Source: https://patents.google.com/patent/US7294401?oq=flatulence
Timestamp: 2018-02-26 04:00:24
Document Index: 415758246

Matched Legal Cases: ['art 1', 'art 2', 'art 1', 'art 2', 'art 1', 'art 2', 'art 1', 'art 2', 'art 1', 'art 2', 'art 1', 'art 2', 'art 1', 'art 2', 'art 1', 'art 2', 'art 1', 'art 2', 'art 1', 'art 2', 'art 1', 'art 2', 'art 1', 'art 2', 'art 1', 'art 2', 'art 1', 'art 2']

US7294401B2 - Mar-resistant oligomeric-based coatings for glass-plastic glazing products - Google Patents
US7294401B2
US7294401B2 US10925842 US92584204A US7294401B2 US 7294401 B2 US7294401 B2 US 7294401B2 US 10925842 US10925842 US 10925842 US 92584204 A US92584204 A US 92584204A US 7294401 B2 US7294401 B2 US 7294401B2
US10925842
US20050077002A1 (en )
This invention is glass laminate article comprising a mar-resistant clearcoat. A laminate of the present invention resists scratches, and is easily repairable and even self-healable at temperatures above about 40° C.
In one aspect the present invention is a glass laminate article comprising: a clearcoat/polymer film bilayer wherein the clearcoat is a. scratch-resistant coating composition obtained from the combination of components (1) and (2), wherein component (1) comprises an oligomeric compound selected from the group consisting of oligomeric compounds having either hydroxyl functionality or anhydride functionality, and wherein component (2) is either an isocyanate oligomer or a compound having epoxy functionality.
The invention is also directed to a process for removing defects from the surface of a transparent laminate comprising the step: heating the defective surface of the laminate to at least 70° C., wherein the surface comprises a clearcoat obtained by combining two components, (1) and (2), at an equivalent ratio of at least 0.90 (component (1): component (2)) and wherein component (1) comprises an oligomer a compound selected from the group consisting of oligomeric compounds having either hydroxyl functionality or anhydride functionality, and wherein component (2) is either an isocyanate oligomer or a compound having epoxy functionality.
In one embodiment, the present invention is a glass laminate comprising a mar-resistant clearcoat. A glass laminate of the present invention comprises at least one layer of glass that is laminated to at least one layer of a thermoplastic polymer interlayer. The thermoplastic polymer interlayer can be any polymeric material that is known and used conventionally in the manufacture of glass laminates. For example, the thermoplastic polymer can be selected from (i) polyurethane (PU), (ii) polycarbonate (PC), (iii) polyvinylbutyral (PVB), (iv) polyesters such as polyethylene terephthalate (PET) or (v) an ethylene acid copolymer obtained from the copolymerization of ethylene with an α,β-unsaturated carboxylic acid, or a derivative thereof. A combination of various conventional interlayer materials can be used in the practice of the present invention. Preferably, the interlayer material is selected from PVB and an ethylene acid copolymer or a derivative thereof. Suitable acid derivatives useful in the practice of the present invention are known to those skilled in the art, and include esters, salts, anhydrides, amides, and the like. Acid copolymers can be fully or partially neutralized to the salt (or partial salt). Fully or partially neutralized acid copolymers are known conventionally as ionomers. Suitable copolymers can include an optional third monomeric constituent which can be an ester of an ethylenically unsaturated carboxylic acid. Suitable acid copolymers useful in the practice of the present invention can be purchased commercially from, for example, E.I. DuPont de Nemours & Company under the tradenames of Surlyn® and Nucrel®, for example.
Suitable isocyanate oligomers are, for example: the isocyanurate trimer of hexamethylene diisocyanate; DESMODUR® 3300 available from Bayer; Tolonate® HDT available from Rhodia; and the isocyanurate trimer of isophorone diamine, and the like.
Suitable anhydride oligomers are linear anhydrides having a structure defined by the general formula: R—CO—O—CO—(R′—CO—O—CO)n—R, wherein R is a monosubstituted hydrocarbon group having from 2 to 50 carbon atoms, R′ is a di-substituted hydrocarbon group having from 2 to 50 carbon atoms, the hydrocarbon R and R′ groups containing or not containing an ether linkage, urethane linkage, or ester linkage, and n is an integer from 1 to 500. Also suitable are anhydrides having a molecular weight of less than about 2000 comprising (1) a central moiety, and (2) greater than one non-cyclic anhydride moieties bonded to each central moiety. Anhydrides suitable for use as an anhydride (b) type anhydride can be obtained by reacting multifunctional alcohols such as pentaerythritol, hexanediol, trimethylol propane, and the like, with cyclic monomeric anhydrides such as hexahydrophthalic anhydride, methylhexalhydrophthalic anhydride, and the like, and further reacting the acid oligomers thus obtained with ketene.
Suitable epoxy oligomers are, for example, the diglycidyl ester of cyclohexane dicarboxylic acid such as Araldite®CY-184 from Ciba Geigy, and cycloaliphatic epoxies such as ERL®-4221, available from Union Carbide, and the like. In another embodiment, the present invention is a process for making a laminate comprising the step of preparing a clearcoat composition. A clearcoat of the present invention can be obtained by combining at least one oligomeric component (1) compound with at least one oligomeric component (2) compound. It is preferable that if component (1) is a hydroxyl-containing oligomer, that component (2) be an isocyanate-containing oligomer, and that if component (1) is an anhydride containing oligomer, that component (2) is an epoxide-containing oligomer. For example, at least one suitable hydroxyl-containing oligomer can be combined with at least one suitable isocyanate oligomer. The isocyanate and hydroxyl oligomers can be combined in a stoichiometric ratio that will result in all of the hydroxyl functionality present being reacted with the isocyanate functionality, that is, with a slight stoichiometric excess of isocyanate being present after all of the hydroxyl functionality has been reacted. Preferably, however, a stoichiometric excess of hydroxyl component is added such that some residual hydroxyl functionality remains after all of the isocyanate functionality is reacted. A molar equivalent, as used herein, is the number of moles of a reactant, such as component (1) required to completely react with one mole of the other reactant, for example component (2). The equivalent ratio is a ratio that can be easily determined by one of ordinary skill in the art by dividing the number of moles of a reactant actually present by the number of moles required for a complete reaction. The equivalent ratio of hydroxyl oligomer to isocyanate oligomer (HY:ISO) is greater than 0.60. Preferably the ratio is in the range of from about 0.70 to about 1.50, more preferably in the range of from about 0.80 to about 1.40; and most preferably in the range of from about 0.90 to about 1.35. In a particularly preferred embodiment, the equivalent ratio of the hydroxyl oligomer to the isocyanate oligomer is in the range of from about 1.10 to about 1.35 with the tetrahydroxyl oligomer. It has been found, surprisingly, that higher HY:ISO ratios result in faster healing of scratches and nicks, and at lower temperature. An anhydride oligomer is preferably combined with an epoxide-containing oligomer in a stoichiometric ratio such that an excess of epoxy remains after all of the anhydride is reacted. Preferably, the equivalent ratio of epoxy oligomer to anhydride is at least 0.70, and preferably from about 0.70 to about 1.40. More preferably the equivalent ratio of epoxide to anhydride is from about 0.90 to about 1.30, and most preferably from about 1.00 to about 1.25.
It is preferable that the clearcoat components (1) and (2) be combined just prior to being applied to the polymer film. Preferably components (1) and (2) are combined less than about 60 minutes prior to the application to the polymer film. After application of the clearcoat to the polymer film, the coating can be allowed to sit for a period, typically less than 30 minutes, at room temperature prior to being placed in a heated environment to cure the clearcoat. The coatings can be cured at a temperature of at least about 100° C., preferably above 120° C., and most preferably above about 125° C. but below about 150° C.
A laminate comprising the cured clearcoat can be obtained by laminating the coated polymer film to a suitable material as described herein. The lamination process used herein can be any that is known or conventional in the art. However, the preferred lamination process may depend on the specific details of the lamination, including the structure of the laminate and/or the materials used to build the laminate. For example, a laminate assembly can be constructed using suitable materials and placing them in the order desired in the assembly. Preferably in the practice of the present invention a glass coverplate is used to cover and protect the exposed surface of the clearcoat film. In some cases it can be desirable to place the assembly in bag, which is in turn placed into a vacuum chamber, remove as much air as possible from the bag and chamber, and then seal the bag while still under vacuum. A laminate assembly whether vacuum-bagged or not, can then heated in an oven set at 90-150° C. for at least about 20 minutes. The oven can be an autoclave, wherein the assembly can be subjected to temperatures above about 125° C. and pressures above about 12 atmospheres. The exact time can depend on the conditions employed, but the temperature and pressure are maintained at the desirable levels for at least about 9 minutes before cooling and depressurizing the autoclave.
A laminate of the present invention has excellent durability, impact resistance, toughness, and resistance by the interlayer to cuts, scratches, nicks, and the like. A laminate of the present invention that is scratched can be easily repaired by applying heat to the clearcoat layer of the laminate. A scratch produced on a coated laminate of the present invention can be removed (healed) by heating the scratched laminate to a temperature of at least about 30° for at least about 15 minutes. Preferably, the laminate surface is heated to a temperature of at least about 35° C. for at least about 30 minutes, and more preferably 40° C. for at least about 30 minutes. Even more preferably, a scratched laminate is heated to a temperature of at least about 60° C. for at least about 45 minutes. Most preferably, a scratched laminate can be healed by heating the laminate surface to a temperature of at least about 70° C. for at least about 60 minutes.
A coating formulation (A) was prepared by combining 71.1 wt % of Part 1 with 28.9 wt % of Part 2. Part 1 consists of: 56.87 wt % tetrahydroxyl oligomer (obtained as described in Procedure 1 of U.S. Pat. No. 6,376,596); 0.68 wt % of 10% BYK 301 in propylene glycol monomethyl ether acetate, available from Byk Chemie; 2.8 wt % of a mixture of 1% dibutyl tin dilaurate in methyl ethyl ketone; and 10.75 wt % butyl acetate. Part 2 is Tolonate® HDT LV, which is an isocyanurate trimer of hexamethylene diisocyanate available from Rhodia. Weight percentages are based on the total weight from the combination of Part 1 and Part 2.
A coating formulation (B) was prepared by combining 72.04 wt % of Part 1 with 27.96 wt % of Part 2. Part 1 consists of: 28.73 wt % tetrahydroxyl oligomer (obtained as described in Procedure 1 of U.S. Pat. No. 6,376,596B1); 29.09 wt % of dihydroxyl oligomer (obtained as described in Procedure 2 of U.S. Pat. No. 6,376,596B1); 0.68 wt % of 10% BYK 301 in propylene glycol monomethyl ether acetate, available from Byk Chemie; 2.77 wt % of a mixture of 1% dibutyl tin dilaurate in methyl ethyl ketone; and 10.77 wt % butyl acetate. Part 2 is Tolonate® HDT LV, which is an isocyanurate trimer of hexamethylene diisocyanate available from Rhodia. Weight percentages are based on the total weight from the combination of Part 1 and Part 2. Part 1 and Part 2 are mixed just prior to application to substrate surface.
A coating formulation (D) was prepared by combining 65.79 wt % of Part 1 with 34.21 wt % of Part 2. Part 1 consists of: 26.17 wt % anhydride resin with pendant groups (as described in Example 1A of U.S. Pat. No. 5,827,910); 24.53 wt % of linear anhydride (as described in Example 1B of U.S. Pat. No. 5,827,910); 1.23 wt % of 10% BYK 301 in propylene glycol monomethyl ether acetate, available from Byk Chemie; 1.23 wt % of a mixture of 25% tetrabutyl phosphonium chloride in propylene glycol monomethyl ether acetate; 1.45 wt % of a mixture of 25% Niax A-99 (a tertiary amine available from Union Carbide) in methyl ethyl ketone; and 7.86 wt % butyl acetate. Part 2 is diglycidyl ester of 1,2-cyclohexane dicarboxylic acid available from Ciba-Geigy as Araldite®CY-184. Weight percentages are based on the total weight from the combination of Part 1 and Part 2. Part 1 and Part 2 are mixed just prior to application to substrate surface.
A glass laminate assembly is constructed as follows: glass/PVB/PET/clearcoat/coverplate. The coverplate can be any rigid material, but is generally float glass. While any surface pattern on the coverplate can be used, for optical applications a smooth surface is desirable. The multilayer construction can be laminated according to conventional techniques. The assemblies described herein are vacuum bagged according to the following procedure. A laminate construction is placed in a plastic bag, which is then placed into a vacuum chamber, which is evacuated to remove air, and thermally sealed while still under vacuum. The vacuum-bagged construction is placed in an autoclave and subjected to a pressure of about 17 atmospheres, and a temperature of about 125° C. to about 150° C. for 30 minutes. The chamber is depressurized and cooled. The laminate is removed from the bag and the coverplate is removed.
The cured coated films of Examples 9-14 were laminated to glass in an autoclave using the lamination procedure of Example 15, at an autoclave temperature of 140° C. Glass coverplates were used, the coverplates were washed with water containing 350 parts per million (ppm) MgSO4 before use to prevent sticking between the coverplate and the clearcoat. The laminates obtained were optically flat and smooth, and the coverplates easily removed.
Scratch behavior for each sample tested was determined using a Taber Shear/Scratch Tester, Model 502, fitted with a diamond stylus lapped to a 90° included angle with a 0.003-inch radius tip. The stylus was positioned on the arm of the tester at an angle of 90° to the surface of the coated film being tested. The coated film sample was positioned horizontally on the disc of the tester with the coated side facing upward to receive the stylus. A given weight was applied to the arm by sliding the weight to a marked position along the arm, The arm with stylus was lowered into contact with the coated film and the disc with attached coated film was rotated at a speed of 0.5 inches/second. The stylus path was then inspected for any scratch, and any visible scratch measured for width. This process was repeated using different weights on the stylus arm. After the degree of visibility and actual scratch width are recorded, the sample was heated in an oven held at 70° C. for 30 minutes to determine the affect on scratch visibility and width. The results for Examples 4-8 are shown in Table 1.
ness Scratch Scratch Scratch Scratch Scratch
Exam- (mi- Widtha Widthb Widthc Widthd Widthe
ple crons) State1 (mm) (mm) (mm) (mm) (mm)
Coating Hazea (%)
Coating adhesion was determined according to ASTM D3359-87 Tape Test usiing PERMACEL™ tape having a peel strength against a stainless steel of 40 ounces per inch. The adhesion was measured before and after immersion in boiling water for 2 hours and for 6 hours. The results of the adhesion test are given in Table 4.
Coating formulations were prepared by combining Part 1 with Part 2 in various ratios, such that the equivalent ratio of hydroxyl to isocyanate was varied as indicated in Table 5. Part 1 consists of: 56.87 wt % tetrahydroxyl oligomer; 0.68 wt % of 10% BYK 301 in propylene glycol monomethyl ether acetate, available from Byk Chemie; 2.8 wt % of a mixture of 1% dibutyl tin dilaurate in methyl ethyl ketone; and 10.75 wt % butyl acetate. Part 2 is Tolonate® HDT LV, which is an isocyanurate trimer of hexamethylene diisocyanate available from Rhodia. Weight percentages are based on the total weight from the combination of Part 1 and Part 2.
PET clearcoated films were obtained by coating the above coating compositions at a thickness 7 mil onto PET film. Laminates were made according to the procedure of Example 15 and were evaluated for optical properties and performance after autoclaving. The laminates did not change color, remained clear and free of haze, conformed perfectly to the coverplate to yield an optically flat surface, and release readily from the coverplate with no tendency to stick. The results are tabulated in Table 6.
Example (%) (%) Clarity (%) 20° Gloss YID Color
Stylus Load Scratch Visibility After heating for 1 hour at:
20° Gloss Cross
Example Haze (%) control exposed hatch unscribed x-scribed
A clear 7 mil flame treated PET film was coated on one side with a water solution of an ELVANOL® PVA formulation to serve as a water-activated adhesive, and was coated on the other side with the oligomeric clearcoat described in Examples 34 (B1) to serve as a scratch resistant healable coating. The film was bonded to glass by wetting the glass and/or the film on the adhesive coated side followed by pressing the wetted film to the glass using a rubber roller or “squeegee” to remove all excess water. The glass and film bonded structure was then allowed to dry at room temperature until the adhesive was dry, that is until the moisture diffused through the PET film and the adhesive layer was “set” and the film was firmly adhered to the glass.
A 7 mil clear CRONAR® PET film, flame treated on both sides, was coated on one side with a 15% water solution containing ELVANOL® type 51-05 powder using a #28 wire-wound coating rod. The coating was allowed to dry at room temperature before coating the opposite side with the clearcoat formulation described in Examples 34 (B1). The formulation was applied coated using a # 28 wire-wound coating rod. The coating was allowed to flash off solvent at room temperature and then allowed to sit at room temperature for 24 hours before the application of the clearcoated PET film to the glass (see “Glass Application Procedure”, Example 39 below).
A 7 mil clear CRONAR® PET film, flame treated on both sides, was coated on one side with a 15% water solution containing ELVANOL® type 51-05 powder using a #28 wire-wound coating rod. The coating was allowed to dry at room temperature before coating the opposite side with the clearcoat formulation described in Examples 35 (B2). The formulation was applied coated using a # 28 wire-wound coating rod. The coating was allowed to flash off solvent at room temperature and then allowed to sit at room temperature for 24 hours before the application of the clearcoated PET film to the glass (see “Glass Application Procedure”, Example 40 below).
Example Haze (%) (%) (%) YID
After 18 As After 18
Example Load (grams) As Scratched hrs (rt) Scratched hrs (rt)
17. The glass laminate of claim 15, wherein the anhydride-containing oligomer have a structure defined by the general formula: R—CO—O—CO—(R ′—CO—O—CO)n-R, wherein R is a monosubstituted hydrocarbon group having from 2 to 50 carbon atoms, R′ is a di-substituted hydrocarbon group having from 2 to 50 carbon atoms, the hydrocarbon R and R′ groups containing or not containing an ether linkage, urethane linkage, or ester linkage, andn is an integer from 1 to 500.
US10925842 2003-09-02 2004-08-25 Mar-resistant oligomeric-based coatings for glass-plastic glazing products Expired - Fee Related US7294401B2 (en)
US49994903 true 2003-09-02 2003-09-02
US10925842 US7294401B2 (en) 2003-09-02 2004-08-25 Mar-resistant oligomeric-based coatings for glass-plastic glazing products
US11709579 US20070160852A1 (en) 2003-09-02 2007-02-22 Process of making mar-resistant oligomeric-based coatings for glass-plastic glazing products
US11709629 US20070144654A1 (en) 2003-09-02 2007-02-22 Process for removing defects from glass laminates
US11709640 US7435481B2 (en) 2003-09-02 2007-02-22 Mar-resistant glass-plastic glazing products
US11709579 Division US20070160852A1 (en) 2003-09-02 2007-02-22 Process of making mar-resistant oligomeric-based coatings for glass-plastic glazing products
US11709640 Division US7435481B2 (en) 2003-09-02 2007-02-22 Mar-resistant glass-plastic glazing products
US20050077002A1 true US20050077002A1 (en) 2005-04-14
US7294401B2 true US7294401B2 (en) 2007-11-13
ID=34434827
US10925842 Expired - Fee Related US7294401B2 (en) 2003-09-02 2004-08-25 Mar-resistant oligomeric-based coatings for glass-plastic glazing products
US11709629 Abandoned US20070144654A1 (en) 2003-09-02 2007-02-22 Process for removing defects from glass laminates
US11709640 Expired - Fee Related US7435481B2 (en) 2003-09-02 2007-02-22 Mar-resistant glass-plastic glazing products
US11709579 Abandoned US20070160852A1 (en) 2003-09-02 2007-02-22 Process of making mar-resistant oligomeric-based coatings for glass-plastic glazing products
US (4) US7294401B2 (en)
JP (1) JP2007504024A (en)
CN (1) CN1878669A (en)
CA (1) CA2537030A1 (en)
EP (1) EP1660322A2 (en)
WO (1) WO2005035241A3 (en)
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EP1660322A2 (en) 2006-05-31 application
US20070154723A1 (en) 2007-07-05 application
WO2005035241A3 (en) 2005-06-23 application
US7435481B2 (en) 2008-10-14 grant
US20070160852A1 (en) 2007-07-12 application
WO2005035241A2 (en) 2005-04-21 application
JP2007504024A (en) 2007-03-01 application
CN1878669A (en) 2006-12-13 application
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ANDERSON, JERREL C.;BARSOTTI, ROBERT J.;REEL/FRAME:015470/0004;SIGNING DATES FROM 20041025 TO 20041122