JP2983237B2 - High refractive index plastic lens - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a high refractive index plastic lens having excellent heat resistance used for various optical lenses such as spectacle lenses and camera lenses.

[Prior Art] In recent years, there has been an increasing demand for plastic lenses, for example, as spectacle lenses in Japan and overseas. As a plastic lens used in recent years, a lens made of a cast resin of diethylene glycol bisallyl carbonate (hereinafter abbreviated as DAC) is generally used. The characteristics of DAC resin are that it is lighter than glass, hard to break, and has excellent dyeability.
It can meet the rich fashion needs of combining color lenses with the current large frame. However, DAC resin (hereinafter abbreviated as N _D) a refractive index of 1.500, for low compared to N _D 1.523 glass spectacle lenses, especially when the lens power is strong, so the thicker was forced to give without user lenses Not preferred.

On the other hand, N _D than DAC resin lens is a polyurethane lens is known as a relatively high refractive index plastic lens and from 1.56 to 1.64. As this polyurethane lens,
For example, in JP-A-63-46213, a polyurethane lens comprising a polymer of a xylylene diisocyanate compound and a polythiol having a mercaptopropionate group has been proposed.
It is widely used in optical lenses such as eyeglass lenses.

[Problems to be Solved by the Invention] However, the polyurethane lens proposed in JP-A-63-46213 generally has poor heat resistance as compared with a radical polymerization type resin of an olefin group, for example, a DAC resin. During post-processing such as dyeing or surface coating of a lens which usually requires thermal processing at about 60 to 90 ° C., there is a disadvantage that the lens is likely to be deformed and the thermal processing temperature must be kept low.

Therefore, an object of the present invention is to provide a degree of freedom in selecting thermal conditions in post-processing such as dyeing and surface coating of a polyurethane lens having a low heat resistance, which comprises a polymer of a xylylene diisocyanate compound and a polythiol having a mercaptopropionate group. Another object of the present invention is to provide a high-refractive-index plastic lens having improved heat resistance.

[Means for Solving the Problems] The present invention has been made to solve the above problems, and (a) general formula (I) (Wherein, R represents a hydrogen atom or a methyl group, X is at least one selected from a chlorine atom, a bromine atom, a methyl group and an ethyl group, a represents an integer of 0 to 4, and b represents 2
At least one kind of polyisocyanate represented by the following general formula (II): (Wherein, R represents a methyl, ethyl, chloromethyl or bromomethyl group, m represents an integer of 0 to 2, and n represents (4
(M) an integer of at least one polythiol represented by the following formula: (c) p (p = 0 or an integer of 1 or more) hydroxyl groups and q (q = 1 or more) mercapto A total number of hydroxyl groups and mercapto groups (p + q) is 3 or more,
An aliphatic thiol compound in which the number of carbon atoms interposed between the most distant hydroxyl group or mercapto group and the hydroxyl group or mercapto group is 6 or less, monothioglycerol,
Dimercaptopropanol, 1-mercaptomethyl 1,1
-Dihydroxymethylpropane, 1,4-dimercapto-
At least one aliphatic thiol compound selected from mercapto-substituted products of 2,3-hydroxybutane and pentaerythritol and mercapto-substituted products of sorbitol (II
It is a high refractive index plastic lens obtained by polymerizing a monomer mixture containing at least one of I).

 Hereinafter, the present invention will be described in detail.

The compound represented by the general formula (I) in the present invention is specifically o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, tetramethyl-p-xylylene diisocyanate,
Tetramethyl-m-xylylene diisocyanate, and nucleated chlorides, bromides, methylated or ethylated products thereof, such as 4-chloro-m-xylylene diisocyanate, 4,5-dichloro-m-xylylene diisocyanate, Examples thereof include 2,3,5,6-tetrabromo-p-xylylene diisocyanate, 4-methyl-m-xylylene diisocyanate, and 4-ethyl-m-xylylene diisocyanate.

The compound represented by the general formula (II) is specifically,
Pentaerythritol tetrakis (mercaptopropionate), trimethylolpropane tris (mercaptopropionate), trimethylolethanetris (mercaptopropionate), dichloroneopentyl glycol bis (mercaptopropionate), dibromoneopentyl glycol bis ( Mercaptopropionate)
And the like.

It has p (p = 0 or an integer of 1 or more) hydroxyl groups and q (q = 1 or an integer of 1 or more) mercapto groups, and the total number of hydroxyl groups and mercapto groups (p + q) is 3 or more. ,
Aliphatic thiol compounds (III) interposed between the most distant hydroxyl group or mercapto group and the hydroxyl group or mercapto group and having 6 or less carbon atoms include monothioglycerol, dimercaptopropanol, 1-mercaptomethyl
It is limited to 1,1-dihydroxymethylpropane, 1,4-dimercapto-2,3-hydroxybutane, mercapto-substituted pentaerythritol and mercapto-substituted sorbitol. These compounds may be used alone or as a mixture. The compound (III) is used in an amount of 10 to 90 equivalent percent based on the polythiol represented by the general formula (II). The reason is that this compound (II
I) is 10 to the polythiol represented by the general formula (II).
When the amount is less than the equivalent percentage, a sufficient improvement in heat resistance cannot be obtained, and when the amount exceeds 90 equivalent percentage, the polymerization reaction runs away and optical distortion occurs in the obtained lens.

Compounds other than the compound (III) described above, for example, divalent thiols such as dimercaptopropane, mercaptohydroxyethane, dimercaptoethane, and dimercaptopropane; monovalent thiols such as mercaptopropane and mercaptoethane; trihydroxybutane; It is not preferable to use a trihydric or higher alcohol containing no mercapto group, such as hydroxypentane and tetrahydroxyhexane. The reason is that even if a lens is produced using a compound other than the compound (III) in a monomer mixture of the compound of the general formula (I) and the compound of the general formula (II), the heat resistance is not improved, Further, the refractive index is lowered, the reaction runs away during polymerization, and optical distortion or pulse occurs in the obtained lens.

At least one kind of polyisocyanate represented by formula (I), at least one kind of polythiol represented by formula (II), and an aliphatic thiol compound (II
The proportion of at least one type of (I) used is -NCO / (-S
H + -OH) in the range 0.5-3.0, preferably 0.5-1.
The range is 5.

Further, in the present invention, a polymerization catalyst for accelerating the polymerization reaction, and also an ultraviolet absorber for improving weather resistance, an antioxidant,
Additives such as a coloring inhibitor, a fluorescent dye, a light stabilizer and an oil-soluble dye may be added as needed. Furthermore, the resin of the present invention can be easily dyed in water or a solvent using a usual disperse dye. At the time of dyeing, a carrier as a dyeing assistant may be added to the dyeing bath to further facilitate the dyeing.

The production of the lens of the present invention is performed by combining at least one kind of the polyisocyanate represented by the general formula (I) with the general formula (I)
At least one kind of polythiol represented by I),
If necessary, an additive is added to a monomer mixture containing at least one or more aliphatic thiol compound (III), and a known casting polymerization method, that is, a glass or metal mold and a resin gasket are used. This is performed by injecting the mixture into the combined mold and heating and curing the mixture. At this time, in order to facilitate removal of the resin after molding, the mold may be treated with a release agent, or a release agent may be added to the monomer.

As the polymerization temperature in the casting polymerization, the initial temperature is 5 to 5.
The temperature is preferably in the range of 40 ° C, and the temperature is preferably raised to 100 to 130 ° C over 10 to 70 hours. If the initial temperature is lower than 5 ° C., the polymerization time is unnecessarily long, and if the initial temperature is higher than 40 ° C., the obtained lens tends to be optically non-uniform. Further, if the final temperature is less than 100 ° C, unreacted substances tend to remain and the degree of polymerization is reduced, and various physical properties such as refractive index and surface hardness are reduced.If the final temperature exceeds 130 ° C, the obtained lens is yellowed. I do.

In the plastic lens of the present invention, a hard coat film and / or a multilayer antireflection film can be provided on the lens substrate as needed.

The hard coat film formed on the lens substrate is preferably composed of an organosilicon polymer, and the organosilicon polymer-based hard coat film is formed from a compound group having the following general formula and / or a hydrolyzate thereof. It can be obtained by forming a layer made of a compound selected from the group consisting of a compound on a lens substrate by a dipping method, a coating method, and the like, followed by curing.

Formula (R ₁ ) _a (R ₂ ) _b Si (OR ₃ ) _{4- (a + b)} (where R ₁ and R ₂ are an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkyl halide, , An organic group having an aryl, alkenyl, or epoxy group, a (meth) acryloxy group, a mercapto group, or a cyano group
Which is bonded to silicon by a Si-C bond;
₃ is an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group or an acyl group, and a and b are 0, 1 or 2
And a + b is 1 or 2. Examples of these compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxy Silane, γ-chloropropyltripropoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycid (Xyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl)
Ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane γ-mercaptopropyltrimethoxy Silane, γ-mercaptopropyltriethoxysilane, N-
trialkoxy or triacyloxysilanes such as β (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane , Γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, γ-chloropropylmethyldimethoxysilane , Γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane , Γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, dialkoxysilane such as methylvinyldimethoxysilanemethylvinyldiethoxysilane or And diacyloxysilanes.

These organosilicon compounds can be used alone or in combination of two or more.

Furthermore, various tetraalkoxysilanes or hydrolysates thereof can be used in combination with the above-mentioned organosilicon compound, although they are not used alone.

Examples of such tetraalkoxysilanes include:
Examples include methyl silicate, ethyl silicate, n-propyl silicate, isopropyl silicate n-butyl silicate, sec-butyl silicate and t-butyl silicate.

Further, these organosilicon compounds can be cured without a catalyst, but various catalysts can be used to further promote the curing.

Examples of such a catalyst include Lewis acids, various acids or bases including Lewis acid salts, or organic carboxylic acids, chromic acid, hypochlorous acid, boric acid, bromate selenite, thiosulfuric acid, orthosilicic acid, thiocyanic acid And metal salts such as nitrous acid, aluminate and carbonic acid, particularly alkali metal salts or ammonium salts, and alkoxides of aluminum, zirconium or titanium, or complex compounds thereof.

Furthermore, it is also possible to use the above-mentioned organosilicon polymer and another organic substance in combination.Examples of the other organic substance to be used in combination include an epoxy resin, an acrylic copolymer, and a hydroxyl group-containing polymer such as polyvinyl alcohol. .

In addition, as other excipients, Sika as disclosed in Optica Actor (July 1962, p. 251)
It is possible to use colloidal sols of inorganic oxides such as i, Al, Ti, and Sb.Furthermore, it is also possible to use solvents and various additives that keep a good storage state in order to facilitate coating work. is there.

The multilayer antireflection film provided on the lens substrate is formed by alternately laminating a low-refractive-index film and a high-refractive-index film.As the high-refractive-index film, a metal oxide containing tantalum, zirconium, and yttrium is used. Those using a mixed vapor deposition film are preferable. As the low refractive index film, it is particularly preferable to use a silicon dioxide (SiO ₂ ) film from the viewpoint of heat resistance.

A mixed vapor deposition film of a metal oxide containing tantalum, zirconium and yttrium is formed by mixing zirconium oxide (ZrO ₂ ) powder, tantalum oxide (Ta ₂ O ₅ powder and yttrium oxide (Y ₂ O ₃ ) powder, Pellets obtained by sintering are preferably deposited by an electron beam heating method, and the composition ratio of a mixed raw material obtained by mixing the respective powders is such that, in terms of molar ratio, ZrO ₂ is 1.0 and Ta is ₂ O ₅ is 0.8 ~
1.8, Y ₂ O ₃ is preferably 0.05 to 0.3.

Mixed deposited film obtained in this way, like the Ta ₂ O _5, is chemically very stable compared with ZrO _2, and has a transparency comparable to ZrO _2. Furthermore, in the refractive index,
For example, it shows a high value of 2.05, which is effective from the viewpoint of film design.

When Ta ₂ O ₅ is less than 0.8 mol or more than 1.8 mol with respect to 1 mol of ZrO ₂ , absorption tends to occur in the obtained mixed vapor-deposited film, and Y ₂ O ₃ exceeds 0.3 mol. Then, the vapor deposition rate is increased, and the resulting mixed vapor-deposited film is easily absorbed, and the vapor deposition raw material is liable to be scattered, making its control difficult.

The film configuration of the multilayer antireflection film is a two-layer film of λ / 2-λ / 4, λ
It is practically good to use a three-layer film of / 4-λ / 4-λ / 4 or λ / 4-λ / 2-λ / 4. It is possible. Here, the first layer λ / 4 film counted from the substrate side of the three-layer film is the above-mentioned mixed vapor-deposited film and SiO ₂
It may be a three-layer symmetric equivalent film using a film or a two-layer composite equivalent film.

In forming the multilayer antireflection film, a method such as a sputtering method using a similar sintered body as a target material or an ion plating method can be used instead of the above-described vacuum deposition method.

By providing a hard coat film and / or a multilayer anti-reflection film on the lens substrate as described above, a thin and lightweight anti-reflective high refractive index plastic lens having heat resistance, An anti-reflective high refractive index plastic lens with improved scratch resistance and optical properties can be obtained without causing deterioration.

Further, the high refractive index plastic lens of the present invention may be subjected to a surface polishing treatment, an antistatic treatment, a light control treatment and the like.

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples.

Example 1 m-xylylene diisocyanate (hereinafter abbreviated as m-XDI) 484 parts by weight pentaerythritol tetrakis (mercaptopropionate) (hereinafter abbreviated as PETMP) 305 parts by weight Dimercaptopropanol (hereinafter abbreviated as DMP) 103 parts by weight Polymerization Dibutyltin dilaurate (DBTL)
0.5 part by weight The mixture consisting of the above four components is stirred at room temperature for 30 minutes and 1 mmHg
The degassed under 60 minutes is poured into a mold composed of a polyethylene gasket and a glass mold, and is then left at 25 ° C. for 5 hours.
5 hours at 40 ° C, 7 hours at 60 ° C, 3 hours at 80 ° C, 12 hours
After polymerization at 0 ° C. for 2 hours, the lens was taken out of the mold. Refractive index of the resulting lens N _D, Abbe number [nu _D, specific gravity, optical distortion, impact resistance and the measurement results of the processability and heat resistance, refractive index N _D is 1.61 as shown in Table 1, the Abbe number [nu _D
Of 36 and a specific gravity of 1.35, and was transparent without optical distortion.
The obtained lens had a center thickness of 1.6 mm, had impact resistance that passed the US FDA standard, had good workability, and had a heat deformation initiation temperature of 107 ° C. indicating heat resistance.

Example 2 A lens was produced in the same manner as in Example 1 using 484 parts by weight of m-XDI, 427 parts by weight of PETMP, 62 parts by weight of DMP and 0.5 parts by weight of DBTL. As a result, N _D is 1.60 as shown in Table 1, [nu _D 36, the specific gravity is
A transparent lens with no optical distortion of 1.35 was obtained. The obtained lens had a center thickness of 1.6 mm, had impact resistance that passed the US FDA standard, had good workability, and had a thermal deformation onset temperature of 97 ° C. showing heat resistance.

Example 3 Tetramethylxylylene diisocyanate (hereinafter referred to as TMXDI
1257 parts by weight PETMP 610 parts by weight Monothioglycerol (hereinafter abbreviated as TG) 180 parts by weight Formate TK-1 (a polymerization catalyst manufactured by Takeda Pharmaceutical Co., Ltd.) 0.5 part by weight and the same as in Example 1 A lens was prepared by the method. As a result, N _D is 1.57 as shown in Table 1, [nu _D 39, the specific gravity is
A transparent lens with no optical distortion of 1.35 was obtained. The obtained lens had a center thickness of 1.6 mm, had impact resistance that passed the US FDA standard, had good workability, and had a heat deformation initiation temperature of 107 ° C. indicating heat resistance.

Example 4 A lens was produced in the same manner as in Example 1 by using 1257 parts by weight of TMXDI, 732 parts by weight of PETMP, 144 parts by weight of TG, and 0.5 parts by weight of Formate TK-1. As a result, N _D is 1.57 as shown in Table 1, [nu _D 39, the specific gravity is 1.
A transparent lens with no optical distortion of 35 was obtained. The obtained lens had a center thickness of 1.6 mm, had impact resistance that passed the US FDA standard, had good workability, and had a heat deformation initiation temperature of 104 ° C. indicating heat resistance.

Example 5 A lens was produced in the same manner as in Example 1 using 1257 parts by weight of TMXDI, 854 parts by weight of PETMP, 108 parts by weight of TG, and 0.5 parts by weight of Form TK-1. As a result, N _D is 1.57 as shown in Table 1, [nu _D 39, the specific gravity is
A transparent lens with no optical distortion of 1.35 was obtained. The obtained lens had a center thickness of 1.6 mm, had impact resistance that passed the US FDA standard, had good workability, and had a heat deformation initiation temperature of 98 ° C. showing heat resistance.

Example 6 A lens was manufactured in the same manner as in Example 1 using 484 parts by weight of m-XDI, 305 parts by weight of PETMP, 90 parts by weight of TG, and 0.3 parts by weight of DBTL. As a result, N _D is 1.59 as shown in Table 1, [nu _D 36, the specific gravity is
A transparent lens with no optical distortion of 1.35 was obtained. The obtained lens had a center thickness of 1.6 mm, had impact resistance that passed the US FDA standard, had good workability, and had a heat deformation onset temperature of 102 ° C. indicating heat resistance.

Example 7 A lens was produced in the same manner as in Example 1 using 484 parts by weight of m-XDI, 366 parts by weight of PETMP, 72 parts by weight of TG, and 0.3 parts by weight of DBTL. As a result, N _D is 1.59 as shown in Table 1, [nu _D 36, the specific gravity is
A transparent lens with no optical distortion of 1.35 was obtained. The obtained lens had a center thickness of 1.6 mm, had impact resistance that passed the US FDA standard, had good workability, and had a heat deformation initiation temperature of 100 ° C. indicating heat resistance.

Example 8 A lens was manufactured in the same manner as in Example 1 using 484 parts by weight of m-XDI, 427 parts by weight of PETMP, 54 parts by weight of TG, and 0.3 parts by weight of DBTL. As a result, N _D is 1.59 as shown in Table 1, [nu _D 36, the specific gravity is
A transparent lens with no optical distortion of 1.35 was obtained. The obtained lens had a center thickness of 1.6 mm, had impact resistance that passed the US FDA standard, had good workability, and had a thermal deformation onset temperature of 97 ° C. showing heat resistance.

Comparative Example 1 A lens was produced using only m-XDI and PETMP without using DMP as a monomer. That is, a lens was produced in the same manner as in Example 1 using 484 parts by weight of m-XDI and 610 parts by weight of PETMP and 0.5 parts by weight of DBTL. As a result, N _D is 1.59 as shown in Table 1, [nu _D 36, the specific gravity is
A transparent lens with no optical distortion of 1.35 was obtained. The obtained lens had a center thickness of 1.6 mm, had impact resistance that passed the U.S. FDA standard, and had good workability. The heat resistance was inferior to the obtained lens.

Comparative Example 2 A lens was prepared using only TMXDI and PETMP without using TG as a monomer. That is, a lens was produced in the same manner as in Example 3 by using 1257 parts by weight of TMXDI, 1220 parts by weight of PETMP, and 0.5 parts by weight of TK-1. As a result, N _D is 1.56 as shown in Table 1, [nu _D of 40, a specific gravity
A transparent lens with no optical distortion of 1.35 was obtained. The obtained lens had a center thickness of 1.6 mm, had impact resistance that passed the US FDA standard, and had good workability. However, the thermal deformation onset temperature showing heat resistance was 86 ° C. The heat resistance was inferior to the obtained lens.

Comparative Example 3 A lens was manufactured using dimercaptopropane (hereinafter abbreviated as MP), which is a divalent thiol, instead of the trivalent thiol used in Example 1. That is, a lens was produced in the same manner as in Example 1 using 484 parts by weight of m-XDI, 305 parts by weight of PETMP, 135 parts by weight of MP, and 0.5 parts by weight of DBTL. As a result, N _D is 1.59 as shown in Table 1, [nu _D 36, the specific gravity is
A transparent lens with no optical distortion of 1.35 was obtained. The obtained lens had a center thickness of 1.6 mm, had impact resistance that passed the US FDA standard, and had good workability. However, the thermal deformation starting temperature showing heat resistance was 79 ° C. The heat resistance was inferior to the lens obtained in 1.

Comparative Example 4 A lens was manufactured using mercaptoethanol (hereinafter abbreviated as ME), which is a divalent thiol, instead of the trivalent thiol used in Example 1. That is, a lens was manufactured in the same manner as in Example 1 using 484 parts by weight of m-XDI, 305 parts by weight of PETMP, 98 parts by weight of ME, and 0.5 parts by weight of DBTL. As a result, N _D is 1.59 as shown in Table 1, [nu _D 36, the specific gravity is
A transparent lens with no optical distortion of 1.35 was obtained. The obtained lens had a center thickness of 1.6 mm, had impact resistance that passed the US FDA standard, and had good workability. However, the thermal deformation onset temperature indicating heat resistance was 76 ° C. The heat resistance was inferior to the obtained lens.

Evaluation of the refractive index, Abbe number, optical distortion, heat resistance, impact resistance, and workability of the lens in Table 1 was performed by the following methods.

(1) Refractive index (N _D), Abbe's number ([nu _D): was measured by Erma Optical Co. Abbe refractometer.

(2) Optical distortion: Using an optical strain meter, those having no optical distortion were visually evaluated as good, and those having optical distortion were evaluated as poor.

(3) Heat resistance: using Rigaku Electric Co., Ltd. TMA8140, thickness 3.0
A test piece cut into mm was heated at a rate of 10 ° C. per minute by an indentation method (pin diameter: 0.5 mm, load: 10 g), and the thermal deformation starting temperature was measured.

(4) Impact resistance: Using a flat plate with a center thickness of 1.6 mm, drop a 16 g steel ball from a height of 127 cm onto the center of this flat plate, FD
A steel ball drop test based on the A standard was performed.

(5) Workability: Grinding with a balling machine for processing eyeglass lenses,
研 削 indicates that the ground surface was good, や indicates that the surface was slightly good, and x indicates that the surface was bad.

Example 9 A hard coat film and a multilayer antireflection film were formed on the high refractive index polyurethane lens obtained in Example 1 as follows.

(1) Formation of Hard Coat Film To 212 parts by weight of γ-glycidoxypropyltrimethoxysilane, 54 parts by weight of a 0.06 N aqueous hydrochloric acid solution were added dropwise with stirring. After completion of the dropwise addition, the mixture was stirred for 24 hours to obtain a hydrolyzate.

Subsequently, 424 parts by weight of antimony pentoxide sol (methanol-dispersed sol, average particle diameter 10 nm, solid content 30%) and Denacol EX-521 (Nagase Kasei Co., Ltd., polyglycerol polyglycidyl ether) 34 as an epoxy compound
After stirring for 5 hours, 6.8 parts by weight of dibutyltin laurate was added as a curing catalyst, and further 100 parts by weight.
After aging for a time, a coating liquid was obtained.

Next, the high-refractive-index polyurethane lens obtained in Example 1 was immersed in a 10% aqueous NaOH solution at 50 ° C. for 5 minutes, washed sufficiently, and then dipped using the coating solution prepared by the above method. Coating was carried out by a method (pulling speed: 12 cm / min), heated at 120 ° C. for 1 hour to cure, and then gradually cooled to obtain a hard coat film.

(2) Formation of a multilayer anti-reflection film A sintered body of SiO ₂ was used as a deposition material for an underlayer and a low-refractive-index film, and ZrO ₂ powder and Ta _{2 were used} as deposition materials for a mixed-deposition film as a high-refractive-index film. O ₅ powder and Y ₂ O ₃ powder in molar ratio
Mix at a ratio of 1: 1.3: 0.2, press-mold, then 1200 ℃
After sintering in a pellet form, a polyurethane lens provided with a hard coat film by the method described above is placed in a vapor deposition tank, heated to 85 ° C. while evacuating, and evacuated to 2 × 10 ^-5 Torr. Then, the above-mentioned deposition material is deposited by an electron beam heating method, and as shown in Table 2, an underlayer composed of a silicon oxide film and a first layer composed of a composite equivalent film of a mixed vapor deposition film and a silicon oxide film. Low refractive index film, the second consisting of mixed vapor deposition film
A multilayer antireflection film having a film configuration in which a high-refractive-index film of a layer and a low-refractive-index film of a third layer made of silicon oxide were sequentially formed was obtained.

Note that the underlayer is preferably used to improve the adhesion to the substrate.

Table 3 shows the measurement results of the absorptance in the visible light wavelength region of the hard coat film and the high refractive index plastic lens provided with the multilayer antireflection film thus obtained. Table-
The absorptance (%) in No. 3 is 380 of the high refractive index plastic lens with the hard coat film and the multilayer antireflection film.
The reflectance (R) and transmittance (T) in the wavelength range of 780780 nm were measured using a Hitachi 340 type recording spectrophotometer manufactured by Hitachi, Ltd., and were calculated by converting to 100− (R + T).

As is clear from Table 3, the high refractive index plastic lens with the hard coat film and the multilayer antireflection film obtained in Example 9 exhibited a low absorptance over the entire visible light wavelength range, and was excellent. It was confirmed that it had optical characteristics.

The appearance of the high refractive index plastic lens with the hard coat film and the multilayer antireflection film obtained in Example 9
Table 4 shows the measurement results of luminous reflectance, scratch resistance, impact resistance, adhesion, heat resistance, alkali resistance and acid resistance.

As shown in Table 4, in the high refractive index plastic lens with the hard coat film and the multilayer antireflection film of Example 9,
Good results were obtained for all items, and it was confirmed that the mechanical properties and the chemical properties were also excellent.

Furthermore, after exposing the high refractive index plastic lens with the hard coat film and the multilayer antireflection film of Example 9 outdoors for one month, the same items, ie, appearance, luminous reflectance, abrasion resistance, impact resistance, and adhesion were observed. Table 5 shows the results of the evaluation of heat resistance, heat resistance, alkali resistance and acid resistance.

From Table 5, the high refractive index plastic lens with the hard coat film and the multilayer antireflection film of Example 9 exhibited the same results as those before exposure shown in Table 4 even after one month of outdoor exposure. It was confirmed that the film had excellent properties.

Examples 10 to 16 Using the high refractive index polyurethane lenses obtained in Examples 2 to 8 as lens substrates, a hard coat film and a multilayer antireflection film were sequentially formed on these lens substrates by the method described in Example 9. Thus, high refractive index plastic lenses with a hard coat film and a multilayer antireflection film of Examples 10 to 16 were obtained.

Appearance, luminous reflectance, scratch resistance, impact resistance, adhesion, heat resistance, alkali resistance and acid resistance of the obtained high refractive index plastic lenses with hard coat films and multilayer antireflection films of Examples 10 to 16 obtained. Table 4 shows the evaluation results of the properties, and Table 5 shows the evaluation results of the same items after one month of outdoor exposure.

As shown in Table 4, in the hard coat film and the high refractive index plastic lens with the multilayer antireflection film of Examples 10 to 16, good results were obtained for all items, and the mechanical properties and chemical properties were also excellent. It was confirmed that.

Also, from Table 5, the high refractive index plastic lenses with the hard coat film and the multilayer antireflection film of Examples 10 to 16 are as follows.
After one month of outdoor exposure, the same results as those before exposure shown in Table 4 were obtained, and it was confirmed that the weather resistance was excellent.

The appearance, luminous reflectance, scratch resistance, impact resistance, adhesion, heat resistance, alkali resistance and acid resistance in Tables 4 and 5 were evaluated by the following methods.

(1) Appearance Using an illuminating device with a fluorescent lamp as a light source, observe visually whether or not the following items 1) to 4) are satisfied. Those that satisfy all of these items are good, and those that do not satisfy either one are good. Was regarded as defective.

1) Be transparent.

2) The surface has no irregularities.

3) No striae.

4) No foreign matter or scratches on the surface.

(2) Luminous reflectance 380 to 780n using a Hitachi 340 type self-recording spectrophotometer
The reflectance in the m wavelength range was measured, and the luminous reflectance was converted from the reflectance and the visibility curve.

(3) Scratchability The surface of the multilayer antireflection film was rubbed with steel wool # 0000, and the scratch resistance was visually determined. The criteria were as follows.

 A: Hardly scratched even if strongly rubbed.

 B: If you rub it hard, it will be quite scratched.

 C: The same damage as the lens substrate is made.

(4) Impact strength Using a flat plate with a center thickness of 1.6 mm, apply 127
A steel ball drop test based on the FDA standard, in which a 16 g steel ball was dropped from a height of cm, was performed. The presence or absence of damage to the lens was examined.

(5) Adhesion The surface of a high refractive index plastic lens with a hard coat film and a multilayer anti-reflection film is cross-cut at 100 mm intervals at 1 mm intervals, and a cellophane tape is strongly attached. The presence or absence of peeling of the formation layer and the hard coat film was examined.

(6) Heat resistance A high refractive index plastic lens provided with a hard coat film and a multilayer antireflection film was placed in an oven for 1 hour and heated to check for cracks. The heating temperature was started at 70 ° C. and increased by 5 ° C. in increments of 5 ° C., and the superiority was determined by the temperature at which cracks occurred. In addition, although the measurement result of heat resistance is also shown in Table 1, it should be noted that the evaluation method of heat resistance in Tables 4 and 5 is different from the evaluation method of heat resistance in Table 1.

(7) Alkali resistance A high refractive index plastic lens with a hard coat film and a multilayer anti-reflection film is immersed in a 10 wt% NaOH aqueous solution for 24 hours, and the erosion state of the multilayer anti-reflection film surface is observed. , And those with erosion change were evaluated as x.

(8) Acid resistance A high refractive index plastic lens with a hard coat film and a multilayer anti-reflection film is immersed in a 10 wt% aqueous HCl solution and a 10 wt% H ₂ SO ₄ aqueous solution for 24 hours, and the erosion state of the surface of the multilayer anti-reflection film is observed. , Those without erosion change were rated as 、, and those with erosion change were rated as x.

[Effect of the Invention] A monomer mixture obtained by adding a specific aliphatic thiol compound (III) to a polyisocyanate represented by the general formula (I) and a polythiol represented by the general formula (II) is polymerized. The obtained high refractive index plastic lens of the present invention does not impair various physical properties of a conventional high refractive index plastic lens obtained by polymerizing a polyisocyanate of the general formula (I) and a polythiol of the general formula (II). In addition, the heat resistance, which is a drawback, was significantly improved. Therefore, it is possible to increase the degree of freedom in selecting thermal conditions in post-processing such as dyeing and surface coating.

Further, by providing a hard coat film and / or an anti-reflection film as required, it has become possible to enhance scratch resistance, alkali resistance, acid resistance, weather resistance, and the like.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Koji Sato, Inventor 2-7-5 Nakaochiai, Shinjuku-ku, Tokyo Inside of Hoya Corporation (72) Tokio Suzuki 2-chome, Nakaochiai, Shinjuku-ku, Tokyo Inside No. 5 Hoya Co., Ltd. (72) Inventor Hajime Kamiya 2-7-5 Nakaochiai, Shinjuku-ku, Tokyo Inside Hoya Co., Ltd. (56) References JP-A-64-26622 (JP, A) ( 58) Field surveyed (Int.Cl. ⁶ , DB name) C08G 18/00-18/87 G02B 1/04

Claims (2)

(57) [Claims] (1) General formula (I) (Wherein, R represents a hydrogen atom or a methyl group, X is at least one selected from a chlorine atom, a bromine atom, a methyl group and an ethyl group, a represents an integer of 0 to 4, and b represents 2
At least one kind of polyisocyanate represented by the following general formula (II): (Wherein, R represents a methyl, ethyl, chloromethyl or bromomethyl group, m represents an integer of 0 to 2, and n represents (4
(M) an integer of at least one polythiol represented by the following formula: (c) p (p = 0 or an integer of 1 or more) hydroxyl groups and q (q = 1 or more) mercapto A total number of hydroxyl groups and mercapto groups (p + q) is 3 or more,
An aliphatic thiol compound in which the number of carbon atoms interposed between the most distant hydroxyl group or mercapto group and the hydroxyl group or mercapto group is 6 or less, monothioglycerol,
Dimercaptopropanol, 1-mercaptomethyl 1,1
-Dihydroxymethylpropane, 1,4-dimercapto-
A high refractive index plastic lens obtained by polymerizing a monomer mixture containing at least one compound (III) selected from mercapto-substituted products of 2,3-hydroxybutane and pentaerythritol and mercapto-substituted products of sorbitol; . 2. The high refractive index plastic lens according to claim 1, further comprising a hard coat film and / or a multilayer antireflection film on the lens substrate.