U.S. patent application number 10/316105 was filed with the patent office on 2003-07-10 for method for producing antireflection film-coated plastic lens, and antireflection film-coated plastic lens.
This patent application is currently assigned to Hoya Corporation. Invention is credited to Arai, Akiko.
Application Number | 20030127756 10/316105 |
Document ID | / |
Family ID | 19188501 |
Filed Date | 2003-07-10 |
United States Patent
Application |
20030127756 |
Kind Code |
A1 |
Arai, Akiko |
July 10, 2003 |
Method for producing antireflection film-coated plastic lens, and
antireflection film-coated plastic lens
Abstract
The method produces a plastic lens with an antireflection film
which have the advantages of good adhesion of the antireflection
film to any type of hard coat film that underlies it and good
abrasion resistance and provides a plastic lens with an
antireflection film. The method includes the steps of applying
water or an aqueous solution to a plastic lens with an
organosilicon compound-containing hard coat film to form a liquid
film of water or the aqueous solution on the surface of the hard
coat film, then allowing ozone gas to contact with the liquid film
to treat the surface of the hard coat film with the ozone gas, and
thereafter forming an antireflection film on the surface of the
hard coat film through vapor deposition.
Inventors: |
Arai, Akiko; (Tokyo,
JP) |
Correspondence
Address: |
Barry E. Bretschneider
Morrison & Foerster LLP
Suite 300
1650 Tysons Boulevard
McLean
VA
22102
US
|
Assignee: |
Hoya Corporation
Tokyo
JP
|
Family ID: |
19188501 |
Appl. No.: |
10/316105 |
Filed: |
December 11, 2002 |
Current U.S.
Class: |
264/1.32 ;
264/1.7; 264/83 |
Current CPC
Class: |
C08J 7/12 20130101; G02B
1/11 20130101 |
Class at
Publication: |
264/1.32 ;
264/1.7; 264/83 |
International
Class: |
B29D 011/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 25, 2001 |
JP |
2001-391306 |
Claims
What is claimed is:
1. A method for producing a plastic lens with an antireflection
film on a surface thereof, comprising: applying water or an aqueous
solution to a plastic lens having an organosilicon
compound-containing hard coat film formed on a surface thereof to
form a liquid film of water or the aqueous solution on the surface
of the hard coat film, allowing ozone gas to contact with the
liquid film so as to treat the surface of the hard coat film with
the ozone gas, and forming the antireflection film on the ozone gas
treated surface of the hard coat film by vapor deposition.
2. The method for producing a plastic lens with an antireflection
film of claim 1, comprising spraying the water or the aqueous
solution on the hard coat-film to form the liquid film on the hard
coat film.
3. The method for producing a plastic lens with an antireflection
film of claim 1, wherein the water or the aqueous solution further
comprises ozone gas.
4. The method for producing a plastic lens with an antireflection
film of claims 1, 2 or 3, wherein the aqueous solution contains a
radical scavenger.
5. The method for producing a plastic lens with an antireflection
film of claim 4, wherein the radical scavenger is a hydrogen
carbonate or a phosphate.
6. The method for producing a plastic lens with an antireflection
film of claim 5, wherein the aqueous solution contains the radical
scavenger in an amount of 0.01 mols/liter or more based on the
aqueous solution.
7. The method for producing a plastic lens of claim 1, wherein the
hard coat film contains metal oxide fine particles.
8. The method for producing a plastic lens of claim 7, wherein the
metal oxide fine particles comprise at least one type of particle
selected from silicon oxide particles, titanium oxide particles and
tin oxide particles.
9. The method for producing a plastic lens of claim 1, wherein the
plastic lens comprises at least one resin selected from the group
consisting of a polythiourethane resin, an epithio group-containing
resin and a diethylene glycol bisallylcarbonate-containing
resin.
10. The method for producing a plastic lens of 1, wherein the
concentration of the ozone gas allowed to contact the liquid film
on the hard coat film is 50 g/Nm.sup.3 or more.
11. The method for producing a plastic lens of claim 1, wherein the
concentration of the ozone gas allowed to contact the liquid film
on the hard coat film is 100 g/Nm.sup.3 or more.
12. The method for producing a plastic lens of claim 1, wherein the
concentration of the ozone gas allowed to contact the liquid film
on the hard coat film is 140 g/Nm.sup.3 or more.
13. The method for producing a plastic lens as claimed in claim 1,
2, 3, 7, 8, 9, 10, 11 or 12, wherein the time for contacting the
ozone gas with the liquid film is between about 10 seconds and
about 10 minutes.
14. The method for producing a plastic lens as claimed in claim 4,
wherein the time for contacting the ozone gas with the liquid film
is between about 10 seconds and about 10 minutes.
15. The method for producing a plastic lens as claimed in claim 5,
wherein the time for contacting the ozone gas with the liquid film
is between about 10 seconds and about 10 minutes.
16. The method for producing a plastic lens as claimed in claim 6,
wherein the time for contacting the ozone gas with the liquid film
is between about 10 seconds and about 10 minutes.
17. The method for producing a plastic lens as claimed in claim 1,
2, 3, 7, 8, 9, 10, 11 or 12, wherein the organosilicon compound
used to form the hard coat film is at least one compound selected
from compounds of general formula (I):
(R.sup.1).sub.a(R.sup.3).sub.bSi(OR.sup.2).sub.4-(a+- b) (I)
wherein R.sup.1 and R.sup.3 each independently represent a
monovalent hydrocarbon group having from 1 to 10 carbon atoms, with
or without a functional group; R.sup.2 represents an alkyl group
having from 1 to 8 carbon atoms, an aryl group having from 6 to 10
carbon atoms, an aralkyl group having from 7 to 10 carbon atoms or
an acyl group having from 1 to 8 carbon atoms; a and b each
independently indicate 0 or 1; and a plurality of the OR.sup.2
groups may be the same or different from each other, and compounds
of general formula (II): 2wherein R.sup.4 and R.sup.5 each
independently represent a monovalent hydrocarbon group having from
1 to 5 carbon atoms, with or without a functional group; X.sup.1
and X.sup.2 each independently represent an alkyl group having from
1 to 4 carbon atoms or an acyl group having from 1 to 4 carbon
atoms; Y represents a divalent hydrocarbon group having from 1 to
20 carbon atoms; x and y each independently indicate 0 or 1; a
plurality of the X.sup.1 groups may be the same or different from
each other; and a plurality of the X.sup.2 groups may be the same
or different from each other, and hydrolyzates of the compounds of
formula (I) and formula (II).
18. The method for producing a plastic lens as claimed in claim 4,
wherein the organosilicon compound used to form the hard coat film
is at least one compound selected from compounds of general formula
(I): (R.sup.1).sub.a(R.sup.3).sub.bSi(OR.sup.2).sub.4-(a+b) (I)
wherein R.sup.1 and R.sup.3 each independently represent a
monovalent hydrocarbon group having from 1 to 10 carbon atoms, with
or without a functional group; R.sup.2 represents an alkyl group
having from 1 to 8 carbon atoms, an aryl group having from 6 to 10
carbon atoms, an aralkyl group having from 7 to 10 carbon atoms or
an acyl group having from 1 to 8 carbon atoms; a and b each
independently indicate 0 or 1; and a plurality of the OR.sup.2
groups may be the same or different from each other, 3and compounds
of general formula (II): wherein R.sup.4 and R.sup.5 each
independently represent a monovalent hydrocarbon group having from
1 to 5 carbon atoms, with or without a functional group; X.sup.1
and X.sup.2 each independently represent an alkyl group having from
1 to 4 carbon atoms or an acyl group having from 1 to 4 carbon
atoms; Y represents a divalent hydrocarbon group having from 1 to
20 carbon atoms; x and y each independently indicate 0 or 1; a
plurality of the X.sup.1 groups may be the same or different from
each other; and a plurality of the X.sup.2 groups may be the same
or different from each other, and hydrolyzates of the compounds of
formula (I) and formula (II).
19. A plastic lens with an antireflection film produced by the
method of claim 13.
20. A plastic lens with an antireflection film produced by the
method of claim 15.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a method for producing a
plastic lens with an antireflection film and to a plastic lens with
an antireflection film. More precisely, the invention relates to a
method of producing a plastic lens having the advantages of good
adhesion of the antireflection film to the hard coat film that
underlies the antireflection film and good abrasion resistance, and
to a plastic lens.
BACKGROUND OF THE INVENTION
[0002] To prevent the deterioration of adhesion between a hard coat
film and an antireflection film of a plastic lens and abrasion
resistance thereof, it is known to treat the surface of the hard
coat film with oxygen radicals, that is, with ozone gas or ozone
water. One example of the method of producing such a plastic lens
is disclosed in JP-A-2001-141905, in which the surface of a hard
coat film of a plastic lens substrate with a hard coat film
containing titanium oxide fine particles is treated with ozone gas
or dipped into ozone water and then an antireflection film is
formed on the treated hard coat film through vapor deposition.
[0003] However, when the hard coat film formed on a plastic lens
substrate contains metal oxide particles other than titanium oxide
particles, such as silicon oxide particles, and when its surface is
treated with ozone gas or ozone water according to this prior art
method, there is a probability that the adhesion of the hard coat
film to the antireflection film that overlies it and also the
abrasion resistance of the thus-coated plastic lenses inevitably
deteriorate.
SUMMARY OF THE INVENTION
[0004] This invention provides a method for producing a plastic
lens with an antireflection film having good adhesion of the
antireflection film to any type of hard coat film that underlies it
and good abrasion resistance, and provides a plastic lens with an
antireflection film.
[0005] This invention involves forming a liquid film of water or an
aqueous solution on the surface of the hard coat film of a plastic
lens before an antireflection film is formed on the hard coat film,
followed by treating the film with ozone gas. Specifically, the
invention provides a method for producing a plastic lens with an
antireflection film, which comprises applying water or an aqueous
solution to a plastic lens with an organosilicon
compound-containing hard coat film to form a liquid film of water
or the aqueous solution on the surface of the hard coat film,
allowing ozone gas to contact with the liquid film to treat the
surface of the hard coat film with the ozone gas, and thereafter
forming the antireflection film on the surface of the hard coat
film through vapor deposition, and provides a plastic lens with an
antireflection film obtained by this production method.
[0006] The method for producing the plastic lens with the
antireflection film of the invention includes applying water or an
aqueous solution to a plastic lens with an organosilicon
compound-containing hard coat film to form a liquid film of water
or the aqueous solution on the surface of the hard coat film,
allowing ozone gas to contact with the liquid film to treat the
surface of the hard coat film with the ozone gas, and thereafter
forming an antireflection film on the treated surface of the hard
coat film by vapor deposition. The production method of the
invention provides a plastic lens with an antireflection film which
has the advantages of good abrasion resistance and good adhesion of
the antireflection film to any type of hard coat film that
underlies it.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 shows an ozone gas-treating apparatus for carrying
out the method of the invention of producing a plastic lens with an
antireflection film.
[0008] FIG. 2 shows an ozone-treating tank in the ozone
gas-treating apparatus for carrying out the method of the invention
of producing a plastic lens with an antireflection film.
DETAILED DESCRIPTION OF THE INVENTION
[0009] Examples of the lens production method of the invention and
the apparatus for carrying out this method are described in detail
hereafter with reference to the drawings attached hereto.
[0010] FIG. 1 shows an ozone-treating apparatus 1 for use in
performing the method of the invention, which basically comprises a
known ozone gas generator 2; an ozone gas-feeding duct 2a; an
ozone-treating tank 3 for contacting ozone gas with the surface of
a hard coat film on a lens; an aqueous ozone waste-decomposing unit
4; a post-treating unit 5 for performing treatments such as drying
of the lens; an ozone gas-decomposing unit 6; a solution-feeding
duct 7; and an ejection tube 8 through which ozone gas is ejected
toward the lens in the ozone-treating tank 3.
[0011] FIG. 2 shows the ozone-treating tank 3, which basically
comprises a space 3a in which water is applied to the hard coat
film of the lens 9 to form a water film thereon and ozone gas is
applied to the lens with the water film on it; a solution pool 3b
arranged in the lower part of the ozone-treating tank 3 and having
the ejection tube therein; and a holder 3c for holding the
lens.
[0012] The ozone-treating apparatus 1 operates as follows. As shown
in FIG. 2, the solution in the solution pool 3b is pumped to spray
nozzle 10 via a circulation duct 11a by pump 11. At that time, the
solution is sprayed through the spray nozzle 10 onto the hard coat
film of the lens 9 to form a film of the solution. The sprayed
solution that drips from the lens surface is pooled in the solution
pool 3b, and may be circulated and reused. The amount of the
solution spray to be applied to the lens is preferably from 0.3 to
3.5 liters/min, for example, when the volume (of the vapor part) of
the treating tank 3 is about 120 liters.
[0013] The solution in the solution pool 3b is preferably water,
ozone water, or an aqueous solution that contains a radical
scavenger. The radical scavenger may be any known one, including,
for example, hydrogen carbonates such as sodium hydrogen carbonate,
and phosphates such as sodium phosphate. The concentration of the
radical scavenger in the solution is preferably from 0.01
mols/liter up to a saturated concentration thereof, more preferably
from 0.1 mols/liter to 1.00 mol/liter, in view of the adhesion of
the hard coat film to the antireflection film. Preferably, the
temperature of the solution pool 3b falls between about 15.degree.
C. and about 30.degree. C.
[0014] The ozone gas generator 2 generates ozone gas. Thus
generated, the ozone gas moves to the ejection tube 8 which has
orifices formed therein, via the feeding duct 2a, and then this
ozone gas is ejected out into the ozone-treating tank 3 through the
orifices. In this stage, the flow rate of the ozone gas that is fed
through the feeding duct 2a is preferably from 2 to 3 liters/min,
for example, when the volume (of the vapor part) of the treating
tank 3 is about 120 liters. Though depending on the type of the
hard coat film of the lens and on the type of the antireflection
film to be formed thereon, the ozone gas concentration to be fed
through the feeding duct 2a is generally 50 g/Nm.sup.3 or more,
preferably 100 g/Nm.sup.3 or more, more preferably 140 g/Nm.sup.3
or more for attaining good adhesion of the hard coat film to the
antireflection film. Preferably, the temperature of the ozone gas
to be fed falls between 15 and 40.degree. C.
[0015] The ozone gas ejected out through the ejection tube 8 is
allowed to come into contact with the solution pool 3b of the
ozone-treating tank 3. The ozone gas thus allowed to contact the
solution pool 3b first dissolves in the solution in the solution
pool 3b, but after it has reached the saturation point, it does not
dissolve further in the solution and moves upward and is brought
into contact with the lenses 9. Based on this principle, the liquid
film of the lens 9 is treated with ozone gas. The treating time
preferably falls between 10 seconds and 10 minutes, though varying
depending on the ozone gas concentration and the composition of the
hard coat film. If the treating time is too long, the hard coat
film may peel off. Therefore, the treatment is carried out to such
a degree that the hard coat film does not peel because the
treatment time is too long.
[0016] When it is not necessary to use the solution in the solution
pool 3b any more, it is led to the aqueous ozone waste-decomposing
unit 4 via a transfer duct 4a, and processed therein. The ozone gas
in the treating tank is led to the ozone-decomposing unit 6 via
ozone gas transfer duct 6a, and is then discharged out of the
apparatus. When a fresh solution is needed, it is fed into the
solution pool 3 via the solution-feeding duct 7.
[0017] The organosilicon compound used to form the hard coat film
is, for example, at least one selected from compounds of general
formula (I):
(R.sup.1).sub.a(R.sup.3 ).sub.bSi(OR.sup.2).sub.4-(a+b) (I)
[0018] wherein R.sup.1 and R.sup.3 each independently represent a
monovalent hydrocarbon group having from 1 to 10 carbon atoms, with
or without a functional group; R.sup.2 represents an alkyl group
having from 1 to 8 carbon atoms, an aryl group having from 6 to 10
carbon atoms, an aralkyl group having from 7 to 10 carbon atoms or
an acyl group having from 1 to 8 carbon atoms; a and b each
independently indicate 0 or 1; and a plurality of the OR.sup.2
groups may be the same or different from each other, and compounds
of general formula (II): 1
[0019] wherein R.sup.4 and R.sup.5 each independently represent a
monovalent hydrocarbon group having from 1 to 5 carbon atoms, with
or without a functional group; X.sup.1 and X.sup.2 each
independently represent an alkyl group having from 1 to 4 carbon
atoms or an acyl group having from 1 to 4 carbon atoms; Y
represents a divalent hydrocarbon group having from 1 to carbon
atoms; x and y each independently indicate 0 or 1; a plurality of
the X.sup.1 groups may be the same or different from each other;
and a plurality of the X.sup.2 groups may be the same or different
from each other, and hydrolyzates of the compounds of formula (I)
and formula (II).
[0020] In formula (I), the monovalent hydrocarbon group having from
1 to 10 carbon atoms for R.sup.1 and R.sup.3 includes an alkyl
group having from 1 to 10 carbon atoms, an alkenyl group having
from 2 to 10 carbon atoms, an aryl group having from 6 to 10 carbon
atoms, and an aralkyl group having from 7 to 10 carbon atoms. The
alkyl and alkenyl groups may be linear, branched or cyclic.
Examples of the alkyl group having from 1 to 10 carbon atoms
include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
sec-butyl, tert-butyl, pentyl, hexyl, octyl, cyclopentyl and
cyclohexyl groups. Examples of the alkenyl group having from 2 to
10 carbon atoms include vinyl, allyl, butenyl, hexenyl and octenyl
groups. Examples of the aryl group having from 6 to 10 carbon atoms
include phenyl, tolyl, xylyl and naphthyl groups. Examples of the
aralkyl group having from 7 to 10 carbon atoms include benzyl,
phenethyl and naphthyhnethyl groups.
[0021] These hydrocarbon groups may have a functional group
introduced thereinto. These functional group include, for example,
a halogen atom, a glycidoxy group, an epoxy group, an amino group,
a cyano group, a mercapto group, and a (meth)acryloxy group.
Examples of the monovalent hydrocarbon group having from 1 to 10
carbon atoms with such a functional group include glycidoxymethyl,
.alpha.-glycidoxyethyl, .beta.-glycidoxyethyl,
.alpha.-glycidoxypropyl, .beta.-glycidoxypropyl,
.gamma.-glycidoxypropyl, .alpha.-glycidoxybutyl,
.beta.-glycidoxybutyl, .gamma.-glycidoxybutyl,
.delta.-glycidoxybutyl, (3,4-epoxycyclohexyl)meth- yl,
.beta.-(3,4-epoxycyclohexyl)ethyl,
.gamma.-(3,4-epoxycyclohexyl)propyl- ,
.delta.-(3,4-epoxycyclohexyl)butyl, chloromethyl,
.gamma.-chloropropyl, 3,3,3-trifluoropropyl,
.gamma.-methacryloxypropyl, .gamma.-acryloxypropyl,
.gamma.-mercaptopropyl, .crclbar.-cyanoethyl,
N-(.beta.-aminoethyl)-.gamma.-aminopropyl and .gamma.-aminopropyl
groups.
[0022] On the other hand, the alkyl group having from 1 to 8 carbon
atoms for R.sup.2 may be linear, branched or cyclic. Examples
thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopentyl and
cyclohexyl groups. Examples of the aryl group having from 6 to 10
carbon atoms for R.sup.2 include phenyl, tolyl and xylyl groups;
and examples of the aralkyl group having from 7 to 10 carbon atoms
for R.sup.2 include benzyl and phenethyl groups. The acyl group
having from 1 to 8 carbon atoms for R.sup.2 is, for example, an
acetyl group.
[0023] Examples of the compounds of formula (I) include methyl
silicate, ethyl silicate, n-propyl silicate, isopropyl silicate,
n-butyl silicate, sec-butyl silicate, tert-butyl silicate,
tetraacetoxysilane, methyltrimethoxysilane, methyltripropoxysilane,
methyltrimethoxysilane, methyltributoxysilane,
methyltriamyloxysilane, methyltriphenoxysilane,
methyltribenzyloxysilane, methyltriphenethyloxysilane,
glycidoxymethyltriethoxysilane, glycidoxymethyltrimethoxysilane,
.alpha.-glycidoxyethyltrimethoxysilane,
.alpha.-glycidoxypropyltrimethoxy- silane,
.beta.-glycidoxyethyltriethoxysilane, .alpha.-glycidoxypropyltrime-
thoxysilane, .alpha.-glycidoxypropyltriethoxysilane,
.beta.-glycidoxypropyltrimethoxysilane,
.beta.-glycidoxypropyltriethoxysi- lane,
.gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-glycidoxypropyltrie- thoxysilane,
.gamma.-glycidoxypropyltripropoxysilane,
.gamma.-glycidoxypropyltriphenoxysilane,
.beta.-glycidoxybutyltrimethoxys- ilane,
.beta.-glycidoxybutyltriethoxysilane,
.gamma.-glycidoxybutyltrimeth- oxysilane,
.gamma.-glycidoxybutyltriethoxysilane, .delta.-glycidoxybutyltr-
imethoxysilane, .delta.-glycidoxybutyltriethoxysilane,
(3,4-epoxycyclohexyl)methyltriethoxysilane,
(3,4-epoxycyclohexyl)methyltr- imethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltriethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltripropoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltributoxysilane,
.beta.-(3,4-epoxycycloh- exyl)ethyltriphenoxysilane,
.gamma.-(3,4-epoxycyclohexyl)propyltrimethoxys- ilane,
.gamma.-(3,4-epoxycyclohexyl)propyltriethoxysilane,
.delta.-(3,4-epoxycyclohexyl)butyltrimethoxysilane,
.delta.-(3,4-epoxycyclohexyl)butyltriethoxysilane,
glycidoxymethylmethyldimethoxysilane,
glycidoxymethylmethyldiethoxysilane- ,
.alpha.-glycidoxyethylmethyldimethoxysilane,
.alpha.-glycidoxyethylmethy- ldiethoxysilane,
.beta.-glycidoxyethylmethyldimethoxysilane,
.beta.-glycidoxyethylmethyldiethoxysilane,
.alpha.-glycidoxypropylmethyld- imethoxysilane,
.alpha.-glycidoxypropylmethyldiethoxysilane,
.beta.-glycidoxypropyhmethyldimethoxysilane,
.alpha.-glycidoxypropylmethy- ldiethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-glycidoxypropylmethyldiethoxysilane,
.gamma.-glycidoxypropylmethy- ldipropoxysilane,
.gamma.-glycidoxypropylmethyldibutoxysilane,
.gamma.-glycidoxypropylmethyldiphenoxysilane,
.gamma.-glycidoxypropylethy- ldimethoxysilane,
.gamma.-glycidoxypropylethyldiethoxysilane,
.gamma.-glycidoxypropylvinyldimethoxysilane,
.gamma.-glycidoxypropylvinyl- diethoxysilane,
.gamma.-glycidoxypropylphenyldimethoxysilane,
.gamma.-glycidoxypropylphenyldiethoxysilane, ethyltrimethoxysilane,
ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane,
vinyltriethoxysilane, phenyltrimethoxysilane,
phenyltriethoxysilane, phenyltriacetoxysilane,
.gamma.-chloropropyltrimethoxysilane,
.gamma.-chloropropyltriacetoxysilane,
3,3,3-trifluoropropyltrimethoxysila- ne,
.gamma.-methacryloxypropyltrimethoxysilane,
.gamma.-mercaptopropyltrim- ethoxysilane,
.gamma.-mercaptopropyltriethoxysilane,
.beta.-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane,
chloromethyltriethoxysilane,
N-(.beta.-aminoethyl)-.gamma.-aminopropyltri- methoxysilane,
N-(.beta.-aminoethyl)-.gamma.-aminopropylmethyldimethoxysil- ane,
.gamma.-aminopropylmethyldimethoxysilane,
N-(.beta.-aminoethyl)-.gamm- a.-aminopropylmethyldiethoxysilane,
dimnethyldimethoxysilane, phenylmethyldimethoxysilane,
dimethyldiethoxysilane, phenylmethyldiethoxysilane,
.gamma.-chloropropylmethyldiethoxysilane,
.gamma.-chloropropylmethyldimethoxysilane, dimethyldiacetoxysilane,
y-methacryloxypropylmethylditnethoxysilane,
.gamma.-methacryloxypropyhnet- hyldiethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane,
.gamma.-mercaptopropylmethyldiethoxysilane,
methylvinyldiimethoxysilane, and methylvinyldiethoxysilane.
[0024] On the other hand, in formula (II), the alkyl group having
from 1 to 4 carbon atoms for X.sup.1 and X.sup.2 includes methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and
tert-butyl groups; and the acyl group having from 1 to 4 carbon
atoms is, for example, preferably an acetyl group. These X.sup.1
and X.sup.2 may independently be the same or different from each
other.
[0025] The monovalent hydrocarbon group having from 1 to 5 carbon
atoms for R.sup.4 and R.sup.5 includes an alkyl group having from 1
to 5 carbon atoms, and an alkenyl group having from 2 to 5 carbon
atoms. These may be linear or branched. Examples of the alkyl group
include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
tert-butyl and pentyl groups. Examples of the alkenyl group include
vinyl, allyl and butenyl groups. These hydrocarbon groups may have
a functional group introduced thereinto. For the functional group
and the functional group-having hydrocarbon group, those mentioned
hereinabove for R.sup.1 and R.sup.3 in formula (I) are exemplified.
These R.sup.4 and R.sup.5 may be the same or different from each
other.
[0026] For the divalent hydrocarbon group having from 1 to 20
carbon atoms for Y, an alkylene group and an alkylidene group are
preferred and examples thereof include, for example, methylene,
ethylene, propylene, butylene, pentylene, hexylene, octylene,
ethylidene and propylidene groups.
[0027] Examples of the compounds of formula (II) include
methylenebis(methyldimethoxysilane),
ethylenebis(ethyldimethoxysilane),
propylenebis(ethyldiethoxysilane), and
butylenebis(methyldiethoxysilane).
[0028] The organosilicon compound to be contained in the hard coat
film in the invention may be one selected from the compounds of
formulas (I) and (II) and their hydrolyzates, or may be a
combination of two or more selected from them. The hydrolyzates may
be prepared by adding an aqueous basic solution such as an aqueous
solution of sodium hydroxide or ammonia, or an aqueous acidic
solution such as an aqueous solution of hydrochloric acid, acetic
acid or citric acid to the compound of formula (I) or (II),
followed by stirring.
[0029] The hard coat film may contain metal oxide fine particles
(in colloid form, for example). The metal oxide fine particles are
not specifically limited, and may be arbitrary selected from any
particles that are known to be or may be found to be suitable for
use in hard coat films for plastic lenses. Examples of the metal
oxide fine particles include fine particles of a single metal
oxides such as aluminum oxide, titanium oxide, antimony oxide, tin
oxide, zirconium oxide, silicon oxide, cerium oxide, iron oxide; as
well as fine particles of a composite oxide, for example, fine
particles of a composite tin oxide-zirconium oxide-tungsten oxide
as disclosed in JP-A-6-25603; fine particles of a composite tin
oxide-tungsten oxide as disclosed in JP-A-3-217230; fine particles
of a composite metal oxide of titanium oxide, cerium oxide and
silicon oxide as disclosed in JP-A-8-113760; fine particles of a
composite titanium oxide-zirconium oxide-tin oxide as disclosed in
JP-A-10-306258; fine particles of a composite titanium
oxide-zirconium oxide-silicon oxide, and those of a composite
stannic oxide-zirconium oxide-tungsten oxide as disclosed in
JP-A-9-21901. Of these metal oxide fine particles known to be
suitable for use in this invention, at least one type selected from
silicon oxide fine particles, titanium oxide fine particles and tin
oxide fine particles is preferred.
[0030] The mean particle size of the metal oxide fine particles may
fall generally between 1 and 500 nm. These metal oxide fine
particles may be used either singly or as a combination of two or
more.
[0031] In the invention, the hard coat film is formed, for example,
by coating a plastic lens substrate with a coating composition. If
desired, the coating composition may contain various organic
solvents and surfactants for improving the wettability of the
substrate with the composition, thereby improving the surface
smoothness of the hard coat film.
[0032] An organic solvent is optionally added to the coating
composition for uniformly hydrolyzing the component in the
composition and for controlling the degree of hydrolysis. Preferred
examples of the organic solvent include cellosolves such as methyl
cellosolve, ethyl cellosolve and butyl cellosolve. More preferably
for the organic solvent, such a cellosolve is combined with any of
isopropyl alcohol or butyl alcohol. In this case, the cellosolve
content is preferably 3% by weight or more, more preferably 10% by
weight or more. Further if desired, the coating liquid for the hard
coat film may contain a silicone surfactant for improving the
surface smoothness of the hard coat film formed of it. In addition,
for improving the lightfastness of the hard coat film and for
preventing the film from deterioration, a UV absorbent,
antioxidant, light stabilizer, antiaging agent and/or like agent
may be added to the coating composition to an extent that does not
interfere with the physical properties of the hard coat film formed
on the lens surface. Thus prepared, the viscosity and solids
content of the coating liquid are not specifically restricted, so
far as it is advantageous applicable to coat the plastic
lenses.
[0033] For applying the coating composition onto the surfaces of
the plastic lens, an ordinary method such as dipping, spin coating,
or spraying may be employed.
[0034] In order to provide high face accuracy of the film formed of
the composition, especially preferred is dipping or spin coating.
The composition is cured by drying it in hot air or by exposing it
to active energy rays. Preferably, it is cured in hot air at 70 to
200.degree. C., more preferably at 90 to 150.degree. C. For the
active energy rays, preferred are far-infrared rays, which suppress
damage of the film by heat in a low degree.
[0035] The plastic lenses to be processed in the invention are not
specifically limited, and examples thereof include, for example,
methyl methacrylate homopolymers, copolymers of methyl methacrylate
with at least one other monomer, diethylene glycol
bisallylcarbonate homopolymers, copolymers of diethylene glycol
bisallylcarbonate with at least one other monomer,
sulfur-containing copolymers, halogen-containing copolymers,
polycarbonates, polystyrenes, polyvinyl chlorides, unsaturated
polyesters, polyethylene terephthalates, polyurethanes, and
polythiourethanes.
[0036] In the method for producing the plastic lens of the
invention, the hard coat film formed on the lens is coated with an
aqueous liquid film which in turn is treated with ozone. Before the
thus-treated hard coat film is further coated with an
antireflection film, it may be ultrasonically rinsed in a tank and
then washed with an alkali for removing any impurities adhering
thereto.
[0037] The inorganic oxide to be used in the invention for forming
the antireflection film is not specifically limited and substances
generally known for use as materials of ordinary antireflection
films may be used. For example, they include Ta.sub.2O.sub.5,
Y.sub.2O.sub.3, ZrO.sub.2, SiO.sub.2, TiO.sub.2, Al.sub.2O.sub.3,
and Nb.sub.2O.sub.5. The antireflection film may be 0 formed by
vapor deposition, which, however, may be combined with any suitable
type of ion beam-assisted deposition, sputtering or ion plating, if
desired.
[0038] The antireflection film may be single-layered or
multi-layered. In view of its reflectivity, adhesion to the
underlying hard coat film and abrasion resistance, it is preferable
that the vapor deposition layer of the antireflection film that is
in contact with the hard coat film be formed mainly of silicon
dioxide. When the antireflection film is single-layered, its
optical thickness is preferably
0.25.lambda..sub.0(.lambda..sub.0=450 to 650 nm). For the
antireflection film, also preferred are multi-layered films, for
example, a two-layered film of
0.25.lambda..sub.0/0.25.lambda..sub.0, in optical thickness, in
which the two layers differ in refractive index, or a three-layered
film of 0.25.lambda..sub.0/0.5.lambda..sub.0/0.25.lambda..sub.0 or
0.25.lambda..sub.0/0.25.lambda..sub.0/0.25.lambda..sub.0 in optical
thickness in which the three layers differ in refractive index, or
other multi-layered films that are partly substituted with any
other equivalent film.
[0039] If desired, an undercoat layer of, for example, a metal film
of niobium or a metal oxide film of silicon dioxide or aluminum
oxide may be disposed between the antireflection film and the hard
coat film formed of the coating composition according to the
invention.
[0040] Also if desired, a primer film may be disposed between the
hard coat film and the plastic lens substrate, in order to improve
the impact resistance of the coated lens and the adhesion of the
hard coat film to the lens substrate, for example, as disclosed in
JP-A-3-109502. One example of this primer film is an urethane film
formed of a polyisocyanate and a polyol as raw materials. The
polyisocyanate includes, for example, adducts prepared by bonding a
few molecules of any of hexamethylene diisocyanate,
4,4'-cyclohexylmethane diisocyanate or hydrogenated xylylene
diisocyanate by various methods; and isocyanurates, allophanates,
biurets or carbodiimides blocked with any of acetacetic acid,
malonic acid or methyl ethyl ketoxime. The suitable polyols
include, for example, polyesters, polyethers, polycaprolactones,
polycarbonates and polyacrylates having two or more hydroxyl groups
in one molecule. Also if desired, the primer film may contain metal
fine oxide particles such as titanium oxide fine particles for
improving its refractivity.
[0041] The invention is described in more detail with reference to
the following Examples, which, however, are not intended to
restrict the scope of the invention. The physical properties of the
samples in Examples and Comparative Examples were evaluated
according to the methods mentioned below.
[0042] (a) Abrasion resistance: The plastic lenses with
antireflection film obtained in the Examples were dipped in warm
water at 50.degree. C. for 48 hours, and then rubbed with 0000
steel wool (produced by Japan Steel Wool Corp.) under a load of 1
kgf/cm.sup.2 in the direction where the steel wool meets the lens
surface at right angles. After rubbed 20 (back and forth) in that
manner, the condition of each sample was evaluated for the scratch
resistance in accordance with the criteria mentioned below.
[0043] UA: Few scratches found.
[0044] A: Only a few scratches found.
[0045] B: Some scratches found.
[0046] C: Many scratches found.
[0047] (b) Adhesion: Each of the plastic lenses with antireflection
film obtained in the Examples were dipped in warm water at
50.degree. C. for 48 hours, and 10.times.10 cross-cuts of 1 mm
square were cut into the surface of the hard coat film on the lens
face. An adhesive tape of Cellophane (manufactured by Nichiban No.
405) was tightly stuck to each sample, and rapidly peeled off at a
90 degree angle. The number of cross-cuts remaining on each sample
was counted.
[0048] (c) YI value: Before and after being treated with ozone, the
hard coat film of each sample was analyzed with a spectrometer
U3410 (manufactured by Hitachi Ltd., trade name). From the XYZ
values of each sample thus analyzed in the visual field of 20 the
light source C, the YI value thereof was derived.
EXAMPLES 1 to 12, and COMPARATIVE EXAMPLES 1 to 5:
[0049] As set forth in Table 1, each plastic lens substrate (a) to
(c) was coated with a hard coat film (A) to (C) and with an
antireflection film (.alpha.) to (.gamma.). The concentration and
the flow rate of the ozone gas used for treating the hard coat
film, and the type and the flow rate of the processing water used
for forming a liquid film on the hard coat film are shown in Table
1. Under these conditions, plastic lenses with antireflection film
were produced. The details of the plastic lens substrates (a) to
(c), the hard coat films (A) to (C), the antireflection films
(.alpha.) to (.gamma.), the method of treating the hard coat film
with ozone gas and the method of forming the antireflection film
are mentioned below.
[0050] (1) Plastic lens substrate: The plastic lens substrates (a)
to (c) used herein are as follows:
[0051] Plastic lens substrate (a): TESLALID (having a refractive
index of 1.71; trade name manufactured by Hoya--this is used in
Example 1 and Comparative Example 1).
[0052] Plastic lens substrate (b): EYAS (having a refractive index
of 1.60) (Trade name, manufactured by Hoya)--this is used in
Examples 2 and 3 and Comparative Example 2).
[0053] Plastic lens substrate (c): diethylene glycol
bisallylcarbonate polymer (having a refractive index of 1.499--this
is used in Examples 4 to 12 and Comparative Examples 3 to 5).
[0054] (2) Preparation of hard coat liquid and formation of hard
coat film: Hard coat films (A) to (C) mentioned below were
formed.
Preparation of Hard Coat Liquid (A), and Formation of Hard Coat
Film of it (The Hard Coat Film Contains Composite Fine Particles of
Titanium Oxide, Zirconium Oxide and Silicon Oxide: This is Formed
in Example 1 and Comparative Example 1):
[0055] 1045 parts by weight of
.gamma.-glycidoxypropyl(trimethoxy)silane and 200 parts by weight
of .gamma.-glycidoxypropylmethyl(diethoxy)silane were put into a
stainless reactor, and 299 parts by weight of hydrochloric acid
(0.01 mols/liter) were added thereto with stirring. The stirring
was continued for one full day in a clean room at 10.degree. C. to
obtain a silane hydrolyzate.
[0056] In another reactor, 4018 parts by weight of methyl
cellosolve and 830 parts by weight of isopropanol were added to and
mixed with 3998 parts by weight of a composite fine particle sol of
titanium oxide, zirconium oxide and silicon oxide (dispersed in
methanol, having a total solid content of 30% by weight and having
a mean particle size of from 5 to 8 microns) with stirring, and 4
parts by weight of a silicone surfactant (manufactured by Nippon
Unicar L-7001) and 100 parts by weight of aluminum acetylacetonate
were added thereto. Like the hydrolyzate discussed above, it was
stirred for one full day in a clean room at 10.degree. C., and then
this was combined with the hydrolyzate and further stirred for one
full day. Thereafter, this was filtered through a 3-.mu.m filter to
obtain a hard coat liquid (A).
[0057] Next, the plastic lens was dipped in the hard coat liquid
(A) for 20 seconds, pulled up at a pulling rate of 20 cm/min, and
then heated in an oven set at 110.degree. C. for 1 hour. Thus
processed, the plastic lens was coated with a hard coat film
(A).
Preparation of Hard Coat Liquid (B), and Formation of Hard Coat
Film of it (The Hard Coat Film Contains Composite Fine Particles of
Stannic Oxide-Zirconium Oxide: This is Formed in Examples 2 and 3
and Comparative Example 2):
[0058] b 142 parts by weight of
.gamma.-glycidoxypropyltrimethoxysilane were put into a glass
reactor equipped with a magnetic stirrer, and 1.4 parts by weight
of 0.01 N hydrochloric acid and 32 parts by weight of water were
added dropwise thereto with stirring. This was then stirred for 24
hours to obtain a hydrolyzate of .gamma.-glycidoxypropyltrimethoxy-
silane. Next, 460 parts by weight of stannic oxide-zirconium oxide
composite fine particles (dispersed in methanol, having a total
metal oxide content of 31.5% by weight and having a mean particle
size of from 10 to 15 millimicrons), 300 parts by weight of ethyl
cellosolve, 0.7 parts by weight of a silicone surfactant serving as
a lubricant, and 8 parts by weight of a curing agent, aluminum
acetyl acetonate were added to the
.gamma.-glycidoxypropyltrimethoxysilane hydrolyzate, well stirred,
and then filtered to obtain a hard coat liquid (B).
[0059] Next, the plastic lens was dipped in an aqueous alkali
solution and washed well. Then, this was dipped in the hard coat
liquid (B), pulled up at a pulling rate of 14 cm/min, and heated in
an oven set at 120.degree. C. for 1 hour. Thus processed, the
plastic lens was coated with a hard coat film (13).
Preparation of Hard Coat Liquid (C), and Formation of Hard Coat
Film of it (The Hard Coat Film Contains Silicon Oxide Fine
Particles, This is Formed in Examples 4 to 12 and Comparative
Examples 3 to 5):
[0060] 120 parts by weight of
.gamma.-glycidoxypropyltrimethoxysilane were put into a glass
reactor equipped with a magnetic stirrer, and 27 parts by weight of
0.1 N hydrochloric acid were added dropwise thereto with stirring.
This was then stirred for 24 hours to obtain a hydrolyzate of the
silane. Next, 200 parts by weight of water-dispersed silica fine
particles (having a solid content of 20% and having a mean particle
size of 15 millimicrons), 100 parts by weight of isopropyl alcohol
and 100 parts by weight of ethyl cellosolve both serving as a
solvent, 1 part by weight of a silicone surfactant serving as a
lubricant, and 7 parts by weight of a curing agent, aluminum
acetylacetonate were added to the hydrolyzate, stirred well, and
then filtered to obtain a hard coat liquid (C).
[0061] Next, the plastic lens was dipped in an aqueous alkali
solution and washed well. Then, this was dipped in the hard coat
liquid (C), pulled up at a pulling rate of 14 cm/min, and heated in
an oven set at 120.degree. C. for 1 hour. Thus processed, the
plastic lens was coated with a hard coat film (C).
[0062] (3) Treatment with ozone gas: The ozone gas-treating
apparatus of FIGS. 1 and 2 was used. For the solution in the
solution pool 3b in the treating tank 3 shown in FIGS. 1 and 2,
pure water (in Examples 1, 2 and 6) or a solution of sodium
hydrogen carbonate of 0.05 mols/liter to 0.2 mols/liter (in
Examples 3 to 5, and 7 to 12) was used. The concentration of ozone
flowing through the ejection tube 8 in FIG. 2 was from 70 to 180
g/Nm.sup.3. The ozone gas flow rate through the ejection tube 8 in
FIG. 2 was from 2.5 to 2.7 liters/min, and the spray ejected out of
the spray nozzle 10 to form a liquid film on the hard coat film was
from 2 to 2.6 liters/min, as in Table 1. The volume of the space in
the treating tank 3 was 118 liters (430.times.430.times.640 mm).
The solution temperature in the solution pool 3b was between
19.degree. C. and 25.degree. C.; and the ozone gas temperature fell
between 21.degree. C. and 36.degree. C.
[0063] (4) Washing after treatment with ozone gas: After being
treated with ozone gas, the plastic lens was dipped in warm water
(pure water of from 1 to 10 .mu.s/cm, at 55.degree. C.) for 30
seconds for rinsing, and then in an alkali solution (containing
0.3% anionic surfactant) at 48.degree. C. for 75 seconds for
removing any impurities adhering to the hard coat film.
[0064] (5) Formation of antireflection film: After the treatment
with ozone gas and washing as in (4), each plastic lens was coated
with any of the following three antireflection films.
Formation of Antireflection Film (c) (in Example 1 and Comparative
Example 1):
[0065] Evaporating materials were deposited through vacuum
evaporation on the hard coat film of each plastic lens to form
thereby a 7-layered antireflection film of SiO.sub.2(0.125
.lambda.)/Ta.sub.2O.sub.5(0.05 .lambda.)/SiO.sub.2(0.5
.lambda.)/Ta.sub.2O.sub.5(0.125 .lambda.)/SiO.sub.2(0.05
.lambda.)/Ta.sub.2O.sub.5(0.25.lambda.)/SiO.sub.- 2(0.25 .lambda.)
on the hard coat layer in that order. In this, .lambda. is 500
nm.
Formation of Antireflection Film (.beta.) (in Examples 2 and 3, and
Comparative Example 2):
[0066] SiO.sub.23/4 .lambda. thick was deposited on the hard coat
film of each plastic lens through vacuum evaporation to be a first
layer. On the other hand, Nb.sub.2O.sub.5 powder, ZrO.sub.2 powder
and Y.sub.2O.sub.3 powder were mixed, shaped under pressure and
sintered to prepare an evaporating composition. This was deposited
on the first layer along with SiO.sub.2 to form thereon a composite
layer {fraction (1/4)} .lambda. thick. Next, another composite
layer of evaporating composition/SiO.sub.21/4 .lambda. evaporating
composition {fraction (1/2)} .lambda. thick was deposited thereon;
and finally SiO.sub.21/4 .lambda. thick was deposited thereon to
form a multi-layered antireflection film on the hard coat layer. In
this, .lambda. is 500 nm.
Formation of Antireflection Film (.gamma.) (in Examples 4 to 12 and
Comparative Examples 3 to 5):
[0067] SiO.sub.2{fraction (6/4)} .lambda. thick was deposited on
the hard coat film of each plastic lens through vacuum evaporation
to be a first layer. With that, ZrO.sub.2 about {fraction (1/17)}
.lambda. thick was deposited thereon, and then SiO.sub.2 was
thereon to form a second layer of SiO.sub.2 and ZrO.sub.2 having an
overall thickness of .lambda./4. Further, ZrO.sub.2 about 1/2
.lambda. thick was deposited thereon to be a third layer; and
finally SiO.sub.21/4 .lambda. thick was thereon to complete a
multi-layered antireflection film on the hard coat film. In this,
.lambda. is 500 nm.
[0068] The coated plastic lens samples of Examples 4 to 12 had the
same substrate, hard coat film and composition of the
antireflection film, but differed with respect to the processing
water, the processing time and the ozone concentration in treating
the hard coat film of each sample.
[0069] In Comparative Example 1, the same substrate as in Example 1
was coated with the same hard coat film, but this was directly
washed as in Example 1, without being coated with a liquid film or
treated with ozone gas, and thereafter this was coated with the
same antireflection film as in Example 1.
[0070] In Comparative Example 2, the same substrate as in Example 2
was coated with the same hard coat film, but this was directly
washed as in Example 2, without being coated with a liquid film or
treated with ozone gas, and thereafter this was coated with the
same antireflection film as in Example 2.
[0071] In Comparative Example 3, the same substrate as in Examples
4 to 12 was coated with the same hard coat film, but this was
directly washed as in Examples 4 to 12, without being coated with a
liquid film nor treated with ozone gas, and thereafter this was
coated with the same antireflection film as in Examples 4 to
12.
[0072] In Comparative Example 4, the same substrate as in Examples
4 to 12 was coated with the same hard coat film, and this was,
after being treated with ozone gas alone (at 15 to 40.degree. C.)
but not coated with a liquid film prior to the treatment, washed as
in Examples 4 to 12, and thereafter this was coated with the same
antireflection film as in Examples 4 to 12.
[0073] In Comparative Example 5, the same substrate as in Examples
4 to 12 was coated with the same hard coat film, and this was,
after being dipped in ozone water (at 15 to 40.degree. C.) but not
coated with a liquid film prior to the dipping, washed as in
Examples 4 to 12, and thereafter this was coated with the same
antireflection film as in Examples 4 to 12.
[0074] The plastic lenses obtained in Examples 1 to 12 and
Comparative Examples 1 to 5 were tested according to test methods
(a) to (c) mentioned above. The results are given in Table 2.
1 TABLE 1 Plas- tic Ozone Lens Hard Antire- Ozone Ozone Gas Gas
Solution Flow Sub- Coat flection Method of Ozone Gas Treating
Concentration Flow Rate Solution for Liquid Film Rate strate Film
Film Treatment Time (sec) (g/Nm.sup.3) (liter/min) Formation
(liter/min) (liter/min) Examples 1 a A .alpha. water spray + ozone
gas 60 145 2.7 pure water 2 2 b B .beta. water spray + ozone gas 60
140 2.5 pure water 2.5 3 b B .beta. water spray + ozone gas 60 140
2.5 0.2 mols/liter NaHCO.sub.3 2.5 4 c C .gamma. water spray +
ozone gas 60 140 2.6 0.2 mols/liter NaHCO.sub.3 2.1 5 c C .gamma.
water spray + ozone gas 240 140 2.7 0.1 mols/liter NaHCO.sub.3 2.3
6 c C .gamma. water spray + ozone gas 60 140 2.7 pure water 2.6 7 c
C .gamma. water spray + ozone gas 30 125 2.7 0.2
mols/literNaHCO.sub.3 2.6 8 c C .gamma. water spray + ozone gas 30
150 2.7 0.05 mols/liter NaHCO.sub.3 2.2 9 c C .gamma. water spray +
ozone gas 300 140 2.7 0.05 mols/liter NaHCO.sub.3 2.4 10 c C
.gamma. water spray + ozone gas 120 180 2.7 0.2 mols/liter
NaHCO.sub.3 2.4 11 c C .gamma. water spray + ozone gas 120 70 2.4
0.2 mols/liter NaHCO.sub.3 2.5 12 c C .gamma. water spray + ozone
gas 120 110 2.4 0.2 mols/liter NaHCO.sub.3 2.5 Comp. Examples 1 a A
.alpha. No -- -- -- -- -- 2 b B .beta. No -- -- -- -- -- 3 c C
.gamma. No -- -- -- -- -- 4 c C .gamma. ozone gas 60 120 2.7 -- --
5 c C .gamma. dipping in ozone water 600 140 2.7 pure water 0
[0075]
2 TABLE 2 Adhesion after accelerated Abrasion aging YI Value YI
Value Resistance (Adhesion before after after after ozone ozone
treatment treatment treatment treatment in warm in warm (hard coat
(hard coat water water) lenses) lenses) Examples 1 A 100 2.18 2.18
2 UA 100 1.05 1.05 3 UA 100 1.05 1.05 4 UA 100 0.81 0.80 5 UA 100
0.81 0.81 6 UA 100 0.81 0.82 7 UA 100 0.80 0.80 8 UA 100 0.82 0.81
9 UA 100 0.81 0.82 10 UA 100 0.81 0.80 11 UA 100 0.82 0.82 12 UA
100 0.81 0.82 Comparative Examples 1 C 0 2.18 -- 2 A 98 1.05 -- 3
UA 0 0.81 -- 4 UA 90 0.81 0.82 5 UA 50 0.81 0.81
* * * * *