrease.
If it exceeds, the heat resistance decreases.

Specific examples of the monomer having an alkylene oxide group represented by the above general formula (I) include:
2,2-bis [4- (methacryloxypentaethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyhexaethoxy) phenyl] propane, 2,
2-bis [4- (methacryloxy heptaethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy octaethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy nonaethoxy) phenyl]
Propane, 2,2-bis [4- (methacryloxydecaethoxy) phenyl] propane, 2,2-bis [4-
(Methacryloxypentadecaethoxy) phenyl] propane, 2,2-bis [4- (methacryloxypentapropoxy) phenyl] propane, 2,2-bis [4-
(Methacryloxyhexapropoxy) phenyl] propane, 2,2-bis [4- (methacryloxyheptapropoxy) phenyl] propane, 2,2-bis [4-
(Methacryloxy octapropoxy) phenyl] propane, 2,2-bis [4- (methacryloxy nonapropoxy) phenyl] propane, 2,2-bis [4- (methacryloxy decapropoxy) phenyl] propane,
2,2-bis [4- (methacryloxypentadecapropoxy) phenyl] propane, 2,2-bis [4- (acryloxypentaethoxy) phenyl] propane,
2,2-bis [4- (acryloxyhexaethoxy)
Phenyl] propane, 2,2-bis [4- (acryloxyheptaethoxy) phenyl] propane, 2,2-bis [4- (acryloxyoctaethoxy) phenyl]
Propane, 2,2-bis [4- (acryloxynonaethoxy) phenyl] propane, 2,2-bis [4- (acryloxydecaethoxy) phenyl] propane, 2,
2-bis [4- (acryloxypentadecaethoxy)
Phenyl] propane, 2,2-bis [4- (acryloxypentapropoxy) phenyl] propane, 2,2-
Bis [4- (acryloxyhexapropoxy) phenyl] propane, 2,2-bis [4- (acryloxyheptapropoxy) phenyl] propane, 2,2-bis [4- (acryloxyoctapropoxy) phenyl]
Propane, 2,2-bis [4- (acryloxy nonapropoxy) phenyl] propane, 2,2-bis [4-
(Acryloxy decapropoxy) phenyl] propane, 2,2-bis [4- (acryloxypentadecapropoxy) phenyl] propane and the like are used, and one or more of these are used.

Among the above-mentioned monomers having an alkylene oxide group represented by the general formula (I), among the above examples, from the viewpoints of dyeability and strength at the time of perforating,
2,2-bis [4- (methacryloxy heptaethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy octaethoxy) phenyl] propane, 2,
2-bis [4- (methacryloxy nonaethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy decaethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy pentadecaethoxy) phenyl] propane 2,2-bis [4- (acryloxy-heptapropoxy) phenyl] propane, 2,2-bis [4- (acryloxy-octapropoxy) phenyl]
Propane, 2,2-bis [4- (acryloxy nonapropoxy) phenyl] propane, 2,2-bis [4-
(Acryloxy decapropoxy) phenyl] propane and 2,2-bis [4- (acryloxypentadecapropoxy) phenyl] propane are preferred. Among them, 2,2-bis [4- (acryloxynonaethoxy) phenyl] propane is preferable. 2,2-bis [4- (acryloxydecaethoxy) phenyl] propane, 2,2-
Bis [4- (acryloxypentadecaethoxy) phenyl] propane, 2,2-bis [4- (acryloxy.
Nonaethoxy) phenyl] propane, 2,2-bis [4
-(Acryloxy decaethoxy) phenyl] propane and 2,2-bis [4- (acryloxypentadecaethoxy) phenyl] propane are particularly preferred.

The amount of the alkylene oxide group-containing monomer represented by the general formula (I) is in the range of 1 to 80 parts by weight based on 100 parts by weight of the total of the above monomers. 1
When the amount is less than the weight part, there is a problem that the strength and the dyeing property at the time of perforation are easily reduced. When the amount exceeds 80 parts by weight, there are problems that the heat resistance is apt to decrease, the hue tends to be yellowish, and the specific gravity is increased.

The monomer having an alkylene oxide group represented by the general formula (I) may be used in a total of 100 parts by weight of the monomer in order to sufficiently improve the strength and the dyeing property at the time of punching. It is preferable to use 5 parts by weight or more.
In order not to lower the heat resistance, not to give the hue a yellowish tinge, and to increase the specific gravity, 50% of the monomer in 100 parts by weight in total is used.
It is preferred to use it in parts by weight or less. Further, it is particularly preferable to use 10 to 40 parts by weight of the total of 100 parts by weight of the monomers.

The polyfunctional (meth) acrylate represented by the general formula (II) includes 2,2-dimethyl-
1,3-propanediol diacrylate, 2-methyl-2-ethyl-1,3-propanediol diacrylate, 2-methyl-2-isopropyl-1,3-propanediol diacrylate, 2-methyl-2-propyl −
1,3-propanediol diacrylate, 2,2-diethyl-1,3-propanediol diacrylate, 2
-Ethyl-2-propyl-1,3-propanediol diacrylate, 2-ethyl-2-isopropyl-1,3
-Propanediol diacrylate, 2-ethyl-2-
Butyl-1,3-propanediol diacrylate,
2,2-dipropyl-1,3-propanediol diacrylate, 2-propyl-2-butyl-1,3-propanediol diacrylate, 2,2-dibutyl-1,3
-Propanediol diacrylate, 2,2-diisopropyl-1,3-propanediol diacrylate, 2
-Propyl-2-isopropyl-1,3-propanediol diacrylate, 2-methyl-2-phenyl-1,
3-propanediol diacrylate, 2-ethyl-2
-Phenyl-1,3-propanediol diacrylate, 2-propyl-2-phenyl-1,3-propanediol diacrylate, 2-isopropyl-2-phenyl-1,3-propanediol diacrylate, 2,2
Diphenyl-1,3-propanediol diacrylate, 2-methyl-2-cyclopentyl-1,3-propanediol diacrylate, 2-ethyl-2-cyclopentyl-1,3-propanediol diacrylate, 2
-Propyl-2-cyclopentyl-1,3-propanediol diacrylate, 2-isopropyl-2-cyclopentyl-1,3-propanediol diacrylate,
2,2-dicyclopentyl-1,3-propanediol diacrylate, 2-methyl-2-cyclohexyl-
1,3-propanediol diacrylate, 2-ethyl-2-cyclohexyl-1,3-propanediol diacrylate, 2-propyl-2-cyclohexyl-1,
Polyfunctional acrylates such as 3-propanediol diacrylate, 2-isopropyl-2-cyclohexyl-1,3-propanediol diacrylate, 2,2-dicyclohexyl-1,3-propanediol diacrylate, 2,2-dimethyl -1,3-propanediol dimethacrylate, 2-methyl-2-ethyl-1,3-propanediol dimethacrylate, 2-methyl-2-isopropyl-1,3-propanediol dimethacrylate, 2-methyl-2- Propyl-1,3-propanediol dimethacrylate, 2,2-diethyl-1,3-propanediol dimethacrylate, 2-ethyl-2-propyl-1,3-propanediol dimethacrylate,
2-ethyl-2-isopropyl-1,3-propanediol dimethacrylate, 2-ethyl-2-butyl-1,
3-propanediol dimethacrylate, 2,2-dipropyl-1,3-propanediol dimethacrylate,
2-propyl-2-butyl-1,3-propanediol dimethacrylate, 2,2-dibutyl-1,3-propanediol dimethacrylate, 2,2-diisopropyl-1,3-propanediol dimethacrylate, 2-propyl -2-isopropyl-1,3-propanediol dimethacrylate, 2-methyl-2-phenyl-1,3
-Propanediol dimethacrylate, 2-ethyl-2
-Phenyl-1,3-propanediol dimethacrylate, 2-propyl-2-phenyl-1,3-propanediol dimethacrylate, 2-isopropyl-2-phenyl-1,3-propanediol dimethacrylate,
2,2-diphenyl-1,3-propanediol dimethacrylate, 2-methyl-2-cyclopentyl-1,3
-Propanediol dimethacrylate, 2-ethyl-2
-Cyclopentyl-1,3-propanediol dimethacrylate, 2-propyl-2-cyclopentyl-1,3
-Propanediol dimethacrylate, 2-isopropyl-2-cyclopentyl-1,3-propanediol dimethacrylate, 2,2-dicyclopentyl-1,3-
Propanediol dimethacrylate, 2-methyl-2-
Cyclohexyl-1,3-propanediol dimethacrylate, 2-ethyl-2-cyclohexyl-1,3-propanediol dimethacrylate, 2-propyl-2-
Cyclohexyl-1,3-propanediol dimethacrylate, 2-isopropyl-2-cyclohexyl-1,
Examples include polyfunctional methacrylates such as 3-propanediol dimethacrylate and 2,2-dicyclohexyl-1,3-propanediol dimethacrylate, and these are used alone or in combination of two or more.

As the polyfunctional (meth) acrylate represented by the general formula (II), among the above examples, 2,2-dimethyl-1,3 is preferred from the viewpoint of specific gravity and heat resistance.
Polyfunctional acrylates such as propanediol diacrylate, 2,2-dimethyl-1,3-propanediol dimethacrylate, 2-methyl-2-ethyl-1,3-
Propanediol dimethacrylate, 2-methyl-2-
Isopropyl-1,3-propanediol dimethacrylate, 2-methyl-2-propyl-1,3-propanediol dimethacrylate, 2,2-diethyl-1,3-
Polyfunctional methacrylates such as propanediol dimethacrylate are preferred, and among them, 2,2-dimethyl-
1,3-propanediol dimethacrylate is particularly preferred.

The amount of the polyfunctional (meth) acrylate represented by the general formula (II) is from 1 to 95 parts by weight based on 100 parts by weight of the total monomers. If the amount is less than 1 part by weight, the heat resistance decreases and the specific gravity increases. If the amount exceeds 95 parts by weight, the strength and the dyeability at the time of punching are reduced.

The polyfunctional (meth) acrylate represented by the general formula (II) should be used in an amount of 5 parts by weight or more based on 100 parts by weight of all monomers in order to sufficiently improve heat resistance. Preferably, it is preferably used in an amount of 50 parts by weight or less in a total of 100 parts by weight of the monomer so as not to decrease the strength and the dyeing property at the time of perforating. It is more preferable to use 10 to 40 parts by weight of the total 100 parts by weight of the monomers, and it is particularly preferable to use 10 to 30 parts by weight.

Specific examples of monofunctional monomers among the other copolymerizable vinyl monomers include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, and acrylic acid. i-butyl, acrylic acid t
-Butyl, pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, dodecyl acrylate, butoxyethyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, naphthyl acrylate, Cyclopentyl acrylate, cyclohexyl acrylate, methylcyclohexyl acrylate, trimethylcyclohexyl acrylate, norbornyl acrylate, norbornyl methyl acrylate, isobornyl acrylate, bornyl acrylate, menthyl acrylate, fentyl acrylate, adamantyl acrylate, acrylic Dimethyladamantyl acrylate, tricyclo [5.2.1.02,6] deca-8-yl acrylate, tricycloacrylate [5.2.2.1.02,
6] Acrylates such as deca-4-methyl, cyclodecyl acrylate, glycerin monoacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-methacrylate
Butyl, t-butyl methacrylate, pentyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, butoxyethyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate , Naphthyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, norbornyl methacrylate, norbornyl methacrylate, isobornyl methacrylate, bornyl methacrylate, menthyl methacrylate, fentyl methacrylate, Adamantyl methacrylate, dimethyl adamantyl methacrylate, tricyclomethacrylate [5.
Methacrylates such as 2.1.0 2,6] dec-8-yl, tricyclo [5.2.1.0 2,6] dec-4-methyl methacrylate, cyclodecyl methacrylate, glycerin monomethacrylate, styrene, α -Methylstyrene, α-ethylstyrene, α-fluorostyrene, α-
Aromatic vinyl compounds such as chlorostyrene, α-bromostyrene, fluorostyrene, chlorostyrene, bromostyrene, methylstyrene, methoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N -Cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, N
N-substituted maleimides such as -methoxyphenylmaleimide, N-carboxyphenylmaleimide, acrylamide, methacrylamide, N-dimethylacrylamide,
(Meth) acrylamides such as N-diethylacrylamide, N-dimethylmethacrylamide, N-diethylmethacrylamide, calcium acrylate, barium acrylate, lead acrylate, tin acrylate, zinc acrylate, calcium methacrylate, methacrylic acid barium,
(Meth) acrylic acid metal salts such as lead methacrylate, tin methacrylate, zinc methacrylate, etc .; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; glycidyl acrylate;
Epoxy group-containing vinyl compounds such as glycidyl methacrylate, hydroxyethyl acrylate, hydroxy group-containing vinyl compounds such as hydroxyethyl methacrylate, γ-
Examples thereof include an alkoxysilyl group-containing vinyl compound such as (methacryloxypropyl) trimethoxysilane, and a vinyl cyanide compound such as acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more.

Specific examples of the polyfunctional monomer among the above-mentioned other copolymerizable vinyl monomers include ethylene glycol diacrylate, nonaethylene glycol diacrylate, tetradecaethylene glycol diacrylate, and glycerin diacrylate. Acrylate, glycerin triacrylate, 1,4-butanediol diacrylate, 1,
6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,12-dodecanediol diacrylate, 1-acryloyl-2-hydroxy-3-acryloylpropane, pentaerythritol tetra Acrylate, 1,1,1-trimethylolpropane triacrylate, dipentaerythritol hexaacrylate,
Hexamethylolmelamine hexaacrylate, N,
N ', N "-tris (2-acryloyloxyethyl)
Acrylic esters such as isocyanurate, ethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, tetradecaethylene glycol dimethacrylate, glycerin dimethacrylate, glycerin triacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol di Methacrylate,
1,9-nonanediol dimethacrylate, 1,10-
Decanediol dimethacrylate, 1,12-dodecanediol dimethacrylate, 1-methacryloyl-2-
Hydroxy-3-methacryloylpropane, pentaerythritol tetramethacrylate, 1,1,1-trimethylolpropane trimethacrylate, dipentaerythritol hexamethacrylate, hexamethylolmelamine hexamethacrylate, N, N ′, N ″ -tris (2-methacryloyloxy Ethyl) methacrylic acid esters such as isocyanurate, ethylene glycol bisallyl carbonate, diethylene glycol bisallyl carbonate, triethylene glycol bisallyl carbonate, tetraethylene glycol bisallyl carbonate, pentaethylene glycol bisallyl carbonate, polypropylene glycol bisallyl carbonate, trimethylene Glycol bisallyl carbonate,
3-hydroxypropoxypropanol bisallyl carbonate, glycerin bisallyl carbonate, triglycerin bisallyl carbonate, diallyl carbonate, diarylidenepentaerythritol, triarylidenesorbitol, diarylidene-2,2,6,6-tetramethylolcyclohexanone, triaryle Lidene hexamethylol melamine, diarylidene-D-glucose,
Bisphenol A diallyl ether, bisphenol S
Diallyl ether, ethylene glycol diallyl ether, 1,1,1-trimethylolpropane triallyl ether, neopentyl glycol triallyl ether,
Allyl acrylates, methallyl acrylates, vinyl acrylates, allyl methacrylates, methallyl methacrylates, vinyl methacrylates, diallyl phthalates (diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate and mixtures of two or more thereof), allyls such as triallyl isocyanurate Compounds, arylidene-based compounds, divinylbenzene, and the like are used, and these are used alone or in combination of two or more.

Among the other copolymerizable vinyl monomers described above, methacrylic monomer is preferred as a monofunctional monomer in view of hue, strength at the time of punching, specific gravity, transparency and heat resistance. Methyl acrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate,
N-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, butoxyethyl methacrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, 5 carbon atoms in the ester portion
Methacrylates such as methacrylates having an alicyclic hydrocarbon group of from 22 to 22, aromatic vinyl compounds such as styrene, hydroxyl-containing vinyl compounds such as hydroxyethyl methacrylate, and γ- (methacryloxypropyl)
Alkoxysilyl group-containing vinyl compounds such as trimethoxysilane are preferred, and polyfunctional monomers include ethylene glycol diacrylate, nonaethylene glycol diacrylate, tetradecaethylene glycol diacrylate, and 1,4-butanediol diacrylate. ,
Diacrylates such as 1,6-hexanediol diacrylate, allyl methacrylate, methallyl methacrylate, ethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, tetradecaethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6 -Dimethacrylates such as hexanediol dimethacrylate are preferred. The other copolymerizable vinyl monomer is in the range of 0 to 90 parts by weight from the refractive index and Abbe number of the obtained resin.

The preferred composition of the monomer for producing the above transparent resin is 1 to 50 parts by weight of a monomer having an alkylene oxide group represented by the general formula (I) (particularly preferably 10 to 40 parts by weight). Parts by weight), 1 to 50 parts by weight of a polyfunctional (meth) acrylate represented by the general formula (II) (particularly preferably 10 to 30 parts by weight), and 15 to styrene.
60 parts by weight (particularly preferably 30 to 50 parts by weight) and 0 to 60 parts by weight (particularly preferably 0 to 30 parts by weight) of the other copolymerizable vinyl monomer add up to 100 parts by weight. It is a combination.

If the amount of styrene is less than 15 parts by weight, it becomes difficult to increase the refractive index (especially, to increase the refractive index to 1.54 or more). When the amount of styrene exceeds 60 parts by weight, it is difficult to make the dispersion optically low, and it is particularly difficult to make the Abbe number 35 or more, and the hue tends to be yellowish.

As the amount of the other copolymerizable vinyl monomer increases, it becomes difficult to keep the refractive index large (particularly to keep the refractive index at 1.54 or more).
Also, it tends to be difficult to keep the specific gravity small (particularly to keep the specific gravity at 1.15 or less).

In the above-mentioned method for producing a transparent resin, the molecular weight regulator used in the polymerization may be a general chain transfer agent, mercaptans, dialkyl disulfides, chloroform, carbon tetrachloride, α-methylstyrene dimer, or the like. However, a dimer of α-methylstyrene is preferable in consideration of the transparency, color, heat resistance and the like of the plastic lens. It is preferable that the molecular weight modifier is used in an amount of 0.1 to 10% by weight based on all the monomers. 0.1
If the amount is less than% by weight, the haze value is high, coloring tends to occur, and the strength at the time of punching tends to decrease. If it exceeds 10% by weight, various physical properties such as heat resistance tend to decrease.

In the above-mentioned method for producing a transparent resin, the polymerization initiator used in the polymerization may be the one used in ordinary radical polymerization. For example, 1,1
-Bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, n-butyl-4,4′-bis (t
-Butylperoxy) valerate, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, m-toluoyl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, dinormal propylperoxydicarbonate , Dimethoxyisopropyl peroxydicarbonate, cumyl peroxy neodecanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, di-t-butyl Organic peroxides such as diperoxyisophthalate and t-butylperoxyisopropyl carbonate, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (4-methoxy-2,4-
Dimethylvaleronitrile), 2,2'-azobis (2,
4-dimethylvaleronitrile), dimethyl-2,2'-
Azobisisobutyrate, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (1-cyclohexanecarbonitrile), 2-phenylazo-2,
4-dimethyl-4-methoxyvaleronitrile, 2,2 ′
And azo-based polymerization initiators such as -azobis (2-methylpropane). Two or more of these polymerization initiators may be used in combination.

The above-mentioned polymerization initiator is preferably used in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of all the monomers, taking into consideration the surface condition of the obtained polymer and the polymerization time. Then, 0.01 to 100 parts by weight of all monomers
It is particularly preferred to use 5 parts by weight.

In the above-mentioned method for producing a transparent resin, it is usually preferable to cure and mold by a cast polymerization method. For example, a cast molding monomer composition containing the above-mentioned molecular weight regulator and a polymerization initiator is preferably used. After pouring into a mold composed of two sheets of glass and a gasket, fixing with a clip with a spring if necessary, and curing by heating. The curing temperature varies depending on the polymerization initiator used,
20 ° C. is preferred. However, in order to suppress the erosion of the gasket material by the monomer mixture, it is preferable to start the polymerization at a relatively low temperature. The gasket material used during casting polymerization includes low-density polyethylene, ultra-low-density polyethylene, soft polyvinyl chloride, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyolefin-based elastomer, polyester-based elastomer, A polyamide-based elastomer, a fluorine-based elastomer, or the like can be used.

In the above method for producing a transparent resin, instead of the above-mentioned mold comprising two sheets of glass and a gasket, 2
A mold in which the side surfaces of the sheets of glass are sealed and fixed with an adhesive tape may be used. In addition, from the viewpoint of preventing coloration and shortening the polymerization induction period, oxygen in the mixed solution is reduced by nitrogen bubbling.
After reducing the amount to 1.0 mg / l or less, it is preferable to pour the mixed solution into a glass mold for casting polymerization and to cure and mold by a casting polymerization method. In addition, from the viewpoint of preventing coloration, when the cured lens is removed from the mold and heat-treated at 120 ° C. for 1 to 2 hours after the main polymerization step, it is preferable to perform the heat treatment in an inert gas atmosphere. Lens molding can be performed by this casting polymerization method.

The transparent resin according to the present invention is obtained by the above-mentioned production method, and has a specific gravity of 1.15 or less and a refractive index of 1.54.
Above and a resin having an Abbe number of 35 or more are preferable. The transparent resin according to the present invention may be used in the form of antioxidants such as phosphites, phenols, thioethers, etc., aliphatic alcohols, fatty acid esters, phthalates from the viewpoints of deterioration prevention, thermal stability, processability, etc. Release agents such as acid esters, triglycerides, fluorine-based surfactants, metal salts of higher fatty acids, and other lubricants, plasticizers, antistatic agents, ultraviolet absorbers, flame retardants, heavy metal deactivators, etc. May be. These are preferably added during polymerization.

An inorganic compound such as MgF ₂ or SiO ₂ is vacuum-evaporated on the surface of the transparent resin lens according to the present invention.
By coating by a sputtering method, ion plating method, etc., by hard coating the lens surface with an organic silicon compound such as a silane coupling agent, vinyl monomer, melamine resin, epoxy resin, fluorine resin, silicone resin, etc. , Moisture resistance, optical properties, chemical resistance, abrasion resistance, antifogging and the like can be improved. Further, an organic silane-based hard coat film and a cured film of an organic silane resin can be laminated on the surface of the lens (plastic lens substrate) made of the transparent resin.

The organic silicone compound is, for example,
Chemical formula 11 [General formula (III)]

Embedded image (Wherein R ₁ is an organic group having an epoxy group having 2 to 8 carbon atoms, R ₂ is an alkyl group, alkenyl group, halogenated alkyl group or allyl group having 1 to 6 carbon atoms, R ₃ is a hydrogen atom, An alkyl group, an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, and a is an integer of 0 to 2)
Or a partially hydrolyzed product thereof. Specifically, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltris (methoxyethoxy) silane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, There is an organic silane compound such as glycidoxypropylmethyldiethoxysilane or a partial hydrolyzate thereof. Commercially available products include KP64C (trade name of Shin-Etsu Chemical Co., Ltd.).

A colloidal solution obtained by dispersing the above organic silicone compound and inorganic fine particles such as antimony oxide sol, silica sol, titania sol and alumina sol in water or an alcohol such as methanol, ethanol, isobutanol or diacetone alcohol is 10 to 80% by weight. The additive is applied to the surface of the plastic lens substrate, and
By heating and curing at 140 ° C., a hard coat layer can be obtained. At this time, if necessary, a primer layer may be provided between the plastic lens substrate surface and the hard coat layer, or a hard coat layer may be provided after performing a surface treatment such as a plasma treatment on the plastic lens substrate surface. it can. In this case, as inorganic fine particles, 1 to 10
A particle size of 0 μm is preferred, and a commercially available colloidal solution dispersed in water or an organic solvent can also be used.

If necessary, the organosilicone compound may be a perchlorate such as aluminum chelate, perchloric acid, ammonium perchlorate or aluminum perchlorate, or an alkali metal such as sodium acetate or potassium propionate. A curing catalyst such as a salt or a quaternary ammonium salt such as tetramethylammonium hydroxide can also be used.

The lens made of the transparent resin can be dyed by immersing it in water in which a dye is dispersed. As the dye, those generally used in the art can be used as they are. For example, C.I. I. Disperse threads 13, 56, 112, C.I. I. Disperse Yellow 3, 7, 31, 42, 54, 198,
C. I. Disperse Blue 1, 3, 5, 54, 56,
197 and the like.

At the time of dyeing, a dyeing aid such as a pH adjuster, a wetting agent, a surfactant, a dispersion accelerator, an antifoaming agent and the like can be added to improve dyeing density and dyeing uniformity. it can. In addition, at the time of dyeing, aromatic compounds such as benzyl alcohol, phenol, butyl benzoate, and methyl salicylate; aliphatic alcohols such as 1-butanol, ethyl cellosolve, and cyclopentanol; and aliphatic compounds such as butyl cellosolve acetate and methyl acetoacetate. By adding an organic compound such as an ester as a carrier, the density of the dyeing can be improved.

[0036]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Examples 1 to 9 As a radical polymerization initiator in a mixture having the composition shown in Table 1,
1.0 part by weight of diisopropyl peroxydicarbonate was added, and 0.1 part by weight of t-butyl peroxyisopropyl carbonate was further added. The mixture was sufficiently stirred and poured into a mold composed of two glass plates and a gasket. Heated to ° C. The cured lens was removed from the mold and heat-treated at 120 ° C. for 2 hours.

Comparative Examples 1 to 7 A mixed solution having the composition shown in Table 2 was used as a radical polymerization initiator.
1.0 part by weight of diisopropyl peroxydicarbonate was added, and 0.1 part by weight of t-butyl peroxyisopropyl carbonate was further added. The mixture was sufficiently stirred and poured into a mold composed of two glass plates and a gasket. Heated to ° C. The cured lens was removed from the mold and heat-treated at 120 ° C. for 2 hours. The refractive index, Abbe number, specific gravity, heat resistance, transparency, perforated tensile strength, hue, dyeability, etc. of the lenses obtained in Examples 1 to 9 and Comparative Examples 1 to 7 were examined. Indicated.

The characteristics were evaluated according to the following methods. Refractive index, Abbe number: Measured at 20 ° C. using an Abbe refractometer (manufactured by Atago). Table 1 shows the D line (58
9.3 nm). -Specific gravity: Measured by an underwater displacement method. Heat resistance: Ts (softening temperature) and penetration (thermal deformation) were measured using TMA (Thermal Mechanical Analyzer, manufactured by Seiko Denshi). Haze value (transparency): according to ASTM D 1003
The haze value of a lens having a center thickness of 5 mm was measured. The smaller the haze value, the better the transparency. Punching tensile strength: A 2.0 mm diameter hole was drilled at both ends of a 2 mm thick lens, screws were inserted, and the screws were pulled with a tensile tester to measure the strength. Hue: YI value (yellowness) was measured using a color difference meter (manufactured by Nippon Denshoku). Dyeability: 5 g of a dye, 2 ml of a dispersing aid, and 10 g of benzyl methacrylate were dissolved in 1 liter of pure water, heated to 90 ° C., and then immersed in the lens for 15 minutes for dyeing. The degree of dyeing of the lens after dyeing was evaluated on a five-point scale.

In the following, ST is styrene, TCDM
A is tricyclo [5.2.1.0 2,6] dec-8-yl methacrylate, NPDM is 2,2-dimethyl-1,3-
Propanediol dimethacrylate, NPDA 2,2
-Dimethyl-1,3-propanediol diacrylate, 10BP is 2,2-bis [4- (methacryloxy pentaethoxy) phenyl] propane, 30BP is 2,2-bis [4- (methacryloxy pentadecaethoxy) Phenyl] propane, EGDM is ethylene glycol dimethacrylate, and 4BP is 2,2-bis [4-
(Methacryloxydiethoxy) phenyl] propane,
α-MSD is a dimer of α-methylstyrene, NOM is n
-Indicates octyl mercaptan. The amounts of α-MSD and NOM used are shown in% by weight based on all monomers.

[0040]

[Table 1] ──────────────────────────────────── Table 1 Composition of mixed solution ─── ───────────────────────────────── Monomer composition (parts by weight) α-MSD ST TCDMA NPDM NPDA 10BP 30BP (% by weight) ──────────────────────────────────── Example 1 50-22-28- 3.0-250-22--28 3.0-34-22-33-3.0-44-22--33 3.0-5 45--22 33-3.0-6 45--22-33 3.0-7 45 10 22-23-3.0 〃 8 45 10 22--23 3.0 ９ 9 45 10 22--23-─────────────────────────── ─────────

──────────────────────────────────── Table 2 Composition of the mixture ──── ──────────────────────────────── Monomer composition (parts by weight) α-MSD ST TCDMA NPDM EGDM 4BP 30BP (% By weight) 比較 Comparative Example 1 50-22-28-3.0 〃 245-22-33-3.0 ３ 345 10 22-23-3.0 ４ 450--22-28 3.0 ５ 545--22-333.0 ６ 645 10-22-233.0 〃 750 28 22 −
− − 3.0 ────────────────────────────────────

[0042]

[Table 3] ──────────────────────────────────── Table 3 Evaluation results ──── ──────────────────────────────── Refractive index Abhe number Specific gravity Ts Penetration Haze value Intensity YI value Dyeability ( −) (−) (G / cm ³ ) (° C) (μm) (%) (kgf) (%) (1-5) ─────────────────── ───────────────── Example 1 1.56 37 1.13 101 〜0 0.5 10 1.23 〃2 1.56 37 1.13 90 〜0 0.5 15 1.25 ３3 1.56 38 1.13 100 〜0 0.5 10 1.2 3 ４4 1.56 38 1.13 85 〜0 0.5 15 1.25 ５5 1.56 38 1.13 90 〜0 0.5 10 1.24 ６6 1.56 38 1.13 75 〜0 0.515 1.25 ７7 1.56 38 1.12 105 〜0 0.5 10 1.0 3 ８8 1.56 38 1.12 93 〜0 0.5 15 1.05 ９9 1.56 38 1.12 90 〜0 1.0 15 1.45 ──────────────────────── ────────────

[0043]

[Table 4] ──────────────────────────────────── Table 4 Evaluation results ──── ──────────────────────────────── Refractive index Abhe number Specific gravity Ts Penetration Haze value Intensity YI value Dyeability ( −) (−) (G / cm ³ ) (° C) (μm) (%) (kgf) (%) (1-5) ─────────────────── ───────────────── Comparative Example 1 1.56 37 1.14 115 〜0 0.5 5 1.2 1 〃2 1.56 38 1.14 118 〜0 0.5 5 1.21 〃 3 1.56 38 1.14 118 〜0 0.5 5 1.2 1 ４ 4 1.56 37 1.15 110 〜 0 0.5 5 1.2 1 ５ 5 1.56 38 1.15 105 〜 0 0.5 5 1.2 1 ６ 6 1.56 38 1.14 113 〜 0 0.5 5 1.2 1 ７ 7 1.55 40 1.09 129 20 0.5 5 1.2 1 ────────────────────────────────────

[0044]

According to the present invention, the transparent resin according to the first aspect is excellent in transparency, strength when drilling, and excellent dyeing properties,
Specific gravity is low. The transparent resin according to the second aspect has the effects of the transparent resin according to the first aspect, and is further excellent in high refractive index, low dispersion (high Abbe number), hue, and heat resistance. The transparent resin obtained by the method according to claim 3 is excellent in transparency, strength at the time of perforation processing, dyeability, and low specific gravity. The transparent resin obtained by the method according to the fourth aspect exhibits the effects of the transparent resin according to the third aspect, and is further excellent in high refractive index, low dispersion (high Abbe number), hue, and heat resistance. The plastic lens according to the fifth aspect is excellent in transparency, strength at the time of perforation processing, dyeability, and low specific gravity. The plastic lens according to the sixth aspect has the effects of the plastic lens according to the fifth aspect, and is further excellent in high refractive index, low dispersion (high Abbe number), hue, and heat resistance. The transparent resin or lens obtained by casting the monomer composition for casting according to claim 7 is excellent in transparency, strength at the time of perforation processing, dyeability, and low specific gravity. A transparent resin or a lens obtained by casting the monomer composition for casting according to claim 8 exhibits the effects of claim 7, and further has high refractive index, low dispersion (high Abbe number), Excellent hue and heat resistance.

Claims (8)

[Claims] 1 to 80 parts by weight of a monomer having an alkylene oxide group represented by the following general formula (I):
1 to 95 parts by weight of the polyfunctional (meth) acrylate represented by the general formula (II) and 0 to 90 parts by weight of another copolymerizable vinyl monomer are added to 100 parts by weight. A transparent resin obtained by polymerizing a polymerizable monomer compounded as follows. Embedded image [However, in the general formula (I), R ₁ and R ₄ are each independently an acryloyl group or a methacryloyl group; R ₂ and R ₃ are each independently an alkylene group having 1 to 5 carbon atoms; n is an integer and is selected so that the sum of m and n is 9 to 50]. [However, in the general formula (II), R ₅ and R ₆ are each independently an acryloyl group or a methacryloyl group, and R ₇ and R ₈ are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms. ] 2. The polymerizable monomer comprises 1 to 50 parts by weight of a monomer having an alkylene oxide group represented by the general formula (I) according to claim 1, and the general formula (II) according to claim 1. 1 to 50 parts by weight of a polyfunctional (meth) acrylate represented by
Claims obtained by polymerizing a polymerizable monomer obtained by mixing 15 to 60 parts by weight of styrene and 0 to 60 parts by weight of another copolymerizable vinyl monomer so that the total thereof becomes 100 parts by weight. Item 4. The transparent resin according to Item 1. 3. An alkylene oxide group-containing monomer represented by the general formula (I): 1 to 80 parts by weight;
1 to 95 parts by weight of the polyfunctional (meth) acrylate represented by the general formula (II) and 0 to 90 parts by weight of another copolymerizable vinyl monomer are added to 100 parts by weight. A method for producing a transparent resin, comprising polymerizing a polymerizable monomer blended in such a manner. Embedded image [However, in the general formula (I), R ₁ and R ₄ are each independently an acryloyl group or a methacryloyl group; R ₂ and R ₃ are each independently an alkylene group having 1 to 5 carbon atoms; n is an integer and is selected such that the sum of m and n is 9 to 50]. [However, in the general formula (II), R ₅ and R ₆ are each independently an acryloyl group or a methacryloyl group, and R ₇ and R ₈ are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms. ] 4. The polymerizable monomer is 1 to 50 parts by weight of a monomer having an alkylene oxide group represented by the general formula (I) according to claim 3, and the general formula (II) according to claim 3. 1 to 50 parts by weight of a polyfunctional (meth) acrylate represented by
It is characterized by polymerizing a polymerizable monomer obtained by blending 15 to 60 parts by weight of styrene and 0 to 60 parts by weight of another copolymerizable vinyl monomer so that the total thereof becomes 100 parts by weight. The method for producing a transparent resin according to claim 3. 5. An alkylene oxide group-containing monomer represented by the following general formula (I): 1 to 80 parts by weight;
1 to 95 parts by weight of the polyfunctional (meth) acrylate represented by the general formula (II) and 0 to 90 parts by weight of another copolymerizable vinyl monomer are added to 100 parts by weight. A plastic lens made of a transparent resin obtained by polymerizing a polymerizable monomer blended in such a manner. Embedded image [However, in the general formula (I), R ₁ and R ₄ are each independently an acryloyl group or a methacryloyl group; R ₂ and R ₃ are each independently an alkylene group having 1 to 5 carbon atoms; n is an integer and is selected so that the sum of m and n is 9 to 50]. [However, in the general formula (II), R ₅ and R ₆ are each independently an acryloyl group or a methacryloyl group, and R ₇ and R ₈ are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms. ] 6. The polymerizable monomer is 1 to 50 parts by weight of a monomer having an alkylene oxide group represented by the general formula (I) according to claim 5, and the general formula (II) according to claim 5. 1 to 50 parts by weight of a polyfunctional (meth) acrylate represented by
A transparent polymer obtained by polymerizing a polymerizable monomer obtained by mixing 15 to 60 parts by weight of styrene and 0 to 60 parts by weight of another copolymerizable vinyl monomer so that the total thereof becomes 100 parts by weight. The plastic lens according to claim 5, which is made of a resin. 7. An alkylene oxide group-containing monomer represented by the general formula (I): 1 to 80 parts by weight;
1 to 95 parts by weight of the polyfunctional (meth) acrylate represented by the general formula (II) and 0 to 90 parts by weight of another copolymerizable vinyl monomer are added to 100 parts by weight. And a monomer composition for casting molding. Embedded image [However, in the general formula (I), R ₁ and R ₄ are each independently an acryloyl group or a methacryloyl group; R ₂ and R ₃ are each independently an alkylene group having 1 to 5 carbon atoms; n is an integer and is selected such that the sum of m and n is 9 to 50]. [However, in the general formula (II), R ₅ and R ₆ are each independently an acryloyl group or a methacryloyl group, and R ₇ and R ₈ are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms. ] 8. The polymerizable monomer is 1 to 50 parts by weight of a monomer having an alkylene oxide group represented by the general formula (I) according to claim 7, and the general formula (II) according to claim 7. 1 to 50 parts by weight of a polyfunctional (meth) acrylate represented by
8. The unit for casting according to claim 7, wherein 15 to 60 parts by weight of styrene and 0 to 60 parts by weight of another copolymerizable vinyl monomer are blended so that the total thereof is 100 parts by weight. Monomer composition.