JPS6045201A - Plastic lens - Google Patents

Abstract

PURPOSE:To obtain a plastic lens having superior scratch resistance, heat resistance and shock resistance by forming a hard coat layer and an antireflection layer on the surface of the prescribed base material of a plastic lens. CONSTITUTION:A hard coat layer 23 of 1-20mum thickness is formed on the base material 24 of a plastic lens such as PMMA, CR-39 or polyester. The layer 23 is made of silicone resin, epoxy resin, acrylic resin or the like which is different from the base material 24 by <=+ or -0.04 in refractive index. A single antireflection layer or a multiple antireflection layer consisting of layers 21, 22 is then laminated on the layer 23. The layers 21, 22 are formed by superposing a layer having a high refractive index and a layer having a low refractive index on each other. The high index layer is made of polystyrene or polycarbonate. Plastic contg. dispersed fine particles of the oxide of Al, Ti or the like may be used as the material of the high index layer.

Description

[Detailed description of the invention]

The present invention has excellent scratch resistance, heat resistance, and impact resistance, and
This invention relates to a synthetic resin lens that prevents reflection. Synthetic resins are superior to glass in terms of impact resistance, lightness, dyeability, ease of processing, etc., so they are used in eyeglass lenses that emphasize safety and fashion, and camera lenses that aim to be lightweight. It is often used in However, synthetic resins have the disadvantage that they are more easily scratched than glass, and this is a major impediment to the widespread use of synthetic resin lenses. In order to eliminate this drawback, two methods have been used in the past. One method is to apply a hard coat layer of silicone resin, acrylic resin, melamine resin, etc. to the surface of a synthetic resin lens by dipping method, spinner method, flow method, etc.
A film is formed by applying by a spray method or the like and curing with heat or ultraviolet light. This method is
The film has the advantage of being highly durable in terms of heat resistance, water resistance, scratch resistance, and adhesion, and can be dyed, and does not reduce the impact resistance of the lens. However, on the other hand, it has no antireflection effect. There were drawbacks. Another method is to form an inorganic material such as silicon oxide or aluminum oxide on the surface of a synthetic resin lens by vacuum evaporation, sputtering, or the like. This method is currently being put into practical use for eyeglass lenses in combination with an antireflection film. The film structure is as shown in Figure 1. First, a hard coat layer made of silicon oxide, aluminum oxide, etc. is provided on a synthetic resin lens base material, and on top of that, a hard coat layer made of silicon oxide, zirconium oxide, etc. Among substances such as ytterbium oxide, yttrium oxide, aluminum oxide, tantalum pentoxide, chromium oxide, and gne7ium fluoride,
It has an anti-reflection layer consisting of several alternating layers of a material with a high refractive index and a material with a low refractive index. This method has the advantage of being both a hard coat and antireflection, but has the disadvantage that the coating has poor durability and impact resistance, and lenses coated with this coating cannot be dyed. Various studies have been conducted to overcome these drawbacks. For example, a method has been considered in which a synthetic resin film is provided as a hard coat layer and an inorganic material is formed thereon by vacuum deposition, and some methods have already been commercialized. In this case, since the node coat layer is made of synthetic resin, the inorganic film can be made thinner, and as a result, durability such as heat resistance and scratch resistance can be improved, but this is not sufficient for practical use. I can't say that. Another idea is to obtain an antireflection effect using synthetic resin. For example, in the case of a transparent material having a film structure as disclosed in JP-A-58'-46301, a synthetic resin coating having a different refractive index from that of the lens base material is provided directly on the surface of the lens base material. The reflection at the interface between the lens base material and the bottom layer of the antireflection layer is high9, and the antireflection effect is impaired.
It has the disadvantage that stable interference colors cannot be obtained. Alternatively, the abrasion resistance may be poor because the thickness of the node coat layer is thin. The present invention eliminates this drawback. The purpose of the present invention is to have excellent scratch resistance, heat resistance, and impact resistance.
Another object of the present invention is to provide a synthetic resin lens having an antireflection effect. That is, in the present invention, the refractive index is 1.48.1 and 1.55.
(...A hard coat layer made of a synthetic resin film having a refractive index difference within ±0.04 from the base material and a film thickness of 1 to 20 μm on the surface of the synthetic resin lens base material. The present invention relates to a synthetic resin lens, further comprising an antireflection layer formed of a single layer or multilayer synthetic resin coating having a thickness of 70 to 200 nm on the surface of the coating. Next, each film constituting the synthetic resin lens in the present invention will be explained.The basic film structure of the present invention is as shown in FIG. Coat layer 23
and a single-layer or multi-layer antireflection layer 21 made of synthetic resin.
22 are provided. Synthetic resin lens base materials include acrylic resin (PMMA), diethylene glycol bisallyl carbonate resin (CR-
, 39), polyester, alkyd resin, epoxy resin, vinyl chloride resin, polyethylene resin, etc. are preferred. As the hard coat layer, commonly used thermosetting or photosetting synthetic resins such as silicone resin, epoxy resin, acrylic resin, etc. can be used. At this time, it is important that the difference in refractive index with the base material is within ±0.04. If the difference in refractive index with the base material is ±0.04 or more, ripple phenomenon occurs due to high reflection at the interface, which adversely affects the antireflection effect, which is one of the characteristics of the present invention, and furthermore, the hard If the thickness of the coating layer is not uniform, the interference color will change slightly, resulting in a fatal defect in the appearance of the lens. Further, 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 abrasion resistance is poor and the film is unsatisfactory as a hard coat layer. On the other hand, if the thickness exceeds 20 μm, the heat resistance tends to decrease and cracks may occur. In the case of the coated layer of the present invention, the difference in refractive index from the base is within ±0.04, so there is no need to strictly control the film thickness, and even within ±1.5 μm. Well, no problem at all. The synthetic resin constituting the antireflection layer must have excellent scratch resistance, like the resin constituting the /-docoat layer. In addition, in order to obtain a good antireflection effect, it is necessary to alternately layer layers with a high refractive index and layers with a low refractive index.
The difference in refractive index between the high refractive index layer and the low refractive index layer must be 0.05 or more. Therefore, as a layer with a high refractive index, synthetic resins with a refractive index of 1°53 or more, such as polystyrene, polystyrene copolymers, polycarbonates, aromatic rings other than polystyrene, heterocycles, alicyclic cyclic groups,
Alternatively, various polymer compositions containing halogens other than fluorine, thermosetting resins using melamine resins, phenolic resins, or epoxy resins as curing agents, and the above compounds can be cured by introducing double bonds into them. Examples include various modified resins that have made this possible. In addition, by mixing inorganic fine particles such as metal oxides into synthetic resins, it is possible to increase the refractive index of resins other than the synthetic resins with relatively high refractive indexes as mentioned above. It is possible to use it as a rate layer. At this time, oxides such as aluminum, titanium, tantalum zirconium, etc. are typical as the fine particles mixed and dispersed in the synthetic resin, and as synthetic resins to be diffused, vinyl resins including acrylic resins and alkyds are typically used. Examples include polyester resins, silicone resins, etc. Furthermore, in the case of silicon-based resins, organic metal compounds such as metal alkoxides,
A high refractive index can be obtained by using it in combination with organic acid salts, metal coordination compounds, etc. On the other hand, as a layer with a low refractive index, a synthetic resin with a refractive index of less than 1°51, for example,
Preferred are acrylic resins, vinyl resins, fluororesins, polyester resins containing alkyds, cellulose resins, and silicone resins. As the silicone resin, organically substituted silane compounds such as widely used silane coupling agents are preferably incorporated. In addition, there is also a method in which various synthetic resins are substituted with fluorine. The film forming the anti-reflection layer has a thickness of 7° to 200n for each layer.
must be managed between m. The variation in film thickness in a single layer is ±10 nm at 10°C.
378.1. stomach.・+1゜The hard coat layer and antireflection layer in the present invention are coated uniformly by dipping coating, spinner coating, spray coating, or flow coating, and then
It is cross-linked and cured by heat drying or ultraviolet irradiation to form a film. When applied to a lens base material, it is used after being diluted with a solvent if necessary. In addition, at this time, it is also possible to use a surfactant for the purpose of improving coating properties, such as a block copolymer of dimethylsiloxane and alkylene oxide, a graft copolymer, a fluorine-based surfactant, etc. is valid. Furthermore, it is also possible to add ultraviolet absorbers, antioxidants, etc. to each layer to improve the durability of the coating. There are many possible combinations of the lens base material, node coat layer, and antireflection layer that achieve the purpose of the present invention, and the optimal conditions should be determined depending on the required performance and purpose. . Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 A 111 synthetic resin lens base diethylene glycol bisallyl carbonate resin lens is immersed in a 4% sodium hydroxide aqueous solution for 3 minutes, and then washed and dried. The refractive index of this lens was 1.50. t2r hard coat layer r-glycidoxyglobil trimethoxysilone 5 parts by weight, methanol-dispersed colloidal silica, Catalysts Kasei Kogyo Co., Ltd.
6.8 parts by weight of 0.05N hydrochloric acid was gradually added dropwise to a solution consisting of 12.5 parts by weight, 8.5 parts by weight of ethylene glycol diglycidyl ether, and 47.0 parts by weight of ethyl cellosolve, with a solid content concentration of 30%. , hydrolysis was performed. Thereafter, 0.1 part by weight of ammonium perchlorate was added and mixed by stirring. Add 0.0% silicone surfactant to this.
1 part by weight was added to prepare a paint. A synthetic resin lens base material was immersed in the solution prepared as described above and pulled up at a speed of 20 (7) 7 minutes to uniformly coat the solution. The coated lenses were heated and dried in a hot air dryer at 80° C. for 30 minutes, and then heated in a hot air dryer at 120° C. for 1 hour. The refractive index of the obtained film was 1.50. Film thickness is 3μ
It was a sacrifice. (31 Antireflection layer Cα) 4 parts by weight of the aforementioned methanol colloidal silica, 5 parts by weight of tetowopoxy titanium, 91 parts by weight of methanol,
and 0.1 part by weight of a silicone surfactant were added and stirred to form a paint. iblγ-glycidoxypropyltrimethoxysilane 1
．． 5 parts by weight, the aforementioned methanol-dispersed colloidal silicone 5
．． 2 parts by weight, ethylene glycol dimericidy A/x-
1.2 parts by weight of 0.05N hydrochloric acid was gradually added dropwise to a solution consisting of 2.0 parts by weight of TeJl/1 part by weight and 90 parts by weight of methanol to perform hydrolysis. Then, add 2 parts by weight of Magne-7940.0 perchlorate and stir to mix.
r: To this, parts by weight of silicone surfactants O and OS were added to prepare a paint. A synthetic resin lens with a (2) Nyo9 hard coat layer formed thereon was immersed in the solution (α1) prepared as above.
It was pulled up at a speed of 7 cm to ensure uniform application. The coated lenses were heat-dried for 20 minutes in a hot air dryer at 80°C, and then for 1 hour in a hot air dryer at 120°C. The obtained film had a refractive index of 1°60° and a film thickness of 83 nm. Next, a coating using solution tb1 was further formed on the above-mentioned coating in the same manner as solution 1al. Solution 1
The refractive index of the film due to b1 is 1.4s, and the H thickness is 90nm.
Met. The average reflectance in the visible light range of the synthetic resin lens obtained by providing the above 111, (21, 131f, in this order) was 2.0% on one side, and a good antireflection effect was obtained. Example 2 (1) (1) of Example 1 was used for the synthetic resin lens material. (1) of Example 1 was used for the 12+ hard coat layer, and the same method was used. A film was formed.

[3) Anti-reflection layer lcl methylolmethane tetophacrylate 3゜6iti*B・) IJ/f I:l-7' Q
3.6 parts by weight, ethylene glycol dimethacrylate 3.
6 parts by weight of 1#1-dihydroperfluorohexyl acrylate, 78 parts by weight of methyl isobutyl ketone, and 2.2 parts by weight of benzoin ethyl ether were mixed and stirred to homogenize. Add (1) of Example 1 and C2 to the solution prepared as above.
1, and 131- ((The synthetic resin lens formed up to the first anti-reflection layer with Ll was immersed, pulled up at a speed of 10 cm for 1 minute, and then irradiated for 3 minutes using a high-pressure mercury lamp in a nitrogen gas atmosphere. The refractive index of the film using the solution (Cl) is 1.45.The film thickness is
It was 91 nm. The surface reflection of the synthetic resin lens thus obtained was 1.89 J, and an excellent antireflection effect was recognized. Example 3 For lenses made of Il1 synthetic resin, No. 111 of Example 1 was used. (21 For the hard coat layer, [2+ of Example 1 was used. ,
0.5 N hydrochloric acid was added to a solution consisting of 10.4 parts by weight of solid content (10 parts by weight) and 88.8 parts by weight of methanol.
．． 2 parts by weight was gradually added dropwise to perform hydrolysis. Then, 0.02 parts by weight of magnesium perchlorate was added,
Stir to make it homogeneous. A coating material was prepared by adding 0.08 parts by weight of a silicone surfactant. Applying the solution adjusted to d+ to a synthetic resin lens that has been formed up to the hard coat layer (according to (2) of Example 1) in the same manner as the application in [31] of Example 1, After curing, a film was further formed using the solution of 131-(61 of Example 1. The refractive index of the film formed from the solution (d+) was 1.57 and the film thickness was 84nrn. The surface reflection of the synthetic resin lens obtained by
It was 2.4%. Example 4 (1) 111 of Example 1 was used as the synthetic resin lens base material. 12) For the hard coat layer, (21 of Example 1) was used. For the 131 antireflection layer, after providing a coating with a solution of 131-Idl of Example 3, +31-1cl of Example 2 was applied.
A film was formed with a solution of The surface reflection of the synthetic resin lens thus obtained was 2.0%), and a good antireflection effect was observed. Example 5 Ill of Example 1 was used for the ill1 synthetic resin lenses. 121 of Example 1 was used for the 121 hard coat layer. (3) Antireflection layer Iel 5 parts by weight of pentaerythritol tetophacrylate, 1 oii of trimethylolpropane triacrylate
parts, 2.2bis(4-methacroyloxyethoxy-3
, 5-dibromphenyl) and 7.3 parts by weight of ethyl celloturu acetate, 1 part of 1-benzoin engineered ethyl ether, and 1 part by weight of a fluorosurfactant were added and mixed. Adjusted the paint. A solution prepared using 1 ml of the above was applied to a synthetic resin lens having up to the hard coat layer formed on 121 in Example 1 in the same manner as the application of ζ31 in Example 2, and was cured. A coating of 3-1 cl of the solution of Example 2 was formed. The refractive index of the coating made from solution e is 1.56.
．． The film thickness was 85 nm. Moreover, the surface reflection of the synthetic resin lens thus obtained was 2.1%. Example 6 (1) Ill from Example 1 was used as a synthetic resin lens base material. C2 1-decoat layer 7.8 parts by weight of γ-glycidoxypropyltrimethoxysilone, 27.6 parts by weight of the aforementioned methanol-dispersed colloidal silica
6.8 parts by weight of 0.05N hydrochloric acid was gradually added dropwise to a solution consisting of 57.6 parts by weight of ethyl cellosolve and 57.6 parts by weight of ethyl cellosolve to perform hydrolysis. Thereafter, 0.1 part by weight of magnesium perchlorate was added to make the mixture uniform. Add 0.0% silicone surfactant to this. The paint was adjusted by adding IM parts. The bath 'G' prepared as described above is used as a synthetic resin lens base. Apply 1゜1゜ in the same way a.tl. It was applied and cured to form a film. The refractive index of the obtained film was 1.48. The film thickness was 3 μm. 131 anti-reflection area contains 131-1α) [b
)It was used. The surface reflection of the synthetic resin lens thus obtained was 2.0%. Example 7 [1] For the synthetic resin lens base material, (1) of Example ↓ was used. (2) t2+ of Example 6 was used for the hard coat layer. For the +31 antireflection layer, 131-1α11G of Example 2 was used.
+ was used. The surface reflection of the synthetic resin lens thus obtained was 1.8%. Example 8 Ill of Example 1 was used for the r11 synthetic resin lenses. (121 of Example 6 was used for the 2+ hard coat layer. 131-1αl 1 of Example 3 was used for the 131 antireflection layer.
61 was used. The surface reflection of the synthetic resin lens thus obtained was 2.2%. Example 9 (11) For the synthetic resin lens base material, 1 of Example ill was used. For the t2121 hard coat, 121 of Example (61) was used. For the 131 antireflection layer, 1 of Example 4 was used. (3+ −idl
(Cl was used. The surface reflection of the synthetic resin lens thus obtained was 1.9%. Example 10 (1) Ill of Example 1 was used as the synthetic resin lens base material. For the 12+ hard coat layer, (21) of Example 6 was used. [3) For the antireflection layer, 131-(e) of Example 5 was used.
lcl was used. The surface reflection of the synthetic resin lens thus obtained was 1.9 inches. Example 11 [11 ill of Example 1 was used as a synthetic resin lens base material. (21 Hard coat layer 20 parts by weight of pentaerythritol tetraacrylate,
20 parts by weight of trimethylolpropane triacrylate,
1 part by weight of a fluorine-based surfactant was added to a monomer composition consisting of 30 parts by weight of ethylene glycol diacrylate, 28 Mfk parts of isopropyl alcohol, and 1 part by weight of benzoin methyl ether and mixed to prepare a paint. This solution was applied to a synthetic resin lens base material in the same manner as the application of 131 in Example 2, and cured. The obtained film had a refractive index of 1.48 and a film thickness of 5 μm. The 131 antireflection layer contained 131-1gl (
C1 was used. The surface reflection of the synthetic resin lens thus obtained was 1.9%. Example 12 A 111 synthetic resin lens base polymethyl methacrylate resin lens was washed and dried. The refractive index of this lens was 1.48. 121 of Example 11 was used for the 12+ hard coat layer. 13) For the antireflection layer, 131-1e11c of Example 3 was used.
l was used. The surface reflection of the synthetic resin lens thus obtained was 1.9%. Example 13 (1) A solution obtained by mixing 0 parts by weight of synthetic resin lens base material CR-3930, 10 parts by weight of benzyl methacrylate, 0 parts by weight of Diallylisof, Talletro, and 3 parts by weight of diisopropyl peroxydicarbonate was heated. - Surface-treat the lens obtained by polymerization in the same manner as +1+ of Example 1. The refractive index of this lens is l. It was 55. 12+ Hard coat layer 25 parts by weight of γ-glycidoxypropyltrimethoxysilone, 12°0 parts by weight of water-dispersed titanium sol (solid content 20q6
), 8.5 parts by weight of glycerin diglycidyl ether, and 47.0 parts by weight of ethyl cellosolve,
6.8 parts by weight of 0.05N hydrochloric acid was gradually added dropwise to carry out hydrolysis. Thereafter, 0.1 part by weight of magnesium perchlorate was added and stirred to make the mixture uniform. A sample was prepared by adding 0°IM part of a silicone surfactant to this. The solution prepared above was molded using ill, a synthetic resin "Ki-Kai" 1. Fruit! 9'li oiz+o application 2 same 4111. . The coating was applied and cured using a method to form a film. The refractive index of the obtained film was 1.54. The film thickness was 3 layers m. The 131 antireflection layer contains 131-1α)(b) of Example 1.
)It was used. The surface reflection of the synthetic resin lens thus obtained was 2.2 inches. Example 14 [1] of Example 13 was used for the il1 synthetic resin lenses. For the C2 hard coat layer, (2+) of Example 13 was used. 13) For the antireflection layer, first, 131-1b of Example 1 was used.
No. 1 was applied in the same manner as No. 131 of Example 1, and a coating having the same structure as No. 131 of Example 3 was provided thereon. The surface reflection of the synthetic resin lens obtained in this way is 2
．． It was 0%. Comparative Example 1 The lit of Example 1 was used as the 111 synthetic resin lens base material. [2] of Example 6 was used for the 12171-decoat layer. 131 Antireflection layer F3i02. ZrO2 was deposited alternately by vacuum evaporation method.
The total optical thickness of the three layers of sio□ and zro2.5io2 is approximately λ/4-first-order 0Zr02 is λ/4. The 5ho2 of the top 1] is constructed in the order of λ/4. The surface reflection of the synthetic resin lens thus obtained was 0.9%. Transmittance, scratch resistance, heat resistance, and impact resistance were evaluated for Examples 1 to 14 and Comparative Example 1, and the results are shown in Table 1. The test method in Table 1 is as follows. The transmittance in the visible range was averaged using an Ill transmittance bispectrophotometer. (2) Scratch Resistance The state of the coating was observed after it was made to reciprocate 100 times under a load of 2002 using Nisu0000 steel wool. A: It hardly gets scratched. B: Slight damage. C: Many scratches occur. 13) Heat resistance: Temperature that does not change in appearance even after being left in a hot air constant temperature bath for 1 hour. 14) Impact resistance: A steel ball drop test was conducted according to FDA standards, and those that passed were rated ○, and those that failed were rated x. Table 1 Transmittance Scratch resistance Heat resistance Impact resistance CR-3992, 2% C130℃ ○Example 1 9
6.0% A 1301: 01/2 97.4%
A 110℃ ○// 3 95.2% A 130C
O// 4 96.0% A xxoc O1/ 5
95.8% A 110℃ 01/6 96.0%
A 120℃ ○tt 7 97.4% A 110℃
○p 8 95.6% A 120℃ ○〃997゜2% A 110℃ ○ tt 10 97.2% A 100℃ 01 11
97.2% A110℃ 01 12 97.2% A
90℃ ○/I 13 95.6% A 1301:
01/14 95.6chi A130℃ ○Comparative example
1 98.2% B 80℃X

[Brief explanation of drawings]

FIG. 1 shows a synthetic resin lens with a conventional antireflection film structure, which has the same performance as that shown in the comparative example. 15 is a synthetic resin lens base material, 14 is a hard coat film made of synthetic resin, 13 is 5hoz, ZrO2
, sho , and the total film thickness is λ/4)
The film is formed by a vacuum evaporation method. 12 is zr
The a2 film and 11 are 5ho2 films each having a film thickness of λ/4. FIG. 2 shows a synthetic resin lens with a film structure according to the present invention, and corresponds to Example 7. 24 is a synthetic resin lens base material, 2 is a hard coat film made of synthetic resin, 22 is a synthetic resin coating with a refractive index of 1.60, and 21 is a synthetic resin coating with a refractive index of 1.48. FIG. 3 shows an application example of a synthetic resin lens with a film structure according to the present invention, and corresponds to Example 14. 35 is a synthetic resin lens base material, 34 is a hard coat film made of synthetic resin, and 33 and 31 are a composite having a refractive index of 1.48. 1' synthetic resin coating; 32 is a synthetic resin coating having a refractive index of 1.57; FIG. 4 shows the spectral reflectance characteristics of a synthetic resin lens having an antireflection film formed by vacuum evaporation as shown in FIG. The straight line in the figure indicates a CR-39 lens. FIG. 5 shows the spectral reflectance characteristics of a synthetic resin lens having an antireflection film according to the present invention, as shown in FIG. Similarly, FIG. 6 shows the spectral reflectance characteristics of FIG. Applicant: Suwa Seikosha Co., Ltd., r, o 0'/, 3zuW3': Iaj4ad X a) ul! 1
)alJ:aH1I″IO

Claims (1)

[Claims] On the surface of a synthetic resin lens base material with a refractive index of 1.48 to 1.55, a synthetic resin having a refractive index difference within ±0.04 from the base material and a film thickness of 1 to 1 μm is applied. A synthetic resin characterized by providing a hard coat layer made of a resin film, and further providing an antireflection layer made of a single layer or multilayer synthetic resin film having a thickness of 70 to 200 nm on the surface of the film. made lens.