JPS6088901A - Plastic lens - Google Patents

Abstract

PURPOSE:To obtain a plastic lens which is highly resistant to scratching, heat and impact and is effective in preventing reflection by providing a specific antireflection layer on the surface of a hard coat layer consisting of a plastic film having a specific refractive index and film thickness. CONSTITUTION:A hard coat layer 23 consisting of a plastic film having within + or -0.04 difference in refractive index from a base material 24 for the plastic lens and 1-20mum film thickness is provided on the surface of said base material having 1.48-1.55 refractive index. Antireflection layrs 22, 21 consisting of single or multilayered plastic films having 70-200mum film thickness are provided on the surface of said film. Acrylic resin, vinyl chloride resin, PE resin, etc. are preferable as the material 24. Tetramethoxysilane, tetraethoxysilane, etc. are preferable as the plastic film. Polystyrene, polycarbonate, aromatic, heterocyclic, alicyclic type cyclic groups except polystyrene, or various polymer compsn. having halogen except fluorine, thermosetting resins for which a melamine resin, phenolic resin or epoxy resin is used as a curing agent and various modified resins which enable radical curing are preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has excellent scratch resistance, 1FI4FA properties, and impact resistance.

This invention relates to a synthetic resin lens that prevents lunar reflection.

Synthetic resin is superior to glass in terms of impact resistance, No. 1 properties, dyeability, and ease of processing, so safety and fashion are important for eyeglass lenses.

It is often used in camera lenses, etc. that aim to achieve a single-length lens.

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, a two-traverse method has conventionally been used. One method is to apply a hard coat layer of silicone resin, acrylic resin, melamine, etc. to the surface of a synthetic resin lens using the deveping method.

Apply using spinner method, flow method, nupure method, etc.

A film is formed by thermal curing or ultraviolet curing. This method improves the heat resistance, water resistance,
Although it has advantages such as excellent durability such as scratch resistance and adhesion and reduces #4 impact resistance of the lens, it has the disadvantage that it does not have an antireflection effect.

Another method is to form silicon oxide, aluminum oxide, etc. on the surface of a synthetic resin lens using a vacuum evaporation method or a Spar 74 IJ song method. It has been put to practical use in optical lenses.The structure is as shown in Figure 1. First, silicon oxide and aluminum oxide are deposited on a composite resin lens base material. etc.)
%i, and on top of that,] This method consists of several layers of alternating materials and materials with a low refractive index; in the form of an anti-irradiation layer.

Although it has the advantage of being both coated and anti-reflective, it has the disadvantage of poor coating durability and poor impact resistance. There is. For example, a method has been proposed in which a synthetic resin film is provided as a node coat layer and a horizontal pipe is formed thereon by vacuum deposition, and some methods have already been commercialized. In this case, since the coating layer is made of 5 synthetic m@, it is possible to reduce the smell of inorganic substances and improve durability such as negative properties, T4 properties, and scratch resistance. There is also a way to obtain an antireflection effect from a synthetic resin thin film (τ).For example, IPilSi!
In the case of an L/lens base material with a side structure as disclosed in 6301 K, since the synthetic resin film with a different refractive index from the lens base material is directly provided on the P surface of the lens base material, the lens base material and The antireflection layer has a defect in that the reflection in the lower layer boundary line 11 becomes high, the antireflection effect is impaired, and a stable interference color cannot be obtained.

In some cases, the thickness of the hard coat layer freezes, resulting in poor scratch resistance.

The present invention eliminates six disadvantages.The purpose of the present invention is to have excellent scratch resistance, heat resistance, and impact resistance.
Sumikoto K provides synthetic resin lenses with anti-reflection effect.
be.

In other words, in accordance with the present invention 1] On the surface of a synthetic resin lens base material A having a refractive index of 148 to 155, the difference in refractive index from the base material is within 1004, and the film thickness is 1 to 20 μm. A hard coat layer made of a synthetic tree coating IIIB is provided, and a layer thickness of 70 to 200 mm is further applied to the surface of the 1C coating. +,? Fl
A synthetic resin lens characterized in that it is provided with antireflection Pfg by a single layer or multilayer synthetic resin coating Rclr.

(2) 1R4 or ld2 among the layers constituting the master synthetic resin coating B and ry7 or the synthetic resin-covered MIC
A synthetic resin lens according to Claim 1'g1, wherein each of the layers contains the following (a), (b), and (c) as main components.

(In the formula, RJ-j is a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group,
an amino group, an imino group, an epoxy group, a (methoxyacryloxy group, a phenyl group, and a chemical compound), R2 is hydrogen, or ) hydrocarbon group, R3 is a hydrocarbon group having 1 to 5 carbon atoms, ano1koxyalkyl, or 1 to 4 carbon atoms ('37 C/l=certain-a, bb and n+b II-tO, + + 1 or 2 or more poles of slave silicon compound shown in (or 2).

(1% diameter, i ~ 100 millimicrons colloidal silica, (・U) Gesium perchlorate (3) The above component (B) is a metal atom such as aluminum, goominilum, zirconium, antimony, etc. The synthetic resin lens described in item 2 of the enclosure of claim 1'F, characterized in that it is an oxide of.

Next, each film constituting the synthetic resin lens according to the present invention will be explained in detail.

The basic 4N configuration of the present invention is 191 seconds of tR2 and 1; Preventive layers 21 to 22 are provided.

Preferred synthetic resin lens base materials include acrylic resins and diethylene glycol bis-gamma lyl carbonate resins, which are widely used in eyeglass lenses, as well as polyester alkyd resins, epoxy resins, vinyl chloride resins, polyethylene resins, etc. The resin coating B must be sufficiently durable as a -.-decoat layer. The purpose of the hard coat layer is to improve the scratch resistance of the lens surface.
The objective is not to adversely affect the antireflection effect of the antireflection layer provided on the hard coat IflL'r1. Therefore, it is necessary to use a synthetic resin whose refractive index difference with the lens base material is within ±004 for the synthetic resin coating B which is formed by the hard coat layer, and whose II@thickness is 1. From 2
It has a thickness of 0 μη7, which is sufficient to improve WI4 scratch resistance and gamma-do staining property. If the difference in refractive index with the base material is ±0.04 or more, reflection will be high at the interface, which will adversely affect the anti-reflection effect, which is one of the characteristics of the present invention, and the hard coat layer film. If the thickness is not uniform, the interference color will be slightly distorted, which will be a fatal drawback for lenses. Further, the film thickness preferably varies from 1 to 2011 μm, more preferably from 2 to 10 μm. When the film thickness is less than 1 μm, the abrasion resistance is poor and it is insufficient 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 hard coat layer in the present invention, there is a difference in refractive index with the substrate.

Since it is within 1004, there is no need to strictly control the film thickness, and the thickness is within ±0.3μ. If it is within 1, there is no problem.

Components (a) and 17 used in synthetic resin coating B are tetramethothodisilanetetramethothodisilanetetraisobroboxysilanetetrabutoxysilaneethyltrimethoxysilanemethyltriethoxysilanemethyltripropoxysilanemethyltriptoxysilaneethyltrimethoxysilane Ethyltriethoxysilane Vinyltriethoxysilane Vinyltriethoxysilane Vinyltriethoxysilane Vinyldria + Toxysilane r-Aminopropyltrimethoxysilane r-Dalisidoxypropyltrimethoxysilane r-Glycidoxypropyltriethoxysilane β-(5 ,4-epoxycyclohexyl)ethyltrimethoxysilane β-(3,4-epoxycyclohexyl)ethyltriethoxysilane r-methacryloxypropyltrimethoxysilane phenyltrimethoxysilane r-mercabutopropyltrimethoxysilane phenyltriacetoxysilane r- Chloropropyltrimethoxysilane β-Cyanoethyltriethoxysilane Dimethyldimethoxysilane Dimethyljethoxysilane r-Glycidoxybrobylmethyldimeth=Psisila r-
Examples include methacryloxypropylmethyldimethoxysilane, phenylmethyldimethoxysilane, vinylutrine (β-methoxyetho-Vsilane) silane, and the like. These may be used alone or in combination of two or more. In addition, it is preferable to use these by hydrolyzing them in an organic solvent such as alcohol in the presence of an acid.
Even if it is mixed with and hydrolyzed, or mixed with component (b) after hydrolysis, the result is white.

Colloidal silica with a particle size of 1 to 100 millimicrons and oxides of metals such as aluminum, titanium, zirconium, and antimony, water, and an alcohol-based dispersion medium with a high molecular weight This is a colloidal solution in which fine metal oxide particles are dispersed. The type of metal oxide depends on whether it is selected and mixed in accordance with the refractive index of the lens base material.

Excellent hot water resistance and dyeability by using line segment (A) type 1 + bamboo type 2 odour, component (B) as a curing catalyst, and component (C) magnesium perchlorate as a curing catalyst. Therefore, it is possible to obtain a paint that has chemical resistance and weather resistance, and a paint that has a long pot life. Aluminum acetylacetonate, ammonium perchlorate, tin octylate, etc. are generally known as curing catalysts, but these have insufficient surface hardness and poor tI hydrothermal properties. It has disadvantages such as short pot life of the liquid,
There is no other product other than magnesium perchlorate that can satisfy you in all aspects.

The synthetic resin that constitutes the anti-reflection W4 must have excellent scratch resistance, just like the resin used for the hard coat layer. In addition, in order to obtain a good antireflection effect, a method is adopted in which layers with a high refractive index and layers with a low refractive index are alternately stacked, so the synthetic resin film C is not limited to single layer and Fi, but can also be used in multilayer cases. be. Fortunately, in the case of 8 layers, a layer with a high refractive index and a low J
A difference in refractive index of 005 or more is required between the layer having the refractive index and the layer having the refractive index. Therefore, as a layer with a high refractive index, a refractive index of 15
3 or more combination 4? L-fats, such as polystyrene, polycarbonate, aromatic rings other than polystyrene V, hetero-A, alicyclic cyclic groups, various polymer compositions containing halogens other than Abutake furion, melamine resins, phenolic resins, etc. 1-1
Thermosetting resins using a curing agent such as a sigboxoxy resin, and various modified resins in which a double bond is introduced into the compound described above to have zero radical curing ability are preferred. Furthermore, the refractive index of the silicone resin can be increased by using it with a metal compound, a metal coordination compound, or the like. In addition, a resin using the synthetic resin coating BK 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 an aluminum sol, a titanium sol, or the like in the metal oxide colloid solution of component (b). As the layer having a low refractive index, synthetic resins having a refractive index of less than 151 are preferable, such as acrylic resins, vinyl resins, fluororesins, polyester resins containing alkyds, cellulose resins, and silicone resins. There is also a method of using various synthetic trees by substituting them with fluorine atoms. In addition, the resin used for the synthetic resin coating 111iB can also be used. In this case, in order to lower the refractive index of VC, it is necessary to adjust each component because it is 1P. Specifically, the ingredients (b)
using silica sol. There are methods such as increasing the proportion of 9F (b) in each component.

The mixing ratio of each component shown in Claims 2 and 3 of the IC of the present invention is preferably determined by fjν (portion) (Si(h binding−c fi ni) solid content 1100
The total of 7ft solids and 11j%il is 50-80
The total amount of component (c) is 50 to 600 parts by weight, and component (c) is used within a range of 0.01 to 5.0 weight percent of the total residual solid content. In addition, more favorable neutrophils 17
Component (a) is 100 to 500 duplicates, above 4.
) Each If is γ/1. Solvents such as coals, /7-tons, cellosolves, carboxylic acids 1, and C can be used alone or mixed together, and if necessary, a small amount of surfactant, antistatic agent, and ultraviolet rays can be used. By adding absorbent f#, the coating properties of the coating liquid and the performance of the film can be improved.The present invention will be explained in more detail with reference to Examples below.

Example 1 (1) Synthetic resin lens base diethylene glycol bisallyl carbonate resin (O
R-39) Soak the lens in a 4-functional sodium hydroxide aqueous solution.
After soaking for a minute, wash and dry. The refractive index of this lens is 1
With 5G.

(2) Hard coat layer 005 was added to a solution consisting of 36 parts by weight of r-glycidoxypropyltrimethoxysilane, 19 parts by weight of methanol-dispersed colloidal silica (manufactured by Catalysts & Chemicals, solid molecule A degree 3 Qlili), and 366 parts by weight of ethyl cellosolve. Hydrolysis was carried out by gradually dropping 1 part of 8.2 parts of specified hydrochloric acid.

Thereafter, a heavy portion of magnesium chlorate 01 was added and stirred to mix. To this, silicone surfactant 01
Parts by weight were added to prepare a paint.

A synthetic resin lens base material was immersed in the solution prepared as described above, and the solution was applied uniformly by pulling at a speed of 20 crnA+. 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 150, and the film thickness was 4μ.
I met you at m.

(3) Anti-reflection layer (a) 6 parts by weight of methanol colloidal silica, 3 parts by weight of tetraptoxythikne, and 1 part by weight of Nukunol 91F as described in fm.
ri part and 01 part silicone surfactant were added and stirred to prepare a paint.

(b> Gradually add 12 parts by weight of hydrochloric acid according to Q and G5 standards to a solution consisting of 20 parts by weight of γ-i lysidoxybrobyltrimethoxysolane, 67 parts by weight of the aforementioned methanol-dispersed colloidal silica, and 1 V part of 90 ml of methanol. Then, 2 parts of magnesium chlorate were added and mixed by stirring.

Add silicone surfactant 0.0871r-17wM
was added to make a paint.

A synthetic resin lens on which a hard coat layer was formed according to (2) was immersed in the solution (α) prepared as above, and 101
It was pulled up at a speed of 1 minute and coated evenly. After the coated lenses were heated and dried in a hot air dryer at 80°C for 20 minutes,
The resulting film was heated and dried in a hot air dryer at 520°C for 1 hour, and the resulting film had a refractive index of 159 and a film thickness of 84 nm.Next, a film of solution (BL) was further applied on top of the above-mentioned film. The solution was coated and cured in the same manner as in [1].The refractive index of the obtained solution was 148, and the humidity was 90 nm. The average reflectance of the synthetic resin lens in the visible light range on one side was 2.OcII, and a favorable antireflection effect was observed.

Example 2 (1) For the synthetic resin lens base material, (1) of Example 1 was used.

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

(3) Anti-reflective coating (car-'lid xyprobilt 1' methoxy 12.
Hydrolysis was carried out by gradually dropping 1 part by weight of 0.3N hydrochloric acid into a solution consisting of 5 parts by weight (manufactured by Nissan Chemical Industries, solids content: 10 parts) and methanol (55 parts by weight, 6 parts by weight). Thereafter, 6 μm 002 parts by weight of perchloric acid was aerated and stirred to make it uniform. 0.08 parts by weight of a silicone surfactant was added to this to prepare a paint.

The above-mentioned solution (a) was applied to a synthetic resin lens which had been formed from (2) K to the node coat layer in Example 1. How to apply and cure.

This was done in the same manner as for solution (c)). The obtained film had a refractive index of 1.58 and a film thickness of 85 ηm.
A further coating of solution 1 was applied on top of the above coating.

The average reflection in the visible light range of the synthetic resin lens thus obtained was 21 on one side, making it difficult to obtain a good antireflection effect.Example 1 (1) Synthetic resin lens base material diethylene glycol Bisγ Lyrcarhones) 3071
A lens obtained by heating and polymerizing a solution obtained by mixing 1 part of pendyl methacrylate, 10 parts of diallyl isophthalate, 3 parts of diaryl isophthalate, and 3 parts of 2 parts by weight of isopropylpa-10,000 cydicarbonate was prepared using the lens of Example 1. Surface treatment is performed in the same manner as in (1). The refractive index of this lens is 15
(2) Hard coat layer r-glycidoxypropyltrimethoxysilane 367 (
005 to a solution consisting of 19 parts by weight, 19 parts by weight of methanol-dispersed titanium sol, and 56.6 parts by weight of ethyl cellosolve.
82 parts of specified hydrochloric acid were gradually added dropwise to carry out hydrolysis. Then add 01 parts of magnesium chlorate,
Stir to mix. This includes 0 silicone surfactants.
．． A synthetic resin lens base material was immersed in the solution prepared above, in which 1 part by weight was used as a paint, and 20cInA+
It was pulled up at a speed of The coated lenses were heated and dried for 30 minutes in a hot air drying chair at 80°C, and then
It was heated and dried for 1 hour in a hot air drying oven at 20°C. refractive index t-
The film thickness was 4 μm.

(6) Anti-reflection PK#-t, (3) -( of Example 1)
61 was used. The synthetic tree PII obtained in this way
The average reflectance in the visible light range of the F lens was 20 cm on one side, and a good anti-reflection +L effect was observed.

Example 4 (1) For the synthetic resin lens material, (1) of Example 3 was used. (2) For the hard coat layer, (2) of Example 1 was used.

(5) For the antireflection layer, (3) of Example 2 was used.

Comparative Example 1 (1) For the synthetic resin lens base material, (1) of Example 1 was used.

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

(3) The anti-reflection layers EJiOt, Ziω are alternately deposited with Vcs scraps by vacuum evaporation, and when viewed from the hard boat M91m, Sma°n, , zjo2. The total thickness of the six layers of SiO2 is approximately λ/4, the next λ/02 is λ/4, and the second layer, SiO2, is λ/4. The surface reflection of the synthetic resin lens thus obtained was 09.

The transmittance, scratch resistance, heat resistance, and impact resistance of the above-mentioned practical examples 1 and 4 were evaluated, and the results are shown in Table IK. A trigram,
The test method at NIK is as follows.

(1) Transmittance: The transmittance in the visible range was averaged using 9 spectrophotometers.

(2) Scratch resistance: The state of the coating was observed after #oooo steel wool was reciprocated 100 times under a load of 200 g.

A: Almost no scratches B: Slight scratches C: Many scratches and

(4) Impact resistance: A steel ball drop test was conducted in accordance with the FIIA standard, and those that passed the O11 layer rating were marked as x.

Table 1

[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 Comparative Example 11. 15-piece synthetic resin lens base material, 141'i synthetic resin hard coat film, 13-piece 5int, ZiCh
, in the Ill configuration of F3i02, the total membrane is λ/
4, and the film was formed by vacuum deposition. , 12keZ? :02R1, also 1 1 tri 5iO
2) Each R has an olfactory thickness of λ/4. FIG. 2 shows a synthetic resin lens with a film structure according to the present invention, and corresponds to Example 1. They are a 24-digit synthetic resin lens base material, a 23-digit synthetic resin hard coat film, a 22-digit synthetic 1flI lucid coating with a refractive index of 160, and a 21-digit synthetic resin coating with a refractive index of 148. FIG. 3 shows an application example of a synthetic resin lens with a film structure according to the present invention, and is equivalent to Example 4. A 35-layer synthetic resin lens base material, a 34-layer synthetic resin coating made of synthetic resin, a 33- and 51-layer synthetic resin coating with a refractive index of 148, and a 32-layer resin coating with a refractive index of 157. FIG. 4 shows the spectral reflectance characteristics of a synthetic resin lens having an anti-reflection lens formed by vacuum evaporation as shown in FIG. The straight line in the figure indicates an 0F-39 lens. FIG. 5 shows the spectral reflectance characteristics of the synthetic resin lens having the antireflection pancreas according to the present invention as shown in FIG. Similarly, FIG. 6 shows the spectral reflectance characteristics of FIG. (10) Applicant Suwa Seikosha Co., Ltd. Agent Patent Attorney Tsutomu Saido

Claims (2)

[Claims] (1) On the surface of a synthetic resin lens base material A having a refractive index of 148 to 155, a synthetic resin having a refractive index difference of 0.004 mm or less from the base material and a film thickness of 1 to 20 μm is applied. A node coat layer made of coating B is provided, and an antireflection layer made of a single layer or multilayer synthetic resin coating C1 having a film IF/ of 70 to 200 nm is further provided on the surface of the coating. A special synthetic resin lens. (2) Out of the layers constituting the synthetic resin coating 1IIKB, the top sheet or the synthetic resin coating 1I*C, 1R4
Alternatively, the synthetic resin lens according to claim 1, wherein the two or more layers have the following (a), (b), and (b) as main components. (a) If the general formula is Il R'(L-'t'OR3)4-aJC formula, R1 is a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, an amino group, an imino group, an epoxy group, An organic group containing at least one selected from a noacryloxy group, a phenyl group, and a mercapto group; a hydrocarbon group, a γ-alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms, where a and b are 0,1 or 2, and σ+b≦0)
One or more organic silicon compounds represented by: (b) Colloidal silica with a particle size of 1 to 100 millimicrons. (c) Magnesium perchlorate (31 above-mentioned DK component) can be used for aluminum rim, titanium,
A synthetic resin lens according to claim 2, characterized in that it is an oxide of a metal element such as sodium luconium or antimony.