JPS61130902A - Plastic lens with antireflective film and capable of easy removal of stain - Google Patents

Abstract

PURPOSE:To easily remove a stain by forming ultra - thin film of an organosilicone compd. on an antireflective film provided on the surface of a plastic lens. CONSTITUTION:The ultra - thin film having <=100Angstrom thickness and composed of the organosilicone compd. is formed on the anti - reflective film provided on the surface of the plastic lens. Said organosilicone compd. comprises the compd. having an alkyl, a phenyl or a polyfluoroalkyl group as the substituent of the side chain of the compd. and preferably a polyorganosiloxane compd. having such as 1-20C perfluoroalkyl group and consisting of a two or a three dimensional structure. By applying the titled lens, the lens having a water and an oil repellent properties is obtd., thereby enabling the removal of a water mark due to a water drop adhered on the lens surface and of an oil stain with an ease, and also enabling the removal of a dust due to a good slip on the lens surface. In the titled lens, as the lens surface is not necessary to strongly wipe, the antireflective film is hardly injured, thereby preventing the deteriora tion and ensuring the good durability.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a plastic lens having an anti-reflection film formed on the surface thereof, which has improved reflective properties on the lens surface to make it easier to remove dirt adhering to the lens surface. This invention relates to a plastic lens with a protective film.

[Conventional technology]

In general, transparent plastic materials such as poly(diethylene glycol bisallyl carbonate), polymethyl methacrylate, polycarbonate, polystyrene, and polyvinyl chloride have advantages such as light weight, easy processability, and impact resistance in addition to transparency. Taking advantage of this, it is widely used in the field of various optical components. In optical components,
In particular, the uses of plastic lenses are expanding to include, for example, eyeglass lenses, camera lenses, projector lenses, 7-lens lenses, prisms, and automobile headlight lenses.

For plastic lenses, polymethyl methacrylate is used as a material for sunglasses because it is easy to mass-produce, polycarbonate is used for industrial safety glasses because of its excellent impact resistance, and poly(diethylene glycol bisallyl carbonate) is used for its transparency. Because of its good workability, it is mainly used in eyeglass lenses for vision correction. However, not only plastic lenses made of the above-mentioned transparent plastic materials but also glass lenses have light reflection on the lens surface, which reduces the light transmittance and impairs the brightness when viewed through the lens. A reflection called a ghost appears. For this reason, an antireflection film is usually formed on the lens surface in order to reduce the reflection of light on the lens surface and increase the light transmittance. The antireflection film is, for example, MgF
s + Li1r+ ThF4 + inorganic fluoride such as cryolite, or 810.

Metal oxides such as 81oz, ZrO*, 0eOz, and AlxOs are formed as a single-layer or multilayer coating on the lens surface by vacuum evaporation, sputtering, or other methods.

During use, lenses are contaminated by dust, water droplets, oil droplets, etc. floating in the atmosphere that adhere to their surfaces and reduce their light transmittance. , skin oils, cosmetics, etc. can also adhere to the skin, obstructing the field of vision and increasing discomfort. For this reason, special silicone-treated cloth paper for wiping the lens surface is commercially available, and ultrasonic cleaners that perform ultrasonic cleaning in a cleaning tank filled with a cleaning agent have also been put into practical use.

In general, there are many proposals regarding methods for cleaning the surface of lenses, cleaning methods, or cleaning agents during the manufacturing of lenses. A cleaning agent for eyeglass lenses is disclosed in JP-A-58-10019. However, there are no proposals for ways to improve the stain resistance of lenses, or to make it easier to remove dirt from the surface of lenses, or to improve the surface of plastic lenses with anti-reflection coatings. Not done.

[Problem to be solved by the invention]

Due to the characteristics of the anti-reflection film material, microscopic pores exist in the film of plastic lenses having an anti-reflection film formed on the surface, so it is particularly difficult to remove adhered dirt. Furthermore, it is not easy to completely remove oils and fats even by wiping with the silicone-treated cloth or paper. In particular, since the anti-reflection film I is wiped forcefully with such cloth or paper, it causes scratches on the film surface, and the film peels off from the scratched part due to deformation due to long-term use. There is.

Of course, when cleaning with ultrasonic waves, such cleaning equipment is expensive, and individuals cannot carry it with them and clean it every time there is dirt.

[Means to solve the problem]

Based on the knowledge of the above-mentioned problems, the invention is based on a plastic lens with an anti-reflection film formed on the surface, which has improved surface properties that allow easy removal of difficult-to-remove dirt adhering to the surface. Regarding plastic lenses, we investigated processing agents and processing methods that mainly remove dirt immediately after forming the antireflection film on the antireflection film.

Anti-reflective coatings are formed by vacuum deposition or sputtering of anti-reflective coating material directly on the surface of a plastic lens or on a hard coat film as a single layer or a thin film of the wavelength of light. Visually, it contains many holes. For this reason, contaminants can enter the pores, and the anti-reflection coating has a high coefficient of friction, making it difficult to remove contaminants. Discovered the fact that certain organosilicon compounds are suitable as treatment materials from which contaminants can be easily removed by treating small substances on the anti-reflection coating and adsorbing and immobilizing them in the pores. This has led to the completion of the present invention.

That is, the present invention provides a plastic lens having an anti-reflection film formed on its surface, which is characterized in that an ultra-thin film of 1ooX or less made of an organosilicon compound is formed on the anti-reflection film. The present invention provides a plastic lens with a protective film.

In the present invention, the organosilicon compound that forms an ultra-thin film on the antireflection film has an alkyl group in its side chain.

Preferably, the polyorganosiloxane has a two-dimensional and/or three-dimensional structure having a phenyl group or a polyfluoroalkyl group. In the polyorganosiloxane formed on the antireflection film, when R represents an alkyl group, phenyl group, or polyfluoroalkyl group, the two-dimensional structure is represented by the following formula (■), and the three-dimensional structure is represented by the following formula ( It consists of a repeating unit represented by I[). R may be the same or different.

In the polyfluoroalkyl group-containing polyorganosiloxane in which R is a polyfluoroalkyl group, the polyfluoroalkyl group is particularly preferably a perfluoroalkyl group having 1 to 20 carbon atoms.
) Here, in order to form the perfluoroalkyl group-containing polyorganosiloxane on the antireflection film, the antireflection film is treated with a perfluoroalkyl group-containing silane compound. When the treated silane compound is heated, dehydration and condensation reactions proceed, forming an ultra-thin film having a siloxane structure. The perfluoroalkyl group-containing silane compound used is Rf(OHs)asi, where the perfluoroalkyl group is Rf.
Xm.

R' Rf(OHs)a day 1(OR'), , Rf(O
H4) asiXm.

R' Rf(OHs)a81 (OR'), (where X is a halogen, R' is a lower alkyl group, a is an integer of 2 to 4), etc. are preferred, and such compounds can be obtained by various methods or routes. . For example, RfCH-OHx and H81
Rf(CMRI18
1C1g is synthesized. This reaction is carried out in the presence of a catalyst, at a reaction temperature of 0 to 150°C, and for a reaction time of 1 to 50 hours. Furthermore, Rt was
(OH'')t(OR')m is synthesized.

In the present invention, representative examples of perfluoroalkyl group-containing silane compounds treated on the antireflection film include OFI (CIF), OFH481 (OOFIm),
.

01m ((Jt)40zHa81(OCHm),
.

OFi (cF*)s C5Ha 81 (00shi)
,.

ays (0?ri102H4B1(oaas), 1a
ys (c)1・CrH481(QClll)m +
ays (OFri110!H4ai(OCHI)m.

ays (a7 heavy) 110 wing H481 (0 (Flm)s
.

OX” (OFm)ua*a4s1(ocis),.

Cam (ON's)s CrH481(oCsHm
), .

CI'l (0'Fx), 0zH481 (0011')
1 + (!71(OFri, O2H4B101M.

OFI (CF,), 02m4day 1011.

CFFL (OFz), 0jH1131 (ocas)
, .

OFI (OFF), OIH@81 (OOHI),
.

' OFm (CFt), Qx[gθ1(OOOH
s), .

CFm ((!IFri, 0IHs81 (oczai
), ICJs (01Px)60sHsBLcLs
.

OFs (OFri 101H' day to 1m.

0IFs (CFt)604Hs81(001M)3
.

OFi (OFri, a4mas1 (ocax),.

011 (C!F2), C4H1lSi (OC2H
&), .

OFI (CFz )a C*HaSi (○CzHs
)s.

etc. can be mentioned. Further, the perfluoroalkyl group may be branched, for example, OH1 c, >0F (OFF), C! 2H481 (OCHa)
, .

(Vs ?Hz CF, >C!F (CFri, 02H4BL (oca
Examples include s)t and nato. Furthermore, for example, 2 of the above-mentioned perfluoroalkyl group-containing silane compounds
It may be a mixture of more than one species. In the per7/L/oloalkyl group-containing cylinide compound, the formula, for example Rf
(c) a-Blxm, and in other formulas, a is 2
It is preferable that it is 4 to 4, and other compounds become unstable.

In the perfluoroalkyl group-containing silane compound,
The critical surface tension of perfluoroalkyl group is 7-15 d
yn15! This is lower than that of water or oils, so when the surface is covered with perfluoroalkyl groups, it imparts water and oil repellency, and the coefficient of friction also decreases, making it easier to remove adhered dirt.

Among the polyorganosiloxanes having a two-dimensional and/or three-dimensional structure of organosilicon compounds that form an ultra-thin film on the antireflection film of the present invention, polyorganosiloxanes having an alkyl group or a phenyl group also have surface properties that make it easy to remove dirt. Useful for improvement. The above-mentioned polyorganosiloxane can be directly treated as the organosilicon compound on the antireflection film. Examples of such polyorganosiloxane include polydimethylsiloxane and polydiethylsiloxane.

Examples include polydipropylsiloxane, polymethylsiloxane, polyethylsiloxane, polybutylsiloxane, polyphenylsiloxane, and polymethylphenylsiloxane. In such polyorganosiloxane,
Coating agents containing polydialkylsiloxane as a main component are commercially available and can be easily obtained.

Moreover, the above-mentioned polyorganosiloxane can be synthesized by a well-known method. For example, polydialkylsiloxane is synthesized by hydrolyzing dichlorodialkylsilane and immediately dehydrating and condensing the produced silanol, as shown in the reaction formula below. .

R', 8401m + 2T1xD R'l E
l(OR)! +2HO1゜nR', 81(OH)1
□ (R', 5iO)n+nHi.

R' here represents a lower alkyl group.

Therefore, a halogenated silane compound such as halogenoalkylsilane, halogenophenylsilane, dihalogenodialkylsilane is treated and hydrolyzed on the antireflection coating of a lens on which an antireflection coating is formed, and then dehydrated. By performing a condensation reaction, an ultra-thin film made of polyorganosiloxane can be formed.

In such a polyorganosiloxane, an alkyl group,
Polyorganosiloxane containing phenyl groups has a small activation energy and tends to cause interfacial orientation.
Formation of an ultra-thin film, particularly an extremely thin film of molecular units, imparts strong water repellency. .

When treating an organosilicon compound on an antireflection film, a silane coupling agent, such as cmx- cHcFLzo (cHt), s
l(OCRm),.

ゝ♂ ca2-casl(ocaa),, ca2-aas
tclx.

J-csu4si(oca3).

etc. may be added.

In the present invention, the method of forming an ultra-thin film by treating an organosilicon compound on the anti-reflective film of a plastic lens on which an anti-reflective film is formed is based on the method of forming an ultra-thin film by adsorbing it into microscopic pores existing in the anti-reflective film. , considering that it solidifies, organosilicon compounds, i.e., perfluoroal-? A silane compound containing a silane group, a polyorganosilane, or a halogenated silane compound is mixed with at least one of a solvent such as water, alcohols, ketones, ethers, and rhodanized hydrocarbon solvents, etc. Prepare the solution to have a concentration of %. Among the above-mentioned organosilicon compounds, a commercially available coach ink agent containing dimethylsiloxane as a product and an alcohol as a solvent is preferably used as the polyorganosiloxane.

The prepared solution is applied by a known method onto the antireflection film of a lens on which an antireflection film has been formed, or the lens is immersed in the solution and then pulled up. In this case, it is preferable to carry out the process immediately after the formation of the anti-reflective film, and it is best to carry out the process in a state where the surface of the anti-reflective film is not contaminated by airborne objects, water droplets, oil droplets, etc. This is an important point in terms of formability, adhesion, and the like.

In addition, thoroughly cleaning the antireflection coating surface with highly purified water and drying it in a clean state before processing the organosilicon compound is also useful for improving the formability and adhesion of ultra-thin films.

The organosilicon compound treated on the antireflection film is fixed. When the organosilicon compound is a polyorganosiloxane, a relatively low temperature of 30°C to 50°C is sufficient, and when the organosilicon compound is an organosilane compound, hydrolysis, dehydration, polycondensation reaction and immobilization can be carried out simultaneously. This is carried out by heating to 40°C to 60°C. This fixation treatment lasts from 2 hours to 24 hours.
The process is completed in a short time, and the antireflection film and the ultra-thin film made of an organosilicon compound are closely bonded, and the durability of the formed ultra-thin film is improved.

The thickness of the ultra-thin film formed by treating the antireflection film with an organosilicon compound is preferably 100X or less, and particularly preferably the thickness is in units of molecules. The ultra-microscopic pores present in the anti-reflection film are filled with organosilicon compounds to form an ultra-thin film. If the thickness of the ultra-thin film is greater than 100X, interference colors or reflected colors will occur, which may impair transparency, which is unsuitable.

In the plastic lens on which the antireflection film is formed according to the present invention, the plastic of the lens base material is, for example, poly(diethylene glycol bisallyl carbonate), polymethyl methacrylate, polycarbonate, polystyrene, polyamide, or the like. It consists of a copolymer containing However, other transparent plastic or glass lenses are not excluded.

The anti-reflection film formed on the lens surface may be made of any material such as fluoride or metal oxide, and may be colored by adding a small amount of gold, silver, copper, chromium, aluminum, etc. It may be. In an antireflection film made of such a material, it is preferable to use a metal oxide in terms of ultra-thin film formation and durability of the organosilicon compound formed on the antireflection film, and 810x is more preferable. For example, 5i(h, ZrO, and z) are alternately formed on the lens surface to a specific thickness from the lens side by vapor deposition, and an organic silane compound is treated on the antireflection film whose surface is made of 5102. A plastic lens with an ultra-thin film can easily remove dirt adhering to its surface.Furthermore, even after forced environmental tests, the ease of removing dirt did not deteriorate.
Furthermore, no change in antireflection properties was observed.

〔Example〕

EXAMPLES The present invention will be explained in more detail below using Examples, but the present invention is not limited to these Examples.

Synthesis example 0nF2B410H-OH (however, n is 6.8.10
．． 12 mixtures, average value 9.0) 99.2P (0,2
mole), H81C! Is 32.5? (0.24 mol) and HxPtO1@.Si00.0521F were weighed into a four-way flask and reacted at 80° C. for 20 hours with slow stirring under a nitrogen stream. After the reaction is completed, the product is distilled to give 0n72H+1 (C!11i*)
, 8101s was obtained. Then, CnF2n41 (c
Ht)t 81℃1m 63.2t (0.1mo/L
/) and 200f of methanol were mixed and reacted while bubbling nitrogen gas to remove the generated HOI.

The completion of this reaction was confirmed by quantifying the amount of HOl produced.

After the reaction, excess methanol is distilled off and Onl'2n
41 (OIIs) 181 (0(Ha)) was obtained.

Example 1 A diopter of 0.00. Center thickness approx. 2.4
m, luminous transmittance measuring device (MODEL D manufactured by Asaki Bunkosha)
! Itl, D81'-G engineering) A glass lens with a luminous transmittance of 92- measured from K was cleaned with an ultrasonic cleaner, dried, and then inserted into a vacuum furnace.
rr, the substrate temperature is 60 to 100°C, and the metal oxide film thickness is 5iOz O,045 from the lens surface side.

ZrOx O,032,5ins O,01,Zr(h
A vacuum evaporation process was performed to form an antireflection film to a designed value of O,086,5iOiO,089 (each μm), thereby obtaining a plastic lens with an antireflection film formed on the surface.

Separately, the synthesis example CnF2n41 (OHz), Si○1
An oil solution was prepared by dissolving S in t-butanol.

The glass lens on which the anti-reflection film was formed was immersed in this prepared solution for 1 minute, and then gently pulled out.
The ultrathin film made of polyfluoroalkyl group-containing siloxane was fixed by holding at 0° C. for 3 hours.

In this way, the ultra-thin film made of polyfluoroalkyl group-containing siloxane was formed on the anti-reflection film, and the film thickness of the ultra-thin film was measured, the interference color was measured, and the ease of removing dirt from the lens surface was evaluated. This was done using the following method.

■Thickness measurement of ultra-thin films: z, s, a, A (surface analysis method)
by.

■Measurement of interference color.Measure the peak wavelength using a two-spectrophotometer.
When there is an interference color, the wavelength shifts to the long wavelength side.

Ease of stain removal evaluation test ■Removability of Suigo: Waterproofing is removable by dropping tap water onto the lens surface and, after drying, wiping the remaining waterproofing on the surface with tissue paper.

■Ink removability of water-based pens: After filling in the lens surface with a commercially available water-based pen, the ink can be removed by rubbing it with a cloth.

■Dust removability: Chalk powder can be removed by spreading white chalk powder on the lens surface, allowing it to adhere to the entire surface, and then wiping it with tissue paper.

The results of (1) to (2) above are shown in Table 1. .

Furthermore, for oil repellency (stain resistance), test liquids with different surface tensions (n-dodecane, n-tetradecane, n-tetradecane, n-
The ease with which oily stains can be removed by dripping (-hexadecane) and wiping with tissue paper was confirmed before and after the forced test shown in Table 2.

The results are shown in Table 2.

Example 2 0nFzH+t ((31
”)t(14011 in the synthesis example OnF B1,000I(OH
z )1 Bi (OCH3)3 Except for changing K, it is an example! Similarly, a lens with an ultra-thin film made of polyfluoroalkyl group-containing siloxane formed on an antireflection film was obtained, and film thickness measurement, interference color measurement, dirt removability evaluation test, and Oil repellency was measured. The results are shown in Table 1 and Table tJJZ.

Example 3 A plastic lens on which an antireflection film was formed in the same manner as in Example 1 was coated with a commercially available coating liquid containing polydimethylsiloxane as the main component (trade name: Siliconize FKt03).
1. Fuji Systems Co., Ltd. product) with ethanol.
After immersing it in a solution diluted to 1% for 20 seconds and pulling it out,
Wash immediately with water, further rinse with distilled water, and store at 40°C for 24 hours.
After drying for a while, the ultra-thin film made of polydimethylsiloxane was fixed.

Example 1 Regarding a lens in which an ultra-thin film made of boridime and f-rusiloxane was formed on the antireflection film, Example 1
Film thickness measurements, interference color measurements, dirt removability evaluation tests, and oil repellency measurements were conducted using the following methods. The results are shown in Tables 1 and 2.

Comparative Example 1 A lens in which a 200% thin film was formed by repeating the process of forming an ultra-thin film made of polyfluoroalkyl group-containing siloxane on the anti-reflection film of a plastic lens on which an anti-reflection film was formed in the same manner as in Example 2. I got it. The obtained lenses were subjected to film thickness measurements, interference color measurements, and dirt removability evaluation tests using the methods of Example 1. The results are shown in Table 1.

Comparative Example 2 Similar to Example 1, a plastic lens on which an antireflection film was formed was subjected to an evaluation test for ease of stain removal using the method of Example 1 (no ultra-thin film was formed). The results are shown in Table 81.

〔Effect of the invention〕

The plastic lens with an anti-reflection film of the present invention has an ultra-thin water- and oil-repellent film formed on the anti-reflection film, and as a result, the lens surface is provided with water- and oil-repellency, and the surface friction - Since the number is small, it is possible to easily remove water droplets adhering to the surface, oil stains, etc. Furthermore, since the lens surface is smooth, it is extremely easy to remove dust and other particles that have adhered to it.

There is no need to forcefully wipe the lens surface to remove dirt, and the anti-reflection coating is less likely to be damaged.

The ease with which stains can be removed does not deteriorate even in forced environment tests, and it has the effect of being excellent in durability.

Claims (3)

[Claims] (1) A plastic lens with an anti-reflection film formed on its surface, which is characterized by an ultra-thin film of 100 Å or less made of an organosilicon compound formed on the anti-reflection film, with an anti-reflection film that is easy to remove dirt. plastic lens. (2) Claims characterized in that the organosilicon compound forming the ultra-thin film is a polyorganosiloxane with a two-dimensional and/or three-dimensional structure having an alkyl group, phenyl group, or polyfluoroalkyl group in the side chain. The plastic lens described in item 1. (3) The plastic lens according to claim 2, wherein the polyfluoroalkyl group is a perfluoroalkyl group having 1 to 20 carbon atoms.