US4049861A
Expired / Lapsed
US
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Abrasion resistant coatings
Assignee: 3M Co
•
Filing: 1976-02-19
•
Granted: 1977-09-20
•
Expires: 1996-02-19
Abstract
Abstract Abrasion resistant coatings comprising epoxy-terminated silanes cured in the presence of highly fluorinated aliphatic sulfonic and sulfonylic catalysts are solvent and abrasion resistant.
Inventors
- 👤 Mohammad S. Nozari
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 03:47
CPC Classifications
G; G03; G03C; G03C11/00; G03C11/06; C; C08; C08G; C08G59/00; C08G59/18; C08G59/20; C08G59/22; C08G59/30; C08G59/306; C08G59/68; C08G59/687; C09; C09D; C09D4/00; Y; Y10; Y10T; Y10T428/00; Y10T428/26; Y10T428/263; Y10T428/264; Y10T428/265; Y10T428/31504; Y10T428/31511; Y10T428/31525; Y10T428/31529; Y10T428/31652; Y10T428/31663
Claims Analysis
Total Claims: 34
Claim 1
Independent Claim
218 words
A coated article comprising a substrate and an abrasion resistant coating on the substrate wherein said coating is from 0.1 to 500 microns thick and comprises a polymer comprising at least 15 percent by weight of units from an epoxy-terminated silane represented by the formulae: ##STR19## wherein each R is independently a non-hydrolyzable divalent hydrocarbon radical of less than 20 carbon atoms, or a divalent radical of less than 20 carbon atoms the backbone of which is C atoms which may be interrupted by individual atoms from the group of N and O, the O atoms in the form of ether linkages, m is 1, 2, or 3, n is 0, or 1, and R' is an aliphatic hydrocarbon radical of less than 10 carbon atoms, an acyl radical of less than 10 carbon atoms, or a radical of the formula (CH 2 CH 2 O) k Z in which k is an integer of at least 1, and Z is hydrogen or an aliphatic hydrocarbon radical of less than 10 carbon atoms, cured in the presence of a catalytically active amount of a highly fluorinated sulfonylic catalyst comprising two highly fluorinated aliphatic sulfonyl groups attached directly to an imide or a methylene or highly fluorinated sulfonic catalyst comprising a highly fluorinated aliphatic sulfonic acid or salt thereof.
Claim 2
Dependent Claim
218 words
A coated article comprising a substrate and an abrasion resistant coating on the substrate wherein said coating is from 0.1 to 500 microns thick and comprises a polymer comprising at least 15 percent by weight of units from an epoxy-terminated silane represented by the formulae: ##STR19## wherein each R is independently a non-hydrolyzable divalent hydrocarbon radical of less than 20 carbon atoms, or a divalent radical of less than 20 carbon atoms the backbone of which is C atoms which may be interrupted by individual atoms from the group of N and O, the O atoms in the form of ether linkages, m is 1, 2, or 3, n is 0, or 1, and R' is an aliphatic hydrocarbon radical of less than 10 carbon atoms, an acyl radical of less than 10 carbon atoms, or a radical of the formula (CH 2 CH 2 O) k Z in which k is an integer of at least 1, and Z is hydrogen or an aliphatic hydrocarbon radical of less than 10 carbon atoms, cured in the presence of a catalytically active amount of a highly fluorinated sulfonylic catalyst comprising two highly fluorinated aliphatic sulfonyl groups attached directly to an imide or a methylene or highly fluorinated sulfonic catalyst comprising a highly fluorinated aliphatic sulfonic acid or salt thereof.
Claim 3
Dependent Claim
27 words
The coated article of claim 1 wherein said polymer further comprises up to 85 percent by weight units derived from materials copolymerizable with epoxy or silane groups.
Claim 4
Dependent Claim
169 words
The coated article of claim 2 wherein said highly fluorinated sulfonyl catalyst is represented by the formula: (R.sub.f SO.sub.2)Q(O.sub.2 SR.sub.f ') wherein R f and R f ' are independently a highly fluorinated alkyl group, and Q is a divalent radical selected from --NH-- and --CHR-- wherein R is selected from Br, Cl, I, H, alkyl groups of 1 to 20 carbon atoms, alkenyl of 3 to 4 carbon atoms, aryl or aralkyl of up to 20 carbon atoms, or R'X, wherein R' is an alkylene group of up to 20 carbon atoms and X is Br, Cl, I, --O 2 SR f , -CH(O 2 SR f ) 2 , ##STR20## or --CY(COOR 2 ) 2 wherein R 4 is H or 1 to 8 alkyl and n is 0 to 8, and wherein R 2 is alkyl of 1 to 4 carbon atoms or phenylalkyl, the alkyl group of which has 1 to 4 carbon atoms, and Y is H, Br, Cl, I, or No 2 .
Claim 5
Dependent Claim
17 words
The coated article of claim 3 wherein R f and R f ' represent perfluorinated alkyl groups.
Claim 6
Dependent Claim
26 words
The coated article of claim 1 wherein the surface of the substrate is coated with a primer to enhance bonding between the coating and the substrate.
Claim 7
Dependent Claim
135 words
The coated article of claim 1 wherein said sulfonic and sulfonylic catalyst are seleted from the formuale: (R.sub.f SO.sub.3).sub.n R and (R.sub.f SO.sub.2)-Q-(SO.sub.2 R.sub.f ') wherein R is selected from hydrogen ammonium cation and metal cation and n is the valence of R, R f and R f ' are independently highly fluorinated aliphatic groups, and Q is selected from ##STR21## wherein R' is selected from hydrogen, chlorine, bromine, iodine, ammonium cation, or metal cation R" is selected from hydrogen, chlorine, bromine, iodine, R f SO 2 , alkenyl of 3 to 4 carbon atoms, alkyl of 1 to 20 carbon atoms, aryl of up to 20 carbon atoms, and alkaryl of up to 20 carbon atoms and R 3 is H, alkenyl of 3 to 4 carbons and aryl of up to 20 carbons.
Claim 8
Dependent Claim
17 words
The coated article of claim 6 wherein R f and R f ' represent perfluorinated alkyl groups.
Claim 9
Dependent Claim
13 words
The coated article of claim 6 wherein said substrate is a painted surface.
Claim 10
Dependent Claim
11 words
The coated article of claim 6 wherein said substrate is metal.
Claim 11
Dependent Claim
17 words
The coated article of claim 6 wherein R f and R f ' represent perfluorinated alkyl groups.
Claim 12
Dependent Claim
21 words
The coated article of claim 6 wherein said coating comprises at least some filler up to 50 weight-percent of the coating.
Claim 13
Dependent Claim
21 words
The coated article of claim 1 wherein said coating comprises at least some filler up to 50 weight-percent of the coating.
Claim 14
Dependent Claim
13 words
The coated article of claim 12 wherein said filler comprises titania and silica.
Claim 15
Dependent Claim
13 words
The coated articles of claim 1 wherein said coating comprises pigments or dyes.
Claim 16
Dependent Claim
12 words
The coated articles of claim 1 wherein said coating comprises heat stabilizers.
Claim 17
Dependent Claim
12 words
The coated article of claim 1 wherein the substrate comprises a polyester.
Claim 18
Dependent Claim
13 words
The coated article of claim 1 wherein the substrate comprises an acrylic resin.
Claim 19
Dependent Claim
11 words
The coated article of claim 1 wherein the substrate is glass.
Claim 20
Dependent Claim
12 words
The coated article of claim 1 wherein the substrate comprises a polycarbonate.
Claim 21
Dependent Claim
14 words
The coated article of claim 1, wherein the substrate comprises a cellulose acetate butyrate.
Claim 22
Dependent Claim
14 words
The coated article of claim 1, wherein said substrate comprises a finished photographic product.
Claim 23
Dependent Claim
202 words
A film from 0.1 to 500 microns thick comprising a polymer having at least 15 percent by weight of units derived from an epoxy-terminated silane represented by the formulae: ##STR22## wherein, each R is independently a non-hydrolyzable divaent hydrocarbon radical of less than 20 carbon atoms, or a divalent radical of less than 20 carbon atoms the backbone of which is C atoms which may be interrupted by individual atoms from the group of N and O, the O atoms in the form of ether linkages, m is 1, 2, or 3, n is 0, or 1, and R' is an aliphatic hydrocarbon radical of less than 10 carbon atoms, an acyl radical of less than 10 carbon atoms, or a radical of the formula (CH 2 CH 2 O) k Z in which k is an integer of at least 1, and Z is hydrogen or an aliphatic hydrocarbon radical of less than 10 carbon atoms, cured in the presence of a catalytically active amount of a highly fluorinated sulfonylic catalyst comprising two highly fluorinated aliphatic sulfonyl groups attached directly to an imide or a methylene or highly fluorinated sulfonic catalyst comprising a highly fluorinated aliphatic sulfonic acid or salt thereof.
Claim 24
Dependent Claim
202 words
A film from 0.1 to 500 microns thick comprising a polymer having at least 15 percent by weight of units derived from an epoxy-terminated silane represented by the formulae: ##STR22## wherein, each R is independently a non-hydrolyzable divaent hydrocarbon radical of less than 20 carbon atoms, or a divalent radical of less than 20 carbon atoms the backbone of which is C atoms which may be interrupted by individual atoms from the group of N and O, the O atoms in the form of ether linkages, m is 1, 2, or 3, n is 0, or 1, and R' is an aliphatic hydrocarbon radical of less than 10 carbon atoms, an acyl radical of less than 10 carbon atoms, or a radical of the formula (CH 2 CH 2 O) k Z in which k is an integer of at least 1, and Z is hydrogen or an aliphatic hydrocarbon radical of less than 10 carbon atoms, cured in the presence of a catalytically active amount of a highly fluorinated sulfonylic catalyst comprising two highly fluorinated aliphatic sulfonyl groups attached directly to an imide or a methylene or highly fluorinated sulfonic catalyst comprising a highly fluorinated aliphatic sulfonic acid or salt thereof.
Claim 25
Dependent Claim
27 words
The film of claim 22 wherein said polymer further comprises up to 85 percent by weight of units derived from materials copolymerizable with silane or epoxy groups.
Claim 26
Dependent Claim
166 words
The film of claim 23 wherein said catalyst is represented by the formula: (R.sub.f SO.sub.2)Q(O.sub.2 SR.sub.f ') wherein R f and R f ' are independently a highly fluorinate alkyl group, and Q is a divalent radical selected from -NH- and -CHR- wherein R is selected from Br, Cl, I, H, alkyl groups of 1 to 20 carbon atoms, alkenyl of 3 to 4 carbon atoms, aryl or aralkyl of up to 20 carbon atoms, or R'X, wherein R' is an alkylene group of up to 20 carbon atoms and X is H, Br, Cl, I, -O 2 SR f , -CH(O 2 SR f ) 2 , ##STR23## or -CY(COOR 2 ) 2 wherein R 4 is H or 1 to 8 alkyl and n is 0 to 8, and wherein R 2 is alkyl of 1 to 4 carbon atoms or phenylalkyl, the alkyl group of which has 1 to 4 carbon atoms, and Y is H, Br, Cl, I, or NO 2 .
Claim 27
Dependent Claim
134 words
The film of claim 22 wherein said sulfonic and sulfonylinc catalyst is represented by the formmulae: (R.sub.f SO.sub.3).sub.n R and (R.sub.f SO.sub.2)-Q-(SO.sub.2 R.sub.f ') wherein R is selected from hydrogen ammonium cation and metal cation and n is the valence of R, R f and R f ' are independently highly fluorinated aliphatic groups, and Q is selected from ##STR24## wherein R' is selected from hydrogen, chlorine, bromine, iodine, ammonium cation, or metal cation R" is selected from hydrogen, chlorine, bromine, iodine, R f SO 2 , alkenyl of 3 to 4 carbon atoms, alkyl of 1 to 20 carbon atoms, aryl of up to 20 carbon atoms, and alkaryl of up to 20 carbon atoms and R 3 is H, alkenyl of 3 to 4 carbons and aryl of up to 20 carbons.
Claim 28
Dependent Claim
165 words
The film of claim 22 wherein said catalyst is represented by the formulae: (R.sub.f SO.sub.2)Q(O.sub.2 SR.sub.f ') wherein R f and R f ' are independently a highly fluorinated aliphatic group, and Q is a divalent radical selected from -NH- and -CHR- wherein R is selected from Br, Cl, I, H, alkyl groups of 1 to 20 carbon atoms, alkenyl of 3 to 4 carbon atoms, aryl or aralkyl of up to 20 carbon atoms, or R'X, wherein R' is an alkylene group of up to 20 carbon atoms and X is Br, Cl, I, -O 2 SR f . -CH(O 2 SR f ) 2 , ##STR25## or -CY(COOR 2 ) 2 wherein R 4 is H or 1 to 8 alkyl and n is 0 to 8, and wherein R 2 is alkyl of 1 to 4 carbon atoms or phenylalkyl, the alkyl group of which has 1 to 4 carbon atoms, and Y is H, Br, Cl, I, or NO 2 .
Claim 29
Independent Claim
220 words
A method of forming an abrasion resistant coating on a substrate of from 0.1 to 500 microns thickness which comprises curing a composition comprising at least 15 percent by weight units derived from an epoxy-terminated silane represented by the formulae: ##STR26## wherein, each R is independently a non-hydrolyzable divalent hydrocarbon radical of less than 20 carbon atoms, or a divalent radical of less than 20 carbon atoms the backbone of which is C atoms which may be interrupted by individual atoms from the group of N and O, the O atoms in the form of ether linkages, m is 1, 2, or 3, n is 0, or 1, and R' is an aliphatic hydrocarbon radical of less than 10 carbon atoms, an acyl radical of less than 10 carbon atoms, or a radical of the formula (CH 2 CH 2 O) k Z in which k is an integer of at least 1, and Z is hydrogen or an aliphatic hydrocarbon radical of less than 10 carbon atoms, in catalytic proximity to a catalytically active amount of a highly fluorinated sulfonic catalyst comprising a highly fluorinated aliphatic sulfonic acid or salt thereof or highly fluorinated sulfonylic catalyst comprising two highly fluorinated aliphatic sulfonyl groups attached directly to an imide or a methylene and thereby bonding said composition to said substrate.
Claim 30
Independent Claim
220 words
A method of forming an abrasion resistant coating on a substrate of from 0.1 to 500 microns thickness which comprises curing a composition comprising at least 15 percent by weight units derived from an epoxy-terminated silane represented by the formulae: ##STR26## wherein, each R is independently a non-hydrolyzable divalent hydrocarbon radical of less than 20 carbon atoms, or a divalent radical of less than 20 carbon atoms the backbone of which is C atoms which may be interrupted by individual atoms from the group of N and O, the O atoms in the form of ether linkages, m is 1, 2, or 3, n is 0, or 1, and R' is an aliphatic hydrocarbon radical of less than 10 carbon atoms, an acyl radical of less than 10 carbon atoms, or a radical of the formula (CH 2 CH 2 O) k Z in which k is an integer of at least 1, and Z is hydrogen or an aliphatic hydrocarbon radical of less than 10 carbon atoms, in catalytic proximity to a catalytically active amount of a highly fluorinated sulfonic catalyst comprising a highly fluorinated aliphatic sulfonic acid or salt thereof or highly fluorinated sulfonylic catalyst comprising two highly fluorinated aliphatic sulfonyl groups attached directly to an imide or a methylene and thereby bonding said composition to said substrate.
Claim 31
Dependent Claim
20 words
The method of claim 27 wherein said bonding is effected by in situ cure of said composition upon said substrate.
Claim 32
Dependent Claim
19 words
The method of claim 27 wherein a primer is applied to said substrate prior to said in situ cure.
Claim 33
Dependent Claim
131 words
The method of claim 27 wherein said catalyst is represented by the formulae: (R.sub.f SO.sub.3).sub.n R and (R.sub.f SO.sub.2)-Q-(SO.sub.2 R.sub.f ') wherein R is selected from hydrogen ammonium cation and metal cation and n is the valence of R, R f and R f ' are independently highly fluorinated aliphatic groups, and Q is selected from ##STR27## wherein R' is selected from hydrogen, chlorine, bromine, iodine, ammonium cation, or metal cation R" is selected from hydrogen, chlorine, bromine, iodine, R f SO 2 , alkenyl of 3 to 4 carbon atoms, alkyl of 1 to 20 carbon atoms, aryl of up to 20 carbon atoms, and alkaryl of up to 20 carbon atoms and R 3 is H, alkenyl of 3 to 4 carbons and aryl of up to 20 carbons.
Claim 34
Dependent Claim
170 words
The method of claim 27 wherein the highly fluorinated aliphatic sulfonylic catalyst is represented by the formula: (R.sub.f SO.sub.2)Q(O.sub.2 SR.sub.f ') wherein R f and R f ' are independently a highly fluroinated aliphatic group, and Q is a divalent radical selected from -NH- and -CHR- wherein R is selected from Br, Cl, I, H, alkyl groups of 1 to 20 carbon atoms, alkenyl of 3 to 4 carbon atoms, aryl or aralkyl of up to 20 carbon atoms, or R'X, wherein R' is an alkylene group of up to 20 carbon atoms and X is H, Br, Cl, I, -O 2 SR f , -CH(O 2 SR f ) 2 , ##STR28## or -CY(COOR 2 ) 2 wherein R 4 is H or 1 to 8 alkyl and n is 0 to 8, and wherein R 2 is alkyl of 1 to 4 carbon atoms or phenylalkyl, the alkyl group of which has 1 to 4 carbon atoms, and Y is H, Br, Cl, I, or NO 2 .
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-09-19 | 1981-03-21 | 1981-09-20 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-09-19 | 1985-03-21 | 1985-09-20 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-09-19 | 1989-03-21 | 1989-09-20 | $7700.00 | Window Closed / Lapsed |