JPH0642001B2 - Synthetic resin lens - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is excellent in scratch resistance, heat resistance and impact resistance, and
The present invention relates to a synthetic resin lens that prevents reflection.

Synthetic resin is superior to glass in impact resistance, lightness, dyeability, easy workability, etc., so it is suitable for eyeglass lenses that emphasize safety and fashionability, camera lenses for weight reduction, etc. Many are used.

However, synthetic resin has a drawback that it is more easily scratched than glass, which greatly hinders the spread of synthetic resin lenses.

In order to eliminate this drawback, two methods have been conventionally used. One method is to apply a hard coat layer of silicon resin, acrylic resin, melamine resin, etc. on the surface of a synthetic resin lens by dipping method, spinner method, flow method,
A coating film is formed by applying by a spray method or the like and then thermally or ultraviolet curing. This method
Although the coating has excellent heat resistance, water resistance, scratch resistance, adhesion, and other durability, it does not reduce the impact resistance of the lens, but on the other hand, it does not have an antireflection effect.

Another method is to form an inorganic substance such as silicon oxide or aluminum oxide on the surface of a synthetic resin lens by a vacuum deposition method, a sputtering method, or the like. This method is currently put to practical use in spectacle lenses in the form of being combined with an antireflection film. The film structure is as shown in FIG. 1. First, a hard coat layer made of silicon oxide, aluminum oxide or the like is provided on a synthetic resin lens substrate, and then a silicon oxide, zirconium oxide, Among the substances such as ytterbium oxide, yttrium oxide, aluminum oxide, tantalum pentoxide, chromium oxide, magnesium fluoride, etc., an antireflection layer in which several high refractive index substances and low refractive index substances are alternately stacked. It is in the form of setting up. This method has an advantage that it has both a hard coat and antireflection, but has a disadvantage that the durability and impact resistance of the coating are poor.

Various studies have been conducted to overcome these drawbacks.
For example, a method of forming a synthetic resin film as a hard coat layer and forming an inorganic substance on it by a vacuum evaporation method has been considered, and some have already been commercialized. In this case, because of the hard coat layer made of synthetic resin, the inorganic film can be made thin, and as a result, durability such as heat resistance and scratch resistance can be improved, but it cannot be said to be practically sufficient. .

There is also an idea to obtain an antireflection effect with a synthetic resin thin film. For example, in the case of a lens substrate having a film structure as disclosed in JP-A-58-46301, since a synthetic resin coating having a refractive index different from that of the lens substrate is directly provided on the surface of the lens substrate, There is a drawback that the reflection at the interface between the lens substrate and the lowermost layer of the antireflection layer becomes high, the antireflection effect is impaired, and stable interference color cannot be obtained.

Alternatively, since the hard coat layer is thin, the scratch resistance may be poor.

The present invention eliminates such drawbacks.

The object of the present invention is excellent in scratch resistance, heat resistance, and impact resistance,
Another object is to provide a synthetic resin lens having an antireflection effect.

That is, the present invention has a refractive index difference of ± 0.04 or less on the surface of a synthetic resin lens substrate A having a refractive index of 1.48 to 1.58, and a film thickness A synthetic resin film B having a thickness of 1 to 20 microns and an antireflection layer made of a synthetic resin film C composed of a single layer or a multilayer having a thickness of 70 to 200 millimicrons on the surface of the hard coat layer, One or more layers of the layers constituting the synthetic resin coating B and / or the synthetic resin coating C are mainly composed of the following (a), (b) and (c). To do.

(B) The general formula is (In the formula, R ¹ is an organic group containing at least one selected from a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, an amino group, an imino group, an epoxy group, and a (methanoacryloxy group, a phenyl group, and a mercapto group. , R ² is hydrogen or 1 to 1 carbon atoms
6 (halogenated) hydrocarbon group, R ³ is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or 1 to 4 carbon atoms
The acyl group, a, b and a + b are 0.1 or 2).

(B) A colloidal dispersion of metal oxide fine particles having a particle size of 1 to 100 millimicrons.

(C) Magnesium Perchlorate Next, each coating constituting the synthetic resin lens of the present invention will be described.

The basic film structure of the present invention is as shown in FIG. 2, but the hard coat layer 23 made of synthetic resin is formed on the synthetic resin lens 24.
And a single-layer or multilayer antireflection layer 21 made of synthetic resin
To 22 are provided.

As the synthetic resin lens base material, acrylic resin and diethylene glycol bisallyl carbonate resin, which are widely used as eyeglass lenses and the like, polyester / alkyd resin, epoxy resin, vinyl chloride resin, polyethylene resin and the like are preferable.

The synthetic resin film B must be one that is sufficiently effective as a hard coat layer. The purpose of the hard coat layer is to improve the scratch resistance of the lens surface and not to adversely affect the antireflection effect of the antireflection layer provided on the hard coat layer. Therefore, it is necessary to use a synthetic resin having a refractive index difference of ± 0.04 or less with the lens substrate for the synthetic resin film B which is a hard coat layer, and the film thickness is 1 to 20 μm. And has a sufficient thickness to improve scratch resistance and dyeability.
When the difference in the refractive index from the base material is ± 004 or more, the reflection at the interface is high, which adversely affects the antireflection effect, which is one of the features of the present invention, and the film thickness of the hard coat layer is If it is not uniform, the interference color changes delicately, which is a fatal external defect as a lens. The film thickness is preferably about 1 to 20 μm, more preferably about 2 to 10 μm. When the film thickness is less than 1 μm, the scratch resistance is poor,
It is insufficient as a hard coat layer. On the other hand, 20
If it exceeds μm, the heat resistance tends to decrease, and cracks may occur. In the case of the hard coat layer of the present invention, since the difference in the refractive index from the substrate is within ^± 0.04, it is not necessary to strictly control the film thickness, and if it is within 0.3 μm,
No problem at all.

As the component (a) used for the synthetic resin coating B, tetramethoxysilane tetraethoxysilane tetraisopropoxysilane tetrabutoxysilane methyltrimethoxysilane methyltriethoxysilane methyltripropoxysilane methyltributoxysilane ethyltrimethoxysilane ethyltriethoxy Silane Vinyltrimethoxysilane Vinyltriethoxysilane Vinyltriethoxysilane Vinyltriacetoxysilane γ-Aminopropyltrimethoxysilane γ-Glycidoxypropyltrimethoxysilane γ-Glycidoxypropyltriethoxysilane β- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane β- (3,4-epoxycyclohexyl) ethyltriethoxysilane γ-methacryloxypropyltrimethoxysilane Lanphenyltrimethoxysilane γ-mercaptopropyltrimethoxysilane phenyltriacetoxysilane γ-chloropropyltrimethoxysilane β-cyanoethyltriethoxysilane dimethyldimethoxysilane dimethyldiethoxysilane γ-glycidoxypropylmethyldimethoxysilane γ-methacryloxypropyl Methyldimethoxysilane, phenylmethyldimethoxysilane, vinyl-tris (β-methoxyethoxy) silane and the like. These may be used alone or in combination of two or more. Further, these are preferably used by hydrolyzing in the presence of an acid in an organic solvent such as alcohol.
It may be either mixed with (ii) and hydrolyzed or mixed with (ii) after hydrolysis.

The colloidal dispersion of the metal oxide fine particles having a particle diameter of 1 to 100 millimicrons of the component (b) is a polymer oxide of a metal element such as silicon, aluminum, titanium, zirconium or antimony in water or another dispersion medium. It is a colloidal solution in which fine particles are dispersed. The type of metal oxide can be selected and mixed according to the refractive index of the lens substrate.

By using magnesium perchlorate of component (c) as a curing catalyst in addition to one or more of component (a) and component (b), excellent hot water resistance, dyeability, and chemicals It is possible to obtain a coating film having good properties and weatherability and to obtain a paint having a long pot life. As the curing catalyst, aluminum acetylacetonate, ammonium perchlorate, tin octylate and the like are generally known, but these have insufficient surface hardness, poor hot water resistance, short pot life of liquid, etc. There is nothing else but magnesium perchlorate that has drawbacks and is satisfactory in all properties.

Like the resin used for the hard coat layer, the synthetic resin coating C that constitutes the antireflection layer must have excellent scratch resistance. Further, in order to obtain a good antireflection effect, a method of alternately stacking layers having a high refractive index and layers having a low refractive index is adopted, so that the synthetic resin film C is not limited to a single layer, but may be a multilayer. In the case of a multilayer, a difference in refractive index of 005 or more is required between the high refractive index layer and the low refractive index layer. Therefore, as the layer having a high refractive index, a synthetic resin having a refractive index of 1.53 or more, for example, polystyrene, polycarbonate, an aromatic ring other than polystyrene, a heterocyclic ring, an alicyclic ring group, or various kinds of halogen having a halogen other than fluorine is used. Preferred are a combined composition, a thermosetting resin having a melamine resin, a phenol resin, or an epoxy resin as a curing agent, and various modified resins capable of radical curing by introducing a double bond into the above compound. Further, the silicone resin can be used in combination with an organic metal compound, a metal coordination compound, or the like to increase the refractive index. In addition, the resin used for the synthetic resin coating B may be used. In this case, it is necessary to adjust each component in order to increase the refractive index. Specifically, there is a method of using alumina sol, titanium sol, or the like for the metal oxide colloidal solution of the component (b). The low refractive index layer is preferably a synthetic resin having a refractive index of less than 1.51, such as acrylic resin, vinyl resin, fluororesin, polyester resin containing alkyd, cellulose resin, and silicon resin. There is also a method in which various synthetic resins are substituted with fluorine. In addition, the resin used for the synthetic resin coating B may be used. In this case, it is necessary to adjust each component in order to lower the refractive index. Specifically the ingredients
Silica sol is used for (b). There is a method such as increasing the proportion of component (b) in each component.

The mixing ratio of each component shown in claims 2 and 3 of the present invention is preferably the component (b) (SiO ₂
(Solid content) calculated based on 100 parts by weight of component (a) The total (calculated as the solid content) is 50 to 800 parts by weight, the total of the component (c) is 50 to 600 parts by weight, and the component (d) is
Is used in the range of 0.01 to 5.0 weight percent of total residual solids. Furthermore, more preferably, the component (a) is 100 to
500 parts by weight. Each of the above components is a solvent such as alcohols, ketones, cellosolves, and carboxylic acids alone,
Alternatively, they can be mixed and added, and if necessary, a small amount of a surfactant, an antistatic agent, or an ultraviolet absorber can be added to improve the coating property of the coating liquid and the performance of the coating film.

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

Example 1 (1) Synthetic resin lens substrate Diethylene glycol bisallyl carbonate resin (CR
-39) The lens is immersed in a 4% aqueous solution of sodium hydroxide for 3 minutes and then washed and dried. The refractive index of this lens was 1.50.

(2) Hard coat layer A solution of 36 parts by weight of γ-glycidoxypropyltrimethoxysilane, 19 parts by weight of methanol-dispersed colloidal silica (manufactured by Catalysts & Chemicals Industries, solid content concentration 30%), and 36.6 parts by weight of ethyl cellosolve, 0.05 Hydrolysis was carried out by gradually dropping 8.2 parts by weight of normal hydrochloric acid. Then, 0.1 part by weight of magnesium perchlorate was added and mixed by stirring. To this, 0.1 part by weight of a silicon-based surfactant was added to obtain a paint.

The synthetic resin lens substrate was immersed in the solution prepared as described above, pulled up at a speed of 20 cm / min, and uniformly applied.
The coated lens was heated and dried in a hot air dryer at 80 ° C. for 30 minutes and then dried in a hot air dryer at 120 ° C. for 1 hour. The obtained coating had a refractive index of 1.50 and a thickness of 4 μm.

(3) Antireflection layer (a) 6 parts by weight of the above-mentioned methanol colloidal silica, 3 parts by weight of tetrabutoxytitanium, 91 parts by weight of methanol, and 0.1 part by weight of a silicon-based surfactant were added and stirred to obtain a coating material.

(b) To a solution consisting of 2.0 parts by weight of γ-glycidoxypropyltrimethoxysilane, 6.7 parts by weight of the above-mentioned methanol-dispersed colloidal silica, and 90 parts by weight of methanol, 1.2 parts by weight of 0.05N hydrochloric acid was gradually added dropwise to obtain a solution. It was disassembled. Then, add 0.02 parts by weight of magnesium perchlorate,
Stir to mix. Silicone surfactant 0.08
Part by weight was added to form a paint.

The synthetic resin lens having the hard coat layer formed in (2) was immersed in the solution (a) prepared as described above, pulled up at a speed of 10 cm / min, and uniformly applied. The coated lens is 8
After heating and drying with a hot air dryer at 0 ° C. for 20 minutes, it was dried with a hot air dryer at 120 ° C. for 1 hour. The obtained coating had a refractive index of 1.59 and a thickness of 84 nm. Next, a coating film of the solution (b) was further provided on the above coating film. The coating and curing methods were the same as those for the solution (a). The obtained coating had a refractive index of 1.48 and a thickness of 90 nm.

The average reflectance in the visible light range of the synthetic resin lens thus obtained was 2.0% on one surface, and a good antireflection effect was recognized.

Example 2 (1) As the synthetic resin lens substrate, (1) of Example 1 was used.

(2) For the hard coat layer, (2) of Example 1 was used.

(3) Antireflection film (c) 0.3 part by weight of a solution consisting of 2.2 parts by weight of γ-glycidoxypropyltrimethoxysilane, 12.5 parts by weight of water-dispersed alumina sol (manufactured by Nissan Chemical Industries, solid content 10%), and 75.3 parts by weight of methanol. 0.1 part by weight of normal hydrochloric acid was gradually added dropwise to carry out hydrolysis. Then, 0.02 part by weight of magnesium perchlorate was added and stirred to make it uniform. To this, 0.08 part by weight of a silicon-based surfactant was added to obtain a paint.

The synthetic resin lens having the hard coat layer formed in (2) of Example 1 was coated with the solution (c). The coating and curing methods were the same as those for the solution (a). The obtained film has a refractive index of 1.58 and a film thickness of 85 nm.
Met. Next, a coating film of the solution (b) was further provided on the above-mentioned coating film.

The average reflection in the visible light region of the synthetic resin lens thus obtained was 2.1% on one side, and a good antireflection effect was obtained.

Example 3 (1) Synthetic resin lens substrate A solution obtained by mixing 30 parts by weight of diethylene glycol bisallyl carbonate, 10 parts by weight of benzyl methacrylate, 60 parts by weight of diallyl isophthalate, and 3 parts by weight of diisopropyl peroxydicarbonate. Heating
The lens obtained by polymerization is surface-treated in the same manner as in (1) of Example 1. The refractive index of this lens was 1.55.

(2) Hard coat layer To a solution consisting of 36 parts by weight of γ-glycidoxypropyltrimethoxysilane, 19 parts by weight of methanol-dispersed titanium sol, and 36.6 parts by weight of ethylcellosolve bupi, 8.2 parts by weight of 0.05N hydrochloric acid was gradually added dropwise. , Hydrolysis was performed. Thereafter, 0.1 part by weight of magnesium perchlorate was added, and the mixture was stirred and mixed. To this, 0.1 part by weight of a silicon-based deactivator was added to obtain a paint.

The synthetic resin lens substrate was immersed in the solution prepared as described above, pulled up at a speed of 20 cm / min, and uniformly applied.
The coated lens was heated and dried in a hot air dryer at 80 ° C. for 30 minutes and then dried in a hot air dryer at 120 ° C. for 1 hour. The refractive index was 1.59 and the film thickness was 4 μm.

(3) For the antireflection layer, (3)-(b) of Example 1 was used.
The average reflectance in the visible light range of the synthetic resin lens thus obtained was 2.0% on one side, and a good antireflection effect was recognized.

Comparative Example 1 (1) As the synthetic resin lens substrate, (1) of Example 1 was used.

(2) For the hard coat layer, (2) of Example 1 was used.

(3) Antireflection layer This is an antireflection layer in which five layers of SiO ₂ and ZiO ₂ are alternately provided by a vacuum deposition method, and when viewed from the hard coat layer side, SiO ₂ , ZiO ₂ ,
The total optical thickness of the three layers of SiO ₂ is about λ / 4, and the next ZiO ₂ is λ.
/ 4, and SiO _{2 of} the uppermost layer is formed in the order of λ / 4. The surface reflection of the synthetic resin lens thus obtained is 0.
It was 9%.

The transmittance, scratch resistance, heat resistance, and impact resistance of the above Examples 1 to 4 were evaluated, and the results are shown in Table 1. The test methods in Table 1 are as follows.

(1) Transmittance: Using a spectroscopic clock, the transmittance in the visible region was averaged.

(2) Scratch resistance: 200g load with # 0000 steel wool
Below, the state of the coating after 100 reciprocations was observed.

A: Almost no scratches B: Slight scratches C: Many scratches (3) Heat resistance: A temperature that does not change in appearance even after left in a hot-air constant temperature bath for 1 hour.

(4) Impact resistance: According to the FDA standard, a steel ball drop test was conducted, and those that passed were rated as ◯ and those that failed were rated as x.

As described above, the synthetic resin lens of the present invention has a refractive index difference of ± 0.04 or less on the surface of the synthetic resin lens substrate A having a refractive index of 1.48 to 1.58. A synthetic resin film B having a refractive index of 1 to 20 μm and having a film thickness of 1 to 20 μm, and a synthetic resin film consisting of a single layer or a multilayer having a film thickness of 70 to 200 mm on the surface of the hard coat layer. An antireflection layer of C is provided, and the synthetic resin coating B and / or the synthetic resin coating C is provided.
One or two or more of the layers constituting the above are mainly composed of the following (a), (b) and (c).

(B) The general formula is (In the formula, R ¹ is an organic group containing at least one selected from a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, an amino group, an imino group, an epoxy group, a (meth) acryloxy group, a phenyl group, and a mercapto group. , R ² is hydrogen or 1 to 1 carbon atoms
6 (halogen) hydrocarbon group, R ³ is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms, and a and b are 0, 1 or 2, and a + b
One or more organic silicon compounds represented by ≧ 0).

(B) A colloidal dispersion of metal oxide fine particles having a particle size of 1 to 100 millimicrons.

(C) Magnesium perchlorate.

It is characterized by taking the configuration.

By adopting the above configuration, the synthetic resin lens of the present invention has the following remarkable effects. That is, firstly, (C) magnesium perchlorate added as a polymerization catalyst suppresses the polymerization of the coating solution at room temperature, and other catalysts exhibiting the effect of promoting polymerization by heating after coating are shown. Has no unique effect. Therefore, the prepared coating liquid can be stored at room temperature for a long time ("pot life is long"). That is, since the viscosity of the coating solution does not change even after a lapse of time after preparation of the solution, it is possible to apply a coating having a constant film thickness, and it is possible to always form a stable film.

Secondly, since the hard coat layer and the antireflection film formed on the surface of the synthetic resin base material A are synthetic resin coatings, the base material and each layer are excellent in affinity, and thus flexibility and impact resistance are achieved. A synthetic resin lens having excellent heat resistance can be obtained. Further, since the antireflection layer is an organic substance, it can be easily dyed and beautiful coloring can be obtained.

Thirdly, since the difference in the refractive index between the base material and the hard coat layer is as small as ± 0.04, the effect of suppressing the occurrence of interference fringes can be obtained.

[Brief description of drawings]

FIG. 1 shows a synthetic resin lens having a conventional antireflection film structure, and has the same performance as that shown in Comparative Example 1. Reference numeral 15 is a synthetic resin lens substrate, 14 is a hard coat film made of synthetic resin, 13 is a film structure of SiO ₂ , ZiO ₂ , and SiO ₂ , and the total film thickness is λ / 4, and a film is formed by a vacuum deposition method. There is a gap. Reference numeral 12 is a ZiO ₂ film, and 11 is a SiO ₂ film each having a film thickness of λ / 4. FIG. 2 shows a synthetic resin lens having a film structure according to the present invention, which corresponds to Example 1. Reference numeral 24 is a synthetic resin lens substrate, 23 is a hard coat film made of synthetic resin, 22 is a synthetic resin film having a refractive index of 1.60, and 21 is a synthetic resin film having a refractive index of 1.48. FIG. 3 shows the spectral reflectance characteristics of a synthetic resin lens having an antireflection film formed by the vacuum evaporation method as shown in FIG.
The straight line in the figure indicates the CR-39 lens. FIG. 4 shows the spectral reflectance characteristics of a synthetic resin lens having an antireflection film according to the present invention as shown in FIG.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Hirokazu, Departure, Hirokazu, 3-5 Yamato, Suwa City, Nagano Prefecture Suwa Seikosha Co., Ltd. (56) References JP-A-58-23001 Kai 56-74202 (JP, A)

Claims (1)

[Claims] 1. The surface of a synthetic resin lens substrate A having a refractive index of 1.48 to 1.58 has a difference in refractive index from the substrate of ±.
A synthetic resin film B having a refractive index of 0.04 or less and a film thickness of 1 to 20 μm, and a single layer or a multilayer having a film thickness of 70 to 200 mm on the surface of the hard coat layer and the film. Of the synthetic resin coating C, and one or more layers of the synthetic resin coating B and / or the layers constituting the synthetic resin coating C are the following (a) and (b): A synthetic resin lens comprising (c) as a main component. (B) The general formula is (In the formula, R ¹ is an organic group containing at least one selected from a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, an amino group, an imino group, an epoxy group, a (meth) acryloxy group, a phenyl group, and a mercapto group. , R ² is hydrogen or 1 to 1 carbon atoms
6 (halogen) hydrocarbon group, R ³ is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms, and a and b are 0, 1 or 2 and a + b
One or more organic silicon compounds represented by ≧ 0). (B) A colloidal dispersion of metal oxide fine particles having a particle size of 1 to 100 millimicrons. (C) Magnesium perchlorate.