US4356233A
Expired / Lapsed
US
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Primed inorganic substrates overcoated with curable protective compositions
Assignee: 3M Co
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Filing: 1981-05-20
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Granted: 1982-10-26
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Expires: 2001-05-20
Abstract
Abstract Primer compositions for adhering overcoatings derived from in situ polymerizations of uncured monomers onto inorganic substrates are disclosed. These primer compositions comprise at least one non-amino- or non-amido-containing silane, at least one of certain metal esters, and preferably an acidic material. The overcoatings are derived from epoxy and vinyl monomers. The primed and overcoated substrates of the present invention provide articles having protective, decorative, or other functional surface layers.
Inventors
- 👤 Roger W. Lange
- 👤 Alek P. Szecsy
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-26 13:10
CPC Classifications
C; C09; C09D; C09D4/00; Y; Y10; Y10T; Y10T428/00; Y10T428/26; Y10T428/263; Y10T428/264; Y10T428/265; Y10T428/31504; Y10T428/31511; Y10T428/31551; Y10T428/31609; Y10T428/31612; Y10T428/31652; Y10T428/31663; Y10T428/31667
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
298 words
A layered structure comprising a. an inorganic substrate selected from metals, metal oxides, and ceramics, b. a primer composition having a thickness in the range of 0.02 to 0.5 microns, coated upon said substrate, said priming composition comprising: (1) one part by weight of a non-amino- or non-amido-containing silane of the formula: [R.sup.1 ].sub.m --Si--[R.sup.2 ].sub.n ( 1) in which R 1 is an alkyl or cycloalkyl group that can be unsubstituted or substituted by an ethenyl, methethenyl, acryloxy, methacryloxy, epoxy, mercapto, or an isocyanato group, said substituted group having a total of two to ten carbon atoms and said unsubstituted group having a total of one to eight carbon atoms; R 2 is a hydrolyzable group selected from alkoxy groups having one to eight carbon atoms, and acyloxy groups having two to eight carbon atoms; m is an integer from 1 to 3; n is an integer from 1 to 3, with the proviso that m+n=4; (2) 1 to 50 parts by weight of metal ester of the formula: M[OR.sup.3 ].sub.x ( 2) in which M is a metal selected from the group comprising titanium, tantalum, zirconium, aluminum, and antimony; R 3 is an alkyl group having from one to eight carbon atoms; and x is equal to the number of valence bonds of M, and (3) 0:1 to 10:1 moles by weight of an inorganic acidic material, or 0:1 to 20:1 moles by weight of an organic acidic material, compared to the total moles by weight of metal ester plus silane, (4) 50 to 99 weight percent of solvent consisting essentially of organic solvent compared to the total composition weight, and c. at least one layer of an overcoating composition polymerized in situ and comprising at least one organic monomer selected from epoxy and vinyl monomers.
Claim 2
Dependent Claim
298 words
A layered structure comprising a. an inorganic substrate selected from metals, metal oxides, and ceramics, b. a primer composition having a thickness in the range of 0.02 to 0.5 microns, coated upon said substrate, said priming composition comprising: (1) one part by weight of a non-amino- or non-amido-containing silane of the formula: [R.sup.1 ].sub.m --Si--[R.sup.2 ].sub.n ( 1) in which R 1 is an alkyl or cycloalkyl group that can be unsubstituted or substituted by an ethenyl, methethenyl, acryloxy, methacryloxy, epoxy, mercapto, or an isocyanato group, said substituted group having a total of two to ten carbon atoms and said unsubstituted group having a total of one to eight carbon atoms; R 2 is a hydrolyzable group selected from alkoxy groups having one to eight carbon atoms, and acyloxy groups having two to eight carbon atoms; m is an integer from 1 to 3; n is an integer from 1 to 3, with the proviso that m+n=4; (2) 1 to 50 parts by weight of metal ester of the formula: M[OR.sup.3 ].sub.x ( 2) in which M is a metal selected from the group comprising titanium, tantalum, zirconium, aluminum, and antimony; R 3 is an alkyl group having from one to eight carbon atoms; and x is equal to the number of valence bonds of M, and (3) 0:1 to 10:1 moles by weight of an inorganic acidic material, or 0:1 to 20:1 moles by weight of an organic acidic material, compared to the total moles by weight of metal ester plus silane, (4) 50 to 99 weight percent of solvent consisting essentially of organic solvent compared to the total composition weight, and c. at least one layer of an overcoating composition polymerized in situ and comprising at least one organic monomer selected from epoxy and vinyl monomers.
Claim 3
Dependent Claim
50 words
A layered structure according to claim 1 wherein said substrate is aluminum; in said silane: R 1 is gamma-methacryloxypropyl, R 2 is methoxy, m is equal to 1, n is equal to 3; in said metal ester M is titanium, R 3 is isopropyl, and x is equal to 4.
Claim 4
Dependent Claim
21 words
The layered structure according to claim 1 wherein said overcoating composition further comprises leveling agents, diluents, colorants, fillers, or viscosity modifiers.
Claim 5
Dependent Claim
26 words
The layered structure according to claim 1 wherein said metal ester and said silane are in a weight ratio in the range of 1:1 to 20:1.
Claim 6
Dependent Claim
26 words
The layered structure according to claim 1 wherein said metal ester and said silane are in a weight ratio in the range of 3:1 to 10:1.
Claim 7
Dependent Claim
28 words
The cured layered structure according to claim 1 wherein said primer composition is heat cured and said overcoating composition is cured by heat, ultraviolet radiation, or electron beam.
Claim 8
Dependent Claim
24 words
The layered structure according to claim 1 wherein said monomer is selected from bis(3,4-epoxycyclohexylmethyl) adipate, trimethylolpropane triacrylate, hexanediol diacrylate, pentaerythritol tetraacrylate, 1,3-bis[3-(2,2,2-triacryloxymethyl)ethoxy-2-hydroxy-propyl]-5,5-dimethyl-2,4-imidazolidinedione, and 1,3-bis[3-(2-acryloxyethoxy)-2-hydroxypropyl]-5,5-dimethyl-2,4-imidazolidinedione.
Claim 9
Dependent Claim
43 words
The layered structure according to claim 1 wherein said mole ratio of acidic material to metal ester plus silane is 0.5:1 to 4:1 moles by weight of an inorganic acidic material, or 0.5:1 to 8:1 moles by weight of an organic acidic material.
Claim 10
Dependent Claim
26 words
The layered structure according to claim 1 wherein said silane is selected from methyltriethoxysilane, octyltriethoxysilane, cyclohexyltrimethoxysilane, vinyltriacetoxysilane, methyl vinyldiethoxysilane, divinyldiethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, and gamma-isocyanatopropyltriethoxysilane.
Claim 11
Dependent Claim
12 words
The layered structure according to claim 9 wherein said silane is gamma-methacryloxypropyltrimethoxysilane.
Claim 12
Dependent Claim
30 words
The layered structure according to claim 1 wherein said metal ester is selected from tetraisopropyl titanate, tetrabutyl titanate, tetraethyl titanate, tetra-2-ethylhexyl titanate, pentaethyl tantalate, aluminum isopropoxide, aluminum-s-butoxide, and tetra-n-propyl zirconate.
Claim 13
Dependent Claim
14 words
The layered structure according to claim 11 wherein said metal ester is tetraisopropyl titanate.
Claim 14
Dependent Claim
23 words
The layered structure according to claim 1 wherein said inorganic substrate is selected from the group consisting of steel, zinc, aluminum, and ceramics.
Claim 15
Dependent Claim
12 words
The layered structure according to claim 13 wherein said substrate is aluminum.
Claim 16
Dependent Claim
13 words
The layered structure according to claim 1 wherein said primer composition is cured.
Claim 17
Dependent Claim
11 words
An article comprising the cured layered structure according to claim 15.
Claim 18
Dependent Claim
293 words
A layered structure comprising: a. an inorganic substrate selected from metals, metal oxides, and ceramics, b. a primer composition having a thickness in the range of 0.02 to 0.5 microns, coated upon said substrate, said priming composition comprising: (1) one part by weight of a non-amino- or non-amido-containing silane of the formula: [R.sup.1 ].sub.m --Si--[R.sup.2 ].sub.n ( 1) in which R 1 is an alkyl or cycloalkyl group that can be substituted by an acryloxy, methacryloxy, epoxy, mercapto, or an isocyanato group, said substituted group having a total of two to ten carbon atoms and said unsubstituted group having a total of one to eight carbon atoms; R 2 is a hydrolyzable group selected from alkoxy groups having one to eight carbon atoms, and acyloxy groups having two to eight carbon atoms; m is an interger from 1 to 3; n is an integer from 1 to 3, with the proviso that m+n=4; (2) 1 to 50 parts by weight of metal ester of the formula: M[OR.sup.3 ].sub.x ( 2) in which M is a metal selected from the group comprising titanium, tantalum, zirconium, aluminum, and antimony; R 3 is an alkyl group having from one to eight carbon atoms; and X is equal to the number of valence bonds of M; and (3) 0:1 to 10:1 moles by weight of an inorganic acidic material, or 0:1 to 20:1 moles by weight of an organic acidic material, compared to the total moles by weight of metal ester plus silane, (4) 50 to 99 weight percent of solvent consisting essentially of organic solvent compared to total composition weight, and c. at least one layer of an overcoating composition polymerized in situ and comprising at least one organic monomer selected from epoxy and vinyl monomers.
Claim 19
Dependent Claim
293 words
A layered structure comprising: a. an inorganic substrate selected from metals, metal oxides, and ceramics, b. a primer composition having a thickness in the range of 0.02 to 0.5 microns, coated upon said substrate, said priming composition comprising: (1) one part by weight of a non-amino- or non-amido-containing silane of the formula: [R.sup.1 ].sub.m --Si--[R.sup.2 ].sub.n ( 1) in which R 1 is an alkyl or cycloalkyl group that can be substituted by an acryloxy, methacryloxy, epoxy, mercapto, or an isocyanato group, said substituted group having a total of two to ten carbon atoms and said unsubstituted group having a total of one to eight carbon atoms; R 2 is a hydrolyzable group selected from alkoxy groups having one to eight carbon atoms, and acyloxy groups having two to eight carbon atoms; m is an interger from 1 to 3; n is an integer from 1 to 3, with the proviso that m+n=4; (2) 1 to 50 parts by weight of metal ester of the formula: M[OR.sup.3 ].sub.x ( 2) in which M is a metal selected from the group comprising titanium, tantalum, zirconium, aluminum, and antimony; R 3 is an alkyl group having from one to eight carbon atoms; and X is equal to the number of valence bonds of M; and (3) 0:1 to 10:1 moles by weight of an inorganic acidic material, or 0:1 to 20:1 moles by weight of an organic acidic material, compared to the total moles by weight of metal ester plus silane, (4) 50 to 99 weight percent of solvent consisting essentially of organic solvent compared to total composition weight, and c. at least one layer of an overcoating composition polymerized in situ and comprising at least one organic monomer selected from epoxy and vinyl monomers.
Claim 20
Dependent Claim
255 words
A primer composition useful for adhering epoxy and vinyl monomer compositions cured in situ onto inorganic substrates, comprising: a. one part by weight of a non-amino- or non-amido-containing silane of the formula: [R.sup.1 ].sub.m --Si--[R.sup.2 ].sub.n ( 1) in which R 1 is an alkyl or cycloalkyl group that can be unsubstituted or substituted by an ethenyl, methethenyl, acryloxy, methacryloxy, epoxy, mercapto, or an isocyanato group, said substituted group having a total of two to ten carbon atoms and said unsubstituted group having a total of one to eight carbon atoms; R 2 is a hydrolyzable group selected from alkoxy groups having one to eight carbon atoms and acyloxy groups having two to eight carbon atoms; m is an integer from 1 to 3; n is an integer from 1 to 3, with the proviso that m+n=4; b. 1 to 50 parts by weight of metal ester of the formula: M[OR.sup.3 ].sub.x ( 2) in which M is a metal selected from a group comprising titanium, tantalum, zirconium, aluminum, and antimony; R 3 is an alkyl group having from one to eight carbon atoms; and x is equal to the number of valence bonds of M, c. 0.5:1 to 4:1 moles by weight of an inorganic acidic material, or 0.5:1 to 8:1 moles by weight of an organic acidic material, compared to the total moles by weight of metal ester plus silane, and d. an amount of solvent consisting essentially of organic solvent sufficient to provide for blending of the components of said primer composition.
Claim 21
Dependent Claim
255 words
A primer composition useful for adhering epoxy and vinyl monomer compositions cured in situ onto inorganic substrates, comprising: a. one part by weight of a non-amino- or non-amido-containing silane of the formula: [R.sup.1 ].sub.m --Si--[R.sup.2 ].sub.n ( 1) in which R 1 is an alkyl or cycloalkyl group that can be unsubstituted or substituted by an ethenyl, methethenyl, acryloxy, methacryloxy, epoxy, mercapto, or an isocyanato group, said substituted group having a total of two to ten carbon atoms and said unsubstituted group having a total of one to eight carbon atoms; R 2 is a hydrolyzable group selected from alkoxy groups having one to eight carbon atoms and acyloxy groups having two to eight carbon atoms; m is an integer from 1 to 3; n is an integer from 1 to 3, with the proviso that m+n=4; b. 1 to 50 parts by weight of metal ester of the formula: M[OR.sup.3 ].sub.x ( 2) in which M is a metal selected from a group comprising titanium, tantalum, zirconium, aluminum, and antimony; R 3 is an alkyl group having from one to eight carbon atoms; and x is equal to the number of valence bonds of M, c. 0.5:1 to 4:1 moles by weight of an inorganic acidic material, or 0.5:1 to 8:1 moles by weight of an organic acidic material, compared to the total moles by weight of metal ester plus silane, and d. an amount of solvent consisting essentially of organic solvent sufficient to provide for blending of the components of said primer composition.
Claim 22
Dependent Claim
24 words
The primer composition according to claim 18 wherein said solvent is present in the range of 50 to 99 weight percent of the composition.
Claim 23
Dependent Claim
19 words
The primer composition according to claim 19 wherein said composition comprises at least 90 weight percent of said solvent.
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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) | 1985-10-25 | 1986-04-26 | 1986-10-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-10-25 | 1990-04-26 | 1990-10-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-10-25 | 1994-04-26 | 1994-10-26 | $7700.00 | Window Closed / Lapsed |