CA1291843C - Siloxane-based tintable coating - Google Patents
Siloxane-based tintable coatingInfo
- Publication number
- CA1291843C CA1291843C CA 578137 CA578137A CA1291843C CA 1291843 C CA1291843 C CA 1291843C CA 578137 CA578137 CA 578137 CA 578137 A CA578137 A CA 578137A CA 1291843 C CA1291843 C CA 1291843C
- Authority
- CA
- Canada
- Prior art keywords
- composition
- polyamine
- epoxysilane
- article
- hydrocarbon radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Abstract
Abstract of the Disclosure An abrasion-resistant coating composition for use on transparent plastic substrates and the like is formed from a first component derived by partial hydrolysis from a hydrolyzable epoxysilane and a second component comprising the reaction product of a non-silane-based aliphatic polyamine and a ketone or aldehyde. The two components are mixed to allow regenerated amino groups of the first component to react with the epoxy groups of the second component to form a partial-ly polymerized mixture which is diluted with a solvent and applied to the substrate and heated to complete the curing process.
Description
~2!~8~3 Title of the lnvention SILOXANE-BASED TINTABLE COATING
Background of the Invention This invention relates to a siloxane-based tintable coating composition for forming abrasion-resistant coatings on lenses or other optical articles, especially those formed from synthetic plastics.
In recent years, synthetic plastics such as poly-,carbonate have replaced glass in many optical applications, particularly opthalmic lenses, because of the lighter weight and superior impact resistance of tlle plastics. However, plas-tics such as polycarbonate are relatively soft, and must receive an abrasion-resistant coating to provide an acceptab]e level of abrasion or scratch resistance. Many abrasion-resistant coating compositions of the prior art are of the polysiloxane type, in which crosslinking is provided by condensation of silane groups formed by hydrolysis of alkoxysilanes. Represen-tative compositions of this type are disclosed in Trcadway ct al U.S. Patent ~,378,250 and the references citcd therein.
Although tho compositions di6closed in these refercllces are useful in the formation of abrasiorl-resi3tal1t coatings, consid-erable room for improvement remains in terms of abrasion resis-tance and tintability.
Summary of the lnvention One object of our invention is to provide a coating that is more abrasion-resistant than those of the prior art.
Another object of our invention is to provide an abrasion-resistant coating that is more readily tintable than those of the prior art.
!' .
Still another object of our invention is to provide an abrasion-resistant coating that is readily applied to the substrate.
A further object of our invention is to provide an abrasion-resistant coating that satisfactorily adheres to the substrate to which it is applied, both before and after tinting.
A still further object of our invention is to provide an abrasion-resistant coating that is cosmetically acceptable.
Other and further objects will be apparent from the description that follows.
In general, our invention contemplates an abrasion-resistant coating composition, for use on transparent plastic substrates and t~e like, which is formed from a first component derived by partial hydrolysis from a hydrolyzable epoxysilane, the epoxysilane being at least about 40%
hydrolyzed, and a second component comprising the reaction product of a non-silane-based aliphatic polyamine and a carbonyl-containing compound selected from the group consisting of ketones and aldehydes. The method aspect of the invention involves mixing the two components to allow regenerated amino groups of the second component to react with the epoxy groups of the first component to form a partially polymerized mixture, which is, preferably, diluted with a solvent and applied to the substrate and heated to complete the curing process.
The second component of the composition should be present in an amount sufficient for the polyamine regenerated therefrom to react with the majority of the epoxy groups otherwise available for forming the reaction product.
Preferably there should be enough of the polyamine present to react with all or substantially all of such groups. This implies that if there are other amines present, the non-silane-based aliphatic polyamine supplies a major portion of the amino groups that react with the epoxy groups to form the final cured coating.
A
rn/
Suitable hydrolyzable epoxysilanes include compounds of the formula ~ 12)m Q ~l-si~(OF~3)3-m ( I
where Q is a group containing the epoxy structure -C-C- ; (II~
~1 is a bivalent hydrocarbon radical~ R2 and R3 are independent-ly selected hydrocarbon radicals; and m is an integer betwecn 0 and 2.
Preferably the epoxy-containing group Q is glycidoxy or epoxycyclohexyl, preferably 3,4-epoxycyclohexyl if the lat-er. ~1 is preferably C1-C4 alkylene, especially trimethylene (-C1l2C112CH2-) if Q i8 glycidoxy and ethylene ~-CH2C112-) if Q is 3,4-epoxycyclohexyl. Thus the preferred cholces for Q-~l~
are ~-glycidoxypropyl and ~-(3,4-epoxycyclohexyl)ethyl.
Preferably 1~2 is Cl-C4 alkyl, especially methyl, while ~3 is preforably C1-C4 alkyl, especially methyl or ethyL, or alkenyl, especially isopropenyl. Although it is possiblc to use compounds of Formula I in which m is 2, m is preferably 0 or 1 and more preferably 0. The preferred compound of F'ormula I, which was used in the bulk of our work, is ~-glycidoxypropyl-trimethoxysilane.
Compounds of Formula I are hydrolyzed to a stoichio-metrically determined degree by the addition of appropriate amounts of water followed by modest heating, in accordance with the following reaction scheme:
, _ .. , ~ .. ~ .. . . . ...... .. .. ... ..... . . . ................... .
~ ?;~ L3 (A) -Si-07~3 + 1i20 >-Si-011 + R3071 (I) (III) (B) 2 -Sli-OR3 + 1~20 > -Si-O-Si- + R30~1 I (I) (IV) lhere R3 is defined as above.
11ydrolysis (reaction A) occurs when the -OR3 groups 1of the epoxysilane ~I) react with water to generate a silanol ¦ (III), bearing hydroxy groups, together with the alcohol R30H.
l Hydrolysis is also accompanied by some degree of condensation l (reaction B), in which the hydroxy groups of the silanol (III) condense to form the siloxy moiety ~IV). Sufficient water should be used to produce at least about ~0% hydrolysis, and prefcrably betwcen about 70~ and about 95% hydrolysis, of the , ~poxysilane. The al~ohol R3011 formed by the condensation re-~5 nains in the system. Residual hydroxy groups are converted to siloxy groups by condensation when the final coating Co111pOsi-tion is cured In general, any non-silane-based aliphatic polyamine will satisfy the requirements for the polyfunctional amine.
13y "polyamine" as used herein is meant a compound having at least two reactive ~i.e., primary or secondary) amino groups.
By "aliphatic" as used herein is meant a compound in which he reactive-amino nitrogens are attached to carbon atoms that ~o not form part of an aromatic nucleus.
1 Suitable amines include compounds of the formula R-N-A-N-R ~V) R R
n which each R is independently hydrogen, a univalent aliphatic ....... --.. , . ... ...... . _ .. .. ......... ., .... ..... , ,,"_. ,, ,, _, _,.. .......... .
il ,hydrocarbon radical or -~-N-R
R
with each R of the latter group being similarly defined and with at least two R's on different nitrogens being l-ydrogen;
and each A is an independently selected bivalent aliphatic hydrocarbon radical. Preferably A is alkylene, especially a straight-chain alkylene of the formula -(CH2) -, while each ~ is -~-N-t~
or hydrogen.
A particular subgroup of said amines includo compounds of the formula H
~ 12N-(-A-N-) -H t Va) in which m is a positive integer and each A is a bivalent ali-phatic hydrocarbon radical. Particular amines of Formula va in which A is ethylene ~-CIt2CH2-) include ethylenediamine (m = 1), diethylenetriamine ~m ~ 2) and triethylenetetramine (m = 3). Most of our work involved the use of ethylenediamine, which is the preferred polyamine.
~ he polyamine ultimately reacts with the epoxy groups of the epoxysilane to form a crosslinked polymeric network.
~he polyamine is, however, first stabilized by the addition of a carbonyl-containing compound (i.e., a ketone or aldehyde) to form a reaction product. The reaction product regenerates , .... . . . . . . . ... .. . . .
~ Jl ~ L3 ¦the amine when heated during the curing cycle, allowing it ¦to crosslink the network at that time.
The reaction product of the polyamine and the carbonyl ~compound depends on the starting materials. Primary amino Igroups of the polyamine react with the cDrbonyl compound ( VI ) ~to form ketimine groups (VII) according to the scheme ( C ) o H 2 N R 3 I ~VI) 10 ¦, R -C-R2 ~ tl2O
,I NR3 ' ~VII) ,¦ Secondary amino groups react with carbonyl compounds l¦containing ~-hydrogens ~VIII) to form enamines (IX) according ,¦to the reaction schemo t D ) R-C~-C-R2 ~ IINR3E~4 r~ 1 I, I' ~VIII) ¦ 1 3 4 20 ll R-C=C-R2 I H2O
(IX) and with carbonyl compounds containing no ~-hydrogens (X) to ¦form aminals (XI) according to the overall reaction scheme tE) 1 ll 2 2 HNR3~4 --~
(X) ~1-C-~2 ~ ~2 (XI) The particular reactions are described in further detail in March, ~dvanced Organic Chemistrv, pp. 817-818 (1977) and the references cited therein.
Suitable carbonyl-containing compoun~s include aliphat-ic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol; aromatic ke~ones such as ace-o-phenone ?nd benzophenone; aliphatic aldehydes such as acel:alde-hyde and propionaldehyde; and aromatic alclehydes such as benz-aldehyde. Diacetone alcohol, however, is preferred. Ultimately the earbonyl-containing eompound is drivon off as a vapor when the amine is regenerated during cure. Preferably an cxcess of carbonyl compound over the stoiehiometric arnount i9 used to ensure that reaction C, D or E is driven to completion.
Suitable solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol and mixtures thereof. Also contemplated are glyeol ethers such as propyleneglycol methyl ether (avail-.. ... . . . . .. ....... . . . . . . .. ..... .
~?.~8'1~3 able under the trademark Dowanol PM), higher acetate esters and the like. The preferred solvent is a mixture of isopro-panol, n-butanol and diacetone alcohol, preferably in a volumet-ric ratio of 4:3:3. The particular step at which the solvent 5 is added is not crltical. The first and second components may be prepared in solution, or all or part of the solvent added later. ~e have found it convenlent, however, to add part of the solvent chilled to the reaction mixture of the first and second components to quench the polymerization reac-tion and later add thc rest of the solvcnt to achieve thedesired viscosity.
Tho composition preferably includes a surfactant, used as a flow-control agent for regulating film thickness and enhancing the cosmetic appearance of tlle coatntl ~rticle.
Of the numerous surfactants that are known, a commonly available one used in the preferred composition is the fluorinated surfac-tant available from Minncsota Mining and Manufacturing Co.
undcr the trademark Fluorad FC-430.
The composition may also include a partially hydro-lyzed alkyltrialkoxysilane such as methyltriethoxysilane tolncrease the siloxy content of the network. I~owever, no im-provement in abrasion resistance was noted using this additive, and it is therefore not includcd in the preferred formulation.
Description of the Preferred Embodiments 807 ml of ~-glycidoxypropyltrimethoxysilane is hydro-lyzed with 188 ml of distilled water by adding them together and warming to 80C for one hour or until the mixture clari-fies. The mixture is allowed to cool to room temperature in ... A . . . _ . ... .
1;'."'1813 a covered container. This effects 9S~ hydrolysis.
Il In a separate container, 121 ml of ethylenediamine ¦lis mixed with 1302 ml of diacetone alcohol, or 1 mole of the ¦Idiamine per 6 moles of diacetone alcohol. This latter mixture ¦Iis allowed to stand at room temperature for one hour to allow ¦the amino groups of the diamine to react with the carbonyl !groups of the alcohol to form ketimine functional groups.
!I The two prepared components are then mixed togcther ¦Iwith stirring at room temperature. This effects a ratio of ,2 moles of epoxysilane to 1 mole of ethylenediamine. Th~ molec-ular weight builds as the system undergoes an exothermic reac-~tion. About one hour later the reaction is quenched by the addition of 414 ml of cold t10F) diacetone alcohol, and the cntire mixture is placed in a refrigerator at 10F for a minirnum lof 3'to 4 hours.
¦ To the mixture are then added 414 ml of n-butanol, 550 ml of isopropanol, and 2 ml of Fluorad ~C-430, all at 10F.
he solution thus formed is mixed until homogenized and storecl at 10F. The above-described formulation provides one gallon ~of coating.
Typically the solution i8 maintained at a working Itcmperature of 30-F. The viscosity of ttle solution preparccl ,in this manncr at 30F i8 27 centipoise. Solids content i9 ll~i. The coating i9 applied to polycarbonate lenses by dipping Ithem into the solution and withdrawing them at a rate of 0.2 inch per second. The lenses are pre-cured at 167F for 15 ~nihutes and finally cured for 3 hours at 265F.
The resultant lenses were tested as follows:
_9_ I . I~
P ~
Test Method l~esult Adheslon Crosshatch, 100~ adhesion 16 squares ~brasion 84 psi, No scratches 0000 steel wool Tintability 25 minutes, 15~ transmission Gentone Tru-Grey Dye at 205 ~
~dhesion Crosshatch, 100% adhesion after 16 squares tlnting Coating Interferometer 4.5 + 0.5 microns thickness EX~MPLE 2 The general procedure of Example 1 is followed except that the ethylencdiamine is mixed with 953 ml of methyl ethyl keto~e instead of diacetone alcohol. The resultant lenscs exhibited properties similar to those noted above but with a modest decrease in the coating adhesion after tinting.
EX~MPLE 3 The general procedure of Example 1 is followc~l except that instead of the butanol-isopropanol-diacetone alcohol systern described, a system comprising 691 ml methanol, 481 ml isopro-panol and 206 ml diacetone alcohol i3 used. The resultantlenses, although useful, exhibited surface cosmetic defects commonly known as orangc peel.
EX~MPLE 4 The~ general procedure of Example 1 is followed except that 390 ml of methyltriethoxysilane is independently hydrolyzed with 84 ml of distilled water at 80C for one hour. The mixture is cooled to room temperature and added to the hydroly~ed epoxy-silane just as it i5 added to the stabilized diamine. Theresultant coated lenses exhibited good adhesion and only moder-ate abrasion, and tinted to a transmittance of 0.25 (25~ trans-mission) at 205DF in the dye bath.
Diethylenetriamine (DTA), triethylenetetramine (TTA) and p-phenylenediamine (PDA) were evaluated as alternatives to ethylenediamine. In each example, the first component was formed from 94 ml ~-glycidoxypropyltrimethoxysilane and 21.6 ml water, while the second component was formcd from the indi-cated amount of the amine listed in the table below and (except for Example 10) 150 ml diacetone alcohol, in a 6:1 molar ratio of alcohol to amine. The solvent used in each example was a mixture of ~6 ml n-butanol, 46 ml diacetone alcohol and 61 ml isopropanol, to which 0.2 ml of the surfactant Fluorad lC-430 was also added. In Examples 7 and 9, equimolar amounts of amine were used with ro3pect to tho amine of Example 5; in Examples 6 and 8, amounts of amine were used tllat were e~uiva-lent in nit~ogcn content to thu amine of Example 5. I~eaction conditions wero otherwiso similar to those of Example 1. Per-cent transmission (T~ was measured after a tintin~ time of 30 minutes. The results aro summarized in the followin~ ta~le:
Exam- Adhe-~ Amine SiOIl ~T
EDA 14 ml Pass 15%
6 DTA 15 ml Pass 1 7 DTA 23 ml Pass 4 8 TTA 16 ml Pass 54%
9 TTA 32 ml Pass 10%
PD~ 22.5 ml -- --.. . ... .. . . . .. . .
I.Z'~ '!3 The p-phenylenediamlne exhibited only very slight olubility in diacetone alcohol, acetone or methyl ethyl ~etone. We wcre unable to ma~e a coating sample using this ¦Iromatic amine, owing to its poor 301ubility in the solvents lltested. The other, aliphatic amines readily formed coatings.
¦~'he triethylenetetramine of Example 8 was less tintable than !the control of Example S, but appeared more abrasion-resistant.
Ii , EX~MPLES 11 to 15 I Various carbonyl-containing compounds were ~valuated ljas alternatives to diacetone alcohol. In each case 150 ml f the carbonyl compound was used. Ingredients and reaction conditions were othcrwise similar to those of Example 5. The rcsults are summarized in the following table:
,, ~ Carbonyl ~dhe-IExample Comooulld s _ ~i 11 Propionaldehyde Fail 3 12 Ethyl propionate 13 ~cetophonone Pass 10 ~ 14 Benzaldehyde Pass 10 , 15 Diacetonc alcohol Pass 6 ln Example 12, a liquid coating was formed which precipitated on tho lens. Tho adhesion tcst of Example 11 land the other examples is a relatively severe test normally performed on commercial articles5 tlle coating of Example 11 yielded a useful article. Improved adhesion results would be expected given suitable reaction conditions such as a longer curing time. The aldehydes of Examples 11 and 14 reacted exo-,thermically with the amine, which had to be added dropwise to prevent the solution from boiling over.
I -12- , 'I i ~L?~8~3 97 ml of Union Carbide A186 ~-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane was used instead of the glycidoxysilane of Example 15. Reaction conditions were otherwise similar.
The coated lens tinted to a transmittance of 0.10 (10~ transmis-sion) and passed the adhesion test.
EX~MPLE 17 108 ml of Petrarch G6710 ~-glycidoxypropylmethyl-diethoxysilane was used instead of the trialkoxysilane of Example 15. Reaction conditions were otherwise similar. The coated lens tinted to a transmittance of 0.03 and passed the adhesion test. Both this composition and that of Example 16 formed good coatings.
~ It will be seen that we llave achieved the objects of our invention. Our coating composition, which is readily applied to tha substrate, provides a highly abrasion-resisLant, readily tintable coating that satisfaetorily adheres to the substrate to which it is applied, both before and after tlnLirlg.
It will be under~tood that certain featurcs and sub-combinations are of utility and may be employad without refer-once to other features and subcombinations. Tl~is is contem-plated by and is within the scope o our claims. It is furthcr obvious that various changes may be made in details within the scope of our invention. It is, therefore, to be understood that our invention i5 not to be limited to the specific details shown and described.
Having thus described our invention, what we claim is:
....
Background of the Invention This invention relates to a siloxane-based tintable coating composition for forming abrasion-resistant coatings on lenses or other optical articles, especially those formed from synthetic plastics.
In recent years, synthetic plastics such as poly-,carbonate have replaced glass in many optical applications, particularly opthalmic lenses, because of the lighter weight and superior impact resistance of tlle plastics. However, plas-tics such as polycarbonate are relatively soft, and must receive an abrasion-resistant coating to provide an acceptab]e level of abrasion or scratch resistance. Many abrasion-resistant coating compositions of the prior art are of the polysiloxane type, in which crosslinking is provided by condensation of silane groups formed by hydrolysis of alkoxysilanes. Represen-tative compositions of this type are disclosed in Trcadway ct al U.S. Patent ~,378,250 and the references citcd therein.
Although tho compositions di6closed in these refercllces are useful in the formation of abrasiorl-resi3tal1t coatings, consid-erable room for improvement remains in terms of abrasion resis-tance and tintability.
Summary of the lnvention One object of our invention is to provide a coating that is more abrasion-resistant than those of the prior art.
Another object of our invention is to provide an abrasion-resistant coating that is more readily tintable than those of the prior art.
!' .
Still another object of our invention is to provide an abrasion-resistant coating that is readily applied to the substrate.
A further object of our invention is to provide an abrasion-resistant coating that satisfactorily adheres to the substrate to which it is applied, both before and after tinting.
A still further object of our invention is to provide an abrasion-resistant coating that is cosmetically acceptable.
Other and further objects will be apparent from the description that follows.
In general, our invention contemplates an abrasion-resistant coating composition, for use on transparent plastic substrates and t~e like, which is formed from a first component derived by partial hydrolysis from a hydrolyzable epoxysilane, the epoxysilane being at least about 40%
hydrolyzed, and a second component comprising the reaction product of a non-silane-based aliphatic polyamine and a carbonyl-containing compound selected from the group consisting of ketones and aldehydes. The method aspect of the invention involves mixing the two components to allow regenerated amino groups of the second component to react with the epoxy groups of the first component to form a partially polymerized mixture, which is, preferably, diluted with a solvent and applied to the substrate and heated to complete the curing process.
The second component of the composition should be present in an amount sufficient for the polyamine regenerated therefrom to react with the majority of the epoxy groups otherwise available for forming the reaction product.
Preferably there should be enough of the polyamine present to react with all or substantially all of such groups. This implies that if there are other amines present, the non-silane-based aliphatic polyamine supplies a major portion of the amino groups that react with the epoxy groups to form the final cured coating.
A
rn/
Suitable hydrolyzable epoxysilanes include compounds of the formula ~ 12)m Q ~l-si~(OF~3)3-m ( I
where Q is a group containing the epoxy structure -C-C- ; (II~
~1 is a bivalent hydrocarbon radical~ R2 and R3 are independent-ly selected hydrocarbon radicals; and m is an integer betwecn 0 and 2.
Preferably the epoxy-containing group Q is glycidoxy or epoxycyclohexyl, preferably 3,4-epoxycyclohexyl if the lat-er. ~1 is preferably C1-C4 alkylene, especially trimethylene (-C1l2C112CH2-) if Q i8 glycidoxy and ethylene ~-CH2C112-) if Q is 3,4-epoxycyclohexyl. Thus the preferred cholces for Q-~l~
are ~-glycidoxypropyl and ~-(3,4-epoxycyclohexyl)ethyl.
Preferably 1~2 is Cl-C4 alkyl, especially methyl, while ~3 is preforably C1-C4 alkyl, especially methyl or ethyL, or alkenyl, especially isopropenyl. Although it is possiblc to use compounds of Formula I in which m is 2, m is preferably 0 or 1 and more preferably 0. The preferred compound of F'ormula I, which was used in the bulk of our work, is ~-glycidoxypropyl-trimethoxysilane.
Compounds of Formula I are hydrolyzed to a stoichio-metrically determined degree by the addition of appropriate amounts of water followed by modest heating, in accordance with the following reaction scheme:
, _ .. , ~ .. ~ .. . . . ...... .. .. ... ..... . . . ................... .
~ ?;~ L3 (A) -Si-07~3 + 1i20 >-Si-011 + R3071 (I) (III) (B) 2 -Sli-OR3 + 1~20 > -Si-O-Si- + R30~1 I (I) (IV) lhere R3 is defined as above.
11ydrolysis (reaction A) occurs when the -OR3 groups 1of the epoxysilane ~I) react with water to generate a silanol ¦ (III), bearing hydroxy groups, together with the alcohol R30H.
l Hydrolysis is also accompanied by some degree of condensation l (reaction B), in which the hydroxy groups of the silanol (III) condense to form the siloxy moiety ~IV). Sufficient water should be used to produce at least about ~0% hydrolysis, and prefcrably betwcen about 70~ and about 95% hydrolysis, of the , ~poxysilane. The al~ohol R3011 formed by the condensation re-~5 nains in the system. Residual hydroxy groups are converted to siloxy groups by condensation when the final coating Co111pOsi-tion is cured In general, any non-silane-based aliphatic polyamine will satisfy the requirements for the polyfunctional amine.
13y "polyamine" as used herein is meant a compound having at least two reactive ~i.e., primary or secondary) amino groups.
By "aliphatic" as used herein is meant a compound in which he reactive-amino nitrogens are attached to carbon atoms that ~o not form part of an aromatic nucleus.
1 Suitable amines include compounds of the formula R-N-A-N-R ~V) R R
n which each R is independently hydrogen, a univalent aliphatic ....... --.. , . ... ...... . _ .. .. ......... ., .... ..... , ,,"_. ,, ,, _, _,.. .......... .
il ,hydrocarbon radical or -~-N-R
R
with each R of the latter group being similarly defined and with at least two R's on different nitrogens being l-ydrogen;
and each A is an independently selected bivalent aliphatic hydrocarbon radical. Preferably A is alkylene, especially a straight-chain alkylene of the formula -(CH2) -, while each ~ is -~-N-t~
or hydrogen.
A particular subgroup of said amines includo compounds of the formula H
~ 12N-(-A-N-) -H t Va) in which m is a positive integer and each A is a bivalent ali-phatic hydrocarbon radical. Particular amines of Formula va in which A is ethylene ~-CIt2CH2-) include ethylenediamine (m = 1), diethylenetriamine ~m ~ 2) and triethylenetetramine (m = 3). Most of our work involved the use of ethylenediamine, which is the preferred polyamine.
~ he polyamine ultimately reacts with the epoxy groups of the epoxysilane to form a crosslinked polymeric network.
~he polyamine is, however, first stabilized by the addition of a carbonyl-containing compound (i.e., a ketone or aldehyde) to form a reaction product. The reaction product regenerates , .... . . . . . . . ... .. . . .
~ Jl ~ L3 ¦the amine when heated during the curing cycle, allowing it ¦to crosslink the network at that time.
The reaction product of the polyamine and the carbonyl ~compound depends on the starting materials. Primary amino Igroups of the polyamine react with the cDrbonyl compound ( VI ) ~to form ketimine groups (VII) according to the scheme ( C ) o H 2 N R 3 I ~VI) 10 ¦, R -C-R2 ~ tl2O
,I NR3 ' ~VII) ,¦ Secondary amino groups react with carbonyl compounds l¦containing ~-hydrogens ~VIII) to form enamines (IX) according ,¦to the reaction schemo t D ) R-C~-C-R2 ~ IINR3E~4 r~ 1 I, I' ~VIII) ¦ 1 3 4 20 ll R-C=C-R2 I H2O
(IX) and with carbonyl compounds containing no ~-hydrogens (X) to ¦form aminals (XI) according to the overall reaction scheme tE) 1 ll 2 2 HNR3~4 --~
(X) ~1-C-~2 ~ ~2 (XI) The particular reactions are described in further detail in March, ~dvanced Organic Chemistrv, pp. 817-818 (1977) and the references cited therein.
Suitable carbonyl-containing compoun~s include aliphat-ic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol; aromatic ke~ones such as ace-o-phenone ?nd benzophenone; aliphatic aldehydes such as acel:alde-hyde and propionaldehyde; and aromatic alclehydes such as benz-aldehyde. Diacetone alcohol, however, is preferred. Ultimately the earbonyl-containing eompound is drivon off as a vapor when the amine is regenerated during cure. Preferably an cxcess of carbonyl compound over the stoiehiometric arnount i9 used to ensure that reaction C, D or E is driven to completion.
Suitable solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol and mixtures thereof. Also contemplated are glyeol ethers such as propyleneglycol methyl ether (avail-.. ... . . . . .. ....... . . . . . . .. ..... .
~?.~8'1~3 able under the trademark Dowanol PM), higher acetate esters and the like. The preferred solvent is a mixture of isopro-panol, n-butanol and diacetone alcohol, preferably in a volumet-ric ratio of 4:3:3. The particular step at which the solvent 5 is added is not crltical. The first and second components may be prepared in solution, or all or part of the solvent added later. ~e have found it convenlent, however, to add part of the solvent chilled to the reaction mixture of the first and second components to quench the polymerization reac-tion and later add thc rest of the solvcnt to achieve thedesired viscosity.
Tho composition preferably includes a surfactant, used as a flow-control agent for regulating film thickness and enhancing the cosmetic appearance of tlle coatntl ~rticle.
Of the numerous surfactants that are known, a commonly available one used in the preferred composition is the fluorinated surfac-tant available from Minncsota Mining and Manufacturing Co.
undcr the trademark Fluorad FC-430.
The composition may also include a partially hydro-lyzed alkyltrialkoxysilane such as methyltriethoxysilane tolncrease the siloxy content of the network. I~owever, no im-provement in abrasion resistance was noted using this additive, and it is therefore not includcd in the preferred formulation.
Description of the Preferred Embodiments 807 ml of ~-glycidoxypropyltrimethoxysilane is hydro-lyzed with 188 ml of distilled water by adding them together and warming to 80C for one hour or until the mixture clari-fies. The mixture is allowed to cool to room temperature in ... A . . . _ . ... .
1;'."'1813 a covered container. This effects 9S~ hydrolysis.
Il In a separate container, 121 ml of ethylenediamine ¦lis mixed with 1302 ml of diacetone alcohol, or 1 mole of the ¦Idiamine per 6 moles of diacetone alcohol. This latter mixture ¦Iis allowed to stand at room temperature for one hour to allow ¦the amino groups of the diamine to react with the carbonyl !groups of the alcohol to form ketimine functional groups.
!I The two prepared components are then mixed togcther ¦Iwith stirring at room temperature. This effects a ratio of ,2 moles of epoxysilane to 1 mole of ethylenediamine. Th~ molec-ular weight builds as the system undergoes an exothermic reac-~tion. About one hour later the reaction is quenched by the addition of 414 ml of cold t10F) diacetone alcohol, and the cntire mixture is placed in a refrigerator at 10F for a minirnum lof 3'to 4 hours.
¦ To the mixture are then added 414 ml of n-butanol, 550 ml of isopropanol, and 2 ml of Fluorad ~C-430, all at 10F.
he solution thus formed is mixed until homogenized and storecl at 10F. The above-described formulation provides one gallon ~of coating.
Typically the solution i8 maintained at a working Itcmperature of 30-F. The viscosity of ttle solution preparccl ,in this manncr at 30F i8 27 centipoise. Solids content i9 ll~i. The coating i9 applied to polycarbonate lenses by dipping Ithem into the solution and withdrawing them at a rate of 0.2 inch per second. The lenses are pre-cured at 167F for 15 ~nihutes and finally cured for 3 hours at 265F.
The resultant lenses were tested as follows:
_9_ I . I~
P ~
Test Method l~esult Adheslon Crosshatch, 100~ adhesion 16 squares ~brasion 84 psi, No scratches 0000 steel wool Tintability 25 minutes, 15~ transmission Gentone Tru-Grey Dye at 205 ~
~dhesion Crosshatch, 100% adhesion after 16 squares tlnting Coating Interferometer 4.5 + 0.5 microns thickness EX~MPLE 2 The general procedure of Example 1 is followed except that the ethylencdiamine is mixed with 953 ml of methyl ethyl keto~e instead of diacetone alcohol. The resultant lenscs exhibited properties similar to those noted above but with a modest decrease in the coating adhesion after tinting.
EX~MPLE 3 The general procedure of Example 1 is followc~l except that instead of the butanol-isopropanol-diacetone alcohol systern described, a system comprising 691 ml methanol, 481 ml isopro-panol and 206 ml diacetone alcohol i3 used. The resultantlenses, although useful, exhibited surface cosmetic defects commonly known as orangc peel.
EX~MPLE 4 The~ general procedure of Example 1 is followed except that 390 ml of methyltriethoxysilane is independently hydrolyzed with 84 ml of distilled water at 80C for one hour. The mixture is cooled to room temperature and added to the hydroly~ed epoxy-silane just as it i5 added to the stabilized diamine. Theresultant coated lenses exhibited good adhesion and only moder-ate abrasion, and tinted to a transmittance of 0.25 (25~ trans-mission) at 205DF in the dye bath.
Diethylenetriamine (DTA), triethylenetetramine (TTA) and p-phenylenediamine (PDA) were evaluated as alternatives to ethylenediamine. In each example, the first component was formed from 94 ml ~-glycidoxypropyltrimethoxysilane and 21.6 ml water, while the second component was formcd from the indi-cated amount of the amine listed in the table below and (except for Example 10) 150 ml diacetone alcohol, in a 6:1 molar ratio of alcohol to amine. The solvent used in each example was a mixture of ~6 ml n-butanol, 46 ml diacetone alcohol and 61 ml isopropanol, to which 0.2 ml of the surfactant Fluorad lC-430 was also added. In Examples 7 and 9, equimolar amounts of amine were used with ro3pect to tho amine of Example 5; in Examples 6 and 8, amounts of amine were used tllat were e~uiva-lent in nit~ogcn content to thu amine of Example 5. I~eaction conditions wero otherwiso similar to those of Example 1. Per-cent transmission (T~ was measured after a tintin~ time of 30 minutes. The results aro summarized in the followin~ ta~le:
Exam- Adhe-~ Amine SiOIl ~T
EDA 14 ml Pass 15%
6 DTA 15 ml Pass 1 7 DTA 23 ml Pass 4 8 TTA 16 ml Pass 54%
9 TTA 32 ml Pass 10%
PD~ 22.5 ml -- --.. . ... .. . . . .. . .
I.Z'~ '!3 The p-phenylenediamlne exhibited only very slight olubility in diacetone alcohol, acetone or methyl ethyl ~etone. We wcre unable to ma~e a coating sample using this ¦Iromatic amine, owing to its poor 301ubility in the solvents lltested. The other, aliphatic amines readily formed coatings.
¦~'he triethylenetetramine of Example 8 was less tintable than !the control of Example S, but appeared more abrasion-resistant.
Ii , EX~MPLES 11 to 15 I Various carbonyl-containing compounds were ~valuated ljas alternatives to diacetone alcohol. In each case 150 ml f the carbonyl compound was used. Ingredients and reaction conditions were othcrwise similar to those of Example 5. The rcsults are summarized in the following table:
,, ~ Carbonyl ~dhe-IExample Comooulld s _ ~i 11 Propionaldehyde Fail 3 12 Ethyl propionate 13 ~cetophonone Pass 10 ~ 14 Benzaldehyde Pass 10 , 15 Diacetonc alcohol Pass 6 ln Example 12, a liquid coating was formed which precipitated on tho lens. Tho adhesion tcst of Example 11 land the other examples is a relatively severe test normally performed on commercial articles5 tlle coating of Example 11 yielded a useful article. Improved adhesion results would be expected given suitable reaction conditions such as a longer curing time. The aldehydes of Examples 11 and 14 reacted exo-,thermically with the amine, which had to be added dropwise to prevent the solution from boiling over.
I -12- , 'I i ~L?~8~3 97 ml of Union Carbide A186 ~-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane was used instead of the glycidoxysilane of Example 15. Reaction conditions were otherwise similar.
The coated lens tinted to a transmittance of 0.10 (10~ transmis-sion) and passed the adhesion test.
EX~MPLE 17 108 ml of Petrarch G6710 ~-glycidoxypropylmethyl-diethoxysilane was used instead of the trialkoxysilane of Example 15. Reaction conditions were otherwise similar. The coated lens tinted to a transmittance of 0.03 and passed the adhesion test. Both this composition and that of Example 16 formed good coatings.
~ It will be seen that we llave achieved the objects of our invention. Our coating composition, which is readily applied to tha substrate, provides a highly abrasion-resisLant, readily tintable coating that satisfaetorily adheres to the substrate to which it is applied, both before and after tlnLirlg.
It will be under~tood that certain featurcs and sub-combinations are of utility and may be employad without refer-once to other features and subcombinations. Tl~is is contem-plated by and is within the scope o our claims. It is furthcr obvious that various changes may be made in details within the scope of our invention. It is, therefore, to be understood that our invention i5 not to be limited to the specific details shown and described.
Having thus described our invention, what we claim is:
....
Claims (33)
1. An abrasion-resistant coating composition comprising a first component derived by partial hydrolysis from a hydrolyzable epoxysilane, said epoxysilane being at least about 40% hydrolyzed, and a second component derived by reaction of a non-silane-based aliphatic polyamine with a carbonyl-containing compound selected from the group consisting of ketones and aldehydes.
2. A composition as in claim 1 in which said polyamine contains at least two primary amino groups.
3. A composition as in claim 1 in which said polyamine is a compound of the formula:
R - ? - A - ? - R
in which each R is independently hydrogen, a univalent aliphatic hydrocarbon radical or:
- A - ? - R1 where each R1 is independently hydrogen or a univalent aliphatic hydrocarbon radical; and each A is independently a bivalent aliphatic hydrocarbon radical.
R - ? - A - ? - R
in which each R is independently hydrogen, a univalent aliphatic hydrocarbon radical or:
- A - ? - R1 where each R1 is independently hydrogen or a univalent aliphatic hydrocarbon radical; and each A is independently a bivalent aliphatic hydrocarbon radical.
4. A composition as in claim 1 in which said polyamine is a compound of the formula:
H2N - (- A - ?-)m - H
in which m is a positive integer and each A is independently a bivalent aliphatic hydrocarbon radical.
H2N - (- A - ?-)m - H
in which m is a positive integer and each A is independently a bivalent aliphatic hydrocarbon radical.
5. A composition as in claim 3 in which A is alkylene.
6. A composition as in claim 3 in which A is - (CH2)n -, where n is a positive integer.
7. A composition as in claim 4 in which A is ethylene.
8. A composition as in claim 4 in which m is between 1 and 3.
9. A composition as in claim 1 in which said polyamine is ethylenediamine, diethylenetriamine or triethylenetetramine.
10. A composition as in claim 1 in which said polyamine is ethylenediamine.
11. A composition as in claim 1 in which said polyamine is diethylenetriamine.
12. A composition as in claim 1 in which said polyamine is triethylenetetramine.
13. A composition as in claim 1 in which said carbonyl-containing compound is a ketone.
14. A composition as in claim 1 in which said carbonyl-containing compound is an aliphatic ketone.
15. A composition as in claim 1 in which said carbonyl-containing compound is diacetone alcohol.
16. A composition as in claim 1 in which said epoxysilane is a glycidoxyalkyltrialkoxysilane.
17. A composition as in claim 1 in which said epoxysilane is a-glycidoxypropyltrimethoxysilane.
18. A method of forming an abrasion-resistant coating on a substrate including the steps of mixing a partially hydrolyzed epoxysilane with the reaction product of a non-silane-based aliphatic polyamine and a ketone or aldehyde, said epoxysilane being at least about 40% hydrolyzed, and applying said mixture to the surface of said substrate.
19. A method as in claim 18 in which said mixture is applied while dissolved in an organic solvent.
20. A method as in claim 18 in which said mixture contains a sufficient amount of said reaction product to react with the majority of the epoxy groups of said epoxysilane.
21. An article of manufacture comprising a substrate and an abrasion-resistant coating thereon comprising the reaction product of a first reactant comprising a partially hydrolyzed epoxysilane, said epoxysilane being at least about 40% hydrolyzed, and a second reactant derived by reacting a non-silane-based aliphatic polyamine with a ketone or aldehyde.
22. An article as in claim 21 in which said substrate is optically transparent.
23. An article as in claim 21 in which said substrate is an optical substrate.
24. An article as in claim 21 in which said substrate comprises an organic plastic material.
25. An article as in claim 21 in which said substrate comprises polycarbonate.
26. An article as in claim 21 in which said polyamine contains at least two primary amino groups.
27. An article as in claim 21 in which said polyamine is a compound of the formula:
H2N - (- A - ?-)m - H
in which m is a positive integer and each A is independently a bivalent aliphatic hydrocarbon radical.
H2N - (- A - ?-)m - H
in which m is a positive integer and each A is independently a bivalent aliphatic hydrocarbon radical.
28. An article as in claim 21 in which said polyamine is ethylenediamine, diethylenetriamine or triethylene-tetramine.
29. A composition as in claim 1 in which said epoxysilane is between about 70% and about 95% hydrolyzed.
30. A composition as in claim 1 containing a sufficient amount of said second component to react with the majority of the epoxy groups of said epoxysilane.
31. An article as in claim 21 in which said second reactant has reacted with the majority of the epoxy groups of said epoxysilane.
32. An article produced by the method of claim 18, 19 or 20.
33. An article as in claim 21 in which said polyamine is a compound of the formula:
R - ? - A - ? - R
in which each R is independently hydrogen, a univalent aliphatic hydrocarbon radical or:
- A - ? - R1 where each R1 is independently hydrogen or a univalent aliphatic hydrocarbon radical; and each A is independently a bivalent aliphatic hydrocarbon radical.
R - ? - A - ? - R
in which each R is independently hydrogen, a univalent aliphatic hydrocarbon radical or:
- A - ? - R1 where each R1 is independently hydrogen or a univalent aliphatic hydrocarbon radical; and each A is independently a bivalent aliphatic hydrocarbon radical.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US099,390 | 1987-09-22 | ||
| US07/099,390 US4800122A (en) | 1987-09-22 | 1987-09-22 | Siloxane-based tintable coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1291843C true CA1291843C (en) | 1991-11-05 |
Family
ID=22274787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 578137 Expired - Fee Related CA1291843C (en) | 1987-09-22 | 1988-09-22 | Siloxane-based tintable coating |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4800122A (en) |
| JP (1) | JPH01108272A (en) |
| CA (1) | CA1291843C (en) |
| DE (1) | DE3830053A1 (en) |
| FR (1) | FR2620720A1 (en) |
| GB (1) | GB2210049B (en) |
| IT (1) | IT1227051B (en) |
| SG (1) | SG44092G (en) |
Families Citing this family (67)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4977029A (en) * | 1988-07-05 | 1990-12-11 | Corning Incorporated | Tintable coatings for glass ophthalmic lenses |
| US5013608A (en) * | 1989-07-07 | 1991-05-07 | Swedlow, Inc. | Highly tintable abrasion resistant coatings |
| JPH04205742A (en) * | 1990-11-29 | 1992-07-27 | Matsushita Electric Ind Co Ltd | Magneto-optical recording medium |
| US5786032A (en) * | 1991-11-22 | 1998-07-28 | Vision-Ease Lens, Inc. | Coating composition and process for producing coated articles |
| US5527871A (en) * | 1992-12-28 | 1996-06-18 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Layered inorganic-organic polymer shaped article thereof and process for producing the same |
| US5314980A (en) * | 1993-01-19 | 1994-05-24 | Minnesota Mining And Manufacturing Company | Epoxy coating compositions with metal-containing stabilizers |
| JPH06331804A (en) * | 1993-05-20 | 1994-12-02 | Nikon Corp | Plastic lens |
| US5866262A (en) * | 1995-10-16 | 1999-02-02 | Galic Maus Ventures | Fully-hydrolized ketimine silane/epoxide silane copolymer liquid hardcoating compositions and processes for dipcoating polycarbonate spectacle lenses |
| US6525159B1 (en) * | 1997-01-21 | 2003-02-25 | The Yokohama Rubber Co., Ltd. | One-pack cold moisture curable resin compositions |
| US5989462A (en) | 1997-07-31 | 1999-11-23 | Q2100, Inc. | Method and composition for producing ultraviolent blocking lenses |
| US6478990B1 (en) * | 1998-09-25 | 2002-11-12 | Q2100, Inc. | Plastic lens systems and methods |
| US6419873B1 (en) | 1999-03-19 | 2002-07-16 | Q2100, Inc. | Plastic lens systems, compositions, and methods |
| US6723260B1 (en) | 2000-03-30 | 2004-04-20 | Q2100, Inc. | Method for marking a plastic eyeglass lens using a mold assembly holder |
| US6960312B2 (en) | 2000-03-30 | 2005-11-01 | Q2100, Inc. | Methods for the production of plastic lenses |
| US6528955B1 (en) | 2000-03-30 | 2003-03-04 | Q2100, Inc. | Ballast system for a fluorescent lamp |
| US6698708B1 (en) | 2000-03-30 | 2004-03-02 | Q2100, Inc. | Gasket and mold assembly for producing plastic lenses |
| US6716375B1 (en) | 2000-03-30 | 2004-04-06 | Q2100, Inc. | Apparatus and method for heating a polymerizable composition |
| US6632535B1 (en) | 2000-06-08 | 2003-10-14 | Q2100, Inc. | Method of forming antireflective coatings |
| US6808381B2 (en) | 2001-02-20 | 2004-10-26 | Q2100, Inc. | Apparatus for preparing an eyeglass lens having a controller |
| US7083404B2 (en) * | 2001-02-20 | 2006-08-01 | Q2100, Inc. | System for preparing an eyeglass lens using a mold holder |
| US7045081B2 (en) | 2001-02-20 | 2006-05-16 | Q2100, Inc. | Method of monitoring components of a lens forming apparatus |
| US7124995B2 (en) * | 2001-02-20 | 2006-10-24 | Q2100, Inc. | Holder for mold assemblies and molds |
| US6790022B1 (en) | 2001-02-20 | 2004-09-14 | Q2100, Inc. | Apparatus for preparing an eyeglass lens having a movable lamp mount |
| US7139636B2 (en) * | 2001-02-20 | 2006-11-21 | Q2100, Inc. | System for preparing eyeglass lenses with bar code reader |
| US6712331B2 (en) | 2001-02-20 | 2004-03-30 | Q2100, Inc. | Holder for mold assemblies with indicia |
| US6840752B2 (en) * | 2001-02-20 | 2005-01-11 | Q2100, Inc. | Apparatus for preparing multiple eyeglass lenses |
| US7037449B2 (en) | 2001-02-20 | 2006-05-02 | Q2100, Inc. | Method for automatically shutting down a lens forming apparatus |
| US6790024B2 (en) | 2001-02-20 | 2004-09-14 | Q2100, Inc. | Apparatus for preparing an eyeglass lens having multiple conveyor systems |
| US6875005B2 (en) | 2001-02-20 | 2005-04-05 | Q1200, Inc. | Apparatus for preparing an eyeglass lens having a gating device |
| US7060208B2 (en) | 2001-02-20 | 2006-06-13 | Q2100, Inc. | Method of preparing an eyeglass lens with a controller |
| US6702564B2 (en) | 2001-02-20 | 2004-03-09 | Q2100, Inc. | System for preparing an eyeglass lens using colored mold holders |
| US6612828B2 (en) | 2001-02-20 | 2003-09-02 | Q2100, Inc. | Fill system with controller for monitoring use |
| US6752613B2 (en) | 2001-02-20 | 2004-06-22 | Q2100, Inc. | Apparatus for preparing an eyeglass lens having a controller for initiation of lens curing |
| US6676399B1 (en) | 2001-02-20 | 2004-01-13 | Q2100, Inc. | Apparatus for preparing an eyeglass lens having sensors for tracking mold assemblies |
| US7004740B2 (en) | 2001-02-20 | 2006-02-28 | Q2100, Inc. | Apparatus for preparing an eyeglass lens having a heating system |
| US6893245B2 (en) | 2001-02-20 | 2005-05-17 | Q2100, Inc. | Apparatus for preparing an eyeglass lens having a computer system controller |
| US7074352B2 (en) | 2001-02-20 | 2006-07-11 | Q2100, Inc. | Graphical interface for monitoring usage of components of a lens forming apparatus |
| US6676398B2 (en) | 2001-02-20 | 2004-01-13 | Q2100, Inc. | Apparatus for preparing an eyeglass lens having a prescription reader |
| US6962669B2 (en) | 2001-02-20 | 2005-11-08 | Q2100, Inc. | Computerized controller for an eyeglass lens curing apparatus |
| US6655946B2 (en) | 2001-02-20 | 2003-12-02 | Q2100, Inc. | Apparatus for preparing an eyeglass lens having a controller for conveyor and curing units |
| US6863518B2 (en) | 2001-02-20 | 2005-03-08 | Q2100, Inc. | Mold filing apparatus having multiple fill stations |
| US7052262B2 (en) | 2001-02-20 | 2006-05-30 | Q2100, Inc. | System for preparing eyeglasses lens with filling station |
| US6709257B2 (en) | 2001-02-20 | 2004-03-23 | Q2100, Inc. | Eyeglass lens forming apparatus with sensor |
| US7011773B2 (en) | 2001-02-20 | 2006-03-14 | Q2100, Inc. | Graphical interface to display mold assembly position in a lens forming apparatus |
| US7025910B2 (en) | 2001-02-20 | 2006-04-11 | Q2100, Inc | Method of entering prescription information |
| US6758663B2 (en) | 2001-02-20 | 2004-07-06 | Q2100, Inc. | System for preparing eyeglass lenses with a high volume curing unit |
| US6726463B2 (en) | 2001-02-20 | 2004-04-27 | Q2100, Inc. | Apparatus for preparing an eyeglass lens having a dual computer system controller |
| US7051290B2 (en) * | 2001-02-20 | 2006-05-23 | Q2100, Inc. | Graphical interface for receiving eyeglass prescription information |
| US6899831B1 (en) | 2001-02-20 | 2005-05-31 | Q2100, Inc. | Method of preparing an eyeglass lens by delayed entry of mold assemblies into a curing apparatus |
| US6785618B2 (en) | 2001-03-02 | 2004-08-31 | Gas Research Institute | In-ground pipeline monitoring |
| SE0101702D0 (en) * | 2001-05-15 | 2001-05-15 | Ardenia Investments Ltd | Novel potentiating compounds |
| US6506921B1 (en) * | 2001-06-29 | 2003-01-14 | Virginia Tech Intellectual Properties, Inc. | Amine compounds and curable compositions derived therefrom |
| US7044429B1 (en) | 2002-03-15 | 2006-05-16 | Q2100, Inc. | Methods and systems for coating eyeglass lens molds |
| US6464484B1 (en) | 2002-03-30 | 2002-10-15 | Q2100, Inc. | Apparatus and system for the production of plastic lenses |
| US20040145701A1 (en) * | 2003-01-29 | 2004-07-29 | Robert Miniutti | Solid color eyewear lenses |
| US20040145802A1 (en) * | 2003-01-29 | 2004-07-29 | Robert Miniutti | Infrared filtering optical lenses and methods of manufacturing |
| US7004583B2 (en) * | 2003-01-29 | 2006-02-28 | East Bay Technologies | Eyewear lenses and methods of manufacturing |
| US7834121B2 (en) * | 2004-09-15 | 2010-11-16 | Ppg Industries Ohio, Inc. | Silicone resin containing coating compositions, related coated substrates and methods |
| US7459515B2 (en) * | 2004-09-15 | 2008-12-02 | Ppg Industries Ohio, Inc. | Fast-curing modified siloxane compositions |
| US20060065989A1 (en) * | 2004-09-29 | 2006-03-30 | Thad Druffel | Lens forming systems and methods |
| JP4742636B2 (en) * | 2005-03-23 | 2011-08-10 | セイコーエプソン株式会社 | Plastic lens dyeing method |
| WO2008020867A2 (en) * | 2005-11-21 | 2008-02-21 | Q2100, Inc. | Methods of making and using metal oxide nanoparticles |
| US8540814B2 (en) * | 2008-10-24 | 2013-09-24 | Trent University | Coatings for corrosion susceptible substrates |
| JP5203284B2 (en) * | 2009-04-13 | 2013-06-05 | オート化学工業株式会社 | Curable composition |
| WO2014119282A1 (en) * | 2013-01-29 | 2014-08-07 | 日本曹達株式会社 | Organosilane composition |
| CN106164710B (en) | 2014-02-12 | 2020-07-03 | 视觉缓解公司 | Easy-to-clean coating |
| MX2022006809A (en) * | 2019-12-05 | 2022-07-11 | Ppg Ind Ohio Inc | Curable compositions. |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2721873A (en) * | 1952-03-11 | 1955-10-25 | Montclair Res Corp | Reaction of silanes with unsaturated aliphatic compounds |
| US2776910A (en) * | 1954-02-10 | 1957-01-08 | Porter W Erickson | Method of coating glass fibers with reaction product of organo halsilanes and glycidol derivatives and then with epoxy resins and the product per se |
| US3291775A (en) * | 1958-12-31 | 1966-12-13 | Shell Oil Co | Process for curing polyepoxides with a polyimine |
| BE791205A (en) * | 1971-11-12 | 1973-05-10 | Exxon Research Engineering Co | SELF-CURING ANTI-CORROSIVE COATINGS |
| JPS6018707B2 (en) * | 1974-10-09 | 1985-05-11 | 日本原子力研究所 | Curable resin composition for anti-fog coating |
| JPS5943051B2 (en) * | 1977-10-26 | 1984-10-19 | 日本原子力研究所 | Plastic surface treatment agent |
| US4151327A (en) * | 1978-02-24 | 1979-04-24 | Lawton William R | Complex amine/silane treated cellulosic materials |
| JPS5525469A (en) * | 1978-08-14 | 1980-02-23 | Japan Atom Energy Res Inst | Thermosetting resin composition |
| JPS5699263A (en) * | 1980-01-10 | 1981-08-10 | Nippon Sheet Glass Co Ltd | Coating composition |
| JPS5767666A (en) * | 1980-10-16 | 1982-04-24 | Nippon Sheet Glass Co Ltd | Coating composition |
| US4348431A (en) * | 1981-02-19 | 1982-09-07 | General Electric Company | Process for coating plastic films |
| US4378250A (en) * | 1981-07-31 | 1983-03-29 | Treadway Gerald D | Organosilicone coating compositions |
| US4560704A (en) * | 1982-11-12 | 1985-12-24 | Purdue Research Foundation | Polyamine based bonded phase chromatography |
| JPS6250199A (en) * | 1985-08-30 | 1987-03-04 | 東レ株式会社 | Sheet-shaped article for writing |
| JPH0830169B2 (en) * | 1986-08-19 | 1996-03-27 | 日本合成ゴム株式会社 | Coating composition |
-
1987
- 1987-09-22 US US07/099,390 patent/US4800122A/en not_active Expired - Fee Related
-
1988
- 1988-09-03 DE DE19883830053 patent/DE3830053A1/en not_active Withdrawn
- 1988-09-08 IT IT2186888A patent/IT1227051B/en active
- 1988-09-13 GB GB8821475A patent/GB2210049B/en not_active Expired - Fee Related
- 1988-09-22 FR FR8812402A patent/FR2620720A1/en not_active Revoked
- 1988-09-22 CA CA 578137 patent/CA1291843C/en not_active Expired - Fee Related
- 1988-09-22 JP JP63236634A patent/JPH01108272A/en active Pending
-
1992
- 1992-04-21 SG SG44092A patent/SG44092G/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3830053A1 (en) | 1989-04-06 |
| US4800122A (en) | 1989-01-24 |
| JPH01108272A (en) | 1989-04-25 |
| SG44092G (en) | 1992-06-12 |
| GB2210049A (en) | 1989-06-01 |
| IT1227051B (en) | 1991-03-14 |
| GB2210049B (en) | 1991-12-18 |
| FR2620720A1 (en) | 1989-03-24 |
| GB8821475D0 (en) | 1988-10-12 |
| IT8821868A0 (en) | 1988-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1291843C (en) | Siloxane-based tintable coating | |
| US6057040A (en) | Aminosilane coating composition and process for producing coated articles | |
| US4170690A (en) | Process of coating weatherable, abrasion resistant coating and coated articles | |
| US4324712A (en) | Silicone resin coating composition | |
| US4159206A (en) | Weatherable, abrasion resistant coating composition, method, and coated articles | |
| AU739863B2 (en) | Coating compositions based on epoxy group-containing silanes | |
| FI114643B (en) | Abrasion-resistant and impact-resistant coated products based on silane hydrates and aluminum compounds | |
| CA1175986A (en) | Coating compositions from derivatives of epoxy and nitrogen containing silanes | |
| US4177315A (en) | Coated Polymeric substrates | |
| US4476281A (en) | Silicone resin coating composition | |
| US4495360A (en) | Ultraviolet light absorbing agents, method for making, compositions and articles containing same | |
| US4368235A (en) | Silicone resin coating composition | |
| AU750507B2 (en) | Coating composition and method for preparing the same, and scuff-resistant plastic lense | |
| US3894881A (en) | Coating composition | |
| EP0379343A1 (en) | Hard coating compositions containing organic silicon compounds. | |
| KR20050059228A (en) | Coating composition and method for the production thereof | |
| CA2406175A1 (en) | Scratch-resistant coating | |
| WO1998040444A1 (en) | Thermosetting coating composition | |
| US4311763A (en) | Silicone resin coating composition | |
| US6358612B1 (en) | Coating compositions with a base consisting of silanes containing epoxide groups | |
| US4525426A (en) | Ultraviolet light absorbing agents, method for making, compositions, and articles containing same | |
| US4486503A (en) | Silicone resin coating composition | |
| US6250760B1 (en) | Silane-based coating composition | |
| US6500486B1 (en) | Controlled tintability on mar-resistant coatings | |
| US4324839A (en) | Silicone resin coating composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |