JPH08258172A - Manufacture of plastic lens - Google Patents

Abstract

PURPOSE: To manufacture a lens of various excellent characteristics by polymerizing partially a composition composed of urethane and/or epoxy (meth)acrylate, multifunctional and monofunctional (meth)acrylate, active energy radiation and heat-sensitive radical polymerization initiator at the specified weight ratio by means of the active energy radiation, and then heating to complete the polymerization and forming. CONSTITUTION: A plastic lens composition is manufactured by using an active energy radiation-sensitive radical polymerization initiator and a heat-sensitive radical initiator of 0.005-5 pts.wt. respectively to the total 100 pts.wt. of at least one kind of urethane (meth)acrylate and/or epoxy (meth)acrylate A of 20-80 pts.wt. at least one kind of multifunctional ester type (meth)acrylate B of 10-70 pts.wt., at least one kind of monofunctional ester (meth)acrylate C of 5-50 pts.wt. and a vinyl monomer D copolymerizable to the above-said components of 0-30 pts.wt. The composition is first partially polymerized by the emission of active energy radiation and then polymerized and cured by heating.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention provides a combination of irradiation with active energy rays and heating to provide transparency, impact resistance, heat resistance,
The present invention relates to a plastic lens manufacturing method capable of manufacturing a plastic lens having excellent surface hardness and chemical resistance with high productivity.

[0002]

2. Description of the Related Art Plastic lenses are widely used in optical products because of their features such as easy molding and light weight. Above all, since transparent plastics used as spectacle lenses are required to have heat resistance and chemical resistance, thermosetting plastics such as polydiethylene glycol bisallyl carbonate (CR-39) are used instead of thermoplastics such as polymethylmethacrylate and polystyrene. Has been used. However, in order to mold-polymerize a thermoplastic resin having an allyl group having a low radical-polymerizability as a functional group without optical distortion, not only a large amount of a heat-sensitive radical polymerization initiator is required but also a long time of 20 to 30 hours. And there was a problem in productivity.

Further, a method of radically copolymerizing a composition using a compound having a methacrylate group or an acrylate group introduced as a radically polymerizable functional group has also been proposed, but these are also polymerized by thermal polymerization in a template. It is necessary to polymerize for several tens of hours in order to prevent optical distortion of the molded product due to convection of the monomer composition at the time of heat generation.

[0004]

On the other hand, as another method for preventing optical distortion of a molded article due to convection, an active energy ray-sensitive radical polymerization initiator is used, and an active energy ray-curable composition is irradiated by irradiation with active energy rays. A method is conceivable in which an object is instantly gelled and made immobile.

However, when the amount of active energy rays required for completing the polymerization is irradiated, the glass mold used for the mold polymerization is discriminated by a diamond needle or the like on the unused surface (surface) of the mold. There is a problem that the number is transferred to the product plastic lens. Therefore, since the glass mold used conventionally cannot be used, there is a problem in terms of cost even though it is a method for producing a plastic lens with high productivity.

Further, as a material for a plastic lens for eyeglasses, which is a thick molded product, not all radical-polymerizable methacrylate or acrylate compounds can be used, and various performances required for a plastic lens are satisfied. It is necessary to select it as the composition.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in the background described above, and its object is transparency,
The present invention relates to a method capable of producing a plastic lens having excellent impact resistance, heat resistance, surface hardness and chemical resistance by combining active energy ray irradiation and heating with good productivity and at low cost.

That is, the present invention provides (A) a urethane (meth) acrylate (a-1) having at least two methacryloyl groups or acryloyl groups in the molecule, and / or an epoxy (meth) acrylate (a-2). At least one kind, 20 to 80 parts by weight, (B) at least one kind of polyfunctional ester type (meth) acrylate having at least two methacryloyl groups or acryloyl groups in the molecule, 10 to 70 parts by weight, (C) At least one monofunctional ester type mono (meth) acrylate having one methacryloyl group or acryloyl group in the molecule, 5 to 50 parts by weight, (D) the above components (A), (B) and (C) Vinyl-based monomer copolymerizable with, 0-3
0 parts by weight, (E) Total amount of the above components (A) to (D) 1
100 parts by weight of the active energy ray-sensitive radical polymerization initiator, 0.005 to 5 parts by weight, and (F) 100 parts by weight of the total amount of the components (A) to (D) with respect to 00 parts by weight. A composition for a plastic lens comprising a radical polymerization initiator, 0.005 to 5 parts by weight (however, (A),
The total amount of components (B), (C) and (D) is 100 parts by weight. (2) is partially polymerized by irradiation with an active energy ray, and a second step of polymerizing by heat treatment is performed to mold the plastic lens.

The method of manufacturing the plastic lens of the present invention will be described in more detail below. First, each component of the plastic lens composition used in the present invention will be described.

Component (A) Component (A), (a-1) a urethane (meth) acrylate having at least two methacryloyl groups or acryloyl groups in the molecule, and / or (a-2) epoxy ( (Meth) acrylate (here, (meth) acrylate means methacrylate and / or acrylate) is a composition for plastic lenses at the time of template polymerization, which causes rapid partial polymerization by irradiation with active energy rays. Reduces optical distortion due to convection, mechanical strength,
It is a component that imparts impact resistance, heat resistance, surface hardness, and chemical resistance.

The urethane (meth) acrylate having at least two methacryloyl groups or acryloyl groups in the molecule (a-1), which is the component (A), specifically includes a hydroxyl group (meth). By reacting a urethanization reaction product of an acrylate with an isocyanate compound having two or more isocyanate groups in the molecule, or a polyisocyanate having two or more isocyanate groups in the molecule, a polyol, a polyester or a polyamide diol is reacted. After synthesizing the adduct, the remaining isocyanate group contains a hydroxyl group (meth)
Examples thereof include urethanization reaction products to which acrylate is added.

In the present invention, the above-mentioned urethane poly (meth) acrylate is preferable in that the surface hardness and heat resistance of the molded plastic lens can be improved, and the weight average molecular weight thereof is 400 to 2000.
It is preferably in the range of.

Specific examples of the polyisocyanate compound used to obtain the above-mentioned urethane (meth) acrylate include 1,6-hexamethylene diisocyanate,
Tris (isocyanatohexyl) isocyanurate,
1,4-tetramethylene diisocyanate, 2,2
4, -Trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, bis (4,4'-isocyanatocyclohexyl) methane, bis (4,4'-isocyanatocyclohexyl) propane, 1,3-bis (isocyanatomethyl)
Cyclohexane, meta-xylylene diisocyanate, para-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
(4,4′-isocyanatophenyl) methane, naphthalene diisocyanate and the like can be mentioned. Among the above,
Tris (isocyanatohexyl) isocyanurate, isophorone diisocyanate, bis (4,4′-isocyanatocyclohexyl) methane, 1,3-bis (isocyanatomethyl) cyclohexane, metaxylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6
-Tolylene diisocyanate is particularly preferred.

The polyol used for synthesizing the adduct of the polyisocyanate compound used to obtain the above-mentioned urethane (meth) acrylate is not particularly limited, but for example, ethylene glycol, propylene glycol, butylene glycol, Alkyl polyols such as neopentyl glycol, trimethylol propane, pentaerythritol, sorbitol, mannitol and glycerin and their polyether polyols, polyester polyols synthesized from polyhydric alcohols and polybasic acids, polyester polyols such as polycaprolactone polyols Etc.

Specific examples of the hydroxyl group-containing (meth) acrylate used for obtaining the above-mentioned urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth)
In addition to acrylate, 4-hydroxybutyl (meth) acrylate, etc., addition reaction products of monoepoxy compounds such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl methacrylate and (meth) acrylic acid, polyethylene glycol, polypropylene glycol Examples thereof include mono (meth) acrylic acid ester and mono (meth) acrylic acid ester of polycaprolactone diol.

In order to obtain the above-mentioned urethane (meth) acrylate, reaction of polyisocyanate with various diols and (meth) acrylates containing a hydroxyl group is carried out.
In the presence of a tin-based catalyst such as n-butyltin dilaurate, the isocyanate group and the hydroxyl group are used in almost equal amounts,
It may be heated at 60 to 70 ° C. for several hours. This reactant is
In general, the viscosity is often high, and therefore it is preferable to dilute with other diluting monomer during or after the reaction.

Another component (A), (a-2)
The epoxy (meth) acrylate having at least two methacryloyl groups or acryloyl groups in the molecule includes a compound (a-2-1) having at least two epoxy groups in the molecule, and (meth) acrylic acid or a molecule. Examples thereof include a glycidyl group ring-opening reaction product with a (meth) acrylate compound (a-2-2) containing a carboxyl group therein.

The compound (a) having the above-mentioned epoxy group
2-1) is obtained by a condensation reaction of various polyol compounds and epichlorohydrin. Specific examples include 1,6-hexanediol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether. Ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether,
Neopentyl glycol diglycidyl ether, neopentyl glycol hydroxypivalate diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, penta Erythritol tetraglycidyl ether, dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, sorbitol tetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, triglycidyl of tris (2-hydroxyethyl) isocyanurate Aliphatic epoxy compounds such as ether, iso Alicyclic epoxy compounds such as diglycidyl ether of rondiol, diglycidyl ether of 1,4-bis (hydroxymethyl) cyclohexane, diglycidyl ether of bis-2,2-hydroxycyclohexylpropane, resorging glycidyl ether, bisphenol A diglycidyl Ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, tetrabromobisphenol A diglycidyl ether, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone diglycidyl ether, bis (3
-Diglycidyl ether of methyl-4-hydroxyphenyl) sulfone, diglycidyl ether of bis (3-phenyl-4-hydroxyphenyl) sulfone, 2,6-
Examples thereof include condensates of xylenol dimer and epichlorohydrin, aromatic epoxy compounds such as orthophthalic acid diglycidyl ether and cresol novolac polyglycidyl ether.

(Meth) acrylic acid or a (meth) acrylate compound containing a carboxyl group in the molecule (a-
As 2-2), specifically, a carboxyl group-containing (meth) acrylate compound obtained by reacting hydroxyethyl (meth) acrylate with an acid anhydride such as o-phthalic anhydride, or glycidyl (meth) Examples thereof include a carboxyl group-containing (meth) acrylate compound obtained by reacting an acrylate with a compound having two or more carboxyl groups in the molecule such as adipic acid.

Among the above, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, and trimethylolpropane, which are (a-2-1) from the viewpoint of the colorless transparency and heat resistance of the molded plastic lens. Diglycidyl ether, glycerol triglycidyl ether, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate,
2,2-bis (4-glycidyloxycyclohexyl)
Propane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, tetrabromobisphenol A diglycidyl ether, tetrabromobisphenol S diglycidyl ether, and (a-2-2) (meth) acrylic It is particularly preferable to use (a-2) epoxy poly (meth) acrylate, which is a reaction product with an acid.

These urethane (meth) acrylates (a
-1), and epoxy (meth) acrylate (a-2)
May be used alone or in combination of two or more.

Of the component (A), the reaction for obtaining the epoxy (meth) acrylate (a-2) having at least two methacryloyl groups or acryloyl groups in the molecule is carried out by specifically The compound (a-2-1) having and the (meth) acrylic acid or the carboxyl group-containing (meth) acrylate compound (a-2-
It can be carried out by mixing 2), adding a tertiary amine such as trimethylamine or a quaternary ammonium salt such as benzyltrimethylammonium chloride as a catalyst, and heating to 60 to 110 ° C.

The proportion of the component (A) used is from (A) to (D).
When the total amount of the components is 100 parts by weight, it is 20 to 80 parts by weight, more preferably 30 to 70 parts by weight. When the amount of the component (A) used is less than 20 parts by weight, sufficient plasticity and heat resistance cannot be imparted to the plastic lens. Further, when the amount of the component (A) used exceeds 80 parts by weight, the viscosity of the composition for a plastic lens becomes high and the workability at the time of injection into the mold is deteriorated, so that various characteristics required for the plastic lens become poor. Not preferable.

Component (B) Component (B), which is a polyfunctional ester type (meth) acrylate having at least two methacryloyl groups or acryloyl groups in the molecule, is used for molded plastic lenses to have impact resistance and heat resistance. , A component that imparts surface hardness and chemical resistance.

Specific examples of the component (B) include bis (4-
(Meth) acryloxyethoxyphenyl) methane, bis (4- (meth) acryloxydiethoxyphenyl) methane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4 -(Meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypentaethoxyphenyl)
Propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxydipropoxyphenyl) propane,
2,2-bis (4- (meth) acryloxypentapropoxyphenyl) propane, 2,2-bis (4- (meth))
Acryloxyethoxy-3,5-dibromophenyl) propane, 2,2-bis (4- (meth) acryloxydiethoxy-3,5-dibromophenyl) propane, 2,2
-Bis (4- (meth) acryloxypentaethoxy-
3,5-dibromophenyl) propane, bis (4- (meth) acryloxyethoxyphenyl) sulfone, bis (4- (meth) acryloxydiethoxyphenyl) sulfone, bis (4- (meth) acryloylthiophenyl) sulfide , An ester of an aromatic skeleton such as bis (4- (meth) acryloxyethylthiophenyl) sulfide, di (meth) acrylate, bis (4- (meth) acryloxycyclohexyl) methane, bis (4- (meth) acryl) Roxyethoxycyclohexyl) methane, bis (4-
(Meth) acryloxydiethoxycyclohexyl) methane, bis (4- (meth) acryloxycyclohexyl)
Ester di (of alicyclic skeleton such as propane, bis (4- (meth) acryloxyethoxycyclohexyl) propane, bis (4- (meth) acryloxydiethoxycyclohexyl) propane, dicyclopentanedi (meth) acrylate) (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol (n = 4 to 15) di (meth) acrylate, propylene glycol di (meth) acrylate , Tripropylene glycol di (meth) acrylate, polypropylene glycol (n = 4
To 15) di (meth) acrylate, 1,4-butanediol di (meth) acrylate, polybutylene glycol (n = 2 to 15) di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxyhivalic acid neo Di (meth) acrylate of pentyl glycol ester, 1,6-hexanediol di (meth) acrylate, ester di (meth) acrylate of aliphatic skeleton such as 1,9-nonanediol di (meth) acrylate, and other trimethylolpropane Poly (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. ) Acrylate, and the like. These compounds can be used alone or in combination of two or more kinds.

The proportions of the component (B) used are (A) to (D).
10 to 70 parts by weight based on 100 parts by weight of the total amount of the components,
It is more preferably 20 to 60 parts by weight. If the amount of component (B) used is less than 10 parts by weight, sufficient surface hardness, impact resistance, and chemical resistance cannot be imparted to the plastic lens, and if it exceeds 70 parts by weight, the heat resistance of the plastic lens is high. Is decreased, which is not preferable.

Component (C) The monofunctional ester type mono (meth) acrylate having one methacryloyl group or acryloyl group in the molecule, which is the component (C), is a component that reduces the viscosity of the plastic lens composition. It is a component that improves the workability of injecting the composition into a mold and also improves the surface accuracy of a molded plastic lens such as preventing deformation of the lens due to relaxation of stress strain due to polymerization shrinkage.

Specific examples of the component (C) include aliphatic mono (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, cyclohexyl ( Alicyclic mono (meth) acrylates such as (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, phenyl-di (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, 2-
Phenylphenoxyethyl (meth) acrylate, 4-
Phenylphenoxyethyl (meth) acrylate, 2-
Phenylphenyl-2-methyloxyethyl (meth) acrylate, 4-phenylphenyl-2-methyloxyethyl (meth) acrylate, 3- (2-phenylphenyl) -2-hydroxypropyl (meth) acrylate, 3- ( 4-phenylphenyl) -2-hydroxypropyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-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, 3- (1-naphthyl) -2-hydroxypropyl (meth) acrylate, 3- (2-naphthyl) -2-hydroxypropyl (meth) acrylate, 2-bromophenyl (meth) acrylate, 4- Bromophenyl (meth) acrylate, 2,4-dibromophenyl (meth) acrylate, 2,4,6-tribromophenyl (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, 2,3,4,5 , 6-Pentabromobenzyl (meth) acrylate, 2-chlorophenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, 2,4-dichlorophenyl (meth) acrylate, 2,4,6-trichlorophenyl (meth) acrylate, 2,3,4,5,6-pentachlorophenyl (meth) acrylate, 2,4,6-trichlorophenoxyethyl (meth) acrylate, 2,
4,6-Trichlorophenyl-di (oxyethyl)-
(Meth) acrylate, phenylthioethyl (meth) acrylate, phenylthioethoxyethyl (meth) acrylate, phenylthio-1-methylethyl (meth) acrylate, phenylthio-1-methylethoxy-1-
Methyl ethyl (meth) acrylate, 3-phenylthio-2-hydroxypropyl (meth) acrylate, 2-
Phenylphenylthioethyl (meth) acrylate, 2
-Phenylphenylthio-1-methylethyl (meth) acrylate, 3- (2-phenylphenylthio) -2-
Examples include aromatic mono (meth) acrylates such as hydroxypropyl (meth) acrylate.

The proportion of component (C) used is from (A) to (D).
The total amount of the components is 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight. (C) component is 5
If the amount is less than the weight part, the viscosity of the plastic lens composition becomes high, the workability of injecting the composition into the mold is deteriorated, and the surface accuracy of the obtained plastic lens is deteriorated. Also,
When the amount of the component (C) exceeds 50 parts by weight, the resulting plastic lens has poor mechanical strength, impact resistance and surface hardness.

The vinyl monomer copolymerizable with the components (A), (B) and (C), which is the component (D), has heat resistance, surface hardness, dyeability and chemical resistance to the lacking plastic lens. It is a component that is added and adjusts the radical polymerizability.

Specific examples of the component (D) include styrene,
Chlorostyrene, bromostyrene, dibromostyrene,
Vinyl compounds such as divinylbenzene, diethylene glycol bisallyl carbonate, diallyl phthalate,
Examples thereof include (meth) allyl compounds such as diallylbiphenylate. These monomers may be used alone or in combination of two or more.

The proportion of the component (D) used is from (A) to (D).
The total amount of the components is 0 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight. (D) component is 30
If it exceeds the weight part, the impact resistance and heat resistance of the plastic lens and the polymerization rate with active energy rays decrease, which is not preferable.

Component (E) The active energy ray-sensitive catalyst which is the component (E) is more preferably a catalyst which mainly produces a radical source in response to ultraviolet rays having a wavelength of 200 to 400 nm.

Specific examples of the component (E) include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethylketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenyl glyoxylate, ethylphenyl glyoxylate, 2-hydroxy-2-methyl-1
A carbonyl compound such as phenylpropan-1-one,
Examples thereof include sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide, and acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide. These are used in one kind or a mixture of two or more kinds.

Among these, benzophenone, benzoin isopropyl ether, methylphenylglyoxylate, 1-hydroxycyclohexylphenyl ketone,
More preferred are benzyl dimethyl ketal and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

The proportion of the component (E) used is from (A) to (D).
It is 0.005 to 5 parts by weight, more preferably 0.02 to 2 parts by weight, based on 100 parts by weight of the total amount of the components.
When the amount of the component (E) is less than 0.005 parts by weight, the curability of the plastic lens composition becomes insufficient, and
When it exceeds the weight part, the deep-part curability is deteriorated and the plastic lens is colored, which is not preferable.

Component (F) As the heat-sensitive catalyst which is the component (F), a usual organic peroxide or an azo compound can be used. Specifically, benzoyl peroxide, octanoylperoxide,
Diisopropylperoxypercarbonate, bis (4
-T-butylcyclohexyl) peroxydicarbonate, t-butylperoxy oxyisobutyrate, t-butylperoxy-2-ethylhexanoate, and other organic peroxides, 2,2′-azobis (2,2 4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile,
Examples thereof include azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2′-azobis (2-methylbutyronitrile).

The proportion of the component (F) used is from (A) to (D).
It is 0.005 to 5 parts by weight, more preferably 0.02 to 2 parts by weight, based on 100 parts by weight of the total amount of the components.
If the amount of the component (F) is less than 0.005 parts by weight, the curability of the plastic lens composition will be insufficient, and if it exceeds 5 parts by weight, the mechanical strength of the plastic lens will decrease and the coloring of the lens will be reduced. It is not preferable because it invites.

The composition for plastic lenses of the present invention contains, if necessary, an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a bluing agent, a pigment, an anti-settling agent, an antifoaming agent, an antistatic agent, Various additives such as antifogging agents may be included.

A concrete method for manufacturing a plastic lens of the present invention is as follows. First, components (A), (B), (C), (D), (E) and (F) are mixed according to desired performance to obtain a plastic lens composition.

The mold for producing the plastic lens is not particularly limited, but the mold used for the mold includes glass and glass, glass and plastic, glass and metal, or a combination thereof, and the inner surface of which is mirror-polished. To use. For example, it is possible to use a matrix made of two molds such as glass, plastic, or metal whose inner surface is mirror-polished, and a gasket made of a thermoplastic resin such as ethylene-vinyl acetate copolymer. . Here, as the gasket, in addition to the thermoplastic resin as described above, 2
The molds may be fixed with a polyester adhesive tape or the like.

The composition comprising the above components (A) to (F) is injected into the obtained mother die, and molding is performed in the following first step and second step.

[First Step] In the present invention, as the first step, an active energy ray is irradiated from one side or both sides of the mold into which the composition for a plastic lens is injected to irradiate the composition in the mold. By partially copolymerizing the substance, it is possible to prevent the convection of the monomer in the subsequent second step by gelling and making it non-fluid, and to prevent the optical distortion from occurring in the plastic lens. The atmosphere upon irradiation with the active energy rays may be air or an inert gas such as nitrogen or argon. Further, the irradiation of active energy rays at this time may be performed by using a high pressure mercury lamp, a metal halide lamp, a halogen lamp or the like as a light source.
0.05 to 5 active energy rays with wavelengths of 0 to 600 nm
The irradiation dose is preferably in the range of J / cm ² . The dose of this active energy ray was injured by the radical polymerization activity of the plastic lens composition comprising the components (A) to (F), the radical polymerization rate and refractive index of the composition, and the glass matrix. It is determined by the transfer state of the scribe scratch to the manufactured plastic lens. In particular, when a plastic lens composition having a relatively high radical polymerization rate or a relatively high refractive index is used, scratches are easily transferred to the plastic lens, and therefore the active energy ray irradiation amount is 0.05. ~ 1 J / cm ²
It is preferable that When a plastic lens composition having a relatively low radical polymerization rate or a relatively low refractive index is used, the active energy ray dose is 0.5.
~ 3 J / cm ² is preferred. However, in general, when the irradiation dose is low, gelation of the plastic lens composition and immobilization are not sufficient, and optical distortion tends to occur. When the irradiation dose of active energy rays is too high, the plastic Since the composition for lenses becomes too hard and also the stress of polymerization shrinkage is generated, "polymerization peeling" is likely to occur in the second step.

[Second Step] Next, as a second step,
Polymerization is completed by heating in a hot air oven at 80 to 150 ° C or in hot water at 70 to 100 ° C for 1 to 5 hours. At this time, if the mother mold filled with the composition is immediately put into a high temperature atmosphere, polymerization and polymerization shrinkage of the composition rapidly occur with heat generation, and therefore, between the polymerized plastic lens and the mother mold. There is a case where a space is generated in the mold, a phenomenon in which the mother mold and the composition inside the mother mold are separated, that is, a phenomenon called “polymerization peeling” occurs, or a crack is generated in the obtained plastic lens. Therefore, for example, by performing the polymerization process by raising the temperature from a region of 50 to 70 ° C. to a high temperature region of 100 to 150 ° C. over 0.5 to 2 hours, a plastic lens can be obtained without causing polymerization peeling or cracks. Can be obtained. By using the production method of the present invention, the step conventionally required for producing a plastic lens, which required a long thermal polymerization time of 20 to 30 hours, is activated as the first step in the present invention. By irradiating with energy rays, gelling and immobilizing the composition for plastic lenses, it is possible to suppress the occurrence of optical distortion due to convection of the monomer during heat polymerization, and it is possible to carry out the polymerization in a short time of several hours. it can.

[0045]

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

The abbreviations of the monomers in Examples and Tables are as follows. UM1: isophorone diisocyanate 1 mol and 2-
Urethane dimethacrylate UA2 obtained by reacting 2.2 moles of hydroxypropyl methacrylate: Urethane diacrylate UM3: 2,6 obtained by reacting 1 mole of 2-hydroxypropyl acrylate 2.1 mole of metaxylylene diisocyanate -Urethane dimethacrylate EM1 obtained by reacting 1 mol of tolylene diisocyanate with 2.2 mol of 2-hydroxypropyl methacrylate: bisphenol A diglycidyl ether 1
Epoxy dimethacrylate EM2 obtained by reacting 2 moles of methacrylic acid with methacrylic acid: Epoxy dimethacrylate obtained by reacting 1 mole of tetrabromobisphenol A diglycidyl ether with 2 moles of methacrylic acid PBGM: nonabutylene glycol dimethacrylate BPEA : 2,2-bis (4-acryloxydiethoxyphenyl) propane PEGA: nonaethylene glycol diacrylate BPEM: 2,2-bis (4-methacryloxypentaethoxyphenyl) propane TEGA: tripropylene glycol diacrylate IBMA: isobor Nyl methacrylate DCPM: Dicyclopentanyl methacrylate PHM: Phenyl methacrylate BZM: Benzyl methacrylate POA: Phenoxyethyl acrylate S T: Styrene DAB: 2,2'-Diallylbiphenylate TPO: 2,4,6-Trimethylbenzoyldiphenylphosphine oxide MPG: Methylphenylglyoxylate TBB: t-Butylperoxyisobutyrate TBEH: t-Butylperoxy 2-Ethylhexanoate CR39: Diethylene glycol bisallyl carbonate IPP: Diisopropyl peroxypercarbonate

The evaluation method of the obtained plastic flat plate and plastic lens is as follows.

Optical distortion: The obtained plastic lens was sandwiched between two polarizing plates orthogonal to each other and visually observed. ◯: No distortion is observed. X: There is convective distortion. Injection workability: The injection workability of the plastic lens composition into a mold was evaluated. ◯: Viscosity is appropriate and injection is easy. X: The viscosity was high and injection was difficult, and injection unevenness occurred. Visible light transmittance (%): The obtained plastic plate having a thickness of 2 mm was measured according to ASTM D-1003. Refractive index: The obtained plastic plate having a thickness of 2 mm was cut into a width of 10 mm and a length of 20 mm, and the refractive index of the D line of 589.3 nm was measured at 20 ° C by an Abbe refractometer. Surface hardness: The Rockwell hardness (L) of the obtained plastic plate having a thickness of 5 mm was measured according to JIS K7202. Heat resistance: TM of the obtained plastic plate with a thickness of 2 mm
The Tg under a load of 10 g was measured by A measurement. Impact resistance: FDA with a minus lens with a thickness of 1.5 mm
A falling ball test was conducted according to the standard. However, the description in the table shows the maximum weight of the steel ball that the lens does not break when the steel ball is dropped from a height of 127 cm. Chemical resistance: The surface of the plastic lens was wiped with a gauze containing acetone and toluene, and the change was examined. ◯: No change. X: The surface was whitened. Moldability and Releasability The molded plastic lens was visually evaluated when it was released from the mother die. ◯: It is a good molded product without polymer peeling and cracks. X: There is polymerization peeling or cracks, and it cannot be used as a plastic lens.

[Example 1] UM1 40 g, PBGM
30g, IBMA 30g, TPO 0.05g, TB
After mixing 0.1 g of B and stirring well at room temperature, 50 m
The pressure was reduced to mHg and degassing was performed for 10 minutes. This composition was combined with two flat glass plates having a diameter of 70 mm and mirror-finished so that the inner thicknesses were 2 mm and 5 mm, and the circumference thereof was surrounded by a polyester tape in two types of molds, and a diameter of 70 mm, a center. Each of them was poured into a mold having a thickness of 1.5 mm and a frequency of minus 6.0. Then, as the first step, 300 mJ / cm ² of ultraviolet rays are radiated from one side of the mold by a high-pressure mercury lamp of 2 kw, and as the second step, the temperature is raised from 60 ° C. to 120 ° C. in a hot air drying furnace for 18 minutes. After that, it was left at 120 ° C. for 2 hours to complete the polymerization and curing. After that, the plastic flat plate and the plastic lens that were cured from the mold were released from the mold, and heated at 130 ° C. for 1 hour for annealing treatment. The evaluation results of the plastic flat plate and the plastic lens thus obtained are shown in Tables 1 and 2.

[Examples 2 to 6] Using the plastic lens compositions in the proportions shown in Table 1, the first shown in Table 1 was used.
A plastic flat plate and a plastic lens were manufactured and evaluated in the same manner as in Example 1 except that molding was performed in the step (indicating light irradiation energy) and the second step (indicating heat treatment temperature and time). The results are shown in Table 1 and Table 2.
Are also shown.

[Comparative Example 1] CR39 100 g, IPP
After mixing 3 g and stirring well, the mixture was poured into the same mold as used in Example 1 and heated in a hot air drying oven at 40 ° C to 55 ° C.
After heating for 15 hours to 55 ° C., the temperature was raised from 55 ° C. to 95 ° C. for 7 hours to complete polymerization and curing, and a plastic flat plate and a plastic lens were molded. Then, the cured plastic flat plate and the plastic lens were removed from the mold, and heated at 120 ° C. for 1 hour to be annealed. The plastic flat plate and the plastic lens thus obtained were evaluated in the same manner as in Example 1, and the evaluation results are shown in Tables 1 and 2.

[Comparative Examples 2 to 9] Plastic flat plates and plastics were prepared in the same manner as in Example 1 except that the composition for plastic lenses in the proportions shown in Table 1 was used and the production method shown in Table 1 was used. The lenses were manufactured and the evaluation results are shown in Tables 1 and 2.

[0053]

[Table 1]

[0054]

[Table 2]

According to the manufacturing method of the present invention, there is no optical distortion, productivity is low in a short time, cost is low, and transparency, impact resistance, heat resistance, surface hardness and chemical resistance are high. It is possible to obtain an excellent plastic lens.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location G02B 1/04 G02B 1/04 // B29K 33:00 C08L 33:06 (72) Inventor Shinji Makino 4-60 Sunadabashi, Higashi-ku, Nagoya-shi, Aichi Mitsubishi Rayon Co., Ltd. Product Development Laboratory

Claims (1)

[Claims] 1. (A) At least one of urethane (meth) acrylate (a-1) and / or epoxy (meth) acrylate (a-2) having at least two methacryloyl groups or acryloyl groups in the molecule. 20 to 20
80 parts by weight, (B) at least one polyfunctional ester type (meth) acrylate having at least two methacryloyl groups or acryloyl groups in the molecule,
70 parts by weight, (C) at least one monofunctional ester type mono (meth) acrylate having one methacryloyl group or acryloyl group in the molecule, 5 to 50 parts by weight, (D) the above (A), ( Vinyl-based monomer copolymerizable with B) and (C) component, 0 to 30 parts by weight, (E)
With respect to 100 parts by weight of the total amount of the components (A) to (D), an active energy ray-sensitive radical polymerization initiator, 0.
005 to 5 parts by weight, (F) composition for a plastic lens comprising a heat-sensitive radical polymerization initiator, 0.005 to 5 parts by weight, based on 100 parts by weight of the total of the components (A) to (D). The first step of partially polymerizing the product (however, the total amount of (A), (B), (C) and (D) and the components is 100 parts by weight, and heating. A method for producing a plastic lens, which comprises curing in a second step of polymerizing by treatment.