JP2000284236A - Plastic lens with cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To inexpensively provide a plastic lens for spectacles having excellent wear resistance, chemical resistance, hot water resistance, etc., by providing the surface of the plastic lens obtained by polymerizing specific raw material monomers with a cured film obtained by coating applying and curing of specific coating compositions. SOLUTION: The plastic lens base material is formed by polymerizing 40 to 89 wt.% diallylphthalate prepolymer expressed by formula I, 10 to 59 wt.% dialkylene glycol bisallylcarbonate prepolymer expressed by formula II and 1 to 30 wt.% vinyl resin expressed by formula III. The resultant plastic lens base material is provided with the cured film obtained by coating applying and curing of the coating compositions essentially consisting of the particulates consisting of >=1 kind of the metal oxides selected from Si, Sn, Sb, etc., of 1 to 100 microns in grain size and/or the composite particulates composed of >=2 kinds of the metal oxides selected from Si, Al, Sn, etc., and the organic silicon compounds expressed by formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a plastic lens for spectacles provided with a cured film. Furthermore, the present invention relates to a plastic lens for spectacles having an antireflection film provided on a cured film.

[0002]

2. Description of the Related Art Synthetic resin lenses, especially diethylene glycol bis (allyl carbonate) resin lenses, are superior to glass lenses in safety, workability, fashionability, and the like.
Due to the development of hard coat technology and hard coat + anti-reflection technology, it has spread rapidly. However, the refractive index of diethylene glycol bis (allyl carbonate) resin is 1.
50, which is lower than that of a glass lens, the near vision lens has a disadvantage that the outer peripheral portion is thicker than the glass lens. For this reason, in the field of plastic lenses for spectacles, technology development for reducing the thickness by using a high-refractive-index resin material has been actively performed. As technical proposals therefor, Japanese Patent Application Laid-Open Nos. 61-134701 and 63-4621
No. 3, JP-A-2-269714, JP-A-3-26914.
No. 134005, JP-A-5-339321,
JP-A-7-252207 and the like have proposed a high refractive index resin material having a refractive index of 1.55 or more.

On the other hand, plastic lenses have a drawback that they are easily scratched. Therefore, a method of providing a cured film obtained by applying and curing a silicone-based coating composition on the surface of a plastic lens is generally used. However, when the same method is applied to a high-refractive-index plastic lens, interference fringes occur due to a difference in the refractive index between the plastic lens and the cured film, which causes poor appearance. As a technical proposal for solving this problem, a colloidal dispersion of silicon dioxide fine particles used in a silicone-based coating composition as disclosed in JP-B-61-54331 and JP-B-63-37142 is highly refracted. Al, Ti,
A coating technique has been disclosed in which Zr, Sn, and Sb are replaced with a colloidal dispersion of inorganic oxide fine particles. JP-A-1-301517 discloses a method for producing a composite sol of titanium dioxide and cerium dioxide, and JP-A-2-264902 discloses a method for producing a composite sol.
And inorganic fine particles of composite inorganic oxide of Ce, JP-A-3-68901
Japanese Patent Application Laid-Open Publication No. H11-139,055 discloses a technique in which fine particles obtained by treating a composite inorganic oxide of Ti, Ce and Si with an organosilicon compound are used in a coating composition.

[0004]

SUMMARY OF THE INVENTION Among the aforementioned prior arts,
JP-A-61-134701, JP-A-63-462
No. 13, JP-A-2-269714, JP-A-3-26914
-134005, JP-A-5-339321, JP-A-7-252207 and the like, the high refractive index resin materials such as surface hardness, abrasion resistance and the like required as a plastic lens for spectacles by these techniques alone. The durability was insufficient. In addition, these compounds for obtaining a high refractive index generally require long steps for synthesis and purification and special equipment and devices, and are often difficult to form lenses. As a result, it has become expensive as a plastic lens for spectacles.

Further, regarding the above-mentioned coating technique, Japanese Patent Publication No. Sho 61-54331 and Japanese Patent Publication No. Sho 63-37
In the coating composition of JP-A-142, there is a limit in the refractive index as a cured film when inorganic oxide fine particles of Al and Sb are used. It was impossible to suppress. Also, Z
When inorganic oxide fine particles of r and Sn were used, their dispersibility was unstable, and when used in large amounts, a transparent cured film could not be formed. Furthermore, since the oxide of Ti has extremely poor weather resistance, the cured film formed from TiO ₂
When combined with the plastic lens substrate of the present invention, there was a problem in terms of durability.

[0006] JP-A-2-264902, JP-A-3
In the coating composition using composite fine particles of titanium dioxide and cerium dioxide disclosed in JP-A-68901, cerium dioxide is used in a composite form to improve the weather resistance of titanium dioxide, but the resulting cured film is poor in weather resistance. It was still insufficient. Furthermore, since cerium dioxide has a yellow tint, the cured film obtained from these composite sols was somewhat yellowish.

In addition, the combination of the plastic lens substrate of the present invention with the coating technique described in the prior art is inferior in heat resistance, falling ball strength, etc. in addition to the above-mentioned problems. The search for a more suitable coating technique was needed.

Accordingly, the present invention has been made to solve these problems, and an object of the present invention is to eliminate interference fringes due to a difference in refractive index between a substrate lens and a cured film formed by a coating composition. An object of the present invention is to provide an inexpensive plastic lens for spectacles having excellent durability such as chemical resistance, warm water resistance, heat resistance, weather resistance, and falling ball strength.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object. As a result, the following A
40 to 89% by weight of the component, 10 to 59% by weight of the B component,
A cured film obtained by applying and curing a coating composition containing the following components D and E as main components is provided on the surface of a plastic lens obtained by polymerizing a raw material monomer containing 1 to 30% by weight of the component C. As a result, it has been found that the object of the present invention is achieved, and the present invention has been completed.

A. A diallyl phthalate prepolymer represented by the following general formula 5

[0011]

Embedded image

B. Dialkylene glycol bisallyl carbonate prepolymer represented by the following general formula 6

[0013]

Embedded image

C. Vinyl compound represented by the following general formula 7

[0015]

Embedded image

D. Si with a particle size of 1 to 100 millimicrons,
Fine particles comprising at least one metal oxide selected from Sn, Sb, Ce, Zr, Ti and / or Si, Al,
Sn, Sb, Ta, Ce, La, Fe, Zn, W, Z
B. Composite fine particles composed of two or more metal oxides selected from r, In, and Ti Organosilicon compound represented by the following general formula 8

[0017]

Embedded image

Further, the plastic lens with a cured film of the present invention is characterized in that the D component is a fine particle composed of a metal oxide of Ti and / or a composite fine particle containing at least a metal oxide of Ti.

Further, the present invention is characterized in that an antireflection film made of an inorganic substance is laminated on the surface of the plastic lens provided with the cured film.

Hereinafter, the present invention will be described in more detail.

[0021] In which is one component A of the essential polymerizable component of the plastic lens substrate of the present invention, when the number of carbon atoms of R ² exceeds 5, the heat resistance and refractive index of the plastic lens is decreased. Further, m in the same component is 0 to 2
Although it is not particularly limited as long as it is an integer of 0, it is difficult to control the molecular weight at the time of production, so that a prepolymer having a constant distribution can be preferably used. The distribution is not particularly limited, but in order to particularly improve the impact resistance, the refractive index, the viscosity, and the like of the obtained plastic lens, m = 0 is 20% by weight to 70% by weight, m = 1 is 20% to 40% by weight, m = 2 is 1% to 20% by weight, m = 3 is 0% to 20% by weight, m =
Preferably, 4 is 0% to 15% by weight, m = 5 is 0% to 10% by weight, and 6 ≦ m ≦ 20 is 0% to 10% by weight. At this time, when m = 1 is less than 20% by weight,
Viscosity is undesirably increased, and if it exceeds 70% by weight, impact resistance is undesirably reduced. When 6 ≦ m ≦ 20 exceeds 10% by weight, the viscosity is undesirably increased. On the other hand, when m exceeds 20, the viscosity increases significantly.

The component A can be prepared, for example, by subjecting a diallyl phthalate to a dihydric alcohol to a transesterification reaction in the presence of a catalyst, preferably at 50 to 200 ° C. for 2 to 12 hours. Obtainable. Especially m
Can be easily adjusted by defining the amount of the raw material and appropriately adjusting the temperature, time and pressure. As the diallyl phthalate that can be used at this time, diallyl phthalate, diallyl isophthalate, diallyl terephthalate and the like can be preferably mentioned. As the dihydric alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, Preferred are 1,4-butanediol, 1,3-butanediol, neopentyl glycol and the like. Preferred examples of the catalyst include potassium hydroxide, sodium hydroxide, alcoholate, calcium compound, magnesium compound, zinc compound, cadmium compound, titanium compound, germanium compound, tin compound, lead compound, manganese compound, antimony compound and the like. be able to. A specific example of the reaction using diallyl isophthalate and ethylene glycol can be represented by the following chemical reaction formula 9.

[0023]

Embedded image

Further, the amount of the component A needs to be 40 to 89% by weight based on the total amount of the raw material monomers. When the use amount of the component A is less than 40% by weight, the refractive index of the obtained plastic lens decreases, and when it exceeds 89% by weight, the impact resistance and the hue of the obtained plastic lens deteriorate.

When the carbon number of R ³ in the B component, which is one of the essential polymerizable components of the plastic lens substrate of the present invention, exceeds 10, the heat resistance of the obtained plastic lens decreases. Not preferred. The above B
In the components, n is not particularly limited as long as it is an integer of 1 to 10, but it is preferable to have a certain distribution because it is difficult to control the molecular weight during production. As the distribution, n = 1 is 20% to 60% by weight, n = 2 is 25% to 40% by weight, n = 3 is 5% to 25% by weight, and n = 4 is 1% to 20% by weight. Weight%, 5 ≦
It is preferable that n ≦ 10 is 0% by weight to 15% by weight because the impact resistance, the refractive index, and the viscosity of the obtained plastic lens are improved.

The component B can be prepared, for example, by subjecting diallyl carbonate and a dihydric alcohol to a transesterification reaction in the presence of a catalyst, preferably at 50 to 200 ° C. for 2 to 12 hours. In particular, in order to make the distribution of n within the above range, it can be easily adjusted by regulating the amount of the raw material and appropriately adjusting the temperature, time and pressure. The dihydric alcohol that can be used in this case includes ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol. And the catalyst is the prepolymer 1
And the like used in the preparation of the catalyst.

The use amount of the component B is 10 to 59% by weight based on the total amount of the raw material monomers. If the amount is less than 10% by weight, the impact resistance, hue and adhesion of the hard coat of the obtained plastic lens decrease, and if it exceeds 59% by weight, the refractive index of the obtained plastic lens decreases.

Specific examples of the vinyl compound represented by the general formula 7 as the component C in the present invention include dibenzyl fumarate, dibenzyl malate, and bis (2-
Chlorobenzyl) fumarate, bis (4-chlorobenzyl) fumarate, bis (2-chlorobenzyl) malate, bis (4-chlorobenzyl) malate, bis (2-chlorobenzyl) fumarate
Bromobenzyl) fumarate, bis (4-bromobenzyl) fumarate, bis (2-bromobenzyl) malate, bis (4-bromobenzyl) malate and the like can be preferably mentioned.

The amount of the C component used is in the range of 1 to 30% by weight, and 3 to 20% by weight based on the total amount of the raw material monomers.
Is particularly preferable in terms of hue, impact resistance and heat resistance. If the amount is less than 1% by weight, the hue and impact resistance of the obtained plastic lens are reduced, and
When the content exceeds 0% by weight, the heat resistance of the obtained plastic lens is reduced.

The polymerizable component used in the plastic lens substrate of the present invention may be only the above-mentioned component A, component B or component C, but other vinyl monomers may be used in combination. In this case, other usable vinyl monomers include styrene, p-methylstyrene, p-chlorostyrene, divinylbenzene, α-methylstyrene, vinyl acetate, vinyl benzoate, allyl benzoate, divinyl phthalate, vinyl naphthalene, (Meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n- Propyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, n-
Butyl (meth) acrylate, allyl (meth) acrylate, methallyl (meth) acrylate, vinyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth)
Acrylate, naphthyl methacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-acryloyloxyglycerin monomethacrylate 2,2-bis [(meth) acryloyloxyethoxyphenyl] propane, 2,2-bis [(meth) acryloyloxydiethoxyphenyl] propane, 2,2-bis [(meth) acryloyloxy (2′-hydroxy) Propyloxy)
[Phenyl] propane, 2- (meth) acryloyloxyethyl succinic acid, diisopropyl fumarate, dicyclohexyl fumarate, dibenzyl fumarate, dibenzyl itaconate, dibenzyl mesaconate, maleic anhydride, itaconic anhydride and the like are preferred. Can be
When used, they can be used alone or as a mixture. The amount of the other vinyl monomer used is preferably 10% by weight or less based on the entire polymerizable component.

In order to prepare the plastic lens substrate of the present invention, for example, a curing agent is added to the above-mentioned raw material monomer to prepare a raw material monomer composition, which is directly charged into a desired mold.
A method of heat polymerization can be preferably used.
At this time, the polymerization system is an inert gas such as nitrogen, helium,
It is preferable that the atmosphere is replaced with carbon dioxide or the like or under an atmosphere. Further, the raw material monomer composition is preferably 3
After preliminarily polymerizing at a temperature of 0 ° C. to 70 ° C., it can be charged in a mold and heated.

The polymerization temperature during the heat polymerization varies depending on the curing agent used, but is preferably in the range of 20 to 130 ° C. Preferably, the polymerization is carried out gradually. Further, the temperature may be raised as appropriate for the purpose of shortening the curing time and treating the unreacted monomer and the curing agent. Further, the polymerization time is preferably 5 to 48 hours.

Further, since the resin obtained by the heat polymerization has an internal strain, it is preferably 80 ° C. to 140 ° C.
C., more preferably annealing at a temperature of 90.degree. C. to 120.degree. C. for 30 minutes or more and less than 6 hours, more preferably 1-4 hours.

As the curing agent that can be used at this time, an organic peroxide having a selected 10-hour half-life temperature of 120 ° C. or less can be preferably used. Specifically, for example, benzoyl peroxide, diisopropyl Oxydicarbonate, di-n-propylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxycarbonate, tertiary butylperoxyisopropyl carbonate, tertiary butylperoxybenzoate, 1,1-bis (t- Butyl peroxy)-
Preferred are 3,3,5-trimethylcyclohexane and the like. When used, they can be used alone or as a mixture. The amount of the curing agent to be used is preferably 0.05 to 5% by weight, more preferably 0.1 to 4% by weight, based on the total amount of the raw material monomers. At this time, if the amount of the curing agent used is less than 0.05% by weight, the polymerization becomes insufficient, and the physical properties of the obtained plastic lens are reduced. It is not preferable because cracks are easily generated.

In the raw material monomer for the plastic lens substrate of the present invention, if necessary, a colorant such as a dye or a pigment, an ultraviolet absorber, an antioxidant, various stabilizers, an antistatic Agents, photochromic compounds, fluorescent whitening agents, mold release agents, and the like can also be added.

Next, the coating composition for forming a cured film in the present invention will be described.

The particle diameter of the D component used in the present invention is from 1 to 100.
Fine particles of one or more metal oxides selected from millimeter microns of Si, Sn, Sb, Ce, Zr, Ti and / or Si, Al, Sn, Sb, Ta, Ce, La,
Specific examples of the composite fine particles composed of two or more metal oxides selected from Fe, Zn, W, Zr, In, and Ti include SiO ₂ , SnO ₂ , Sb ₂ O ₅ , CeO ₂ , and Zr.
O _2, of the TiO ₂ fine inorganic oxide particles is a dispersion medium such as water, in which the alcohol or other organic solvent is colloidally dispersed. Or Si, Al, S
n, Sb, Ta, Ce, La, Fe, Zn, W, Zr,
Composite fine particles composed of two or more kinds of inorganic oxides of In and Ti are colloidally dispersed in water, an alcohol-based or other organic solvent. Further, it is also possible to use those obtained by treating the surface of these fine particles with an organosilicon compound or an amine compound in order to enhance the dispersion stability in the coating liquid. As the organosilicon compound used at this time, there are monofunctional silane, difunctional silane, trifunctional silane, tetrafunctional silane and the like. In the treatment, the hydrolyzable group may be untreated or hydrolyzed. Further, after the treatment, a state in which the hydrolyzable group has reacted with the —OH group of the fine particles is preferable, but there is no problem in stability even when a part remains. As the amine compound, ammonium or ethylamine, triethylamine, isopropylamine,
There are alkylamines such as n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, and alkanolamines such as monoethanolamine and triethanolamine. The addition amount of the organosilicon compound and the amine compound is 1 to 1 with respect to the weight of the fine particles.
It needs to be added within the range of about 5%. In any case, the particle diameter is preferably about 1 to 300 mμ, and the kind applied to the coating composition of the present invention and the amount used are determined by the target cured film performance.
It is desirably about 50% by weight. That is, if it is less than 10% by weight, the adhesion to the inorganic vapor-deposited film becomes insufficient, or the scratch resistance of the coating film becomes insufficient. Also 5
If the content exceeds 0% by weight, cracks occur in the coating film.

Subsequently, in the component E, R ⁷ is an organic group having a polymerizable reactive group, such as a vinyl group, an allyl group,
Acryl group, methacryl group, an epoxy group, a mercapto group, a cyano group, a silane compound having an isocyano group, polymerizable reactive group such as an amino group, R ⁸ is 1 to carbon atoms
The hydrocarbon group of No. 6 is specifically exemplified by a methyl group, an ethyl group, a butyl group, a vinyl group, a phenyl group and the like. X ¹ is a hydrolyzable functional group, and specific examples thereof include an alkoxy group such as a methoxy group, an ethoxy group and a methoxyethoxy group, a halogen group such as a chloro group and a bromo group, and an acyloxy group.

Specific examples of the silane compound include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, methacryl Oxypropyl dialkoxymethylsilane, γ-glycidoxypropyl trialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyl trialkoxysilane, mercaptopropyl trialkoxysilane, γ-aminopropyl trialkoxysilane, N-β (Aminoethyl) -γ-aminopropylmethyldialkoxysilane and the like.

The component E may be used as a mixture of two or more kinds.

The amount of the component (E) is from 20 to 60 of the total composition.
% By weight. That is, if it is less than 20% by weight, the adhesion to the inorganic vapor deposition film tends to be insufficient. On the other hand, if it exceeds 60% by weight, it is not preferable because it causes cracks in the cured film.

In the coating composition of the present invention, it is effective to further add a phenolic antioxidant to the above-mentioned main component. Specific examples include 2,6-di-t-butyl-4-methylphenol, 2,2′-methylenebis- (4-methyl-6-t-butylphenol),
2'-methylenebis- (4-ethyl-6-t-butylphenol), 4,4'-methylenebis- (2,6-di-
t-butylphenol), 1,3,5-trimethyl-
2,4,6-tris- (3,5-di-t-butyl-4-
(Hydroxybenzyl) benzene, tris- (2-methyl-4-hydroxy-5-t-butylphenyl) -butane, 4,4′-thiobis (3-methyl-6-t-butylphenol), 4,4′-thiobis (2-methyl-6-
t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate], 2,4-bis-
(N-octylthio) -6- (4-hydroxy-3,5
-Di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N,
N'-hexamethylenebis (3,5-di-t-butyl 4
-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-
2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-
Ethyl butyl-4-hydroxybenzylphosphonate) calcium, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, octylated diphenylamine, 2,4-bis [(octylthio) methyl] —O-cresol and the like. Among them, the thiobisphenol-based antioxidant exhibits the most effect in the present invention.

In the present invention, it is also useful to add a polyfunctional epoxy compound as a dyeing component. Multifunctional epoxy compounds are widely used for paints, adhesives, casting, and the like.For example, polyolefin epoxy resins synthesized by a peroxide method, cyclopentadiene oxide, cyclohexene oxide, or hexahydrophthalic acid And alicyclic epoxy resins such as polyglycidyl esters obtained from epichlorohydrin and polyphenols such as bisphenol A, catechol, and resorinol, or (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, glycerin, trimethylolpropane, Polyglycidyl ether obtained from polyhydric alcohols such as pentaerythritol, diglycerol and sorbitol and epichlorohydrin, epoxidized vegetable oil, novolak phenolic resin and epichlorohydrin Epoxy novolaks obtained from phosphorus, epoxy resins obtained from phenolphthalein and epichlorohydrin, copolymers of glycidyl methacrylate and methyl methacrylate acrylic monomers or styrene, and the above epoxy compounds and monocarboxylic acid-containing (meth) acrylic acid And epoxy acrylates obtained by a glycidyl group ring-opening reaction.

Specific examples of the polyfunctional epoxy compound include 1,6-hexanediol diglycidyl 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, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether,
Tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl ether of neopentyl glycol hydroxyhivalic acid ester, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl Ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, Aliphatic epoxy compounds such as rubitol tetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, isophorone diol diglycidyl ether, bis-2 Alicyclic epoxy compounds such as 1,2-hydroxycyclohexylpropane diglycidyl ether, resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, ortho phthalic acid diglycidyl ester, phenol novolak polyglycidyl And aromatic epoxy compounds such as ether and cresol novolak polyglycidyl ether.

Among the above, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, tris (2- Aliphatic epoxy compounds such as triglycidyl ether of (hydroxyethyl) isocyanurate are particularly preferred.

Further, in order to adjust the refractive index of the cured film or to further improve the durability of the cured film, the general formula is Si (O
The addition of tetrafunctional silane compound represented by R) ₄ are also useful. Specific examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, tetraallyloxysilane, tetrakis (2-methoxyethoxy) silane, tetrakis ( 2-ethylbutoxy) silane, tetrakis (2-ethylhexyloxy) silane and the like. These may be used alone or as a mixture of two or more. Further, it is preferable to use them after hydrolysis in the absence of a solvent or in an organic solvent such as an alcohol in the presence of an acid.

The coating composition thus obtained can be used after being diluted with a solvent, if necessary. As the solvent, solvents such as alcohols, esters, ketones, ethers, and aromatics are used.

The coating composition of the present invention may contain a small amount of a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a disperse dye, an oil-soluble dye, a fluorescent dye, Addition of a pigment, a photochromic compound, a light- and heat-resistant stabilizer such as a hindered amine / hindered phenol compound or the like can also improve the coating properties of the coating solution and the performance of the cured film after curing.

Further, in applying the coating composition, the surface of the substrate is previously treated with an alkali, an acid, a surfactant, an inorganic or organic material for the purpose of improving the adhesion between the plastic lens substrate and the cured film. It is effective to perform a polishing treatment, a primer treatment or a plasma treatment with fine particles.

Further, as a coating and curing method, a coating liquid is applied by a dipping method, a spinner method, a spray method or a flow method, and then heated and dried at a temperature of 40 to 200 ° C. for several hours to form a cured film. can do. In particular, for a plastic lens substrate having a heat deformation temperature of less than 100 ° C., a spinner method that does not require fixing the lens substrate with a jig is preferable.

In the present invention, the pH of the coating solution
Is preferably 4.5 to 6.5. That is, when the pH is less than 4.5, the pot life of the coating liquid is shortened,
Productivity decreases. If it exceeds 6.5, the scratch resistance is reduced. In the present invention, the pH of the coating liquid is a measured value after diluting the coating liquid ten times with pure water.

It is also useful to add a curing catalyst for silanol or epoxy compound.

Preferred curing catalysts include perchloric acids such as perchloric acid, ammonium perchlorate and magnesium perchlorate, Cu (II), Zn (II), Co (II) and Ni (I
I), Be (II), Ce (III), Ta (III), Ti (I
II), Mn (III), La (III), Cr (III), V (I
II), Co (III), Fe (III), Al (III), Ce
(IV), amino acids such as acetylacetonate, amine and glycine having a central metal atom such as Zr (IV) and V (IV), Lewis acids, and organic acid metal salts. Among these, the most preferred curing catalysts include magnesium perchlorate and acetylacetonate of Al (III) and Fe (III). The amount of addition is 0.01-5.
It is desirable to be within the range of 0%.

The thickness of the cured film is 0.05 to
It is preferably 30 μm. That is, if the thickness is less than 0.05 μ, basic performance is not obtained, and if it exceeds 30 μ, the surface smoothness is impaired and optical distortion occurs, which is not preferable.

The coating method includes a dipping method and a spray method.
Method, roll coat method, spin coat method, flow coat method and the like.

As a method for forming an anti-reflection film made of an inorganic substance on the surface of the cured film thus obtained, a vacuum deposition method, an ion plating method, a sputtering method and the like can be mentioned. In the vacuum evaporation method, an ion beam assist method in which an ion beam is simultaneously irradiated during the evaporation may be used. Also, as the film configuration,
Either a single-layer antireflection film or a multilayer antireflection film may be used.

Specific examples of the inorganic substance used include Si
O ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ ,
Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO, Y ₂
O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like can be mentioned. These inorganic substances are used alone or as a mixture of two or more.

When forming the antireflection film, it is desirable to perform a surface treatment on the cured film. Specific examples of the surface treatment include an acid treatment, an alkali treatment, an ultraviolet irradiation treatment, a plasma treatment by a high-frequency discharge in an argon or oxygen atmosphere, and an ion beam irradiation treatment with argon, oxygen or nitrogen.

Hereinafter, the present invention will be described in more detail with reference to examples.

[0060]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of Plastic Lens Substrate Consisting of 60 g of a prepolymer represented by the following general formula 10, 30 g of a prepolymer represented by the following general formula 11, and 10 g of dibenzyl fumarate 3 g of diisopropyl peroxydicarbonate was mixed with the raw material monomer to obtain a raw material monomer composition. The obtained raw material monomer composition is poured into a mold prepared by fixing two glass plates with an adhesive tape, and the curing temperature is reduced from 40 ° C. to 90 ° C. in a constant temperature bath.
Heated to 20 ° C over 20 hours. After the heating, the cured plastic lens substrate was taken out of the mold and subjected to an annealing treatment at 120 ° C. for 2 hours.

[0062]

Embedded image

[0063]

Embedded image

(2) Preparation of coating composition 826.5 g of methanol, 824.6 g of 1,4-dioxane
5 g, methyl cellosolve-dispersed titanium dioxide-iron trioxide-
Silicon dioxide composite fine particle sol (solid content concentration 20% by weight)
5483 g and 1700 g of γ-glycidoxypropyltrimethoxysilane were mixed. Add 0.05 to this mixture
720 g of N hydrochloric acid aqueous solution was added dropwise with stirring, and 4 g of
The mixture was aged for 24 hours after stirring for an hour. After adding 45 g of a 1 wt% aqueous sodium hydroxide solution to this solution, 10.5 g of magnesium perchlorate, 3 g of a silicon-based surfactant (trade name “L-7001” manufactured by Nippon Unicar Co., Ltd.) and a phenolic antioxidant ( 12.5 g of Kawaguchi Chemical Industry Co., Ltd., trade name "ANTAGE W-400") was added, and the mixture was stirred for 4 hours and aged all day and night to obtain a coating liquid. (3) Coating and curing The plastic lens substrate obtained in the above (1) is added with 40
After surface treatment with 5% by weight aqueous solution of caustic soda at
The coating composition obtained in the above (2) was applied by a dipping method. The lifting speed was 18 cm / min.
After the application, the resultant was air-dried at 80 ° C. for 20 minutes and baked at 125 ° C. for 100 minutes. The thickness of the cured film thus obtained was about 2 microns.

(4) Formation of anti-reflection thin film After the lens obtained by the above method is subjected to plasma treatment (argon plasma 400 W × 60 seconds), SiO ₂ , ZrO ₂ , SiO ₂ are sequentially transferred from the substrate to the atmosphere. ₂ , Zr
An antireflection multilayer film composed of five layers of O ₂ and SiO ₂ was formed by a vacuum evaporation method. The optical thickness of each layer is
The iO ₂ layer, the next equivalent film layer of ZrO ₂ and SiO ₂ , the next ZrO ₂ layer, and the uppermost SiO ₂ layer were each formed to have λ / 4. The design wavelength λ was 520 nm.

(5) Test and Evaluation Results Each of the lenses obtained by the above-described methods was tested by the following method, and the results are shown in Table 1.

Appearance: The presence or absence of coloring of an unstained lens (white lens) was visually evaluated.

Transmittance: The average transmittance of visible light of an unstained lens (white lens) was measured with a spectrophotometer.

Interference fringes: Regarding the presence or absence of occurrence of interference fringes,
The light of the fluorescent lamp was reflected on the lens surface while the background was blackened, and the occurrence of a rainbow pattern due to light interference was visually observed. The judgment was made as follows.

：: no rainbow pattern is observed Δ: slight rainbow pattern is observed ×: clear rainbow pattern is observed Scratch resistance: load of 1 k with # 0000 steel wool
The state of the cured film after 10 reciprocations at g / cm ² was examined.

○: scarcely scratched △: slightly scratched ×: many scratches Adhesion: After immersion in warm water of 70 ° C. for 2 hours, 11 lenses were scribed vertically and horizontally on the lens surface at 1 mm intervals each Was made to form 100 squares, and the number of squares remaining without peeling of the cured film after adhesion and peeling of the cellophane tape was determined.

Weather resistance: After exposure for 150 hours using a xenon long life fade meter (manufactured by Suga Test Instruments Co., Ltd.), the following evaluation was performed.

A. Appearance: The presence or absence of coloring of an unstained lens (white lens) was visually evaluated.

B. Transmittance: After the test, the average transmittance of visible light of an unstained lens (white lens) was measured with a spectrophotometer.

C. Adhesion: A cross-cut tape test similar to that described above was performed on the exposed surface of the lens after the test.

Heat resistance The lens framed in a metal frame was placed in a constant temperature bath at 80 ° C. for 30 minutes and cooled to room temperature, and the degree of film cracking was examined.

：: Almost no film cracks ：: Some film cracks X: Many film cracks Example-2 (1) Preparation of Plastic Lens Substrate 50 g of prepolymer represented by the above general formula 10 2.5 g of diisopropyl peroxydicarbonate was mixed with 20 g of the prepolymer represented by the general formula 11 and 30 g of bis (2-chlorobenzyl) fumarate to obtain a raw material monomer composition. The obtained raw material monomer composition was poured into a mold formed by fixing two glass plates with an adhesive tape, and was heated in a thermostat from 40 ° C. to 90 ° C. over 20 hours. .
After the heating, the cured plastic lens substrate was taken out of the mold and subjected to an annealing treatment at 120 ° C. for 2 hours.

(2) Preparation of coating composition 350 g of butyl cellosolve, 8 g of a 1 wt% aqueous sodium hydroxide solution, 445 g of cerium dioxide-titanium dioxide-silicon dioxide composite fine particle sol (solid content concentration: 20 wt%) dispersed in methyl cellosolve, and colloidal dispersion of methyl cellosolve After mixing 22.5 of silica (solid content: 30 wt%), 106 g of γ-glycidoxypropyltrimethoxysilane and 39 g of γ-glycidoxypropylmethyldimethoxysilane were mixed. Add 0.05N to this mixture
38 g of an aqueous hydrochloric acid solution was added dropwise with stirring, and the mixture was stirred for 4 hours.
5g, silicone surfactant (manufactured by Nippon Unicar Co., Ltd.
Add 0.3 g of trade name "FZ-2110") and 1.2 g of phenolic antioxidant (trade name "Seanox 226M" manufactured by Cipro Kasei Co., Ltd.) And

(3) Coating and Curing The coating liquid obtained as described above was applied to the plastic lens substrate obtained in the above (1) by a spinner method.

The coating conditions are as follows.

Rotation speed: 500 rpm for 10 seconds (coating liquid is applied during this time) Rotation speed: 2,000 rpm for 1 second Rotation speed: 500 rpm for 5 seconds
Baking was performed for minutes. The thickness of the cured film thus obtained was about 2.3 microns.

(4) Formation of Antireflection Thin Film After the lens obtained by the above method is subjected to plasma treatment (argon plasma 400 W × 60 seconds), ZrO ₂ , SiO ₂ , ZrO are sequentially transferred from the substrate to the atmosphere. ₂ , Si
An antireflection multilayer film composed of four layers of O ₂ was formed by a vacuum evaporation method. The optical film thickness of each layer is as follows: the first equivalent film layer of ZrO ₂ and SiO ₂ , the next ZrO ₂ layer, and the uppermost Si layer.
The O ₂ layers were formed so as to be λ / 4 each. The design wavelength λ was 520 nm.

(5) Test and Evaluation Results The lenses thus obtained were tested in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 (1) Preparation of Plastic Lens Substrate 80 g of the prepolymer represented by the general formula 10, 10 g of the prepolymer represented by the general formula 11, and bis (2-chlorobenzyl) 2 g of diisopropyl peroxydicarbonate as raw material monomer consisting of 10 g of malate
Were mixed to obtain a raw material monomer composition. The obtained raw material monomer composition is poured into a mold prepared by fixing two glass plates with an adhesive tape, and the curing temperature is set to 40 in a constant temperature bath.
Heated from ℃ to 90 ℃ over 20 hours. After the heating, the cured plastic lens substrate was taken out of the mold and subjected to an annealing treatment at 120 ° C. for 2 hours.

(2) Preparation of Coating Composition After mixing 400 g of isopropyl cellosolve, 68 g of pure water and 325 g of methanol-dispersed tin dioxide-tungsten dioxide composite fine particle sol (solid content concentration: 30 wt%), γ-methacryloxypropyltrimethoxysilane 1
15 g and γ-glycidoxypropyltrimethoxysilane 22 g were mixed. 38 g of a 0.1N hydrochloric acid aqueous solution was added dropwise to this mixture with stirring. After further stirring for 5 hours, the mixture was aged all day long. To this liquid, 28 g of trimethylolpropane diglycidyl ether, 1.2 g of Fe (III) acetylacetonate, 0.3 g of a silicon-based surfactant (trade name “L-7604” manufactured by Nippon Unicar Co., Ltd.) and hindered Phenolic antioxidant (trade name “Irganox 1222”, manufactured by Ciba-Geigy Japan)
5 g was added, and the mixture was stirred for 4 hours and then aged all day and night to obtain a coating solution.

(3) Coating and Curing The coating liquid obtained in this manner was applied to the plastic lens substrate obtained in the above (1) by a spinner method. The coating conditions were the same as in Example-2.

After air-drying at 80 ° C. for 15 minutes after application, 13
The firing was performed at 0 ° C. for 2 hours. The thickness of the cured film thus obtained was about 2.1 microns.

(4) Formation of anti-reflection thin film The lens obtained by the above method was prepared by mixing ZrO ₂ of Example 1 with a mixture of ZrO ₂ and Ti oxide (ZrO ₂ / Ti oxide =
65/35 (weight ratio)), except that the antireflection film was formed in the same manner.

(5) Test and Evaluation Results The lenses thus obtained were tested by the same method as in Example 1, and the results are shown in Table 1.

Example-4 (1) Preparation of Plastic Lens Substrate 70 g of the prepolymer represented by the general formula 10, 20 g of the prepolymer represented by the general formula 11, and bis (2-bromobenzyl) 2.5 g of diethylene glycol bisallyl carbonate was mixed with a raw monomer composed of 10 g of fumarate to obtain a raw monomer composition. The obtained raw material monomer composition was poured into a mold formed by fixing two glass plates with an adhesive tape, and was heated in a thermostat from 40 ° C. to 90 ° C. over 20 hours. . After the heating, the cured plastic lens substrate was taken out of the mold and subjected to an annealing treatment at 120 ° C. for 2 hours.

(2) Preparation of Coating Composition After mixing 421 g of methyl cellosolve, 112 g of a 1 wt% aqueous sodium hydroxide solution and 330 g of an aqueous dispersion of antimony pentoxide fine particle sol (solid content concentration: 30 wt%), γ-
Glycidoxypropylmethyldimethoxysilane 31 g,
γ-glycidoxypropyltrimethoxysilane 120 g
And 38 g of tetramethoxysilane. 61 g of a 0.1N aqueous hydrochloric acid solution was added dropwise to this mixed solution with stirring, and the mixture was stirred for 4 hours and then aged for 24 hours. To this solution, 4 g of stannous chloride, 0.2 g of a silicon-based surfactant (manufactured by Big Chemie Co., Ltd .; trade name "BYK-300") and a hindered phenol-based antioxidant (manufactured by Nippon Ciba Geigy Co., Ltd.) Name "Ilganox 1010") 1.5
g was added, and the mixture was stirred for 4 hours and then aged all day long to obtain a coating solution.

(3) Coating and curing The coating liquid obtained in this manner was applied to the plastic lens substrate obtained in the above (1) by a spray method.

The spray was performed using Iwata Weider 61 (nozzle diameter: 1 mm) at a spray pressure of 3 kg / cm 2.
The test was performed at a paint discharge rate of 100 ml / min.

After air-drying at 80 ° C. for 10 minutes after application, 130
Calcination was performed at 2 ° C. for 2 hours. The thickness of the cured film thus obtained was about 4 microns, and both the appearance and the dyeability were excellent.

(4) Formation of anti-reflection thin film After subjecting the lens obtained in the above (3) to an ion beam irradiation treatment with an oxygen gas (acceleration voltage: 500 V × 60 seconds), SiO 2 is sequentially applied from the substrate to the atmosphere. ₂ , ZrO ₂ ,
An anti-reflection multilayer film composed of five layers of SiO ₂ , TiO ₂ , and SiO ₂ was formed by a vacuum evaporation method. At this time, a fourth layer of TiO2 was formed by ion beam assisted evaporation. The optical film thickness of each layer is as follows: first SiO ₂ , next Z
The equivalent film layer of rO ₂ and SiO ₂ is λ / 4, and the TiO ₂ layer is λ /
2. The uppermost SiO2 layer was formed to have a wavelength of λ / 4.
The design wavelength λ was 520 nm.

(5) Test and Evaluation Results The lenses thus obtained were subjected to tests in the same manner as in Example 1, and the results are shown in Table 1.

Example-5 (1) Preparation of Plastic Lens Substrate Consisting of 65 g of the prepolymer represented by the general formula 10, 30 g of the prepolymer represented by the general formula 11, and 5 g of dibenzyl fumarate 4 g of dinormal propyl peroxydicarbonate was mixed with the starting monomer to obtain a starting monomer composition. The obtained raw material monomer composition is poured into a mold formed by fixing two glass plates with an adhesive tape, and the curing temperature is reduced from 40 ° C. to 90 ° C. in a constant temperature bath.
Heated to 20 ° C over 20 hours. After the heating, the cured plastic lens substrate was taken out of the mold and subjected to an annealing treatment at 120 ° C. for 2 hours.

(2) Preparation of coating composition 3111 g of butyl cellosolve, 4590 g of sol of methanol-dispersed titanium dioxide-zirconium dioxide-silicon dioxide composite fine particles (solid content concentration: 20% by weight), 283 g of γ-glycidoxypropyltrimethoxysilane and γ- Glycidoxypropylmethyldimethoxysilane 1130 g
Was mixed. This mixed solution is added with a 0.05N aqueous hydrochloric acid solution 275
g was added dropwise with stirring, and after further stirring for 4 hours, the mixture was aged all day and night. To this solution, 587 g of glycerol diglycidyl ether and 27 parts of Fe (III) acetylacetonate were added.
g, 3 g of a silicon surfactant (trade name “L-7001” manufactured by Nippon Unicar Co., Ltd.) and a thiobisphenol antioxidant (trade name “Antage Crystal” manufactured by Kawaguchi Chemical Industry Co., Ltd.) 5 g was added, and the mixture was stirred for 4 hours and then aged all day and night to obtain a coating solution.

(3) Coating and curing The plastic lens substrate obtained in the above (1) was subjected to an alkali treatment, and then the coating composition obtained in the above (2) was applied by a dipping method. . The lifting speed was 20 cm / min. After the application, it was air-dried at 95 ° C. for 30 minutes, and then baked at 130 ° C. for 120 minutes. The thickness of the cured film thus obtained was about 2 microns.

(4) Formation of Antireflection Thin Film The lens obtained by the above method was provided with an antireflection film in the same manner as in Example-1.

(5) Test and Evaluation Results The lenses thus obtained were tested in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example-1 (1) Preparation of Plastic Lens Base Material 3.5 g of diisopropyl peroxydicarbonate was mixed with a raw material monomer composed of 47.5 g of diallyl terephthalate, 20 g of benzyl methacrylate, and 30 g of diethylene glycol bis (allyl carbonate). Thus, a raw material monomer composition was obtained. The obtained raw material monomer composition is poured into a mold prepared by fixing two glass plates with an adhesive tape, and the curing temperature is reduced from 40 ° C. to 90 ° C. in a constant temperature bath.
Heated to 20 ° C over 20 hours. After the heating, the cured plastic lens substrate was taken out of the mold and subjected to an annealing treatment at 120 ° C. for 2 hours.

(2) Application and Curing of Coating Composition The same coating composition as in Example 1 was applied and cured on the obtained plastic lens substrate by the same method.

(3) Formation of antireflection film An antireflection film was formed in the same manner as in Example-1.

Comparative Example 2 (1) Preparation of Plastic Lens Substrate 60 g of diallyl isophthalate, allyl benzoate 2
0 g and 20 g of propylbenzylmalate were mixed with 3 g of diisopropyl peroxydicarbonate to obtain a raw monomer composition. The obtained raw material monomer composition was poured into a mold formed by fixing two glass plates with an adhesive tape, and was heated in a thermostat from 40 ° C. to 90 ° C. over 20 hours. . After the heating, the cured plastic lens substrate was taken out of the mold and subjected to an annealing treatment at 120 ° C. for 2 hours.

(2) Application and Curing of Coating Composition The same coating composition as in Example 3 was applied and cured on the obtained plastic lens substrate by the same method.

(3) Formation of antireflection film An antireflection film was formed in the same manner as in Example-2.

Comparative Example-3 (1) Preparation of Coating Composition 3111 g of butyl cellosolve, 4590 g of water-dispersed alumina sol, 283 g of γ-glycidoxypropyltrimethoxysilane and 1130 g of γ-glycidoxypropylmethyldimethoxysilane were mixed. To this mixture, 275 g of 0.05N hydrochloric acid aqueous solution was added dropwise while stirring,
After further stirring for 4 hours, the mixture was aged for one day. To this solution, 587 g of glycerol diglycidyl ether, Fe (III)
27 g of acetylacetonate, silicon surfactant (trade name "L-7001" manufactured by Nippon Unicar Co., Ltd.) 3
g and thiobisphenol-based antioxidant (trade name “Antage Crystal” manufactured by Kawaguchi Chemical Industry Co., Ltd.)
5 g was added, and the mixture was stirred for 4 hours and then aged all day long to obtain a coating solution.

(2) Coating and Curing The same plastic lens substrate as in Example 1 was subjected to an alkali treatment, and then the coating composition obtained in the above (1) was applied by a dipping method. The lifting speed is
20 cm / min. After the application, it was air-dried at 95 ° C. for 30 minutes, and then baked at 130 ° C. for 120 minutes. The thickness of the cured film thus obtained was about 2 microns.

(3) Formation of Anti-Reflection Thin Film An anti-reflection film was provided on the lens obtained by the above method in the same manner as in Example-1.

(4) Test and Evaluation Results The lenses thus obtained were subjected to tests in the same manner as in Example 1, and the results are shown in Table 1.

[0112]

[Table 1]

[0113]

According to the present invention, a cured film excellent in appearance without interference fringes due to a difference in refractive index between the substrate lens and the cured film is formed by forming the cured film most suitable for the plastic lens substrate. You can get a plastic lens with. Further, it is possible to provide a plastic lens for a spectacle with a cured film which is particularly excellent in heat resistance and weather resistance as compared with conventional plastic lenses.

Claims (3)

[Claims] 1. A plastic lens substrate obtained by polymerizing a raw material monomer containing 40 to 89% by weight of the following component A, 10 to 59% by weight of component B, and 1 to 30% by weight of component C, A plastic film provided with a cured film obtained by applying and curing the coating composition containing the D component and the E component as main components. A. A diallyl phthalate prepolymer represented by the following general formula 1 B. Dialkylene glycol bisallyl carbonate prepolymer represented by the following general formula 2: C. Vinyl compound represented by the following general formula 3 D. Si, Sn, Sb,
Fine particles comprising at least one metal oxide selected from Ce, Zr, Ti and / or Si, Al, Sn, Sb,
Ta, Ce, La, Fe, Zn, W, Zr, In, Ti
Composite fine particles composed of two or more metal oxides selected from E. Organosilicon compound represented by the following general formula 4 2. The plastic lens with a cured film according to claim 1, wherein the D component is fine particles made of a metal oxide of Ti and / or composite fine particles containing at least a metal oxide of Ti. 3. A plastic lens with a cured film, wherein an antireflection film made of an inorganic substance is laminated on the surface of the plastic lens with a cured film according to claim 1.