US3900689A
Expired / Lapsed
US
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Substrates treated with chromium(iii) complexes to increase the adhesion of organic polymers thereto
Assignee: EIDP Inc
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Filing: 1973-06-25
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Granted: 1975-08-19
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Expires: 1993-06-25
Abstract
Abstract Coordination complexes of chromium (III) and fumaric acid and certain substituted fumaric acids; the preparation of aqueous solutions of such complexes; and the use of such solutions for treating metal, metal oxide and glass substrates for the purpose of improving the bonding thereto of subsequently applied organic polymer adhesives. Preferred coordination compounds of fumaric acid have the approximate formulas (Cr(H2O)5(C4H3O4))aX2, (Cr(H2O)4(C4H2O4))aX, and (Cr2(H2O)10(C4H2O4))aX4, where X is a noncoordinated anion and a is its valence. The preferred anion is nitrate. Also a method for treating substrates to improve adhesion of polymers thereto, by contacting the substrate with an aqueous solution of fumaric acid or certain substituted fumaric acids and a Cr 3 salt which yields the Cr(H2O)6 3 ion, at 90*100*C. and a pH of 1.8-2.4.
Inventors
- 👤 Alden J Deyrup
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 05:05
CPC Classifications
C; C23; C23C; C23C22/00; C23C22/05; C23C22/06; C23C22/48; B; B05; B05D; B05D3/00; B05D3/10; B05D3/102; C01; C01G; C01G37/00; C07; C07C; C07C51/00; C07C51/41; C07C51/418; C07C57/00; C07C57/02; C07C57/13; C07C57/15; C07F; C07F11/00; C07F11/005; C23C2222/00; C23C2222/10; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31551; Y10T428/31645; Y10T428/31678; Y10T428/31692; Y10T428/31855; Y10T428/31909
Claims Analysis
Total Claims: 34
Claim 1
Independent Claim
68 words
The method of treating a metal, metal oxide or glass substrate to improve the subsequent bonding thereto of an organic polymer, said method comprising contacting said substrate with the aqueous solution of a composition comprising one or more water-soluble coordination complexes of (a) chromium (III) derived from a water-soluble salt thereof with a noncoordinated anion, which salt yields Cr(H2O)63 in water; with (b) a trans-acid of the formula
Claim 2
Independent Claim
68 words
The method of treating a metal, metal oxide or glass substrate to improve the subsequent bonding thereto of an organic polymer, said method comprising contacting said substrate with the aqueous solution of a composition comprising one or more water-soluble coordination complexes of (a) chromium (III) derived from a water-soluble salt thereof with a noncoordinated anion, which salt yields Cr(H2O)63 in water; with (b) a trans-acid of the formula
Claim 3
Dependent Claim
11 words
The method of claim 1 wherein said trans-acid is fumaric acid.
Claim 4
Dependent Claim
78 words
A method according to claim 1 wherein the aqueous solution contains one or more chromium (III)/fumaric acid coordination compounds selected from the group consisting of compounds of the approximate formulae: (Cr(H2O)5(C4H3O4))X2 (Type I), and (Cr2(H2O)10(C4H2O4))X4 (Type III), wherein X is the said noncoordinated anion, said aqueous solution having a pH of 0.2 to 4 and a concentration of said Type I or Type II compounds equivalent to about from 0.0005 to 0.5 gram atoms of chromium per liter.
Claim 5
Dependent Claim
16 words
A method according to claim 3 wherein the selected compound is that identified in Type I.
Claim 6
Dependent Claim
11 words
A method according to claim 3 wherein the substrate is glass.
Claim 7
Dependent Claim
43 words
The method of forming a composite article comprising a base metal, metal oxide or glass substrate having adhesively bonded thereto an organic polymer, said method comprising treating said substrate by the method of claim 1, and then applying said polymer to said substrate.
Claim 8
Dependent Claim
51 words
The method of claim 6, wherein the polymer that is applied to the substrate has dispersed therein 0.4 to 10% by weight of a finely divided alumina having a combined water content not exceeding about 9% by weight and a specific surface area of at least 5 square meters per gram.
Claim 9
Dependent Claim
63 words
The method of claim 6 wherein the substrate is from the group consisting of aluminum, iron, steel, stainless steel, copper, brass, titanium, magnesium, nickel, tin, tin plate, zinc, zinc plate, aluminum oxide, titanium oxide and glass; and the polymer is from the group consisting of polyethylene, polypropylene, ethylene/vinyl acetate copolymers, polyvinylidene fluoride, vinyl chloride/vinyl acetate copolymers, polycarbonates, polysulfones, polyamides, polyesters and butadiene/styrene copolymers.
Claim 10
Dependent Claim
10 words
The method of claim 6 wherein the substrate is glass.
Claim 11
Independent Claim
67 words
The method of treating a metal or metal oxide substrate to improve the subsequent bonding thereto of an organic polymer, said method comprising contacting said substrate with an aqueous solution of the composition comprising one or more water-soluble coordination complexes of (a) chromium (III) derived from a water-soluble salt thereof with a noncoordinated anion, which salt yields Cr(H2O)63 in water; with (b) a trans-acid of the formula
Claim 12
Independent Claim
67 words
The method of treating a metal or metal oxide substrate to improve the subsequent bonding thereto of an organic polymer, said method comprising contacting said substrate with an aqueous solution of the composition comprising one or more water-soluble coordination complexes of (a) chromium (III) derived from a water-soluble salt thereof with a noncoordinated anion, which salt yields Cr(H2O)63 in water; with (b) a trans-acid of the formula
Claim 13
Dependent Claim
69 words
A method according to claim 10 wherein the aqueous solution contains a chromium (III)/fumaric acid coordination compound of the approximate formula: (Cr(H2O)4(C4H2O4))X (Type II) wherein X is the said noncoordinated anion, said aqueous solution having a pH either in the range of 1 to 2.4 or in the range of 3.0 to 5.5 and a concentration equivalent to about from 0.0001 to 0.1 gram atom of chromium per liter.
Claim 14
Dependent Claim
42 words
The method of forming a composite article comprising a base metal or metal oxide substrate having adhesively bonded thereto an organic polymer, said method comprising treating said substrate by the method of claim 10, and then applying said polymer to said substrate.
Claim 15
Dependent Claim
51 words
The method of claim 12, wherein the polymer that is applied to the substrate has dispersed therein 0.4 to 10% by weight of a finely divided alumina having a combined water content not exceeding about 9% by weight and a specific surface area of at least 5 square meters per gram.
Claim 16
Dependent Claim
62 words
The method of claim 12 wherein the substrate is from the group consisting of aluminum, iron, steel, stainless steel, copper, brass, titanium, magnesium, nickel, tin, tin plate, zinc, zinc plate, aluminum oxide and titanium oxide; and the polymer is from the group consisting of polyethylene, polypropylene, ethylene/vinyl acetate copolymers, polyvinylidene fluoride, vinyl chloride/vinyl acetate copolymers, polycarbonates, polysulfones, polyamides, polyesters and butadiene/styrene copolymers.
Claim 17
Dependent Claim
59 words
A COMPOSITE ARTICLE COMPRISING A METAL OR METAL OXIDE OR GLASS SUBSTRATE HAVING BONDED THERETO AN ORGANIC POLYMER THROUGH A THIN LAYER OF THE COMPOSITION COMPRISING ONE OR MORE WATER-SOLUBLE COORDINATION COMPLEXES OF (A) CHROMIUM (III) DERIVED FROM A WATER-SOLUBLE SALT THEREOF WITH A NONCOORDINATED ANION, WHICH SALT YIELDS CR(H2O)6**3+ IN WATER, WITH (B) A TRANS-ACID OF THE FORMULA
Claim 18
Dependent Claim
59 words
A COMPOSITE ARTICLE COMPRISING A METAL OR METAL OXIDE OR GLASS SUBSTRATE HAVING BONDED THERETO AN ORGANIC POLYMER THROUGH A THIN LAYER OF THE COMPOSITION COMPRISING ONE OR MORE WATER-SOLUBLE COORDINATION COMPLEXES OF (A) CHROMIUM (III) DERIVED FROM A WATER-SOLUBLE SALT THEREOF WITH A NONCOORDINATED ANION, WHICH SALT YIELDS CR(H2O)6**3+ IN WATER, WITH (B) A TRANS-ACID OF THE FORMULA
Claim 19
Dependent Claim
45 words
A composite article according to claim 15 wherein the coordination complexes include one or more chromium (III)/fumaric acid coordination compounds selected from the group consisting of compounds of the approximate formulae: (Cr(H2O)5(C4H3O4))X2 (Type I), and (Cr2(H2O)10(C4H2O4))X4 (Type III) wherein X is the said noncoordinated anion.
Claim 20
Dependent Claim
16 words
A composite article of claim 16 wherein the selected compound is that identified as Type I.
Claim 21
Dependent Claim
13 words
A composite article of claim 16 wherein the organic polymer is polyvinyl butyral.
Claim 22
Dependent Claim
47 words
A composite article according to claim 16 wherein the polymer has dispersed therein 0.4 to 10% by weight of a finely divided alumina having a combined water content not exceeding about 9% by weight and a specific surface area of at least 5 square meters per gram.
Claim 23
Dependent Claim
65 words
A composite article according to claim 16 wherein the substrate is from the group consisting of aluminum, iron, steel, stainless steel, copper, brass, titanium, magnesium, nickel, tin, tin plate, zinc, zinc plate, aluminum oxide, titanium oxide and glass; and the polymer is from the group consisting of polyethylene, polypropylene, ethylene/vinyl acetate copolymers, polyvinylidene fluoride, vinyl chloride/vinyl acetate copolymers, polycarbonates, polysulfones, polyamides, polyesters and butadiene/styrene copolymers.
Claim 24
Dependent Claim
12 words
A composite article according to claim 20 wherein the substrate is glass.
Claim 25
Dependent Claim
40 words
A composite article according to claim 15 wherein the coordination complexes are present as an absorbed layer, and they include a chromium (III)/fumaric acid coordination compound of the approximate formula: (Cr(H2O)4(C4H2O4))X (Type II) wherein X is the said noncoordinated anion.
Claim 26
Dependent Claim
47 words
A composite article according to claim 22 wherein the polymer has dispersed therein 0.4 to 10% by weight of a finely divided alumina having a combined water content not exceeding about 9% by weight and a specific surface area of at least 5 square meters per gram.
Claim 27
Dependent Claim
64 words
A composite article according to claim 22 wherein the substrate is from the group consisting of aluminum, iron, steel, stainless steel, copper, brass, titanium, magnesium, nickel, tin, tin plate, zinc, zinc plate, aluminum oxide and titanium oxide; and the polymer is from the group consisting of polyethylene, polypropylene, ethylene/vinyl acetate copolymers, polyvinylidene fluoride, vinyl chloride/vinyl acetate copolymers, polycarbonates, polysulfones, polyamides, polyesters and butadiene/styrene copolymers.
Claim 28
Dependent Claim
13 words
A composite article of claim 15 wherein the organic polymer is polyvinyl butyral.
Claim 29
Independent Claim
90 words
A method of treating a metal or metal oxide substrate to improve the subsequent bonding thereto of an organic polymer, said method comprising contaCting said substrate, for a sufficient time to produce an improvement in adhesion, with an aqueous solution of (a) a trans-1,2-ethylene dicarboxylic acid having 4 to 10 carbon atoms and (b) a water soluble chromium (III) salt which gives Cr(H2O)6 3 in solution; said aqueous solution being held at a temperature in the range of about 90*-100*C. and having a pH in the range of about 1.8-2.4.
Claim 30
Independent Claim
90 words
A method of treating a metal or metal oxide substrate to improve the subsequent bonding thereto of an organic polymer, said method comprising contaCting said substrate, for a sufficient time to produce an improvement in adhesion, with an aqueous solution of (a) a trans-1,2-ethylene dicarboxylic acid having 4 to 10 carbon atoms and (b) a water soluble chromium (III) salt which gives Cr(H2O)6 3 in solution; said aqueous solution being held at a temperature in the range of about 90*-100*C. and having a pH in the range of about 1.8-2.4.
Claim 31
Dependent Claim
12 words
A method according to claim 26 wherein said acid is fumaric acid.
Claim 32
Dependent Claim
12 words
A method according to claim 26 wherein said acid is mesaconic acid.
Claim 33
Dependent Claim
20 words
A method according to claim 26 wherein said substrate is contacted with said solution for up to about 5 minutes.
Claim 34
Dependent Claim
16 words
A method according to claim 26 wherein said water-soluble chromium (III) salt is chromium (III) nitrate.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-08-18 | 1979-02-17 | 1979-08-19 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-08-18 | 1983-02-17 | 1983-08-19 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-08-18 | 1987-02-17 | 1987-08-19 | $7700.00 | Window Closed / Lapsed |