AU679728B2 - Thermosetting polysiloxane compositions for anti-abrasion coating, process for their production and corresponding coated articles, especially ophthalmic glasses and lenses - Google Patents
Thermosetting polysiloxane compositions for anti-abrasion coating, process for their production and corresponding coated articles, especially ophthalmic glasses and lenses Download PDFInfo
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- AU679728B2 AU679728B2 AU62103/94A AU6210394A AU679728B2 AU 679728 B2 AU679728 B2 AU 679728B2 AU 62103/94 A AU62103/94 A AU 62103/94A AU 6210394 A AU6210394 A AU 6210394A AU 679728 B2 AU679728 B2 AU 679728B2
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- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 238000005299 abrasion Methods 0.000 title claims abstract description 16
- 238000000576 coating method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000011248 coating agent Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 4
- 239000011521 glass Substances 0.000 title description 11
- 229920001187 thermosetting polymer Polymers 0.000 title description 4
- -1 polysiloxane Polymers 0.000 title description 3
- 229920001296 polysiloxane Polymers 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 239000000413 hydrolysate Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008119 colloidal silica Substances 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 150000001399 aluminium compounds Chemical class 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 239000000470 constituent Substances 0.000 claims description 28
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011343 solid material Substances 0.000 claims description 11
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 5
- 239000008199 coating composition Substances 0.000 claims description 5
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000011368 organic material Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 101710180366 CDP-L-myo-inositol myo-inositolphosphotransferase Proteins 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 14
- 150000004756 silanes Chemical class 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 210000002268 wool Anatomy 0.000 description 8
- JHQVCQDWGSXTFE-UHFFFAOYSA-N 2-(2-prop-2-enoxycarbonyloxyethoxy)ethyl prop-2-enyl carbonate Chemical compound C=CCOC(=O)OCCOCCOC(=O)OCC=C JHQVCQDWGSXTFE-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000000007 visual effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012505 colouration Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920002578 polythiourethane polymer Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- QHUNJMXHQHHWQP-UHFFFAOYSA-N trimethylsilyl acetate Chemical compound CC(=O)O[Si](C)(C)C QHUNJMXHQHHWQP-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Eyeglasses (AREA)
Abstract
Setting composition for use as an anti-abrasion coating comprising: A) an epoxysilane hydrolysate having from two to three alkoxy group directely linked to the silicon atom, B) colloidal silica, C) an aluminium compound. The composition which has at least a 1 % by weight water content is characterized in that the aluminium compound is selected from compounds corresponding to formula (I) or (II) wherein R and R' are alkyl group having a linear or branched chain with 1 to 10 carbon atoms. R" is an alkyl group having a linear or branched chain with 1 to 10 carbon atoms, a phenyl group, an alpha group where R has the above-mentioned meaning, n is an integer from 1 to 3. The invention also relates to a process for the production of these compositions and articles coated using same.
Description
THERMOSETTING POLYSILOXANE COMPOSITIONS FOR ANTI-ABRASION COATING PROCESS FOR THEIR PRODUCTION AND CORRESPONDING COATED ARTICLES ESPECIALLY OPHTHALMIC GLASSES AND
LENSES.
The present invention concerns thermosetting polysiloxane compositions, in particular those obtained by hydrolysis and prepolymerisation of organofunctional alkoxysilanes which are suitable for use in coating articles of organic material, in particular ophthalmic lenses, to protect them against abrasion.
Ophthalmic lenses of transparent organic material (organic glass) are lighter than mineral glass and are now widely used.
However, a problem with organic glass is that it is more sensitive to scratching and abrasion than conventional mineral glass. This tendency is more marked in high refractive index organic glass (polycarbonates, polythiourethanes) which recently has begun to be used in ophthalmic optics.
Abrasion and scratch resistance of organic glass can be improved by applying a thermally or photochemically hardenable composition to its surface to produce a coating hav'ng the desired features.
Apart from abrasion and scratch resistance, the coating produced must optimally satisfy a number of criteria.
It must have the required transparency for optical applications. It must not diffuse light or crack.
It must adhere well to the substrate lens.
It must preferably be capable of being coloured in the colour baths employed to treat bare organic glass.
Further, it is important that the thermosetting compositions are durable.
It is particularly desirable for the compositions to have constant viscosity (this parameter governing ^'2I' i i their use) and for coatings to be produced which have the same characteristics over the whole period of their use.
Several techniques have been studied to attempt to produce compositions satisfying these criteria.
A known technique for producing abrasion resistant coatings consists in polymerising alkoxysilanes in the presence of aluminium derivatives.
United States patent US-A-4 042 749 describes articles having an abrasion resistant coating obtained by reacting a reactive silane containing a vinyl, methacrylic or epoxy group with a metallic ester having formula M(OR)x where M is Ti, Al or Zr and R is an alkyl radical with 1 to 8 carbon atoms, x representing the valency of the metal.
These compositions have not been entirely satisfactory, particularly as regards abrasion resistance.
Other techniques use epoxysilane hydrolysates associated with fillers, for example silica.
United States patent US-A-4 211 823 describes such compositions comprising in a solvent medium containing more than 1% by weight of water: a silane hydrolysate containing an epoxy group and not les.s than two alkoxy groups bonded directly to the silicon atom, fine particles of silica, certain aluminium chelates.
Coatings in accordance with US-A-4 211 823 do not colour well and do not combine colourability and high abrasion resistance.
The Lresent invention overcomes the problems of the prior art by using catalysts other than the aluminium chelates used in US-A-4 211 823.
A coating composition in accordance with the invention comprises the following constituents: A an epoxysilane hydrolysate containing 2 to 3 alkoxy groups directly bonded to the silicon atom, B colloidal silica, C .n aluminium compound, saia compound containing at least 1% by weight of water, characterised in that the aluminium compound is selected from the compounds corresponding to formula or (II): Al(OCR)n(OR') 3 -n
(I)
0
(R'O)
3 _nAl(OSiR" 3 )n (II) wherein R and R' are linear or branched alkyl groups with 1 to carbon atoms, R" is a linear or branched alkyl group with 1 to carbon atoms, a phenyl group, a -OCR group where R ]as
II
the meaning given above, 0 and n is a whole number from 1 to 3.
When the compound of formula contains several R groups, these can be identical or different.
The same applies for R' groups if there are several R' groups in compounds of formula and (II) and for R" groups if there are several R" groups in the compound of formula (II).
R groups in the compounds of formula or (II) are preferably identical to each other and the R' groups are identical to each other, as are the R" groups.
Constituent A of the composition is preferably an epoxysilane hydrolysate having formula (III)
R
3
(RO
1 )mSi-(CH 2 )a-(OCH 2
CH
2
)-OCH
2
-C-CH
2
(III)
R 23-m
O
wherein
R
1 is an alkyl group with 1 to 6 carbon atoms, preferably a methyl or ethyl group,
I'-
3
R
2 is an alkyl group with 1 to 6 carbon atoms or an aryl group,
R
3 is a methyl group or a hydrogen atom, m is 2 or 3, a is a whole number from 1 to 6, b is 0, 1 or 2.
The following are examples of such epoxysilanes: P-glycidoxypropyltrimethoxysilane, -glycidoxypropyltriethoxysilane, Y-glycidoxypropylmethyldirethoxysilane, Y-glycidoxypropylmethyldiethoxysilane and Y-glycidoxyethyc.xypropylmethyldimethoxysilane.
Epoxysilanes of formula (III) containing three alkoxy groups directly bonded to the silicon atom, in particular -glycidoxypropyltrimethoxysilane, are preferably used.
Epoxysilanes with three alkoxy groups produce compositions according to the invention with a high degree of crosslinking in the final polymer constituting the coating, and thus high abrasion resistance.
Compositions in accordance with the invention preferably further comprise an alkoxysilone hydrolysate having formula (IV)
R
6
R
7 Si(OR 4
)(OR
5
(IV)
wherein
R
4 and R 5 are linear or branched alkyl groups with 1 to carbon atoms, and
R
6 and R 7 are selected from linear or branched alkyl groups with 1 to 10 carbon atoms and phenyl groups.
The following are examples of such alkoxysilanes: dimethyldimethoxysilane, dimethyldiethoxysilane and methylphenyldimethoxysilane.
Silane hydrolysates with formula (III) or (IV) are prepared using known methods.
The techniques described in United States patent r
,L
US-A-4 211 823 can be employed.
When using two silanes of formula (III) and (IV), the silanes can be mixed and the mixture then hydrolised, for example.
It is preferable to use a stoichiometric amount of water, i.e. a molar quantity of water which corresponds to the number of moles of hydrolysable functions Si-O-Alkyl and silanes (III) and (IV).
Constituent B of the composition is colloidal silica, i.e. fine particles of silica with a diameter of the order of 1 pm to 100 pm in dispersion in a solvent, preferably an alcohol type solvent.
Constituent C is essential to the advantageous results of the invention and is an aluminium compound having formula: Al(OCR)n(OR') 3 -n or (R'O) 3 nAL(OSiR" 3 )n (II) 0 wherein R, R' and R" and n have the meanings given above.
These compounds are the hardening catalysts of the coating composition.
They are less active than the aluminium chelates of US-A-4 211 823 and result in good colourability of coated lenses in accordance with the invention.
It is preferable to use constituents C where R' is an isopropyl or ethyl group and R and R" are methyl groups.
The proportions of constituents A, B, C and D in the composition are selected to produce the following theoretical dry content in the composition: 30% to 80% by weight, preferably 40% to 50% by weight of solid material from constituent A, 0% to 20% by weight, preferably 5% to 15% by weight of solid material from constituent D, 20% to 60% by weight, preferably 35% to 50% by weight of solid material from constituent B, i i' 0.5% to preferably 1% to 2% by weight of constituent C.
The expression "weight of solid materi&l from constituents A or D" means the calculated weight of unit QkSiO(4_k)/2 where Q is an organic group which is directly bonded to a silicon atom by a Si-C bond and QkSiO(4_k)/2 is from QkSi(OX)(4_k) where X is an alkyl group and k is 0, 1 or 2.
The expression "weight of solid material from cor, tuent B" means the weight of SiO 2 The theoretical dry content is the total calculated weight of solid material from constituents A, B and D, with the addition of the weight of constituent C.
Compositions in accordance with the invention further comprise at least 1% by weight of water.
The water may be the result of incomplete hydrolysis of the starting silanes or of the condensation reaction of the silanols formed during hydrolysis.
The water may also be added to the composition either directly or by means of the organic solvents which contain a certain percentage of water.
The compositions may further include various additives, such as surfactants to improve spreading of the composition over the surface to be coated, UV absorbers or pigments.
The present invention further relates to a process for the preparation of the compositions described above, in accordance with which constituent C or catalyst is prepared in advance from compounds having formula (V)
AI(OR')
3 where R' is a linear or branched alkyl group with 1 to 10 carbon atoms.
Compounds with formula are readily commercially available at low cost.
The compound with formula is reacted with i i I-- I either an acid of formula (VI) RCOOH or a compound with formula (VII) R"3SiOCR iI 0 where R and R" have the meanings given for formulae and (II) described for constituent C.
The molar proportions of compounds (VI) or (VII) used with respect to compound vary from 1 to 3.
This catalyst preparation step is preferably carried out in an organic solvent such as toluene.
The catalyst obtained may then be directly added to the hydrolysate of silanes, optionally with a silica SiO 2 filler. It is not necessary to isolate the catalyst which can be used in its solvent medium.
Coated articles in accordance with the invention are organic material articles, particularly those used in ophthalmic optics and especially an organic material obtained by polymerisation of diethylene glycol di(allylcarbonate) or bis phenol A di(allylcarbonate).
The compositions may be applied using any appropriate known technique (in particular dipping and centrifuging).
They are then thermally hardened at a temperature ranging from 60*C to 150 0
C.
The following examples serve to illustrate the invention in more detail without limiting its scope.
Properties of coated lenses produced for the examples were estimated by measurement of: Abrasion resistance, using the value obtained from the BAYER test carried out in accordance with standard ASTM F735.81.
A high value in the BAYER test corresponds to a high degree of abrasion resistance.
Scratch resistance using a steel wool test.
Extra fine no 000 STARWAX steel wool was used.
A piece of steel wool about 3 cm by 3 cm was folded I i -3 on itself and used to make ten to-and-fro rubbing movements on the coated lens in the fibre direction using a constant pressure throughout the operation.
The lens was then rubbed with a dry cloth and rinsed with alcohol.
The condition of the lens was then estimated and classified as follows: 0 no observed scratching, 1 lens very slightly scratched (0 to scratches), 2 lens slightly scratched (up to scratches), 3 lens somewhat scratched (up to scratches), 4 lens very scratched (more than scratches), bare substrate (ORMA Colourimetric divergence.
This is the difference between the (test) transmission Tv of a coloured coated lens and the (reference) transmission Tv of a reference lens (uncoated substrate) coloured under the same conditions.
CD T v (Test) T v (reference) The smaller the divergence, the better the colouration.
When a diethylene glycol di(allylcarbonate) polymer is used as the reference, the coated lens is considered to be uncolourable when CD The lenses were coloured under conventional conditions by soaking in aqueous baths containing dispersed pigments at 94 0
C.
The appearance of the coated lens, estimated visually.
r EXAMPLE 1 40.4 g of an aqueous solution of 0.1 N hydrochloric acid was added dropwise to 176.7 g of P-glycidoxypropyltrimethoxysilane.
Stirring was continued for 24 hours after hydrolysis.
416.7 g of NISSAN Sun Colloid MAST colloidal silica SiO 2 content in methanol) was then added followed by 0.8 g of Fc 430 surfactant.
The catalyst was prepared by dissolving 3.6 g of aluminium isopropoxide (Al(OiPr) 3 in 30 g of toluene and adding 1.1 g of acetic acid to this mixture. One isopropoxide group only was thus substituted by an acetoxy group to produce a compound with formula (I) given above where R CH 3 R' isopropyl and n 1.
This mixture was then added to the silicacontaining hydrolysate obtained previously.
The composition obtained was allowed to age for three weeks (21 days).
The aged composition was then applied to an ophthalmic ORMA lens of organic glass constituted by a diethylene glycol di(allylcarbonate) polymer then hardened at a temperature of 100 0 C for three hours.
The coated glass had the following properties: BAYER test 3 steel wool test score 1 colourimetric divergence +39.7 visual appearance good coating thickness 3.32 p EXAMPLE 2 162.5 g of Y-glycidoxypropyltrimethoxysilane was mixed with 85 g of dimethyldiethoxysilane.
57.7 g of an aqueous solution of 0.1 N hydrochloric acid was then added dropwise, with stirring, Stirring was continued for 24 hours following hydrolysis.
525 g of NISSAN Sun Colloid MAST colloidal silica was then added followed by 0.9 g of FC430 surfactant.
The catalyst was prepared by dissolving 3.4 g of aluminium isopropoxide (AlOiPr) 3 in 30 g of toluene and adding 1 g of acetic acid.
When the viscosity of the toluene solution started to rise, the prepared silica-containing hydrolysate was added to produce the coating composition.
Two samples of the composition were taken. The first sample was used immediately to coat an ORMA® ophthalmic lens. The second sample was left to age for 21 days and then used to coat a similar lens.
Hardening conditions for each sample were identical and as described in example 1.
The following properties were measured for the coated lenses: Sample 1 (T 0 days) Sample 2 (T 21 days) BAYER 2 2 Steel wool 1.5 Colourimetric divergence +16.4 +16.7 Visual appearance good good Thickness 3.3 2 p 3.17 J It can be seen that ageing the compositions did not affect the properties of the coatings.
EXAMPLE 3 325 g of Y-glycidoxypropyltrimethoxysilane was mixed with 170.1 g of dimethyldiethoxysilane.
115.5 g of an aqueous solution of 0.1 N hydrochloric acid was then added dropwise, with stirring.
Stirring was continued for 24 hours following hydrolysis.
1 050 g of NISSAN Sun Colloid MAST colloidal silica '*Ai Vi was added, followed by 64.1 g of methylethylketone and 0.9 g of FC430 surfactant.
The catalyst was prepared by dissolving 5.28 g of aluminium ethoxide (AlOEt) 3 in 20 g of toluene and adding 1.96 g of acetic acid.
One ethoxy group only was thus substituted by an acetoxy group to obtain a compound having formula (I) where R CH 3 R' ethyl and n 1.
This catalyst solution was then added to the prepared silica-containing hydrolysate. No viscosity increase or gel formation was observed.
The composition obtained was used to coat an ORMA ophthalmic lens, then hardened as described for example 1.
The coated lenses had the following properties: BAYER 2.7 Steel wool 1 Colourimetric divergence +17.1 Visual appearance good Thickness 3.7 p EXAMPLE 4 A mixture of the hydrolysate of Y-glycidoxypropyltrimethoxysilane and dimethyldiethoxysilane and of colloidal silica was prepared using the method described in example 2.
Catalyst C having formula (II) given above where R' propyl and R" CH 3 was prepared by dissolving 3.40 g of aluminium isopropoxide in 30 g of toluene and adding 2.2 g of trimethylacetoxysilane.
The prepared catalyst was then added to the silicacontaining hydrolysate.
The coating composition thus produced was applied (without ageing) to an ORMA lens and then hardened under the conditions described for example 1.
The coated lenses had the following properties: PI_ r ill BAYER 2.3 Steel wool 1 Colourimetric divergence +32.2 Visual appearance good Thickness 4.2 p COMPARATIVE EXAMPLE 1 A composition was prepared in accordance with the method of example 1 using 11.4 g of aluminium acetylacetonate as the catalyst instead of the aluminium a-etoxy diisopropoxide of example 1.
As in example 1, the composition was aged for 21 days then applied to an ORMA lens and hardened.
Colouration tests showed that the coated lens was not coloured at all by treatment in conventional colour baths.
COMPARATIVE EXAMPLE 2 A composition was prepared in accordance with the method of example 2 using 10.8 g of aluminium acetylacetonate as the catalyst instead of aluminium acetoxydiisopropoxide.
The composition was applied to an ORMA lens without ageing and hardened under the same conditions as those described for example 2.
The coated lenses had the following properties: BAYER Steel wool Thickness 3.5 p Visual appearance good The coated lens was not coloured at all by treatment in conventional colour baths.
~I I i I
Claims (16)
1. A hardenable composition for an abrasion resistant coating comprising the following constituents: A an epoxysilane hydrolysate containing 2 to 3 alkoxy groups directly bonded to the silicon atom, B colloidal silica, C an aluminium compound, said composition containing at least 1% by weight of water, characterised in that the aluminium compound is selected from the compounds corresponding to formula or (II): Al(OCR)n(OR') 3 -n (I) 0 (R'O) 3 nAl(OSiR" 3 )n (II) wherein: R and R' are linear or branched alkyl groups with 1 to 10 carbon atoms, R" is a linear or branched alkyl group with 1 to carbon atoms, a phenyl group, a -OCR group where R has the meaning given above, 0 and n is a whole number from 1 to 3.
2. Composition according to claim 1 characterised in that the epoxysilane has the following formula (III): R3 (RIO)mSi-(CH 2 )a-(OCHCH 2 )b-OCH 2 CH 2 (III) R 2
3-m wherein R 1 is an alkyl group with 1 to 6 carbon atoms, R 2 is an alkyl group with 1 to 6 carbon atoms or an aryl group, R 3 is a methyl group or a hydrogen atom, la I- m is 2 or 3, a is a whole number from 1 to 6, b is 0, 1 or 2. 3. Composition according to claim 1 or claim 2 characterised in that the epoxysilane contains three alkoxy groups directly bonded to the silicon atom.
4. Composition according to claim 3 characterised in that the epoxysilane is P-glycidoxypropyltrimethoxy- silane.
5. Composition according to any one of the preceding claims characterised in that it further comprises D) an alkoxysilane hydrolysate having formula (IV): R 6 R 7 Si(OR 4 )(OR 5 (IV) wherein R 4 and R 5 are independent of each other and represent linear or branched alkyl groups with 1 to carbon atoms, R 6 and R 7 are independently selected from linear or branched alkyl groups with 1 to 10 carbon atoms and phenyl groups.
6. Composition according to claim 5 characterised in that the alkoxysilane having formula (IV) is dimethyldiethoxysilane.
7. Composition according to any one of the preceding claims characterised in that constituent C is selected from compounds with formula or (II) as defined in claim 1 wherein R and R" are methyl groups and R' is an isopropyl or ethyl group.
8. Composition according to any one of claims 5 to 7 characterised in that the proportions of constituents C) and D) are selected to produce a theoretical dry conten' in said composition of: to 80% by weight of solid material from constituent A, I i I Ilp~~ i 0% to 20% by weight of solid material from constituent D, to 60% by weight of solid material from constituent B, 0.5% to 5% of constituent C.
9. Composition according to claim 8 characterised in that said dry content comprises: to 50% by weight of solid material from "-nstituent A, 5% to 15% by weight of solid material from constituent D, to 50% by weight of solid material from constituent B and 1% to 2% by weight of constituent C.
10. Process for the preparation of an abrasion resistant coating composition in accordance with any e of the preceding claims including a step for the production of an epoxysilane hydrolysate including two to three alkoxy groups directly bonded to the silicon atom followed by addition of a constituent C as defined in claim 1 characterised in that constituent C is obtained by reacting a compound having formula Al(OR') 3 with either an acid having formula RC-OH (VI) 0 or a compound having formula R" 3 SiOCR (VII) 0 where R, R' and R" have the meanings given in claim 1, the molar proportions of compounds (VI) or (VII) with respect to compound varying between 1 and 3.
11. Process according to claim 10 characterised in that the colloidal silica is introduced into the epoxysilane hydrolysate before addition of constituent C. Si''
12. Organic material article having a coating obtained by hardening a composition in accordance with any one of claims 1 to 9.
13. Coated article according to claim 12 characterised in that said article is a diethylene glycol di(allylcarbonate) polymer.
14. Coated article according to claim 12 or claim 13 characterised in that it is in the form of an ophthalmic lens. o^ I -;I INTERNATIONAL SEARCH REPORT Inter n-al Application No IPCT/FR 94/00246 A. CLASSIFICATION OF SUBJECT MATTER IPC 5 C090183/06 C08J7/04 C08K5/00 According to International Fatent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHFU Minimum documentas'.on searched (classification system followed by classification symbols) IPC 5 C09D C08J C08K CCSL Documentation searched other than rmmmum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the mternational search (name of data base and, where practcal, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category Citation of document, with indication, where approprate, of the relevant passages Relevant to claim No. X FR,A,2 383 220 (TORAY INDUSTRIES) 6 1-8 October 1978 cited in the application see claims 1-4,9,13 see page 1, line 1 line see page 2, line 21 page 3, line see page 5, line 10 line 38 X DATABASE WPI 1 Derwent Publications Ltd., London, GB; AN 92-101607 JP,A,4 045 129 (DAIHACHI KAGAKU KOG KK.) 14 February 1992 see abstract f 1 I Further documents are listed in the continuation of box C. Patent family members are listed in annex. Special categoes of cited documents "T later document published after the interational filing date or priority date and not in conflict with the application but document defining the general state of the art which is not ored to tderstand the principle or theory underlying the considered to be of particular relevance invention *E earlier document but published on or after the international "X document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step when the document is taken alone which is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the itermational filing date but in the art. later than the priority date claimtd document member of the same patent family Date of the actual completion of the international search Date of mailing of the international search report 12 July 1994
15. 07. 94 Name and mailing address of the ISA Authonzed officer Eurapan Patent Office, P.B. 5818 Patentlaan 2 NL 2280 HV Rijswijk Tt. (+31-70) 340-2040, Tx. 31651 eponl, Depijper, R Fax 31-70) 340-3016 p R Form PCT/ISA/210 lrend shoat) (July 1992) I II LIL I I -I III INTERNATIONAL SEARCH REPORT rte, mal Application No P~tCT/FR 94/00246 C.(Coitiruatioo) DOCUMENTS CONSIDERED TO BE RELEVANT Category' Ciitaion of doctument, with indication, where appropriate, of the relevant pamages Relevant to claim No. X US,A,4 355 135 (JAMES R. JANUARY) 19 1 October 1982 see claims 1,19,20,36,43 see column 6, line 15 -line X DATABASE WPI 1 Derwent Publications Ltd., London, GB; AN 90-23540 1 JP,A,2 163 178 (SHINETSU CHEM IND KK.) 22 June 1990 see abstract EP,A,0 035 609 (SWEDLOW INC.) 1981 see claims 1,5,10 see page 2, line 32 line 38
16 September Form PCT/ISA/210 (coninuation of secnd sheet) (July 1992) I INTERNATIONAL SEARCH REPORT nePudApiaonN Infcrmaan on pio.'nt famnily mcrnbers Inte .pi 94/00246n N PCT/R9/04 Patent document I Publication IPatent family -7 Publication cited in search report date Tmember(s) date FR-A-2383220 06-10-78 JP-C- 1112154 16-09-82 JP-A- 53111336 28-09-78 JP-B- 57002735 18-01-82 AU-B- 520716 25-02-82 AU-A- 3397678 13-09-79 BE-A- 864691 11-09-78 CA-A- 1118929 23-02-82' CH-A- 628366 26-02-82 OE-A,C 2810072 21-09-78 GB-A- 1596107 19-08-81 NL-A- 7802636 13-09-78 SE-B- 444444 14-04-86 SE-A- 7802753 12-09-78 US-A- 421182^3 08-07-80 US-A-4355135 19-10-82 AU-B- 550470 20-03-86 AU-A- 8150882 12-05-83 CA-A- 1173579 28-08-84 OE-A,C 3212771 11-05-83 FR-A,B 2515667 06-05-83 GB-A,B 2108985 25-05-83 JP-C- 1511062 09-08-89 JP-A- 58080359 14-05-83 JP-B- 63061981 30-11-88 EP-A-0035609 16-09-81 NONE Fom pcT/1SA421 (patent family annex) (July 1992)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9302650A FR2702487B1 (en) | 1993-03-08 | 1993-03-08 | Thermosetting polysiloxane compositions for abrasion-resistant coatings, process for obtaining them and corresponding coated articles, in particular ophthalmic. |
| FR9302650 | 1993-03-08 | ||
| PCT/FR1994/000246 WO1994020581A1 (en) | 1993-03-08 | 1994-03-07 | Thermosetting polysiloxane compositions for anti-abrasion coating, process for their production and corresponding coated articles, especially ophthalmic glasses and lenses |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU6210394A AU6210394A (en) | 1994-09-26 |
| AU679728B2 true AU679728B2 (en) | 1997-07-10 |
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| AU62103/94A Ceased AU679728B2 (en) | 1993-03-08 | 1994-03-07 | Thermosetting polysiloxane compositions for anti-abrasion coating, process for their production and corresponding coated articles, especially ophthalmic glasses and lenses |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0688349B1 (en) |
| JP (1) | JPH08507804A (en) |
| AT (1) | ATE152467T1 (en) |
| AU (1) | AU679728B2 (en) |
| BR (1) | BR9406129A (en) |
| DE (1) | DE69402969T2 (en) |
| FR (1) | FR2702487B1 (en) |
| WO (1) | WO1994020581A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2702486B1 (en) * | 1993-03-08 | 1995-04-21 | Essilor Int | Abrasion resistant coating compositions based on silane hydrolysates and aluminum compounds, and corresponding coated articles resistant to abrasion and impact. |
| DE4338361A1 (en) * | 1993-11-10 | 1995-05-11 | Inst Neue Mat Gemein Gmbh | Process for the preparation of compositions based on silanes containing epoxy groups |
| US5677050A (en) * | 1995-05-19 | 1997-10-14 | Minnesota Mining And Manufacturing Company | Retroreflective sheeting having an abrasion resistant ceramer coating |
| JP2000505143A (en) * | 1996-11-22 | 2000-04-25 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | Lacquer composition |
| US5938697A (en) | 1998-03-04 | 1999-08-17 | Scimed Life Systems, Inc. | Stent having variable properties |
| US7410691B2 (en) | 2001-12-27 | 2008-08-12 | Ppg Industries Ohio, Inc. | Photochromic optical article |
| US7465414B2 (en) | 2002-11-14 | 2008-12-16 | Transitions Optical, Inc. | Photochromic article |
| WO2004092250A1 (en) * | 2003-04-15 | 2004-10-28 | Biogenon Ltd. | Biocompatible material |
| US8582192B2 (en) | 2003-07-01 | 2013-11-12 | Transitions Optical, Inc. | Polarizing photochromic articles |
| US7189456B2 (en) | 2004-03-04 | 2007-03-13 | Transitions Optical, Inc. | Photochromic optical article |
| US7261843B2 (en) | 2004-03-04 | 2007-08-28 | Transitions Optical, Inc. | Photochromic optical article |
| CN101040006A (en) * | 2004-10-08 | 2007-09-19 | 株式会社德山 | Coating compositions and process for production thereof |
| US7258437B2 (en) | 2005-09-07 | 2007-08-21 | Transitions Optical, Inc. | Photochromic multifocal optical article |
| ES2973880T3 (en) | 2011-06-06 | 2024-06-24 | Transitions Optical Inc | Polarizing photochromic items |
| BR112016007979B1 (en) | 2013-10-11 | 2021-11-16 | Transitions Optical, Inc | METHOD FOR PREPARING A PHOTOCHROMIC ARTICLE |
| US10688522B2 (en) | 2013-11-20 | 2020-06-23 | Transitions Optical, Inc. | Method of coating a lens and lens support |
| AU2015324313B2 (en) | 2014-09-30 | 2018-11-15 | Transitions Optical, Inc. | Ultraviolet light absorbers |
| CN107438514B (en) | 2015-01-22 | 2019-10-18 | 光学转变公司 | Optical goods with luminescence generated by light label |
| CN107430227B (en) | 2015-03-10 | 2020-08-21 | 光学转变公司 | Method for producing optical elements colored in non-uniform linear patterns |
| EP3268774B1 (en) | 2015-03-10 | 2019-03-06 | Transitions Optical, Ltd. | Optical element having a coating for enhanced visibility of a mark and method for making the optical element |
| AU2015385868B2 (en) | 2015-03-10 | 2020-11-05 | Transitions Optical, Inc. | Method for coloring an optical element in a non-uniform linear pattern |
| WO2016200394A1 (en) | 2015-06-12 | 2016-12-15 | Transitions Optical, Inc. | Alignment polymers |
| MX2018016002A (en) | 2016-07-15 | 2019-09-13 | Transitions Optical Ltd | Apparatus and method for precision coating of ophthalmic lenses with photochromic coatings. |
| MX2019006555A (en) | 2016-12-23 | 2019-08-21 | Transitions Optical Ltd | Method of manufacture of a lens with gradient properties using imbibition technology. |
| CN119329096A (en) | 2016-12-28 | 2025-01-21 | 光学转变有限公司 | Method for imparting light-influencing properties to an optical element in a gradient pattern |
| US10884288B2 (en) | 2016-12-30 | 2021-01-05 | Transitions Optical, Ltd. | Polarizing article and method of forming a polarizing article |
| WO2019110102A1 (en) | 2017-12-07 | 2019-06-13 | Transitions Optical, Ltd. | Controllable tint photochromic article |
| WO2019129343A1 (en) | 2017-12-27 | 2019-07-04 | Transitions Optical, Ltd. | System and method for customization of a photochromic article |
| EP3923038A1 (en) * | 2020-06-09 | 2021-12-15 | Essilor International | Optical article with a durability improved hard coating |
| IT202000014581A1 (en) * | 2020-06-18 | 2021-12-18 | Luxottica Srl | POLARIZED LENS AND METHOD OF MAKING A POLARIZED LENS |
| US20230416609A1 (en) | 2020-11-10 | 2023-12-28 | Transitions Optical, Ltd. | Method for Preparing a Coated Article |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53111336A (en) * | 1977-03-11 | 1978-09-28 | Toray Ind Inc | Coating composition |
| EP0035609A1 (en) * | 1980-02-29 | 1981-09-16 | Swedlow, Inc. | Transparent abrasion resistant coating composition |
| US4355135A (en) * | 1981-11-04 | 1982-10-19 | Dow Corning Corporation | Tintable abrasion resistant coatings |
| JPH0699664B2 (en) * | 1988-12-16 | 1994-12-07 | 信越化学工業株式会社 | Hard coating agent and plastic optical products |
| JPH0786185B2 (en) * | 1990-06-11 | 1995-09-20 | 大八化学工業株式会社 | Coating composition for coating |
-
1993
- 1993-03-08 FR FR9302650A patent/FR2702487B1/en not_active Expired - Fee Related
-
1994
- 1994-03-07 AU AU62103/94A patent/AU679728B2/en not_active Ceased
- 1994-03-07 AT AT94909155T patent/ATE152467T1/en not_active IP Right Cessation
- 1994-03-07 BR BR9406129A patent/BR9406129A/en not_active Application Discontinuation
- 1994-03-07 DE DE69402969T patent/DE69402969T2/en not_active Expired - Fee Related
- 1994-03-07 JP JP6519663A patent/JPH08507804A/en active Pending
- 1994-03-07 EP EP94909155A patent/EP0688349B1/en not_active Expired - Lifetime
- 1994-03-07 WO PCT/FR1994/000246 patent/WO1994020581A1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| DE69402969D1 (en) | 1997-06-05 |
| FR2702487B1 (en) | 1995-04-21 |
| ATE152467T1 (en) | 1997-05-15 |
| BR9406129A (en) | 1995-12-12 |
| JPH08507804A (en) | 1996-08-20 |
| EP0688349B1 (en) | 1997-05-02 |
| EP0688349A1 (en) | 1995-12-27 |
| WO1994020581A1 (en) | 1994-09-15 |
| AU6210394A (en) | 1994-09-26 |
| FR2702487A1 (en) | 1994-09-16 |
| DE69402969T2 (en) | 1997-08-28 |
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