U.S. patent application number 10/722396 was filed with the patent office on 2004-06-03 for coated article.
Invention is credited to Kayanoki, Hisayuki.
Application Number | 20040105156 10/722396 |
Document ID | / |
Family ID | 26498858 |
Filed Date | 2004-06-03 |
United States Patent
Application |
20040105156 |
Kind Code |
A1 |
Kayanoki, Hisayuki |
June 3, 2004 |
Coated article
Abstract
To provide a plastic spectacle lens which has a very durable
hard coat layer and primer layer and prevents the cracking and
peeling off of the layer and a reduction in the hardness of the
layer, and other coated articles. This coated article has a coat
layer containing titanium oxide and an organic Co(II)compound on
the surface of a substrate.
Inventors: |
Kayanoki, Hisayuki;
(Ichihara-shi, JP) |
Correspondence
Address: |
WENDEROTH, LIND & PONACK, L.L.P.
2033 K STREET N. W.
SUITE 800
WASHINGTON
DC
20006-1021
US
|
Family ID: |
26498858 |
Appl. No.: |
10/722396 |
Filed: |
November 28, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10722396 |
Nov 28, 2003 |
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09763455 |
Feb 23, 2001 |
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6703131 |
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09763455 |
Feb 23, 2001 |
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PCT/JP00/03993 |
Jun 19, 2000 |
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Current U.S.
Class: |
359/581 |
Current CPC
Class: |
C08J 7/043 20200101;
C09D 183/06 20130101; C08J 7/046 20200101; Y10T 428/31663 20150401;
Y10T 428/31598 20150401; G02B 1/18 20150115; C08J 7/06 20130101;
G02B 1/16 20150115; G02B 1/14 20150115; C08J 7/044 20200101; C09D
183/06 20130101; C08L 2666/54 20130101 |
Class at
Publication: |
359/581 |
International
Class: |
G02C 007/02; G02B
001/10 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 24, 1999 |
JP |
11-178780 |
Nov 10, 1999 |
JP |
11-319136 |
Claims
1. A plastic lens comprising a plastic lens substrate having a
refractive index of 1.50 or more, a primer layer which is formed on
the surface of the substrate, and a hard coat layer which is formed
on the surface of the primer layer and comprises a silicon resin as
a resin component, the primer layer comprising: (1) 2 to 70 wt % of
titanium oxide or a composite oxide thereof having a particle
diameter of 1.0 to 100 nm, the titanium oxide containing at least
one titanium oxide selected from the group consisting of rutile
type titanium oxide and anatase type titanium oxide in an amount of
50 wt % or more; (2) 1 to 10 wt % of a chelate compound or fatty
acid salt containing Co(II); and (3) 20 to 97.9 wt % of an urethane
resin, and having a refractive index of 1.48 or more and a
thickness of 0.5 to 5 .mu.m, the weight percentages of the above
components (1), (2) and (3) being based on 100 wt % of the total
weight of the components (1), (2) and (3).
2. The plastic lens of claim 1 which further has an anti-reflection
layer on the exterior surface of the hard coat layer.
3. The plastic lens of claim 1, wherein the primer layer has been
formed from a solution composition comprising: (1) 2 to 70 wt % of
titanium oxide or a composite oxide thereof having a particle
diameter of 1.0 to 100 nm, the titanium oxide containing at least
one titanium oxide selected from the group consisting of rutile
type titanium oxide and anatase type titanium oxide in an amount of
50 wt % or more; (2) 1 to 10 wt % of a chelate compound or fatty
acid salt containing Co(II); (3) 10 to 87.9 wt % of a polyol; and
(4) 10 to 87.9 wt % of a polyisocyante, the weight percentages of
the above components (1), (2), (3) and (4) being based on 100% of
the total weight of all the above components
Description
FIELD OF THE INVENTION
[0001] The present invention relates to an article coated with a
resin film, particularly a coated plastic lens having a titanium
oxide-containing resin coat layer, other coated articles and a
composition for forming a titanium oxide-containing resin coat
layer.
DESCRIPTION OF THE PRIOR ART
[0002] Since plastic spectacle lenses have such a defect that they
are easily scratched, a silicon-based resin or other hard coat
layer has been conventionally formed on the surface of a plastic
lens substrate. A primer layer made from a resin such as an
urethane-based resin has also been formed between this hard coat
layer and the surface of the substrate to improve the adhesion of
the hard coat layer and the impact resistance of a plastic
lens.
[0003] However, when a silicone-based hard coat layer is formed on
a high-refractive resin lens having a refractive index of 1.50 or
more, an interference fringe is formed by the difference of
refractive index between the resin lens and the hard coat layer (or
primer layer), thereby worsening the appearance of the lens. To
solve this problem, JP-A 7-325201 and JP-A 10-332902 (the term
"JP-A" as used herein means an "unexamined published Japanese
patent application") propose the addition of an oxide having a high
refractive index such as titanium oxide (TiO.sub.2) (or a composite
oxide containing TiO.sub.2) to a hard coat or primer to reduce the
difference of refractive index between the hard coat layer or
primer layer and the substrate so as to prevent an interference
fringe.
[0004] JP-A 11-131021 discloses a composition for coating
comprising the following essential ingredients:
[0005] (A) a composite oxide fine particle of tin oxide, titanium
oxide and zirconium oxide;
[0006] (B) a silane compound having at least one polymerizable
reactive group; and
[0007] (C) an epoxy (meth)acrylate having a glycidyl group and
(meth)acryloyl group in one molecule at the same time.
[0008] In the above publication, a silanol or epoxy compound curing
catalyst may be added and acetylacetonato containing Co(II) as the
center metal is enumerated as one example of the curing
catalyst.
[0009] However, the hard coat layer or primer layer containing
titanium oxide has such problems as the cracking and peeling off of
the layer and a reduction in the hardness of the layer due to
insufficient durability.
SUMMARY OF THE INVENTION
[0010] It is an object of the present invention to provide a coated
article which has a highly durable resin coat layer containing
titanium oxide and prevents the cracking and peeling off of the
layer and a reduction in the hardness of the layer.
[0011] It is another object of the present invention to provide a
plastic lens which has a highly durable hard coat layer or primer
layer and prevents the cracking and peeling off of the layer and a
reduction in the hardness of the layer.
[0012] It is still another object of the present invention to
provide a solution composition for forming a hard coat layer for a
plastic lens.
[0013] A further object of the present invention is attained by a
solution composition for forming a primer layer for a plastic
lens.
[0014] Other objects and advantages of the present invention will
become apparent from the following description.
[0015] Firstly, according to the present invention, the above
objects and advantages-of the present invention are attained by a
coated article comprising a substrate and a coat layer made from a
resin composition containing titanium oxide and an organic Co(II)
compound and formed on the surface of the substrate.
[0016] Secondly, according to the present invention, the above
objects and advantages of the present invention are attained by a
plastic lens which comprises a plastic lens substrate having a
refractive index of 1.50 or more and a hard coat layer formed on
the surface of the substrate directly or through a primer layer,
the hard coat layer comprising:
[0017] (1) 2 to 70 wt % of titanium oxide or a composite oxide
thereof having a particle diameter of 1.0 to 100 nm;
[0018] (2) 0.1 to 10 wt % of an organic Co(II) compound;
[0019] (3) 20 to 97.9 wt % of a silicon resin; and
[0020] (4) 0.001 to 10 wt % of a curing catalyst, and having a
refractive index of 1.48 or more and a thickness of 0.1 to 5 .mu.m,
the weight percentages of the above components (1), (2) and (3)
being based on 100 wt % of the total weight of the components (1),
(2) and (3), and the weight percentage of the above component (4)
being based on the total weight of the above components (1), (2)
and (3).
[0021] Thirdly, the above objects and advantages of the present
invention are attained by a plastic lens which comprises a plastic
lens substrate having a refractive index of 1.50 or more, a primer
layer formed on the surface of the substrate, and a hard coat layer
comprising a silicone resin as a resin component and formed on the
surface of the primer layer, the primer layer comprising:
[0022] (1) 2 to 70 wt % of titanium oxide or a composite oxide
thereof having a particle diameter of 1.0 to 100 nm;
[0023] (2) 0.1 to 10 wt % of an organic Co(II) compound; and
[0024] (3) 20 to 97.9 wt % of an urethane resin, and having a
refractive index of 1.48 or more and a thickness of 0.5 to 5 .mu.m,
the weight percentages of the above components (1), (2) and (3)
being based on 100 wt % of the total weight of the components (1),
(2) and (3).
[0025] In the fourth place, according to the present invention, the
above objects and advantages of the present invention are attained
by a solution composition for forming a hard coat layer which
comprises:
[0026] (1) 2 to 70 wt % in terms of solid content of a sol
containing titanium oxide or a composite oxide thereof having a
particle diameter of 1.0 to 100 nm dispersed in water or an organic
medium;
[0027] (2) 0.1 to 10 wt % of an organic Co(II) compound;
[0028] (3) 20 to 97.9 wt % of an epoxy group-containing silicon
compound represented by the following formula (1):
R.sup.1R.sup.2.sub.aSi(OR.sup.3).sub.3-a (1)
[0029] wherein R.sup.1 is a group having an epoxy group and 2 to 12
carbon atoms, R.sup.2 is an alkyl group or halogenoalkyl group
having 1 to 6 carbon atoms, alkenyl group having 2 to 6 carbon
atoms, phenyl group or halogenophenyl group, R.sup.3 is a hydrogen
atom, alkyl group or acyl group having 1 to 4 carbon atoms, and a
is 0, 1 or 2,
[0030] or a partial hydrolysate thereof; and
[0031] (4) 0.001 to 10 wt % of a curing catalyst, the weight
percentages of the above components (1), (2) and (3) being based on
100 wt % of the total weight of the components (1), (2) and (3),
and the weight percentage of the above component (4) being based on
the total weight of the above components (1), (2) and (3).
[0032] In the fifth place, according to the present invention, the
above objects and advantages of the present invention a are
attained by a solution composition for forming a primer layer
comprising:
[0033] (1) 2 to 70 wt % in terms of solid content of a sol
containing titanium oxide or a composite oxide thereof having a
particle diameter of 1.0 to 100 nm dispersed in water or an organic
medium;
[0034] (2) 0.1 to 10 wt % of an organic Co(II) compound;
[0035] (3) 10 to 87.9 wt % of a polyol; and
[0036] (4) 10 to 87.9 wt % of a polyisocyanate, the weight
percentages of the above components (1), (2), (3) and (4) being
based on 100 wt % of the total weight of all the components.
[0037] The present invention will be described in detail
hereinafter.
[0038] A description is first given of the coated article of the
present invention.
[0039] The coat layer of the coated article is made from a resin
composition containing titanium oxide and an organic Co(II)
compound.
[0040] Co(II) is characterized in that it has an absorption peak at
a wavelength of 420 to 550 nm and an organic compound having
Co(III) with the main absorption peak at a wavelength of 600 to 800
nm cannot be used in the present invention because it does not have
the effect of the organic Co(II) compound of the present
invention.
[0041] When the titanium oxide-containing resin coat layer contains
an organic Co(II) compound and this coat layer is irradiated with
ultraviolet rays from sunlight, fluorescent light or other light,
ultraviolet rays collide with a titanium oxide particle contained
in the coat layer. The titanium oxide particle is excited by
ultraviolet rays, thereby forming electrons excited to a conduction
band and electron holes having a valence band. The exited electrons
and electron holes move toward a polymer in the coat layer, reach
the polymer and try to cause an optical catalytic reaction there to
decompose the polymer by dissociating a bond, for example, a C--C
bond in the polymer. When the organic Co(II) compound is existent
in this coat layer, part of excited energy of titanium oxide moves
toward the organic Co(II) compound and is converted into heat.
Thereby, the decomposition of the polymer is suppressed, thereby
retarding the deterioration of the coat layer. As a result, the
adhesion of the coat layer to the substrate is retained, the
cracking of the coat layer hardly occurs, and the hardness of the
coat layer is maintained. Since the excitation energy of titanium
oxide is about 3 eV, it-is desired that a compound containing this
metal ion should have an energy gap corresponding to 2.1 to 2.8 eV
in order to receive this energy efficiently. The wavelength of an
optical absorption band corresponding to this energy gap is 420 to
550 nm. Therefore, an organic Co(II) compound having an optical
absorption peak at 420 to 550 nm is effective. However, it cannot
be said that all compounds having this energy gap can receive this
energy.
[0042] Preferably, the organic. Co(II) compound having an
absorption peak at a wavelength of 420 to 550 nm used in the
present invention dissolves in a solvent for a titanium
oxide-containing resin coat layer, such as an alcohol or propylene
glycol ether, has compatibility with the resin component of the
coat layer and does not impede the physical properties of the resin
of the coat layer. Preferred examples of the compound include the
above Co(II) ion chelate compounds and fatty acid salts.
[0043] The ligand of the chelate compound is preferably what
contains an aliphatic chelate structure, as exemplified by
acetylacetone, di-n-butoxide-mono-ethyl acetate,
di-n-butoxide-mono-methyl acetate, methyl ethyl ketooxime,
2,4-hexanedione, 3,5-heptanedione and acetooxime. A preferred
example of the chelate compound is cobalt (II) acetylacetonato.
[0044] Preferred examples of the acid of the fatty acid compound
include 2-ethyl-hexylic acid, stearic acid, lauric acid, oleic
acid, acetic acid, sebacic acid, dodecane diacid, propionic acid,
brassylic acid, isobutylic acid, citraconic acid and tetraethylene
diamine tetraacetic acid. The fatty acid compound is, for example,
a cobalt(II) salt of 2-ethyl-hexylic acid.
[0045] Examples of the resin component of the resin coat layer in
the present invention include silicon resin, urethane resin,
acrylic resin, methacrylic resin, allyl resin, polyester resin,
polycarbonate resin, epoxy resin and urethane acrylic resin. The
resin coat layer contains titanium oxide and an organic Co(II)
compound in addition to the above resin component. The amount of
titanium oxide is preferably 2 to 70 wt % and the amount of the
organic Co(II) compound is preferably 0.1 to 10 wt %. The resin
coat layer preferably has a refractive index of 1.48 or more. The
amount of titanium oxide is more preferably 10 to 70 wt %, the most
preferably 15 to 60 wt %. The amount of the organic Co(II) compound
is more preferably 0.2 to 5 wt %.
[0046] The above titanium oxide may have an amorphous structure but
preferably a rutile, anatase or brookite crystal structure.
Preferably, at least 1/2, that is, at least 50% of the amount of
titanium oxide has at least one of rutile, anatase or brookite
crystal structures. Out of these crystal structures, the rutile
type is more preferred and at least 1/2, that is, 50% of the amount
of titanium oxide has a rutile type crystal structure. However, as
rutile type titanium dioxide is more expensive than anatase type
titanium dioxide, anatase type titanium dioxide is preferably used
from an economical point of view. The titanium oxide may be a
titanium oxide fine particle or a composite oxide of titanium and
at least one element selected from the group consisting of Si, Al,
Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr and In. Examples of the composite
oxide include a composite oxide fine particle of titanium and iron
(TiO.sub.2.cndot.Fe.sub.2O.sub.3), composite oxide fine particle of
titanium and silicon (TiO.sub.2.cndot.SiO.sub.2), composite oxide
fine particle of titanium and cerium (TiO.sub.2.cndot.CeO.sub.2),
composite oxide fine particle of titanium, iron and silicon
(TiO.sub.2.cndot.Fe.sub- .2O.sub.3.cndot.SiO.sub.2), composite
oxide fine particle of titanium, iron and cerium
(TiO.sub.2.cndot.CeO.sub.2.cndot.SiO.sub.2), composite oxide
fine-particle of titanium, zirconium and silicon
(TiO.sub.2.cndot.ZrO.sub.2.cndot.SiO.sub.2) and composite oxide
fine particle of titanium, aluminum and silicon
(TiO.sub.2.cndot.Al.sub.2O.sub- .3.cndot.SiO.sub.2).
[0047] The titanium oxide fine particle or titanium composite oxide
fine particle can be obtained by any known method. For example, a
hydrous titanic acid gel or sol is prepared by adding an alkali to
an aqueous solution of a titanium salt such as titanium chloride or
titanium sulfate for neutralization or bypassing an aqueous
solution of a titanium salt through an ion exchange resin.
Thereafter, hydrogen peroxide water is added to the hydrous titanic
acid gel or sol, or a mixture thereof to dissolve the hydrous
titanic acid so as to prepare a uniform aqueous solution. Further,
titanic acid is hydrolyzed by heating to obtain a titanium oxide
sol containing titanium oxide dispersed therein. In the step before
the heat treatment, an inorganic compound of one element or two or
more elements selected from the group consisting of Si, Al, Sn, Sb,
Ta, Ce, La, Fe, Zn, W, Zr and In is added to obtain a composite
oxide sol. For example, JP-A 63-185820 discloses a process for
producing a silica-titanium or titanium-silica-zirconia composite
oxide sol.
[0048] Further, the surface of the above titanium oxide fine
particle or titanium composite oxide fine particle may be surface
coated with (one layer or two or more layers of) silicon oxide, a
mixture of silicon oxide and an oxide of at least one element
selected from the group consisting of Al, Sn, Sb, Ta, Ce, La, Fe,
Zn, W, Zr and In, or a composite oxide. The fine particle can be
obtained by any known method. For example, JP-A 8-48940 discloses a
process for producing a composite oxide sol by coating a
titanium-silica composite oxide fine particle with silica-zirconia
composite oxide. When titanium oxide is existent in the form of a
composite oxide fine particle or surface coated fine particle, the
weight of a metal oxide other than titanium oxide contained in the
fine particle is excluded (ignored) in the calculation of the
amount of titanium oxide.
[0049] The titanium oxide may be amorphous but preferably has an
anatase or rutile crystal structure. Particularly preferably, the
titanium oxide has a rutile crystal structure.
[0050] When the titanium oxide is a composite oxide fine particle,
to improve its dispersibility in a solvent, the surface of the
composite oxide fine particle can be modified by an organic silane
compound or an amine. The amount of the organic silane compound is
0 to 20 wt % based on the weight of the fine particle. This surface
modification may be carried out while an organic silane compound
having a hydrolyzable group is not hydrolyzed or after it is
hydrolyzed.
[0051] The organic silane compound for modifying the surface of the
composite oxide fine particle is, for example, an organic silane
represented by the formula R.sub.3SiX, R.sub.2SiX.sub.2, RSiX.sub.3
or SiX.sub.4 (R is an organic group having alkyl, phenyl, vinyl,
methacryloxy, mercapto, amino, epoxy or ureide and X is a
hydrolyzable group), such as trimethyl methoxysilane, diphenyl
dimethoxysilane, vinyl trimethoxysilane,
.gamma.-methacryloxypropyldimethyl methoxysilane,
.gamma.-aminopropyl triethoxysilane, glycidoxypropyl
trimethoxysilane, .gamma.-ureidepropyl triethoxysilane or
tetraethyl orthosilicate.
[0052] Examples of the amine for modifying the surface of the fine
particle include alkylamines such as ammonium and ethylamine,
aralkylamines such as benzylamine, alicyclic amines such as
piperidine and alkanolamines such as monoethanolamine.
[0053] To modify the surface of the fine particle with an organic
silicon compound or amine, for example, a composite oxide fine
particle is mixed with an alcohol solution of the compound, a
predetermined amount of water and optionally a catalyst are added,
and the resulting mixture is left to stand at normal temperature
for a predetermined time or heated. The surface of the composite
oxide fine particle can be modified by adding a hydrolysate of the
compound and a composite oxide fine particle to a mixture of water
and an alcohol and by heating.
[0054] The resin coat layer of the present invention may contain an
inorganic oxide, antioxidant, ultraviolet light absorber, leveling
agent, lubricity modifier, antistatic agent, bluing agent and the
like as required in addition to the above resin, titanium oxide and
organic Co(II) compound. The inorganic oxide is an oxide or
composite oxide of at least one element selected from the group
consisting of Si, Al, Sn, Sb, Ta, La, Zn, W, Zr and In and a fine
particle having a particle diameter of 1 to 100 nm. The inorganic
oxide may be contained in an amount of 0 to 70 wt % in terms of
nonvolatile content.
[0055] The above antioxidant is preferably what has a sulfide
structure (C--S--C structure), more preferably a hindered phenolic
compound having a sulfide structure. Examples of the antioxidant
include 4,4'-thiobis(3-methyl-6-t-butylphenol),
2,2-thio-diethylenebis[3-(3,5-di--
t-butyl-4-hydroxyphenyl)propionate],
2,4-bis-(n-octylthio)-6-(4-hydroxy-3,-
5-di-t-butylanilino)-1,3,5-triazine, didodecyl
3,3'-thiobispropionate, dioctadecyl3,3'-thiobispropionate,
dimyristyl 3,3'-thiobispropionate and
2,4-[bis(octylthio)methyl]-O-cresol. The antioxidant is preferably
contained in an amount of 5 wt % or less.
[0056] The leveling agent or lubricity modifier is preferably a
copolymer of polyoxyalkylene and polydimethylsiloxane or a
copolymer of polyoxyalkylene and fluorocarbon. They are preferably
used in an amount of 0.001 to 10 parts by weight based on the total
amount of the coating solution.
[0057] The thickness of the resin coat layer in the present
invention, which differs according to the purpose of a resin coated
article, is preferably 0.10 to 10 .mu.m.
[0058] The coated article of the present invention is produced by
coating the surface of the substrate with a coating solution for a
resin coat layer by dip coating, spinner coating, spray coating or
flow coating and drying the coating solution to form a film and
heating the film thus formed on the surface of the substrate at a
temperature lower than the heat resistant temperature of the
substrate.
[0059] When an ultraviolet curable resin is used as a matrix
component of the coating solution for a resin coat layer, the
coated article of the present invention can be produced by coating
the surface of the substrate with the coating solution and
irradiating the surface of the substrate coated with the coating
solution with ultraviolet radiation having a predetermined
wavelength to cure the resin.
[0060] The coated article of the present invention can be a plastic
lens having a hard coat layer directly on the surface of a
substrate. In this case, the titanium oxide-containing a resin coat
layer in the present invention is used as the hard coat layer. The
coated article of the present invention can be a plastic lens
having a primer layer and a hard coat layer formed on the surface
of a substrate in the order named. In this case, the titanium
oxide-containing resin coat layer of the present invention is used
as either one or both of the primer layer and hard coat layer.
[0061] A preferred mode of the titanium oxide-containing resin coat
layer of the present invention is a hard coat layer of a titanium
oxide-containing silicon resin having a refractive index of 1.48 or
more and a thickness of 0.1 to 5 .mu.m formed on the surface of the
substrate of a plastic lens having a refractive index of 1.50 or
more directly or through a primer layer.
[0062] Another preferred mode of the titanium oxide-containing
resin coat layer of the present invention is a primer layer of a
titanium oxide-containing urethane resin having a refractive index
of 1.48 or more and a thickness of 0.5 to 5 .mu.m formed between
the surface of the substrate of a plastic lens having a refractive
index of 1.5.0 or more and a hard coat layer of a silicon resin
having a refractive index of 1.48 or more formed thereon.
[0063] Still another preferred mode of the titanium
oxide-containing resin coat layer of the present invention is a
combination of a primer layer and a hard coat layer in a plastic
lens which comprises the surface of the substrate of a plastic lens
having a refractive index of 1.50 or more, a primer layer of a
titanium oxide-containing urethane resin having a thickness of 0.5
to 5 .mu.m formed on the surface of the substrate and a hard coat
layer of a titanium oxide-containing silicon resin having a
refractive index of 1.48 or more and a thickness of 0.1 to 5 .mu.m
formed on the primer layer. That is, the titanium oxide-containing
resin coat layer of the present invention is used as the both
layers.
[0064] The hard coat layer when the titanium oxide-containing
silicon resin coat layer of the present invention is formed on the
surface of a plastic lens substrate as a hard coat layer will be
described in detail hereinafter.
[0065] Hard Coat Layer
[0066] A coating solution (solution composition) for forming a
silicone hard coat layer will be described.
[0067] The coating solution for forming a hard coat layer comprises
the following components (1) to (4):
[0068] (1) 2 to 70 wt % in terms of solid content of a sol
containing titanium oxide or a composite oxide thereof having a
particle diameter of 1.0 to 100 nm dispersed in water or an organic
medium;
[0069] (2) 0.1 to 10 wt % of an organic Co(II) compound;
[0070] (3) 20 to 97.9 wt % of an epoxy group-containing silicon
compound represented by the following formula (1):
R.sup.1R.sup.2.sub.aSi(OR.sup.3).sub.3-a (1)
[0071] wherein R.sup.1 is a group having an epoxy group and 2 to 12
carbon atoms, R.sup.2 is an alkyl group or halogenoalkyl group
having 1 to 6 carbon atoms, alkenyl group having 2 to 6 carbon
atoms, or phenyl group or halogenophenyl group, R.sup.3 is a
hydrogen atom, alkyl group or acyl group having 1 to 4 carbon
atoms, and a is 0, 1 or 2,
[0072] or a partial hydrolysate thereof; and
[0073] (4) 0.001 to 10 wt% of a curing catalyst.
[0074] The components (1) and (2) have already been described
above.
[0075] Examples of the epoxy group-containing silicon compound as
the component (3) include .gamma.-glycidoxypropyl trimethoxysilane,
.beta.-glycidoxypropyl trimethoxysilane, .gamma.-glycidoxypropyl
triethoxysilane, .beta.-glycidoxypropyl triethoxysilane,
.gamma.-glycidoxypropylmethyl dimethoxysilane,
.gamma.-glycidoxypropylmet- hyl diethoxysilane and
.beta.-(3,4-epoxycyclohexyl)ethyl trimethoxysilane.
[0076] Examples of the curing catalyst (4) of the composition for
forming a hard coat layer include alkali metal salts and ammonium
salts of carboxylic acids, metal salts and ammonium salts of
acetylacetone, metal salts of ethyl acetoacetate, metal salts
coordinated with acetylacetone and ethyl acetoacetate, metal salt
hydrates of ethylene diamine, primary to tertiary amines,
polyalkylene amines, sulfonates, magnesium perchlorate, ammonium
perchlorates, and combinations of these compounds and organic
mercaptan or mercaptoalkylenesilane. The curing catalyst may be
added when a composition for forming a hard coat layer is prepared
or right before a composition for forming a hard coat layer is
applied.
[0077] The weight percentages of the above components (1), (2) and
(3) are based on 100 wt % of the total weight of the components
(1), (2) and (3), and the weight percentage of the above component
(4) is based on the total weight of the above components (1), (2)
and (3).
[0078] The amount of the component (1) is preferably 5 to 60 wt %,.
the amount of the component (2) is preferably 0.2 to 5 wt %, and
the amount of the component (3) is preferably 35 to 94.8 wt %. The
amount of the component (4) is preferably 0.01 to 8 wt %.
[0079] The coating solution for forming a hard coat layer may
contain the following components (D) and (E) as required in
addition to the above components (1) to (4).
[0080] Component (D)
[0081] A fine particle of an oxide of at least one element selected
from the group consisting of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W,
Zr and In, such as SiO.sub.2, Al.sub.2O.sub.3, SnO.sub.2,
Sb.sub.2O.sub.5, Ta.sub.2O.sub.5, CeO, La.sub.2O.sub.3,
Fe.sub.2O.sub.3, ZnO, WO.sub.3, Zro.sub.2 or In.sub.2O.sub.3 in the
form of a sol solution and having a particle diameter of 1.0 to 100
nm may be contained in a total amount of 80 wt % or less.
[0082] When the fine particle is a composite oxide, its surface may
be modified by an organic silane compound or amine to improve its
dispersibility in a solvent. It should be understood that surface
modification is completely the same as that for a titanium
composite oxide. When the above titanium oxide is a titanium
composite oxide, for example, a TiO.sub.2--ZrO.sub.2--SiO.sub.2
composite oxide fine particle, a metal oxide other than titanium
oxide contained in the composite oxide, for example, zirconium
oxide and silicon oxide are the components (D).
[0083] The fine particle of the component (D) is preferably
dispersed in water or an organic solvent such as an alcohol in an
amount of 5 to 80 wt %. The fine particle of the component (D) is
contained in the coating solution for forming a hard coat layer in
an amount of 70 wt % or less in terms of solid content.
[0084] Component (E)
[0085] The component (E) is an antioxidant, preferably an
antioxidant having a C--S--C structure as described above.
[0086] The following components (F-1) to (F-14) which can react
with a hydrolyzed silanol group and epoxy group may be used to
improve physical properties such as dyability, heat resistance,
water resistance, antistatic properties and surface hardness or
assist a catalytic function, in addition to the above components
(A) to (E).
[0087] Component (F-1)
[0088] The component (F-1) is an organic compound having only one
OH or SH group in the molecule, at least one group selected from
the group consisting of --O--, --CO--O--, --S--, --CO--S-- and
--CS--S-- in the molecular main chain and further at least one
unsaturated group and soluble in water or a lower alcohol having 4
or less carbon atoms.
[0089] The above compound is preferably a compound represented by
the following formula (2):
R.sup.4--X--R.sup.5YH (2)
[0090] wherein R.sup.4 is a monovalent hydrocarbon group having at
least one unsaturated group and may contain oxygen and sulfur
atoms, R.sup.5 is a divalent hydrocarbon group having 2 or more
carbon atoms and may contain oxygen and sulfur atoms, and X and Y
are each independently an oxygen atom or sulfur atom.
[0091] Examples of the compound represented by the above formula
(2) include polyethylene glycol monomethacrylate,
poly(butanediol)monoacrylat- e, poly(butanediol)monomethacrylate,
1,4-butanediol monovinyl ether, 1,6-hexanedithiol monoacrylate,
di(acryloxyethyl)hydroxyethylamine, 2-hydroxy-3-phenoxypropyl
acrylate, pentaerythritol triacrylate, 2-hydroxybutyl acrylate,
3-acryloyloxyglycerin monomethacrylate,
2-hydroxy-1,3-dimethacryloxypropane and 2-mercaptoethyl
acrylate.
[0092] Out of the above compounds of the formula (2), preferred are
compounds represented by the following formula (3): 1
[0093] wherein R.sup.6 is a hydrogen atom or methyl group, and b is
an integer of 2 to 10, preferably 4 to 6, compounds represented by
the following formula (4): 2
[0094] wherein R.sup.6 is a hydrogen atom or methyl group,
R.sup.7is --CH.sub.2CH.sub.2--, --CH.sub.2CH(CH.sub.3)-- or
--CH(CH.sub.3)CH.sub.2-- -, and c is an integer of 2 to 9,
preferably 2 to 4,
[0095] compounds represented by the following formula (5):
CH.sub.2.dbd.CH--(CH.sub.2).sub.d--O--(CH.sub.2).sub.b--OH (5)
[0096] wherein b is an integer of 4 to 10, and d is 0 or 1, and
compounds represented by the following formula (6):
CH.sub.2.dbd.CH--(CH.sub.2).sub.d--O--(OR.sup.7).sub.c--OH (6)
[0097] wherein R.sup.7 is --CH.sub.2CH.sub.2--,
--CH.sub.2CH(CH.sub.3)-- or --CH(CH.sub.3)CH.sub.2--, c is an
integer of 2 to 9, and d is 0 or 1.
[0098] The compounds of the above formula (3) include
4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate.
[0099] The compounds of the above formula (4) include diethylene
glycol monoacrylate, tetraethylene glycol monoacrylate,
polyethylene glycol monoacrylate, tripropylene glycol monoacrylate,
polypropylene glycol monoacrylate, diethylene glycol
monomethacrylate, tetraethylene glycol monomethacrylate,
polyethylene glycol monomethacrylate, tripropylene glycol
monomethacrylate and polypropylene glycol monomethacrylate.
[0100] The compounds of the above formula (5) include
4-hydroxybutylallyl ether and 4-hydroxybutylvinyl ether.
[0101] The compounds of the above formula (6) include diethylene
glycol monoallyl ether and triethylene glycol monovinyl ether.
[0102] The above component (F-1) is used in an amount of 0.001 to
50 wt % based on the total solid content of the base resin.
[0103] Component (F-2)
[0104] The component (F-2) is an-unsaturated dibasic acid. Examples
of the component (F-2) include itaconic acid, succinic acid,
malonic acid, glutaric acid, adipic acid, pimelic acid, suberic
acid, azelaic acid, sebacic acid, fumaric acid and maleic acid.
[0105] Component (F-3)
[0106] The component (F-3) is an cyclic anhydride of an unsaturated
dibasic acid. Examples of the component (F-3) include succinic
anhydride, glutaric anhydride, trimellitic anhydride, pyromellitic
anhydride, phthalic anhydride and maleic anhydride.
[0107] Component (F-4)
[0108] The component (F-4) is an imide compound of an unsaturated
dibasic acid. Examples of the component (F-4) include succinic acid
imide, glutaric acid imide, phthalic acid imide and maleic acid
imide.
[0109] Component (F-5)
[0110] The component (F-5) is a saturated polycarboxylic acid.
Examples of the component (F-5) include adipic acid and suberic
acid.
[0111] Component (F-6)
[0112] The component (F-6) is an cyclic anhydride of a saturated
polycarboxylic acid. Examples of the component (F-6) include cyclic
anhydrides of saturated polycarboxylic acids as the component
(F-5), such as adipic anhydride.
[0113] Component (F-7)
[0114] The component (F-7) is an imide compound of a saturated
polycarboxylic acid. Examples of the component (F-7) include cyclic
anhydrides of the above saturated polycarboxylic acids (component
(F-5)), such as adipic acid imide.
[0115] Component (F-8)
[0116] The component (F-8) is an amine. Examples of the component
(F-8) include polymethylene diamine, polyether diamine, diethylene
triamine, iminobispropylamine, bishexamethylene triamine,
diethylene triamine, tetraethylene pentaamine, pentaethylene
hexaamine, pentaethylene hexamine, dimethylamino propylamine,
aminoethyl ethanolamine, methyliminobispropylamine,
menthanediamine, N-aminomethyl piperazine, 1,3-diaminocyclohexane,
isophorone diamine, metaxylene diamine, tetrachloroparaxylene
diamine, methaphenilene diamine, 4,4-methylene dianiline,
diaminodiphenylsulfone, benzidine, toluidine, diaminodiphenyl
ether, 4,4'-thiodianiline, 4,4'-bis(o-toluidine)dianisidine,
o-phenylene diamine, 2,4-toluene diamine,
methylenebis(o-chloroaniline), diaminiditolylsulfone,
bis(3,4-diaminophenyl)sulfone, 2,6-diaminopyridine,
4-chloro-o-phenylene diamine, 4-methoxy-6-methyl-m-phenylene
diamine, m-aminobenzylamine, N,N,N',N'-tetramethyl-1,3-butane
diamine, N,N,N',N'-tetramethyl-p-phenyle- ne diamine, tetramethyl
guanidine, triethanol amine, 2-dimethylamino-2-hydroxypropane,
N,N'-dimethylpiperazine, N,N'-bis[(2-hydroxy)propyl]piperazine,
N-methylmorpholine, hexamethylene tetramine, pyridine, piperazine,
quinoline, benzyldimethylamine, .alpha.-methylbenzylmethylamine,
2-(dimethylaminomethyl)phenol,
2,4,6-tris(dimethylaminomethylol)phenol, N-methylpiperazine,
pyrrolidine and morpholine.
[0117] An adduct of the above mine with an organic carboxylic acid,
cyclic ether, ketone, aldehyde or hydroquinone, or a condensate of
the above amine may be used like the above amines.
[0118] Component (F-9)
[0119] The component (F-9) is urea and a formaldehyde adduct
thereof.
[0120] Component (F-10)
[0121] The component (F-10) is an alkyl-substituted methylol
melamine.
[0122] Component (F-11)
[0123] The component (F-11) is a compound having two or more OH
groups or SH groups. Examples of the component (F-11) include
1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol,
ethylene glycol, diethylene glycol, triethylene glycol,
tetraethylene glycol, polyethylene glycol, propylene glycol,
tripropylene glycol, polypropylene glycol, trimethylol propane,
neopentyl glycol, catechol, resorcinol, alkylene glycol, polyvinyl
alcohol, polycaprolactone diol, polycaprolactone triol and
polycaprolactone tetraol.
[0124] Component (F-12)
[0125] The component (F-12) is a compound having two or more epoxy
groups. Examples of the component (F-12) include glycidyl ethers of
polyhydric alcohols as the component (F-11).
[0126] Component (F-13)
[0127] The component (F-13) is a dicyandiamide, hydrazide,
thiourea, guanidine, ethyleneimine, sulfoneamide or derivative
thereof.
[0128] Component (F-14)
[0129] The component (F-14) is an organic silicon compound
represented by the following formula (7):
R.sup.8.sub.fR.sup.9.sub.eSi(OR.sup.10).sub.4-f-e (7)
[0130] wherein R.sup.9 is an alkyl group having 1 to 6 carbon
atoms, aryl group, alkenyl group, halogenated alkyl group or
halogenated aryl group, R.sup.10 is a hydrogen atom, alkyl group
having 1 to 4 carbon atoms, acyl group or alkylacyl group, R.sup.8
is selected from an alkyl group having 1 to 4 carbon atoms,
halogenated alkyl group, aryl group and halogenated aryl group
having 6 to 12 carbon atoms, methacryloxyalkyl group having 5 to 8
carbon atoms, ureidealkylene group having 2 to 10 carbon atoms,
aromatic ureidealkylene group, halogenated aromatic alkylene group
and mercaptoalkylene group, f is 1, 2 or 3, and e is 0, 1 or 2,
[0131] or a partial hydrolysate thereof.
[0132] The component (F-14) may be added in an amount of 100 parts
or less by weight in terms of solid content based on 100 parts by
weight of the total solid content of the base resin.
[0133] Examples of the compound of the above formula (7) include
trimethylmethoxysilane, triethylmethoxysilane,
trimethylethoxysilane, triethylethoxysilane,
triphenylmethoxysilane, diphenylmethylmethoxysilane- ,
phenyldimethylmethoxysilane, phenyldimethylmethoxysilane,
vinyldimethylmethoxysilane, vinyldimethylethoxysilane,
.gamma.-acryloxypropyldimethylmethoxysilane,
.gamma.-methacryloxypropyldi- methylmethoxysilane,
.gamma.-mercaptopropyldimethylmethoxysilane,
.gamma.-mercaptopropyldimethylethoxysilane, N-.beta.(aminoethyl)
.gamma.-aminopropyldimethylmethoxysilane,
.gamma.-aminopropyldimethylmeth- oxysilane,
.gamma.-aminopropyldimethylethoxysilane,
.gamma.-glycidoxypropyldimethylmethoxysilane,
.gamma.-glycidoxypropyldime- thoxyethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyldimethylmethoxysilane,
dimethyldimethoxysilane, diethyldimethoxysilane,
dimethyldiethoxysilane, diethyldiethoxysilane,
diphenyldimethoxysilane, phenylmethyldimethoxysila- ne,
phenylmethyldiethoxysilane, vinylmethyldimethoxysilane,
vinylmethyldiethoxysilane,
.gamma.-acryloxypropylmethyldimethoxysilane,
.gamma.-methacryloxypropyldimethyldimethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane,
.gamma.-mercaptopropylmethyl- diethoxysilane, N-.beta.(aminoethyl)
.gamma.-aminopropylmethyldimethoxysil- ane,
.gamma.-aminopropylmethyldime-thoxysilane,
.gamma.-aminopropylmethyld- iethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-glycidoxypropylmethoxydiethoxysilane,
.beta.-(3,4-epoxycyclohexyl- )ethylmethyldimethoxysilane,
methyltrimethoxysilane, ethyltrimethoxysilane,
methyltriethoxysilane, ethyltriethoxysilane,
phenyltrimethoxysilane, phenyltriethoxysilane,
vinyltrimethoxysilane, vinyltriethoxysilane,
vinyl(.beta.-methoxyethoxy)silane,
.gamma.-acryloxypropyltrimethoxysilane,
.gamma.-methacryloxypropyltrimeth- oxysilane,
.gamma.-mercaptopropyltrimethoxysilane, .gamma.-mercaptopropylt-
riethoxysilane, N-.beta.(aminoethyl)
.gamma.-aminopropyltrimethoxysilane,
.gamma.-aminopropyltrimethoxysilane,
.gamma.-aminopropyltriethoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane,
.beta.-glycidoxypropyltrimethoxy- silane,
.gamma.-glycidoxypropyltriethoxysilane, .beta.-glycidoxypropyltrie-
thoxysilane, .beta.-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
tetraethyl orthosilicate and tetramethyl orthosilicate.
[0134] The above components (F-1) to (F-14) may be added in a total
amount of 0.001 to 70 wt % based on the total solid content of the
base resin.
[0135] The solvent for the composition for forming a hard coat
layer is a glycol, aliphatic cyclic ketone, acetate or alcohol.
Examples of the glycol include ethylene glycol monomethyl ether
acetate, ethylene glycol monoethyl ether acetate, ethylene glycol
monopropyl ether acetate, ethylene glycol monobutyl ether acetate,
propylene glycol monomethyl ether acetate, propylene glycol
monoethyl ether acetate, propylene glycol monopropyl ether acetate,
propylene glycol monobutyl ether acetate, ethylene glycol dimethyl
ether, ethylene glycol diethyl ether, ethylene glycol dipropyl
ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl
ether, diethylene glycol diethyl ether, diethylene glycol dipropyl
ether, diethylene glycol dibutyl ether, propylene glycol dimethyl
ether, propylene glycol diethyl ether, propylene glycol monomethyl
ether, ethylene glycol monoethyl ether and ethylene glycol
monobutyl ether. Examples of the aliphatic cyclic ketone include
cyclohexanone, o-methylcyclohexanone, m-methylcyclohexanone and
p-methylcyclohexanone. Examples of the acetate include ethyl
acetate, n-propyl acetate and n-butyl acetate. Examples of the
alcohol include methanol, ethanol, 1-propanol and 2-propanol.
Solvent naphtha and methyl ethyl ketone may also be used as a
solvent.
[0136] The solvent is used to ensure that the solids content of the
composition for forming a hard coat layer should be 5 to 50 wt
%.
[0137] Water is necessary to hydrolyze the component (C) and the
component (F-14) and used in an amount 1.0 to 10 times the
theoretical amount of hydrolysis.
[0138] The composition for forming a hard coat layer may further
contain a leveling agent, weather ability modifier, antistatic
agent, colorant and dye for a cured film. Examples of the leveling
agent out of these include a copolymer of polyoxyalkylene and
polydimethylsiloxane and a copolymer of polyoxyalkylene and
fluorocarbon. The leveling agent is used in an amount of 0.001 to
10 parts by weight in terms of solid content in the composition for
forming a hard coat layer.
[0139] The composition for forming a hard coat layer is applied to
the surface of the substrate directly or the surface of the primer
layer formed on the surface of the substrate and cured. Coating is
appropriately selected from dip coating, flow coating, spinner
coating and spray coating. Curing conditions include a temperature
of 90 to 120.degree. C. and a time of 30 minutes to 24 hours, for
example. The optimum conditions are preferably selected from these
conditions.
[0140] The thickness of the hard coat layer is preferably 0.1 to 5
.mu.m. When the thickness of the film is smaller than 0.1 .mu.m,
hardness may lower and when the thickness is larger than 5 .mu.m,
the film may crack. The thickness of the hard coat layer is more
preferably 0.5 to 5 .mu.m.
[0141] A detailed description is subsequently given of a case where
the titanium oxide-containing urethane resin coat layer of the
present invention is formed on the surface of the plastic lens
substrate as a primer layer.
[0142] Primer Layer
[0143] A solution composition for forming a primer layer (film)
contains the following components (1) to (4):
[0144] (1) 2 to 70 wt % in terms of solid content of a sol
containing titanium oxide or a composite oxide thereof having a
particle diameter of 1.0 to 100 nm dispersed in water or an organic
medium;
[0145] (2) 0.1 to 10 wt % of an organic Co(II) compound;
[0146] (3) 10 to 87.9 wt % of a polyol; and
[0147] (4) 10 to 87.9 wt % of a polyisocyanate.
[0148] The components (1) and (2) has already described above.
[0149] Examples of the polyol as the component (3) include
polyester polyols, polyether polyols, acrylic polyols and
polycarbonate polyols. Out of these, polyester polyols are
preferred.
[0150] The polyester polyols are obtained by carrying out the
dehydration condensation of a polybasic acid and a compound having
active hydrogen. Examples of the polybasic acid include organic
acids such as isophthalic acid, phthalic acid, phthalic anhydride,
hydrogenated phthalic acid, fumaric acid, dimerized linolenic acid,
maleic acid and saturated aliphatic dibasic acids having 4 to 8
carbon atoms. These polybasic acids may be used alone or in
combination of two or more. Examples of the compound having active
hydrogen include glycols such as ethylene glycol, propylene glycol,
butylene glycol, hexylene glycol and diethylene glycol; adducts of
trimethylolpropane, hexanetriol, glycerin, trimethylolethane,
pentaerythritol, polycaprolactone diol, polycaprolactone triol,
polycaprolactone tetraol and bisphenol A with ethylene glycol and
propylene; adducts of the above compounds with bromine; and diols
having a chemical structure composed of 4,4'-thiobisbenzenethiol.
These compounds having active hydrogen may be used alone or in
combination of two or more.
[0151] The above polyester polyols may be acquired as commercially
available products such as Demosphen Series (of Sumitomo-Bayer Co.,
Ltd.), Nipporan Series (of Nippon Polyurethane Co. Ltd.), Takerac
Series (of Takeda Chemical Industries, Ltd.) Adeca New Ace Series
(of Asaki Denka Kogyo K. K.) and Barnoc (of Dainippon Ink and
Chemicals, Inc.).
[0152] The polycarbonate polyols may be acquired as commercially
available products such as Nipporan 980 Series (of Nippon
Polyurethane Co., Ltd.) and Carbodiol (of Toa Corporation.), the
polyether polyols may be acquired as commercially available
products such as Adecapolyether (of Asahi Denka Kogyo K. K.),
Actocall (of Takeda Chemical Industries, Ltd.) and PPG-Diol Series
(of Mitsui Toatsu Chemicals Inc.), and the acrylic polyols may be
acquired as commercially available products such as Takerac (of
Takeda Chemical Industries, Ltd.) and Acrydic (of Dainippon Ink and
Chemicals, Inc.). They are preferably used to adjust the physical
properties of urethane resins.
[0153] The polyisocyanate may be an aliphatic polyisocyanate or
polyisocyanate having an aromatic ring. The polyisocyanate is
preferably diisocyanate having two or more isocyanate groups (NCO
group) in the molecule.
[0154] Examples of the polyisocyanate include hexamethylene
diisocyanate, 1,3,3-trimethylhexamethylene diisocyanate, isophorone
diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, xylylene
diisocyanate, tetramethylxylylene diisocyanate, hydrogenated
xylylene diisocyanate, tolylene diisocyanate, diphenylmethane
diisocyanate, hydrogenated diphenylmethane diisocyanate,
1,5-naphthalene diisocyanate and tetramethylxylylene diisocyanate.
These polyisocyanates may be used as a modified product,
isocyanurate, allophanate, burette, carbodiimide or adduct such as
trimer.
[0155] The polyisocyanate may be blocked by a blocking agent.
Examples of the blocking agent include acetylacetone, diethyl
malonate, dimethyl malonate, 2,4-hexanedione, 3,5-heptanedione,
acetooxime, butanoneoxime, methyl ethyl ketooxime and caprolactam.
Out of these, .beta.-diketone such as acetylacetone and methyl
ethyl ketooxime are preferred.
[0156] The isocyanate blocked by a blocking agent can be
synthesized by known technologies such as methods described in
British Patent No. 1442024, Polym. Sci. Technol., 36. 197 (1987),
and Coating Technology 31, 161 (1992).
[0157] When the polyisocyanate is an aromatic polyisocyanate such
as xylylene diisocyanate or tetramethylxylene diisocyanate, it can
be advantageously used as a modified product, adduct or
prepolymer.
[0158] When the polyisocyanate is an aliphatic polyisocyanate, it
is blocked by .beta.-diketone and advantageously used. Particularly
when hexamethylene diisocyanate is used as a cyclic trimer blocked
by .beta.-diketone, the primer composition can be advantageously
provided as a one-part type composition.
[0159] The primer composition may contain the above polyol and
polyisocyanate while they are not reacted with each other or may
contain a prepolymer or thermoplastic (linear) polymer obtained by
reacting the above polyol and polyisocyanate.
[0160] When the primer composition contains the above polyol and
polyisocyanate while they are not reacted with each other, the
ratio (NCO/OH) of the number of equivalents of the isocyanate group
(NCO) of the polyisocyanate to the number of equivalents of the
hydroxyl group (OH) of the polyol is preferably in the range of 0.7
to 1.5. When the ratio is smaller than 0.7, the adhesion of the
hard coat layer to the obtained primer layer may decrease and when
the ratio is larger than 1.5, the primer layer may whiten or the
adhesion of the hard coat layer may lower. The (NCO/OH) ratio is
more preferably in the range of 0.8 to 1.2.
[0161] In the primer composition, the weight percentages of the
above components (1), (2), (3) and (4) are based on 100 wt % of the
total weight of all the components.
[0162] The amount of the component (1) is preferably 3 to 65 wt %,
the amount of the component (2) is preferably 0.2 to 5 wt %, the
amount of the component (3) is preferably 12 to 84.8 wt %, and the
amount of the component (4) is preferably 12.to 84.8 wt %.
[0163] The primer composition may further contain the same oxide
fine particle (component (D)) as in the above hard coat composition
in an amount of 80 wt % or less as required to, approximate the
refractive index of the primer layer to that of the lens.
[0164] The primer composition may optionally contain a curing
catalyst, leveling agent, lubricity modifier, weatherability
modifier, antistatic agent, colorant, bluing agent and the like.
The type and content of the curing catalyst are the same as the
curing catalyst for the above composition for forming a hard coat
layer.
[0165] The primer composition in the present invention is provided
as an organic solvent or aqueous solution. Examples of the organic
solvent are the same as those enumerated for the above hard coat,
such as glycols, aliphatic cyclic ketones, acetates and alcohols.
The solvent is used in an amount of 2 to 50 wt % in terms of solid
content in the primer composition.
[0166] The primer composition is applied to the surface of the
substrate and cured. Coating is appropriately selected from dip
coating, flow coating, spinner coating and spray coating. Preferred
curing conditions include a temperature of 85 to 120.degree. C. and
a time of 15 minutes to 10 hours. The optimum conditions are
preferably selected from the above conditions.
[0167] The thickness of the primer layer is preferably 0.5 to 5
.mu.m. When the thickness is smaller than 0.5 .mu.m, the effect of
improving the impact resistance of a coated article is small and
when the thickness is larger than 5 .mu.m, the hardness of the hard
coat layer to be formed on the primer layer may lower.
[0168] An anti-reflection layer which comprises a single-layer or
multiple layers of an inorganic material may be formed on the hard
coat layer. This makes it possible to suppress the reflection of
visible light and improve visible light transmission and
weatherability. Examples of the inorganic material include SiO,
SiO.sub.2, Si.sub.3N.sub.4, TiO.sub.2, ZrO.sub.2, Al.sub.2O.sub.3,
MgF.sub.2 and Ta.sub.2O.sub.5. The anti-reflection film can be made
thin by a vacuum deposition method or the like.
[0169] The substrate in the present invention may be a transparent
substrate made from a plastic such as a polyurethane resin,
methacrylic polymer, allyl polymer or copolymer thereof, or glass
having a refractive index of 1.50 or more. Examples of the
substrate include substrates for use in optical lenses such as
spectacle lenses and camera lenses, display element filters, glass
sheets for construction, auto window glass and light covers for use
in automobiles.
[0170] To produce the resin coated article of the present
invention, a substrate whose surface has been treated with an
alkali, acid or surfactant, which is polished with inorganic or
organic fine particles, or which is subjected to a primer
treatment, plasma treatment, corona treatment or flame treatment
may be used as the substrate to improve the adhesion of the coat
layer to the lens substrate.
[0171] One preferred mode of the liquid composition for forming a
primer layer for the coated article of the present invention is a
liquid composition for forming a primer layer which contains the
following components (1) to (4):
[0172] (1) a sol containing titanium oxide or a composite oxide
thereof having a particle diameter of 1.0 to 100 nm dispersed in
water or an organic solvent;
[0173] (2) a Co(II) chelate compound or fatty acid compound,
[0174] (3) a polyester polyol; and
[0175] (4) a polyisocyanate.
[0176] Preferably, the above component (1) is contained in an
amount of 2 to 70 wt %, the component (2) in an amount of 0.1 to 10
wt %, the component (3) in an amount of 10 to 87.9 wt % and the
component (4) in an amount of 10 to 87.9 wt % in terms of solid
content.
[0177] One preferred mode of the coated article of the present
invention is a plastic lens comprising a substrate having a
refractive index of 1.50 or more and a hard coat layer which is
essentially composed of a silicon resin, has a thickness of 0.1 to
5 .mu.m and a refractive index of 1.48 or more, and is formed on
the surface of the plastic lens substrate directly or through a
primer layer, the hard coat layer comprising:
[0178] (1) 2 to 70 wt % of titanium oxide or a composite oxide
thereof having a particle diameter of 1.0 to 100 nm;
[0179] (2) 0.1 to 10 wt % of a Co(II) chelate compound or fatty
acid compound;
[0180] (3) 20 to 97.9 wt % of a silicon-based resin; and
[0181] (4) 0.001 to 10 wt % of a curing catalyst.
[0182] Another preferred mode of the coated article of the present
invention is a plastic lens comprising a substrate having a
refractive index of 1.50 or more, a primer layer which is
essentially composed of an urethane resin and has a thickness of
0.5 to 5 .mu.m and a refractive index of 1.48 or more, and a hard
coat layer which is essentially composed of a silicon resin, are
formed on the surface of the substrate in the order named, the
primer layer comprising:
[0183] (1) 2 to 70 wt % of titanium oxide or a composite oxide
thereof having a particle diameter of 1.0 to 100 nm;
[0184] (2) 0.1 to 10 wt % of a Co(II) chelate compound or fatty
acid compound; and
[0185] (3) 20 to 97.9 wt % of an urethane-based resin.
EXAMPLES
[0186] The following examples are provided for the purpose of
further illustrating the present invention but are in no way to be
taken as limiting.
[0187] Preparation of Primer Coat Solutions 1 to 5
[0188] 64 g of a polyester polyol comprising isophthalic acid and
1,6-hexanediol and having an average molecular weight of 940 and a
hydroxyl group value of 120 mgKOH/g and 65 g of a butyl acetate
solution containing 75 wt % of a trimer of hexamethylene
diisocyanate blocked by .beta.-diketone were prepared and mixed
with 710 g of propylene glycol monomethyl ether and stirred until a
uniform solution was obtained, 160 g of a composite oxide sol 1
which consisted of TiO.sub.2, Fe.sub.2O.sub.3 and SiO.sub.2
(TiO.sub.2/Fe.sub.2O.sub.3/SiO.sub.2=81/1/18 (weight ratio),
titanium oxide was of an anatase type, dispersed in methanol, and
had an average particle diameter of 10 nm and a nonvolatile content
of 30%) was added, stirred and mixed until a uniform solution was
obtained, and then 0.5 g of the Florad FC-430 of 3M Co., Ltd. was
added as a leveling agent and stirred. The obtained composition was
designated as primer coat solution 1.
[0189] 1 g of Co(II) acetylacetonato dihydrate was added to 1,000 g
of the separately prepared primer coat solution 1 and stirred to
prepare a primer coat solution 2.
[0190] 31 g of a polyester polyol comprising isophthalic acid and
adipic acid (molar ratio of 6:4), 1,6-hexanediol and
trimethylolpropane and having an average molecular weight of 650
and a hydroxyl group value of 260 mgKOH/g, 68 g of a butyl acetate
solution containing 75 wt % of a trimer of hexamethylene
diisocyanate blocked by .beta.-diketone and 634 g of propylene
glycol monomethyl ether were stirred and mixed together until a
uniform solution was obtained, 266 g of a composite oxide sol 2
consisting of TiO.sub.2, ZrO.sub.2 and SiO.sub.2
(TiO.sub.2/ZrO.sub.2/SiO- .sub.2=65/5/30 (weight ratio), titanium
oxide was of an anatase type, dispersed in methanol and had an
average particle diameter of 10 nm and a nonvolatile content of
30%) was added, stirred and mixed until a uniform solution was
obtained, and 0.5 g of the Florad FC-430 of 3M Co., Ltd. was added
as a leveling agent and stirred. The obtained composition was
designated as primer coat solution 3.
[0191] 61 g of a polyester polyol consisting of isophthalic acid
and 3-methyl-1,5-pentanediol and having an average molecular weight
of 490 and a hydroxyl group value of 226 mgKOH/g, 118 g of a
propylene glycol methyl acetate solution containing 70 wt % of a
trimer of hexamethylne diisocyanate blocked by .beta.-diketone and
630 g of propylene glycol monomethyl ether were stirred and mixed
together until a uniform solution was obtained, 187 g of a
composite oxide sol 3 consisting of TiO.sub.2, ZrO.sub.2 and
SiO.sub.2(TiO.sub.2/ZrO.sub.2/SiO.sub.2=79/1/20 (weight ratio),
titanium oxide was of a rutile type, dispersed in methanol and had
an average particle diameter of 10 nm and a nonvolatile content of
30%) was added, stirred and mixed until a uniform solution was
obtained, and 0.5 g of the Florad FC-430 of 3M Co., Ltd. was added
as a leveling agent and stirred. The obtained composition was
designated-as primer coat solution 4.
[0192] 61 g of a polyester polyol consisting of adipic acid and
3-methyl-1,5-pentanediol and having an average molecular weight of
485 and a hydroxyl group value of 231 mgKOH/g, 119 g of a propylene
glycol methyl acetate solution containing 70 wt % of a trimer of
hexamethylne diisocyanate blocked by .beta.-diketone and 624 g of
propylene glycol monomethyl ether were stirred and mixed together
until a uniform solution was obtained, 187 g of the above composite
oxide sol 3 was added, stirred and mixed until a uniform solution
was obtained, 2 g of a Co(II) salt of 2-ethyl-hexylic acid was
added and stirred, and 0.5 g of the Florad FC-430 of 3M Co., Ltd.
was added as a leveling agent and stirred. The obtained composition
was designated as primer coat solution 5.
[0193] Preparation of Hard Coat Solutions 1 to 9.
[0194] 235 g of the same composite oxide sol 1 as used in the
preparation of the above primer coat solution 1 was weighed. 140 g
of distilled water was added under agitation. 191 g of
.gamma.-glycidoxypropyltrimethoxysila- ne and 42 g of
tetramethoxysilane were gradually added. After the end of addition,
they were stirred for another 2 hours. Thereafter, 373 g of
propylene glycol monomethyl ether was added while the mixed
solution was stirred and then 2 g of tetraethylene glycol
monomethacrylate was added. 8 g of acetylacetone aluminum as a
curing catalyst and 0.4 g of a silicone surfactant (L-7001 of
Nippon Unicar Co., Ltd.) as a leveling agent were further added and
stirred for 1 hour. The above mixed solution was aged at room
temperature for 48 hours to obtain a hard coat solution 1.
[0195] 235 g of the above composite oxide sol 1 was weighed. 140 g
of distilled water was added under agitation. 191 g of
.gamma.-glycidoxypropyltrimethoxysilane and 42 g of
tetramethoxysilane were gradually added. After the end of addition,
they were stirred for another 2 hours. Thereafter, 373 g of
propylene glycol monomethyl ether was added while the mixed
solution was stirred and then 2 g of tetraethylene glycol
monomethacrylate was added. 8 g of acetylacetone aluminum as a
curing catalyst and 0.4 g of a silicone surfactant (L-7001 of
Nippon Unicar Co., Ltd.) as a leveling agent were further added and
stirred for 1 hour. 2 g of Co(II) acetylacetonato dehydrate was
still further added and stirred. The above mixed solution was aged
at room temperature for 48 hours to obtain a hard coat solution
2.
[0196] 295 g of the above composite oxide sol 2 was weighed. 115 g
of distilled water was added under agitation. 178 g of
.gamma.-glycidoxypropyltrimethoxysilane was gradually added. After
the end of addition, it was stirred for another 2 hours.
Thereafter, 378 g of isopropyl alcohol was added while the mixed
solution was stirred and then 15 g of tetraethylene glycol
monomethacrylate was added. 7 g of acetylacetone aluminum as a
curing catalyst and 0.4 g of a silicone surfactant (L-7001 of
Nippon Unicar Co., Ltd.) as a leveling agent were further added and
stirred for 1 hour. The above mixed solution was aged at room
temperature for 48 hours to obtain a hard coat solution 3.
[0197] 295 g of the above composite oxide sol 2 was weighed. 115 g
of distilled water was added under agitation. 178 g of
.gamma.-glycidoxypropyltrimethoxysilane was gradually added. After
the end of addition, it was stirred for another 2 hours.
Thereafter, 378 g of isopropyl alcohol was added while the mixed
solution was stirred and then 15 g of tetraethylene glycol
monomethacrylate was added. 7 g of acetylacetone aluminum as a
curing catalyst and 0.4 g of a silicone surfactant (L-7001 of
Nippon Unicar Co., Ltd.) as a leveling agent were further added and
stirred for 1 hour. 4.6 g of Co(II) acetylacetonato dehydrate and
2.3 g of 4,4'-thiobis(3-methyl-6-t-butylphenol) were still further
added and stirred. The above mixed solution was aged at room
temperature for 48 hours to obtain a hard coat solution 4.
[0198] A hard coat solution 5 was obtained in the same manner as
the hard coat solution 4 except that 6.9 g of a Co(II) salt of
2-ethyl-hexylic acid was added in place of the Co(II)
acetylacetonato dihydrate and
4,4'-thiobis(3-methyl-6-t-butylphenol) in the preparation of the
hard coat solution 4.
[0199] 261 g of the above composite oxide sol 3 was weighed. 140 g
of distilled water was added under agitation. 181 g of
.gamma.-glycidoxypropyltrimethoxysilane was gradually added.
Thereafter, 39 g of tetraethyl orthosilicate was added under
agitation and then further stirred for 2 hours. Thereafter, 361 g
of propylene glycol monomethyl ether was added while the mixed
solution was stirred, and then 2 g of tetraethylene glycol
monomethacrylate was added. 9 g of acetylacetone aluminum as a
curing catalyst and 0.4 g of a silicone surfactant (L-7001 of
Nippon Unicar Co., Ltd.) as a leveling agent were further added and
stirred for 1 hour. The above mixed solution was aged at room
temperature for 48 hours to obtain a hard coat solution 6.
[0200] After 1 kg of the above hard coat solution 6 was prepared
separately, 2 g of Co(II) acetylacetonato dihydrate was added and
stirred for 1 hour. The above mixed solution was aged at room
temperature for 48 hours to obtain a hard coat solution 7.
[0201] 348 g of the above composite oxide sol 3 was weighed. 110 g
of distilled water was added under agitation. 148 g of
.gamma.-glycidoxypropyltrimethoxysilane was gradually added and
further stirred for 2 hours. Thereafter, 368 g of propylene glycol
monomethyl ether was added while the mixed solution was stirred,
and then 11 g of tetraethylene glycol monomethacrylate was added. 6
g of acetylacetone aluminum as a curing catalyst and 0.4 g of a
silicone surfactant (L-7001 of Nippon Unicar Co., Ltd.) as a
leveling agent were further added and stirred for 1 hour. The above
mixed solution was aged at room temperature for 48 hours to obtain
a hard coat solution 8.
[0202] After 1 kg of the above hard coat solution 8 was prepared
separately, 5.0 g of a Co(II) salt of 2-ethyl-hexylic acid was
added and stirred for 1 hour. The above mixed solution was aged at
room temperature for 4.8 hours to obtain a hard coat solution
9.
Examples 1 to 14 and Comparative Examples 1 to 8
[0203] The above primer coat solutions 1 to 5 were each applied to
the following two different lens substrates by the following
methods and cured by heating and then the above hard coat solutions
1 to 9 were each applied to the above substrates by the following
dip coating and cured by heating. The evaluation results of the
properties of the obtained coated lenses are shown in Table 2. The
thickness and refractive index (nD) of each film measured by the
following methods are shown in Table 1. The results of a
weatherability test measured by the following method are shown in
Tables 3 and 4.
[0204] Lens Substrate:
[0205] The following lens substrates A and B were used.
[0206] substrate A: plastic spectacle lens made from a thiourethane
resin having a refractive index of 1.594 and manufactured by
molding and thermosetting the MR-6 monomer of Mitsui Toatsu
Chemicals, Inc.
[0207] substrate B: plastic spectacle lens made from a thiourethane
resin having a refractive index of 1.66 and manufactured by molding
and thermosetting the MR-7 monomer of Mitsui Toatsu Chemicals,
Inc.
[0208] Application and Curing Methods of Primer Coat Solution:
[0209] The lens substrate is immersed in a primer coat solution,
pulled up at a rate of 10 cm/min, dried at room temperature for
about 10 minutes and heated at 95.degree. C. for 30 minutes to cure
a coating film.
[0210] Application and Curing Methods of Hard Coat Solution:
[0211] The lens substrate (or substrate with a cured primer layer)
is immersed in a hard coat solution, pulled up at a rate of 15
cm/min, dried at room temperature for about 5 minutes and heated at
120.degree. C. for 1 hour to cure a hard coat layer.
[0212] Measurement of Film Thickness:
[0213] Each of the coat solutions is applied to a glass plate and
is cured, part of the coating film is chipped off and the resulting
level difference is measured to obtain the thickness of the film.
It has been confirmed that whether the substrate is the above
substrate A or B, the thickness of the obtained film remains the
same as that of the above glass plate.
[0214] Measurement of Weatherability:
[0215] The appearance, adhesion and hardness of a film after 60,
120, 180 and 240 hours of irradiation are evaluated as follows
using a xenon weather-ometer weatherability tester (black panel
temperature of 63.degree. C., water sprayed for 18 minutes every 2
hours, irradiation intensity of 0.35 W/m.sup.2 at 340 nm).
[0216] appearance: observed with the eye and ranked as follows.
[0217] A-no change
[0218] B-part of the lens slightly cracks
[0219] C-about 1/3 of the area of the lens cracks
[0220] D-all the surface of the lens cracks
[0221] adhesion: A cross-hatch test is conducted in accordance with
a cross cut adhesion test JIS K5400. That is, 11 parallel lines are
cut on the surface of the film in both longitudinal and transverse
directions at intervals of 1 mm by a knife to form 100 squares and
Cellotape is affixed to the squares and then peeled off to count
the number of squares adhered to the substrate from which the film
is not peeled. The proportion (%) of the number of the squares to
the total number of squares is taken as adhesion.
[0222] hardness: The film is rubbed with steel wool #0000 10 times
under a load of 1 kg to measure the scratching of the film based on
the following criteria.
[0223] 5: not scratched at all
[0224] 4: slightly scratched
[0225] 3: scratched
[0226] 2: badly-scratched
[0227] 1: scratched to the substrate
1TABLE 1 type of solution film thickness (.mu.m) refractive index
primer 1 1.1 1.59 primer 2 1.2 1.59 primer 3 1.1 1.66 primer 4 1.2
1.59 primer 5 1.2 1.59 hard coat 1 2.2 1.59 hard coat 2 2.2 1.59
hard coat 3 1.5 1.63 hard coat 4 1.5 1.63 hard coat 5 1.5 1.63 hard
coat 6 2.1 1.59 hard coat 7 2.1 1.59 hard coat 8 2.1 1.63 hard coat
9 2.1 1.63
[0228]
2TABLE 2 lens Primer hard coat No. substrate solution solution
adhesion hardness Ex. 1 A 1 2 100% 5 Ex. 2 A 2 1 100% 5 Ex. 3 A 2 2
100% 5 Ex. 4 A none 2 100% 5 Ex. 5 B 3 4 100% 4 Ex. 6 B 3 5 100% 4
Ex. 7 B none 4 100% 4 Ex. 8 B none 5 100% 4 Ex. 9 A 5 7 100% 5 Ex.
10 A 6 6 100% 5 Ex. 11 A 6 7 100% 5 Ex. 12 A none 7 100% 5 Ex. 13 B
3 9 100% 4 Ex. 14 B none 9 100% 4 C. Ex. 1 A 1 1 100% 5 C. Ex. 2 A
none 1 100% 5 C. Ex. 3 B 3 3 100% 4 C. Ex. 4 B none 3 100% 4 C. Ex.
5 A 5 7 100% 5 C. Ex. 6 A none 7 100% 5 C. Ex. 7 B 3 9 100% 4 C.
Ex. 8 B none 9 100% 4
[0229]
3 TABLE 3 weatherability test after 60 hours after 120 hours adhe-
hard- adhe- appearance sion ness appearance sion hardness Ex. 1 A
100 5 A 100 5 Ex. 2 A 100 5 A 100 5 Ex. 3 A 100 5 A 100 5 Ex. 4 A
100 5 A 100 5 Ex. 5 A 100 4 A 100 4 Ex. 6 A 100 4 A 100 4 Ex. 7 A
100 4 A 100 4 Ex. 8 A 100 4 B 100 4 C. Ex. 1 A 100 5 A 100 5 C. Ex.
2 A 100 5 A 100 5 C. Ex. 3 A 100 4 B 100 4 C. Ex. 4 A 100 4 B 100 4
weatherability test after 180 hours after 240 hours adhe- hard-
adhe- appearance sion ness appearance sion hardness Ex. 1 A 100 4 B
100 2 Ex. 2 B 100 3 C 100 2 Ex. 3 A 100 4 B 100 2 Ex. 4 A 100 4 B
100 2 Ex. 5 A 100 3-4 B 100 2 Ex. 6 A 100 3-4 B 100 2 Ex. 7 A 100
3-4 B 100 2 Ex. 8 A 100 3 B 100 2 C. Ex. 1 B 0 2 D 0 1 C. Ex. 2 B 0
2 C 0 1 C. Ex. 3 C 0 2 D 0 1 C. Ex. 4 C 0 2 D 0 1
[0230]
4 TABLE 4 weatherability test after 60 hours after 120 hours adhe-
hard- adhe- appearance sion ness appearance sion hardness Ex. 9 A
100 5 A 100 5 Ex. 10 A 100 5 A 100 5 Ex. 11 A 100 5 A 100 5 Ex. 12
A 100 5 A 100 5 Ex. 13 A 100 4 A 100 4 Ex. 14 A 100 4 A 100 4 C.
Ex. 5 A 100 5 A 100 5 C. Ex. 6 A 100 5 A 100 5 C. Ex. 7 A 100 4 A
100 4 C. Ex. 8 A 100 4 A 100 4 weatherability test after 180 hours
after 240 hours adhe- hard- adhe- appearance sion ness appearance
sion hardness Ex. 9 A 100 5 A 100 4 Ex. 10 A 100 4 B 100 3-4 Ex. 11
A 100 5 A 100 4 Ex. 12 A 100 5 A 100 4 Ex. 13 A 100 4 A 100 3-4 Ex.
14 A 100 4 A 100 3-4 C. Ex. 5 A 100 2-3 B 0 1-2 C. Ex. 6 A 100 2 A
0 1-2 C. Ex. 7 B 100 2 B 0 1-2 C. Ex. 8 B 100 2 B 0 1-2
[0231] Examples 1 to 14 and Comparative Examples 1 to 8 are
satisfactory in terms of appearance, film adhesion and film
hardness after 120 hours of a weatherability test but differences
in these properties is observed among them after 180 hours of the
weatherability test.
[0232] Film adhesion is satisfactory even after 240 hours in
Examples 1 to 14 but film adhesion is lost after 240 hours in
Comparative Examples 1 to 8.
[0233] When anatase type titanium oxide is used, film hardness is
satisfactory after 180 hours in Examples 1 to 8 but it deteriorates
after 180 hours in Comparative Examples 1 to 4. When rutile type
titanium oxide is used, film hardness is satisfactory after 240
hours in Examples 9 to 14 but it deteriorates after 180 hours in
Comparative Examples 5 to 8. When anatase type titanium oxide is
used, Examples 1 to 8 are superior in film appearance to
Comparative Examples 1 to 4. When rutile type titanium oxide is
used, both Examples and Comparative Examples are satisfactory after
240 hours.
[0234] According to the present invention, there can be obtained a
plastic spectacle lens which prevent the cracking and peeling off
of a hard coat layer or primer layer and a reduction in film
hardness and has excellent durability, and other coated
articles.
* * * * *