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HK1113933A - Coating compositions, articles, and methods of coating articles - Google Patents

Coating compositions, articles, and methods of coating articles Download PDF

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Publication number
HK1113933A
HK1113933A HK08103105.8A HK08103105A HK1113933A HK 1113933 A HK1113933 A HK 1113933A HK 08103105 A HK08103105 A HK 08103105A HK 1113933 A HK1113933 A HK 1113933A
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HK
Hong Kong
Prior art keywords
coating
multifunctional
composition
substrate
multifunctional crosslinker
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Application number
HK08103105.8A
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Chinese (zh)
Inventor
Andreas Schneider
Ren-Zhi Jin
Original Assignee
Sdc Coatings, Inc.
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Application filed by Sdc Coatings, Inc. filed Critical Sdc Coatings, Inc.
Publication of HK1113933A publication Critical patent/HK1113933A/en

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Description

Coating composition, article and method of coating an article
Cross Reference to Related Applications
This application claims priority and any other benefit from U.S. provisional application serial No. 60/618,014, filed on 12/10/2004, which is incorporated herein by reference in its entirety.
Technical Field
The present invention relates to coating compositions, articles, and methods of coating articles. More particularly, the present invention relates to stable coating compositions that provide abrasion resistant formable coatings when cured on a substrate.
Background
The glazing may be replaced by a transparent material (e.g. plastic) which does not crack or is more resistant to cracking than glass. Transparent materials made of synthetic organic polymers, for example, are used in public transportation vehicles, such as trains, buses, taxis and airplanes. Transparent plastics resistant to cracking can also be used for lenses for spectacles and other optical instruments and for glass of large buildings. In addition, the lightweight of these plastics compared to glass is another advantage, particularly in the transportation industry where the weight of the vehicle is a major factor in fuel economy.
While the main advantages of transparent plastics are resistance to breakage, lighter weight than glass, and flexibility of design, a serious disadvantage is that these plastics are susceptible to scratching and marring due to daily contact with abrasive materials such as dust or cleaning equipment. Scratches lead to reduced visibility and poor appearance, and often require replacement of glass or lenses, etc.
In order to improve the abrasion resistance of plastics, scratch-resistant coatings have been developed. The main disadvantage of these wear resistant compositions is that they cannot be shaped after curing. Poor formability means that bending or handling of the coated article often results in cracking or crazing of the coating. Therefore, the article must be coated after molding, a time delay may be caused, and the uncoated article inevitably wears in transportation. Thus, there remains a need in the art for coatings having good abrasion resistance and formability.
Summary of The Invention
Embodiments of the present invention provide compositions that, when applied to a substrate and cured, provide an abrasion resistant formable coating on the substrate. The composition may comprise an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of at least one of an epoxy-functional silane and a diol-functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein the molar ratio of the at least one of the epoxy-functional silane and the diol-functional organopolysiloxane to the multifunctional crosslinker is from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the epoxy functional silane, the diol functional organopolysiloxane, and the silylated multifunctional crosslinker.
In one embodiment, the molar ratio of the at least one of the epoxy-functional silane and the diol-functional organopolysiloxane to the multifunctional crosslinker is from about 2: 1 to 1: 2. In another embodiment, a coating having a radius of about 1 inch to less than about 10 inches may be formed on a polycarbonate substrate. In another embodiment, a coating having a radius of about 3 inches to about 5 inches may be formed on a polycarbonate substrate.
In another embodiment, the coating has a taber value of less than about 10% after 50 revolutions of the taber wheel or less than about 2% after 50 revolutions of the taber wheel. In another embodiment, the coating has a taber value of less than about 45% after 200 revolutions of the taber wheel or less than about 15% after 200 revolutions of the taber wheel.
In one embodiment, the at least one of an epoxy functional silane and a diol functional organopolysiloxane is present in an amount of about 5 to about 93 percent by weight of the solids of the composition and the multifunctional crosslinker is present in an amount of about 7 to about 95 percent by weight of the solids of the composition. In another embodiment, the at least one of the epoxy functional silane and the diol functional silane is from about 30 to about 70 percent by weight of the solids of the composition and the multifunctional crosslinker is from about 30 to about 70 percent by weight of the solids of the composition. In another embodiment, the solvent component of the water-organic solvent mixture is from about 40 to about 98 percent by weight of the composition. In yet another embodiment, the solvent component of the water-organic solvent mixture is from about 65 to about 95% by weight of the composition.
In one embodiment, the solvent component of the aqueous-organic solvent mixture is selected from the group consisting of ethers, glycol or glycol ethers, ketones, esters, glycol ether acetates, and combinations thereof. In another embodiment, the solvent component of the aqueous-organic solvent mixture is selected from alcohols having the formula ROH, wherein R is an alkyl group containing from 1 to about 10 carbon atoms. In another embodiment, the solvent component of the aqueous-organic solvent mixture is selected from the group consisting of those having the formula R1-(OR2)x-OR1In which x is 0, 1, 2, 3 or 4, R1Is hydrogen or alkyl containing 1 to about 10 carbon atoms, R2Alkylene groups containing from 1 to about 10 carbon atoms and combinations thereof.
In one embodiment, the epoxy functional silane is of the formula R3 xSi(OR4)4-xIs shown, in which: x is an integer 1, 2 or 3; r3Is H, an alkyl group containing from 1 to about 10 carbon atoms and having at least one epoxy functional group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether, and combinations thereof; r4Is H, alkyl containing 1 to about 5 carbon atoms, acetyl, -Si (OR)5)3-yR6 yGroups and combinations thereof, wherein y is an integer of 0, 1, 2 or 3; r5Is H, alkyl containing 1 to about 5 carbon atoms, acetyl OR another-Si (OR)5)3-yR6 yGroups and combinations thereof; r6Is H, an alkyl group containing from 1 to about 10 carbon atoms, a functionalized alkyl group, an alkylene group, an aromatic hydrocarbonAlkyl ethers, and combinations thereof.
In one embodiment, the water-organic solvent mixture further comprises a leveling agent in an amount effective to spread the water-organic solvent mixture over the substrate to substantially uniformly contact the water-organic solvent mixture with the substrate, and in another embodiment, the composition further comprises at least one catalyst, at least one ultraviolet stabilizer, or at least one surfactant and combinations thereof.
Other embodiments of the present invention provide compositions that, when applied to a substrate and cured, provide an abrasion resistant formable coating on the substrate. The composition may comprise an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the molar ratio of the diol functional organopolysiloxane to the multifunctional crosslinker is from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the diol functional organopolysiloxane and the silylated multifunctional crosslinker. In one embodiment, the aqueous-organic solvent mixture further comprises hydrolysis products and partial condensates of the epoxy functional silane and at least one multifunctional crosslinker.
Other embodiments of the present invention provide compositions that, when applied to a substrate and cured, provide an abrasion resistant formable coating on the substrate. The composition may comprise an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the at least one epoxy functional silane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker, wherein the composition comprises at least one of a tetrafunctional silane, a disilane, and an alkylsilane in an amount insufficient to impart rigidity to the coating on the substrate. In one embodiment, the aqueous-organic solvent mixture further comprises hydrolysis products and partial condensates of the diol-functional organopolysiloxane and the multifunctional crosslinker.
Embodiments of the present invention provide compositions that, when applied to a substrate and cured, provide an abrasion resistant formable coating on the substrate. The composition may comprise an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the epoxy functional silane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to about 1: 10; water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker; and at least one of a tetrafunctional silane and a disilane, wherein the epoxy functional silane is present in a molar ratio to the at least one of the tetrafunctional silane and the disilane of at least about 5.5: 1. In one embodiment, the aqueous-organic solvent mixture further comprises hydrolysis products and partial condensates of the diol-functional organopolysiloxane and the multifunctional crosslinker.
In another embodiment, the tetrafunctional silane has the formula Si (OR)9)4Wherein R is9Is H, alkyl containing 1 to about 5 carbon atoms and ethers thereof, (OR)9) Carboxylic acid group (carboxylate), -Si (OR)10)3Group (wherein R10Is H, alkyl containing 1 to about 5 carbon atoms and ethers thereof, (OR)10) Carboxylic acid group OR another-Si (OR)10)3Groups) and combinations thereof. In another embodiment, the disilane has the formula (R)11O)xR12 3-xSi-R13 y-SiR14 3-x(OR15)x(ii) a Wherein x is 0, 1, 2 or 3 and y is 0 or 1; wherein R is12And R14Including H, alkyl groups containing from about 1 to about 10 carbon atoms, functionalized alkyl groups, alkylene groups, aryl groups, alkyl polyether groups, and combinations thereof; wherein R is11And R15Comprises H, containsAlkyl groups of from about 1 to about 10 carbon atoms, acetyl groups, and combinations thereof; wherein if y is 1, then R13Including alkylene groups containing from about 1 to about 12 carbon atoms, alkylene polyethers (alkylene polyethers) containing from about 1 to about 12 carbon atoms, aryl groups, alkylene substituted aryl groups, alkylene groups which may contain one or more olefinic bonds, S or O; wherein if x is 0, then R12And R14Including Cl or Br; and wherein if y is 0, then a direct Si-Si bond is present.
Embodiments of the present invention provide compositions that, when applied to a substrate and cured, provide an abrasion resistant formable coating on the substrate. The composition may comprise an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the epoxy functional silane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to about 1: 10; water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker; and at least one alkylsilane, wherein the molar ratio of said epoxy functional silane to said at least one alkylsilane is at least about 2.5: 1.
In one embodiment, the aqueous-organic solvent mixture further comprises hydrolysis products and partial condensates of the diol-functional organopolysiloxane and the multifunctional crosslinker. In another embodiment, the alkylsilane has the formula R16 xSi(OR17)4-xWherein x is the number 1, 2 or 3; r16Is H or an alkyl group containing from 1 to about 10 carbon atoms, a functionalized alkyl group, an alkylene group, an aryl group, an alkoxy polyether (alkoxypropylolether) group, and combinations thereof; r17Is H, alkyl containing 1 to about 10 carbon atoms, acetyl; and combinations thereof.
Other embodiments of the present invention provide compositions that, when applied to a substrate and cured, provide an abrasion resistant and formable coating on the substrate. The composition may comprise an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of at least one epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the at least one epoxy functional silane and the multifunctional crosslinker are present in a molar ratio of from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker, wherein the composition does not comprise tetrafunctional silanes, disilanes, and alkylsilanes. In one embodiment, the aqueous-organic solvent mixture further comprises hydrolysis products and partial condensates of the diol-functional organopolysiloxane and the multifunctional crosslinker.
Embodiments of the present invention provide articles of manufacture. The article may comprise a substrate and an abrasion resistant formable coating present on at least one surface of the substrate by curing a coating composition comprising: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of at least one of an epoxy functional silane and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein the at least one of the epoxy functional silane and the diol functional organopolysiloxane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the epoxy functional silane, the diol functional organopolysiloxane, and the silylated multifunctional crosslinker. In one embodiment, at least one primer is disposed on at least one surface of the substrate between the substrate and the coating.
Other embodiments of the present invention provide articles of manufacture. The article may comprise a substrate and an abrasion resistant formable coating present on at least one surface of the substrate by curing a coating composition comprising: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the at least one diol functional organopolysiloxane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the diol functional organopolysiloxane and the silylated multifunctional crosslinker.
Other embodiments of the present invention provide articles of manufacture. The article may comprise a substrate and an abrasion resistant formable coating present on at least one surface of the substrate by curing a coating composition comprising: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the at least one epoxy functional silane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker, wherein the composition comprises at least one of a tetrafunctional silane, a disilane, and an alkylsilane in an amount insufficient to impart rigidity to the coating on the substrate.
Embodiments of the present invention provide articles of manufacture. The article may comprise a substrate and an abrasion resistant formable coating present on at least one surface of the substrate by curing a coating composition comprising: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the epoxy functional silane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to about 1: 10; water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker; and at least one of a tetrafunctional silane and a disilane, wherein the epoxy functional silane is present in a molar ratio to the at least one of the tetrafunctional silane and the disilane of at least about 5.5: 1.
Other embodiments of the present invention provide articles of manufacture. The article may comprise a substrate and an abrasion resistant formable coating present on at least one surface of the substrate by curing a coating composition comprising: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the epoxy functional silane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to about 1: 10; water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker; and at least one alkylsilane, wherein the molar ratio of said epoxy functional silane to said at least one alkylsilane is at least about 2.5: 1.
Embodiments of the present invention provide articles of manufacture. The article may comprise a substrate and an abrasion resistant formable coating present on at least one surface of the substrate by curing a coating composition comprising: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of at least one epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the at least one epoxy functional silane and the multifunctional crosslinker are present in a molar ratio of from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker, wherein the composition does not comprise tetrafunctional silanes, disilanes, and alkylsilanes.
Embodiments of the present invention provide shaped articles. The article may comprise a shaped substrate and an abrasion resistant formable coating present on at least one surface of the substrate by applying a coating composition, curing the coating composition, and subsequently shaping the substrate, wherein the coating composition comprises: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of at least one of an epoxy functional silane and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein the at least one of the epoxy functional silane and the diol functional organopolysiloxane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the epoxy functional silane, the diol functional organopolysiloxane, and the silylated multifunctional crosslinker. In one embodiment, the shaped article further comprises at least one primer disposed on at least one surface of the substrate between the substrate and the coating.
Other embodiments of the present invention provide shaped articles. The shaped article may comprise a shaped substrate and an abrasion resistant formable coating present on at least one surface of the substrate by applying a coating composition, curing the coating composition, and subsequently shaping the substrate, wherein the coating composition comprises: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the at least one diol functional organopolysiloxane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the diol functional organopolysiloxane and the silylated multifunctional crosslinker.
Other embodiments of the present invention provide shaped articles. The shaped article may comprise a shaped substrate and an abrasion resistant formable coating present on at least one surface of the substrate by applying a coating composition, curing the coating composition, and subsequently shaping the substrate, wherein the coating composition comprises: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the at least one epoxy functional silane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker, wherein the composition comprises at least one of a tetrafunctional silane, a disilane, and an alkylsilane in an amount insufficient to impart rigidity to the coating on the substrate.
Embodiments of the present invention provide shaped articles. The article may comprise a shaped substrate and an abrasion resistant formable coating present on at least one surface of the substrate by applying a coating composition, curing the coating composition, and subsequently shaping the substrate, wherein the coating composition comprises: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the epoxy functional silane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to about 1: 10; water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker; and at least one of a tetrafunctional silane and a disilane, wherein the epoxy functional silane is present in a molar ratio to the at least one of the tetrafunctional silane and the disilane of at least about 5.5: 1.
Other embodiments of the present invention provide shaped articles. The shaped article comprises a shaped substrate and an abrasion resistant formable coating present on at least one surface of the substrate by applying a coating composition, curing the coating composition, and subsequently shaping the substrate, wherein the coating composition comprises: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the epoxy functional silane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to about 1: 10; water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker; and at least one alkylsilane, wherein the molar ratio of said epoxy functional silane to said at least one alkylsilane is at least about 2.5: 1.
Embodiments of the present invention provide shaped articles. The shaped article may comprise a shaped substrate and an abrasion resistant formable coating present on at least one surface of the substrate by applying a coating composition, curing the coating composition, and subsequently shaping the substrate, wherein the coating composition comprises: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of at least one epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the at least one epoxy functional silane and the multifunctional crosslinker are present in a molar ratio of from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker, wherein the composition does not comprise tetrafunctional silanes, disilanes, and alkylsilanes.
Embodiments of the present invention provide methods of providing abrasion resistant formable coatings. The method can include applying a coating composition to a substrate; subsequently curing the coating composition, wherein the coating composition comprises: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of at least one of an epoxy functional silane and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein the at least one of the epoxy functional silane and the diol functional organopolysiloxane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the epoxy functional silane, the diol functional organopolysiloxane, and the silylated multifunctional crosslinker. In one embodiment, the method further comprises the step of shaping the coated substrate. In another embodiment, the method further comprises applying a primer to the substrate, followed by applying the coating composition to the substrate over the primer.
Embodiments of the present invention provide methods of providing abrasion resistant formable coatings. The method includes applying a coating composition to a substrate; subsequently curing the coating composition, wherein the coating composition comprises: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the at least one diol functional organopolysiloxane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the diol functional organopolysiloxane and the silylated multifunctional crosslinker.
Embodiments of the present invention provide methods of providing abrasion resistant formable coatings. The method can include applying a coating composition to a substrate; subsequently curing the coating composition, wherein the coating composition comprises: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the at least one epoxy functional silane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker, wherein the composition comprises at least one of a tetrafunctional silane, a disilane, and an alkylsilane in an amount insufficient to impart rigidity to the coating on the substrate.
Embodiments of the present invention provide methods of providing abrasion resistant formable coatings. The method includes applying a coating composition to a substrate; subsequently curing the coating composition, wherein the coating composition comprises: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the epoxy functional silane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to about 1: 10; water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker; and at least one of a tetrafunctional silane and a disilane, wherein the epoxy functional silane is present in a molar ratio to the at least one of the tetrafunctional silane and the disilane of at least about 5.5: 1.
Embodiments of the present invention provide methods of providing abrasion resistant formable coatings. The method includes applying a coating composition to a substrate; subsequently curing the coating composition, wherein the coating composition comprises: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the epoxy functional silane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to about 1: 0; water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker; and at least one alkylsilane, wherein the molar ratio of said epoxy functional silane to said at least one alkylsilane is at least about 2.5: 1.
Embodiments of the present invention provide methods of providing abrasion resistant formable coatings. The method includes applying a coating composition to a substrate; subsequently curing the coating composition, wherein the coating composition comprises: an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of at least one epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the at least one epoxy functional silane and the multifunctional crosslinker are present in a molar ratio of from about 10: 1 to 1: 10; and water in an amount sufficient to hydrolyze the epoxy functional silane and the silylated multifunctional crosslinker, wherein the composition does not comprise tetrafunctional silanes, disilanes, and alkylsilanes.
It will be understood that various changes may be made without departing from the scope of the invention and are not to be considered limited to what is described in the specification.
Detailed description of embodiments of the invention
The invention will now be described with occasional reference to specific embodiments thereof. This invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety.
Unless otherwise indicated, all numbers expressing quantities of ingredients, properties (e.g., molecular weights), reaction conditions, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated otherwise, the numerical properties set forth in the following specification and claims are approximations that may vary depending upon the desired properties to be obtained in the embodiments of the present invention. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. However, any numerical value itself may have errors due to errors in the corresponding measurement method.
The present invention relates to stable coating compositions that, when applied to a variety of substrates and cured, form abrasion resistant formable coatings. For the purposes of defining and describing the present invention, the term "stable" is understood to mean that the coating composition is suitable for a particular use over a period of time. Furthermore, the present invention relates to a coated article, a shaped coated article and a method of shaping a coated article. The coated article may be formed in any suitable manner. For example, the coated article may be thermoformed. "thermoforming" is a term well known in the plastics art to describe the process of shaping a thermoplastic sheet by heating it until softened and then forming the softened sheet into the desired shape using any suitable method, such as molding, shaking (or vacuum forming).
Embodiments of the present invention provide stable coating compositions that form abrasion resistant formable coatings. The coating composition is cured to form a transparent coating on the substrate. The coating composition comprises an aqueous-organic solvent mixture containing hydrolysis products and partial condensates of at least one epoxy functional silane and at least one diol functional organopolysiloxane or combinations thereof and at least one multifunctional crosslinker to form a cured organopolysiloxane coating on a substrate. The molar ratio of the at least one of the epoxy-functional silane and the diol-functional organopolysiloxane to the multifunctional crosslinker is from about 10: 1 to about 1: 10. In one embodiment, the molar ratio of the at least one of the epoxy-functional silane and the diol-functional organopolysiloxane to the multifunctional crosslinker is from about 2: 1 to about 1: 2.
In one embodiment, the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, silylated multifunctional carboxylic acids and silylated multifunctional anhydrides, and combinations thereof. In another embodiment, the multifunctional crosslinker is at least one silylated multifunctional anhydride or at least one silylated multifunctional carboxylic acid. The coating composition also includes water in an amount sufficient to hydrolyze at least one of the epoxy-functional silane and the diol-functional organopolysiloxane and the silylated multifunctional crosslinker.
The solvent component of the water-organic solvent mixture can be present in any suitable amount. The solvent component, for example, a water-organic solvent mixture, is about 40 to about 98 percent by weight of the coating composition. In another embodiment, the solvent component of the water-organic solvent mixture is from about 65 to about 95 percent by weight of the coating composition. It will be appreciated by those skilled in the art that hydrolysis by-products of the reaction as a coating composition may form the solvent component of at least a portion of the water-organic solvent mixture. At least one of the epoxy-functional silane and the diol-functional organopolysiloxane can be present in any suitable amount. For example, the at least one of an epoxy functional silane and a diol functional organopolysiloxane is present in an amount of from about 5 to about 93 percent by total weight of the composition solids. In another embodiment, the at least one of an epoxy functional silane and a diol functional organopolysiloxane is present in an amount of about 30 to about 70 percent by total weight of solids of the coating composition. The multifunctional crosslinker can be present in any suitable amount. In one embodiment, the multifunctional crosslinker is from about 7 to about 95 percent by weight of the total solids of the composition, and in another embodiment, the multifunctional crosslinker is from about 30 to about 70 percent by weight of the total solids of the coating composition.
In another embodiment of the invention, the coating composition may comprise a non-epoxy functional tetrafunctional silane, disilane, or other alkylsilane. However, tetrafunctional silanes, disilanes, and other alkyl silanes are present in amounts insufficient to impart rigidity to the cured coating. For the purposes of defining and describing the present invention, the term "rigid" is understood to mean a coating that is not formable as defined herein. In one embodiment, the molar ratio of the at least one epoxy-functional silane to the tetrafunctional silane of the coating composition is at least about 5.5: 1. In another embodiment, the molar ratio of the at least one epoxy-functional silane to disilane of the coating composition is at least about 5.5: 1. In another embodiment, the molar ratio of the at least one epoxy-functional silane to the alkylsilane of the coating composition is at least about 2.5: 1. The amount of non-epoxy functional tetrafunctional silanes, disilanes, and other alkyl silanes incorporated into the coating compositions of the present invention can vary over a wide range and generally depends on the desired properties of the cured coating prepared from the coating composition and the desired stability of the coating composition. Non-epoxy functional tetrafunctional silanes, disilanes, and alkylsilanes can improve the abrasion resistance, chemical resistance, and optical properties of the cured coating. In other embodiments of the present invention, the coating composition may comprise other additives, such as anti-fog components, leveling agents, catalysts, and the like, as will be further described herein.
To test the abrasion resistance of the coated substrate, any quantitative test method can be used, including Taber test (ASTM D-4060), abrasion test, and oscilloting Sand test (ASTMF 735-81). In addition, there are various quantitative test methods available for determining abrasion resistance, including steel wool tests and rubber tests. In the steel wool test and the rubber test, coated substrate specimens are scratched under reproducible conditions (constant load, frequency, etc.). The scratched test specimens were then compared and rated according to the standard specimen. Semi-quantitative applications of these test methods include the determination of the haze increment of scratches on coated substrates using an instrument such as a spectrophotometer or colorimeter.
Whether measured by the taber test, steel wool test, rubber test, abrasion test, etc., the portion of the abrasion resistance of the cured coating on the substrate measured is a function of the curing temperature and curing time. Generally higher temperatures and longer cure times result in higher measured abrasion resistance. The curing temperature and curing time are generally chosen to match the substrate. However, due to processing and/or equipment limitations, sometimes less than optimal curing temperatures and curing times. Those skilled in the art recognize that other variables (e.g., coating thickness and substrate properties) also affect the measured abrasion resistance. Usually, there is an optimum coating thickness for each type of substrate and each coating composition. The optimum curing temperature, curing time, coating thickness, etc. can be readily determined empirically by one skilled in the art.
Taber abrasion was performed using a Teledyne model 5150 Taber abrasion tester (Taber Industries, North Tonawanda, N.Y.) equipped with 500g accessory load and a CS-10F wheel (Taber Industries, North Tonawanda, N.Y.). Before the measurements, the wheels were dressed with ST-11 dressed stone (Taber Industries, North Tonawanda, N.Y.). And turning a CS-10F wheel on the shaving stone by 25 turns to perform shaving. The Haze of the samples was recorded 4 times using a Haze-gard Plus (BYK-Gardner, Columbia, MD) equipped with a Taber abrasion stand (BYK-Gardner, Columbia, MD). Haze was recorded 4 times using a Haze-gard Plus (BYK-Gardner, Columbia, MD) equipped with a Taber abrasion rack (BYK-Gardner, Columbia, MD) after 50 revolutions on the coupon from the CS-10F wheel. The average haze of the initial haze readings, the haze readings after 50 and 200 revolutions were determined using a new CS-10F round available at least as early as 7 months of 2003. The difference between the average haze reading and the initial haze reading was then recorded for 50 and 200 revolutions.
The taber method is considered to be a semi-quantitative method for determining wear resistance. The precision and accuracy of the method depends on various factors, including the condition of the CS-10F test wheel. Varying the condition of the CS-10F test wheel can significantly affect the wear resistance test results. For example, recent changes in the composition of CS-10F wheels by Taber Industries have resulted in standard specimens having 1% haze and 5% haze (recorded as 1%/5%) after 100 and 500 revolutions, respectively, to 7% and 25%, respectively. Throughout the tests performed herein, all samples were tested using the same set of new CS-10F Taber wheels. According to embodiments of the invention, the taber value of the coating after 50 revolutions is less than about 30%, less than about 10% or less than about 5%. According to other embodiments of the invention, the coating has a taber value of less than about 2% after 50 revolutions, and in other embodiments, the coating has a taber value of less than about 45%, less than about 30%, or less than about 15% after 200 revolutions.
The formability of the coating can be tested using the following method. The oven with the glass plates was preheated to 165 ℃. A2 inch by 7 inch test specimen coated with 1/4 inch Lexan polycarbonate (1/4 inch Lexan PC, Regal Plastics, Santa Fe Springs, Calif.) was laid flat on a glass plate and heated at 165 ℃ for 18 minutes. The thickness of the coating may be about 1-20 microns or about 2-10 microns. The samples were removed from the oven and immediately placed on a cylindrical mandrel. The formability of the test specimens was assessed by determining the minimum radius of the mandrel at which cracking, spalling or debonding of the coating was observed. For the purposes of defining and describing the present invention, the terms "formable" and "formability" are understood to refer to a cured coating that can be bent at a radius of less than about 10 inches according to the methods described above. In one embodiment, the cured coating can be bent at a radius of about 3 to about 5 inches according to the above method without cracking or crazing the coating.
The presence of water in the water-organic solvent mixture is required to form a hydrolysis product of the silane component of the mixture. The actual amount of water used may vary within wide limits. Sufficient water is required to provide a suitably uniform coating mixture of the silane component of the coating composition with hydrolysis products and partial condensates of other added components. One skilled in the art recognizes that the amount of water can be determined empirically.
The solvent component of the water-organic solvent mixture of the coating composition of the present invention can be any solvent or combination of solvents that is compatible with the components of the coating composition, including but not limited to epoxy-functional silanes, diol-functional organopolysiloxanes, non-epoxy-functional silanes, tetrafunctional silanes, disilanes, and multifunctional crosslinkers, or any combination thereof. For example, the solvent component of the aqueous-organic solvent mixture can be water, an alcohol, an ether, a glycol or glycol ether, a ketone, an ester, a glycol ether acetate, and combinations thereof. Suitable alcohols can be represented by the formula ROH, wherein R is an alkyl group containing from 1 to about 10 carbon atoms. Some examples of alcohols useful in the present invention are methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, cyclohexanol, pentanol, octanol, decanol, and mixtures thereof.
Suitable diols, ethers, glycol ethers may be represented by the formula R1-(OR2)x-OR1Wherein x is 0, 1, 2, 3 or 4, R1Is hydrogen or alkyl containing 1 to about 10 carbon atoms, R2Alkylene groups containing from 1 to about 10 carbon atoms and combinations thereof.
Examples of glycols, ethers, and glycol ethers having the above-defined formula include, but are not limited to, di-n-butyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol dibutyl ether, ethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, ethylene glycol ethyl ether, ethylene glycol diethyl ether, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, dibutylene glycol, tributylene glycol, and combinations thereof. In addition to the substances mentioned above, cyclic ethers such as tetrahydrofuran and dioxane are also suitable ethers for the water-organic solvent mixture.
Examples of ketones suitable for use in the water-organic solvent mixture include, but are not limited to, acetone, diacetone alcohol, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, and combinations thereof. Examples of esters suitable for use in the water-organic solvent mixture include, but are not limited to, ethyl acetate, n-propyl acetate, n-butyl acetate, and combinations thereof. Examples of glycol ether acetates suitable for use in the aqueous-organic solvent mixture include, but are not limited to, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, ethylene glycol ethyl ether acetate, and combinations thereof.
Any suitable epoxy-functional silane, diol-functional organopolysiloxane derived from hydrolyzed epoxy-functional silane, or combination thereof may be used in the coating composition of the present invention. For example, the epoxy-functional silane or diol-functional organopolysiloxane can be any epoxy-functional silane or diol-functional organopolysiloxane that is compatible with the multifunctional carboxylic acid. For example, epoxy-functional silanes of the formula R3 xSi(OR4)4-xWherein x is an integer of 1, 2 or 3, R3Is H, an alkyl group containing from 1 to about 10 carbon atoms and having at least one epoxy functional group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether, and combinations thereof, R4Is H, alkyl containing 1 to about 5 carbon atoms, acetyl, -Si (OR)5)3-yR6 yA group (wherein y is an integer of 0, 1, 2 or 3) and combinations thereof, wherein R5Is H, alkyl containing 1 to about 5 carbon atoms, acetyl OR another-Si (OR)5)3-yR6 yRadicals and combinations thereof, R6Alkyl groups containing 1 to about 10 carbon atoms which are H, may also contain epoxy functional groups, functional groupsAlkylated alkyl, alkylene, aryl, alkyl ether, and combinations thereof.
In another embodiment, the diol functional organopolysiloxane is the ring-opening reaction product of an epoxy functional silane and water. The ring-opening reaction is accomplished by hydrolysis and condensation of the alkoxy group. The ring-opening reaction is illustrated below:
wherein R is any suitable group. In another example, a commercial source of diol-functional organopolysiloxane HS2926 is available from DEGUSSA Corp. HS2926 can be used "as is" without further purification. The diol functional organopolysiloxane can be prepared by mixing the epoxy functional silane with an excess of water adjusted to a pH of 3 with an acid, followed by refluxing for several hours. The alcohol formed during the hydrolysis of the alkoxysilane groups can be removed by distillation.
Examples of suitable epoxy-functional silanes include, but are not limited to, glycidoxymethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethylhydroxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyltributoxysilane, 1, 3-bis (glycidoxypropyl) tetramethyldisiloxane, 1, 3-bis (glycidoxypropyl) tetramethoxydisiloxane, 1, 3-bis (glycidoxypropyl) -1, 3-dimethyl-1, 3-dimethoxydisiloxane, 2, 3-epoxypropyltrimethoxysilane, 3, 4-epoxybutyltrimethoxysilane, 6, 7-epoxyheptyltrimethoxysilane, 9, 10-epoxydecyltrimethoxysilane, 1, 3-bis (2, 3-epoxypropyl) tetramethoxydisiloxane, 1, 3-bis (6, 7-epoxy-heptyl) tetramethoxydisiloxane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
Any suitable multifunctional crosslinking agent or combination of multifunctional crosslinking agents can be used in the present invention. The multifunctional crosslinker can be any multifunctional carboxylic acid, multifunctional anhydride, silylated multifunctional carboxylic acid, and combinations thereof that are compatible with the epoxy functional silane, diol functional organopolysiloxane, or other component of the coating composition. The silylated multifunctional anhydrides and carboxylic acids have-Si (OR') groups that are capable of reacting with each other with epoxy-functional silanes, diol-functional organopolysiloxanes, tetrafunctional silanes, hydrolysis products of disilanes and alkylsilanes and partial condensates.
The multifunctional crosslinking agent may include, but is not limited to, multifunctional carboxylic acids and anhydrides that yield multifunctional carboxylic acids. Carboxylic acid functional compounds may be used of formula R7(COOR8)xWherein x is an integer of 1, 2, 3 or 4, wherein R7Selected from the group consisting of H, alkyl, functionalized alkyl, alkylene, aryl, functionalized aryl, alkyl ether and combinations thereof, wherein each of the alkyl, alkylene, aryl, functionalized alkyl and alkyl ether is further characterized as containing from 1 to about 10 carbon atoms, and wherein R is8Selected from the group consisting of H, formyl, carbonyl, or acyl, wherein the acyl group can be functionalized with an alkyl, functionalized alkyl, alkylene, aryl, functionalized aryl, alkyl ether, and combinations thereof, wherein each of said alkyl, functionalized alkyl, alkylene, aryl, functionalized aryl, and alkyl ether is further characterized as containing from 1 to about 10 carbon atoms.
Examples of multifunctional carboxylic acids that can be used to prepare the coating compositions of the present invention include, but are not limited to, malic acid, aconitic acid (cis, trans), itaconic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, cyclohexylsuccinic acid, 1, 3, 5-trimellitic acid, 1, 2, 4, 5-pyromellitic acid, 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1-cyclohexanediacetic acid, 1, 3, 5-cyclohexanedicarboxylic acid, and unsaturated dibasic acids such as fumaric acid and maleic acid, and combinations thereof.
Examples of polyfunctional anhydrides that can be used in the coating composition of the present invention include, but are not limited to, anhydrides of the above carboxylic acids, such as the above cyclic anhydrides of dibasic acids, for example succinic anhydride, itaconic anhydride, glutaric anhydride, 1, 2, 4-trimellitic anhydride, 1, 2, 4, 5-pyromellitic anhydride, phthalic anhydride, maleic anhydride, and combinations thereof.
The multifunctional crosslinking agent may also include, but is not limited to, carboxylic acids OR anhydrides containing-Si (OR') groups. An example of such a material is 3-triethoxysilylpropyl succinic anhydride.
In addition to the multifunctional crosslinker of the coating composition, an optional inorganic acid such as hydrochloric acid or nitric acid may be used as a hydrolysis-promoting catalyst for hydrolyzing the silane compounds described herein.
Any suitable tetrafunctional silane or combination of tetrafunctional silanes in an amount insufficient to impart rigidity to the coating may be used in the present invention. For example, the tetrafunctional silane may have the formula Si (OR)9)4Wherein R is9Is H, alkyl containing 1 to about 5 carbon atoms and ethers thereof, -Si (OR)10)3Group (wherein R10Is H, an alkyl group containing from 1 to about 5 carbon atoms and ethers thereof OR another-Si (OR)10)3Groups) and combinations thereof. Formula Si (OR)9)4Examples of tetrafunctional silanes represented are tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetraisopropyl orthosilicate, tetrabutyl orthosilicate, tetraisobutyl orthosilicate, tetrakis (methoxyethoxy) silane, tetrakis (methoxypropoxy) silane, tetrakis (ethoxyethoxy) silane, tetrakis (methoxyethoxyethoxy) silane, trimethoxyethoxy-silane, dimethoxydiethoxysilane, triethoxymethoxy-silane, poly (dimethoxysiloxane), poly (diethoxysiloxane), poly (dimethoxy-diethoxysiloxane), tetrakis (trimethoxysiloxy) silane, tetrakis (triethoxysilyloxy) silane, and the like. In addition to R of the above tetrafunctional silanes9And R10Other than the substituent, R9And R10Together with Oxygen (OR)9) And (OR)10) May be a carboxylic acid group. Examples of tetrafunctional silanes containing carboxylic acid group functionality are silicon tetraacetate, silicon tetraacrylate and silicon tetrabutyrate.
The composition may comprise any suitable disilane in an amount insufficient to impart rigidity to the coating. For example, disilanes can be used of the formula (R)11O)xR12 3-xSi-R13 y-SiR14 3-x(OR15)xRepresents; wherein x is 0, 1, 2 or 3 and y is 0 or 1; r12And R14Is H, an alkyl group containing from about 1 to about 10 carbon atoms, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl polyether group, and combinations thereof; r11And R15Is H, alkyl groups containing from about 1 to about 10 carbon atoms, acetyl, and combinations thereof. If y is 1, R13May be an alkylene group containing from about 1 to about 12 carbon atoms, an alkylene polyether containing from about 1 to about 12 carbon atoms, an aryl group, an alkylene substituted aryl group, an alkylene group which may contain one or more olefinic bonds, S or O. If x is 0, then R12、R14Is Cl or Br. If y is 0, a direct Si-Si bond is present. Examples of such disilanes include, but are not limited to, bis (triethoxysilyl) ethane, bis (triethoxysilyl) methane; bis (trichlorosilyl) methane, bis (triethoxysilyl) ethylene, 1, 3-bis (triethoxysilyl) ethane, hexaethoxydisiloxane, and hexaethoxydisilane. The choice of disilane and the amount of such disilane incorporated into the coating composition depends on the particular properties to be enhanced or imparted to the coating composition or the cured coating composition.
The composition may include any other suitable alkylsilane (i.e., trifunctional silane, difunctional silane, monofunctional silane, and mixtures thereof, hereinafter referred to as silane additives) in an amount insufficient to impart rigidity to the coating. The alkylsilane additives which may be incorporated into the coating compositions of the present invention may have the formula R16 xSi(OR17)4-xWherein x is the number 1, 2 or 3; r16Is H or an alkyl group containing from 1 to about 10 carbon atoms, functionalizedAlkyl, alkylene, aryl, alkoxy polyether groups of (a), and combinations thereof; r17Is H, alkyl groups containing 1 to about 10 carbon atoms, acetyl, and combinations thereof. Examples of silane additives of the above-defined formula are methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexylmethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, dimethyldimethoxysilane, 2- (3-cyclohexenyl) ethyltrimethoxysilane, 3-cyanopropyl-trimethoxysilane, 3-chloropropyltrimethoxysilane, 2-chloroethyltrimethoxysilane, phenethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, ethyltrimethoxysilane, Phenyltrimethoxysilane, 3-isocyanopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 4- (2-aminoethylaminomethyl) phenethyltrimethoxysilane, chloromethyltriethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltriethoxysilane, phenyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, and the like, 2- (3-cyclohexenyl) ethyltriethoxysilane, 3-cyanopropyltriethoxysilane, 3-methacrylamidopropyltriethoxysilane, 3-methoxypropyltrimethoxysilane, 3-ethoxypropyltrimethoxysilane, 3-propoxypropyltrimethoxysilane, 3-methoxyethyltrimethoxysilane, 3-ethoxyethyltrimethoxysilane, 3-propoxyethyltrimethoxysilane. The choice of silane additive and the amount of such silane additive incorporated into the coating composition depends on the coating composition to be enhanced or imparted with or curedSpecific properties.
In certain applications, an amount of colloidal silica that is insufficient to impart rigidity to the cured coating may be added to the coating composition. Colloidal silica is available from a variety of different trade names, including Nalco (Nalco Chemical co., Naperville, IL); nyacol (Nyacol products, inc., Ashland, MA); snowtex (Nissan Chemical Industries, ltd., Tokyo, Japan); ludox (DuPont Company, Wilmington, Delaware); and Highlink OG (Clariant, Charlotte, NC). Colloidal silica is an aqueous or organic solvent dispersion of particulate silica, the main differences between the various products being particle size, silica concentration, pH, presence of stabilizing ions, solvent composition, etc. It will be appreciated by those skilled in the art that significantly different product properties can be obtained by selecting different colloidal silicas.
Colloidal silica is considered an active material when added to a coating composition. The surface of the silica is covered with silicon-bonded hydroxyl groups, some of which, deprotonation, may interact with species in the coating composition. The extent of these interactions depends on various factors including the solvent system, pH, concentration, and ionic strength. Processing methods also affect these interactions. One skilled in the art recognizes that colloidal silica can be added to a coating formulation in different ways to achieve different results. Colloidal silica may be added to the coating composition at any suitable time.
The addition of colloidal silica to the coating compositions of the present invention may also enhance the abrasion resistance of the cured coating composition and may also contribute to the overall stability of the coating composition. In the same manner, other metal oxides may be added to the coating composition of the present invention. Other metal oxides may be added in place of or in addition to any colloidal silica. Metal oxides may be added to the coatings of the present invention to provide or enhance specific properties of the cured coating, such as abrasion resistance, refractive index, antistatic properties, antireflective properties, weatherability, and the like. Those skilled in the art will recognize that the same type of reason for adding colloidal silica to the compositions of the present invention also applies more generally to the addition of metal oxides. Examples of metal oxides that can be used in the coating composition of the present invention are silica, zirconia, titania, ceria, tin oxide, and combinations thereof.
The amount of colloidal silica incorporated into the coating composition of the present invention can vary over a wide range and generally depends on the desired properties of the cured coating prepared from the coating composition and the desired stability of the coating composition. Likewise, the amount of metal oxide incorporated into the coating composition of the present invention can vary over a wide range and generally depends on the desired properties of the cured coating prepared from the coating composition and the desired stability of the coating composition. Typically, the colloidal silica and/or metal oxide will have a particle size of from 2 to 150 nanometers, and more desirably from about 2 to 50 nanometers.
Although the catalyst is not an essential component of the present invention, the addition of the catalyst can affect the abrasion resistance and other properties of the coating, including stability, porosity, aesthetics (cosmetics), corrosion resistance, water resistance, and the like. The amount of catalyst used can vary over a wide range, but when present, is generally sufficient to provide from about 0.1 to about 10 percent by weight of the total solids of the coating composition.
Examples of catalysts that may be incorporated into the coating compositions of the present invention include, but are not limited to, (i) metal acetylacetonates, (ii) diamides, (iii) imidazoles, (iv) amines and ammonium salts, (v) organosulfonic acids and amine salts thereof, (vi) alkali metal salts of carboxylic acids, (vii) alkali metal hydroxides, and (viii) fluoride salts. Thus, examples of such catalysts include: (i) compounds such as aluminum acetylacetonate, zinc acetylacetonate, iron acetylacetonate and cobalt acetylacetonate; (ii) such compounds as dicyandiamide; (iii) such as 2-methylimidazole, 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-propylimidazole; (iv) such as benzyldimethylamine and 1, 2-diaminocyclohexane; (v) such compounds as trifluoromethanesulfonic acid; (vi) such compounds as sodium acetate; (vii) compounds such as sodium hydroxide and potassium hydroxide; and (viii) compounds such as tetra-n-butylammonium fluoride and the like.
An effective amount of a leveling or flow control agent can be incorporated into the composition to more evenly spread or level the composition on the surface of the substrate so that substantially uniform contact with the substrate is achieved. The amount of leveling agent or flow control agent can vary over a wide range, but the amount of leveling agent or flow control agent can be sufficient to be from about 10 to about 5,000ppm of the coating composition. Any conventional commercial leveling or flow control agent that is compatible with the coating composition and the substrate, is capable of leveling the coating composition on the substrate, and enhances the wetting of the coating composition with the substrate may be used. The use of leveling and flow control agents is well known in the art and is described in the Handbook of coating additives (edited by Leonard J.Calbo, published by Marcel Dekker), pp 119-145, the entire contents of which are incorporated herein by reference.
Examples of such leveling or flow control agents that may be incorporated into the coating compositions of the present invention include, but are not limited to, organic polyethers such as TRITON X-100, X-405, and N-57 (available from Rohm and Haas); polysiloxanes, such as Paint Additive 3, Paint Additive 29 and Paint Additive 57 (from Dow Corning); SILWET L-77 and SILWETL-7600 (available from OSi Specialties); and fluorinated surfactants such as FLUORADFC-4430 (available from 3M Corporation).
In addition, other additives may be added to the coating composition of the present invention to enhance the utility of the coating composition or a coating layer prepared by curing the coating composition. For example, ultraviolet absorbers, antioxidants, and the like can be incorporated into the coating compositions of the present invention, if desired.
In one embodiment, a uv stabilizer may be added to the coating composition. Any suitable uv stabilizer and radical scavenger at any concentration effective to protect the substrate from photodegradation can be used in the present invention. The use of these Additives is described in Handbook of coating Additives (Handbook of coating Additives), edited by Leonard J.Calbo, published by Marcel Dekker, p.225-269. In another embodiment, a uv stabilizer may be added to the primer composition.
In another embodiment, a surfactant or mixture of surfactants may be included in the coating composition to impart anti-fog properties to the coated article. The inclusion of the surfactant results in a high surface wetting tension of the dry coating, and the high wetting tension prevents the formation of fine droplets (i.e., mist) on the coating surface. The surfactant also enhances wetting of the water to maintain a clear, non-atomized surface. An example of a suitable surfactant is dioctyl sulfosuccinate, trade name AerosolOT 75, available from Cytec Industries inc. The surfactant component may be present in an amount of about 0.4-15% by weight of the coating composition. Higher levels of surfactant may be used, however, may result in increased haze, which is undesirable in many applications. The antifogging effect of the coating can be determined by storing the article having the cured coating on its surface at 20 ℃ and subsequently subjecting the coated article to saturated water vapor at 60 ℃. The coating resists fogging if the coated article becomes transparent after 10 seconds, remaining transparent for at least 1 minute.
The coating composition can be prepared in any suitable manner. For example, the multifunctional crosslinker and at least one of the epoxy functional silane and the diol functional organopolysiloxane can be added to a solvent and water and subsequently reacted at room temperature overnight. Other additives, such as leveling agents, may be added subsequently. The coating composition can be applied to a substrate and cured to form a coating.
Embodiments of the present invention may provide articles of manufacture. The article may comprise a substrate and a coating formed on at least one surface of the substrate by curing the coating composition of the present invention. Any suitable substrate can be coated with the coating composition of the present invention. For example, plastic materials, wood, metal, printed surfaces and leather can be coated. The compositions are particularly useful as coatings for synthetic organic polymeric substrates in sheet or film form, such as acrylic polymers, poly (ethylene terephthalate), polycarbonates, polyamides, polyimides, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene copolymers, polyvinyl chloride, butyrates, and the like. The transparent polymeric materials coated with these compositions are useful as flat or curved covers, such as windows, skylights and windshields, particularly for traffic equipment. Plastic lenses, such as acrylic, poly (diethylene glycol-bis-allyl carbonate) (ADC) or polycarbonate lenses, can also be coated with the compositions of the present invention.
The coating composition can be applied to the substrate in any suitable manner. For example, the compositions of the present invention can be applied to a solid substrate by conventional methods (e.g., flow coating, spray coating, curtain coating, dip coating, spin coating, roll coating, etc.) to form a continuous surface film.
By selecting the appropriate coating composition, coating conditions and pretreatment (including the use of primers) of the substrate, the coating compositions of the present invention can adhere to substantially all solid surfaces. After application of the coating composition of the present invention to a solid substrate, the coating can be thermally cured at any suitable temperature for any suitable time. For example, the coating can be thermally cured at a temperature of 50-200 ℃ or higher for a period of several seconds to 18 hours or more. It will be appreciated that the coating may be cured in any other suitable manner. For example, a uv-activated photoinitiator capable of initiating cationic curing may be added such that the coating is at least partially curable by uv light. It will be appreciated that the coating may be subsequently cured by another method, such as thermal curing. Any suitable photoinitiator may be used. For example, an aromatic onium salt or an arene iron salt complex available from Ciba specialty Chemicals Corp., Terrytown, NY may be used.
The coating thickness can vary by the particular coating technique, but the coating thickness can be from about 0 to about 5 to 20 microns or from about 1 to about 10 microns. It is to be understood that the coating may be substantially transparent.
According to one embodiment of the present invention, the coating composition may be applied to a substrate on which the primer is distributed. Any suitable primer may be used. For example, a polyurethane dispersion-based primer can be used. Examples of such suitable primers are described in detail in U.S. patent 5,316,791, the entire contents of which are incorporated herein by reference. An example of such a suitable primer is PR1180 available from SDC Technologies, inc. In another embodiment, to improve the weatherability of the coated substrate, the primer may be modified with ultraviolet light absorbing substances and/or free radical scavengers. The primer can be applied to a substrate and subsequently air dried or heat dried, e.g., air dried for less than about 2 hours, and the coating composition can be subsequently applied and cured, at which time a coated substrate can be formed.
Other embodiments of the present invention provide shaped articles. The shaped article comprises on at least one surface a shaped substrate having a coating according to the invention. The coating is applied to a shaped article, which is then shaped.
Examples
The following examples are for illustrative purposes only and are not intended to limit the scope of the appended claims. All references cited herein are specifically incorporated by reference.
Example 1: preparation of diol-functional organopolysiloxanes
1000g of 3-glycidoxypropyltrimethoxysilane epoxy-functional silane (A-187, Witco Corporation, Greenwich, CT) was added to a 5 liter glass flask equipped with a distillation apparatus. A mixture of 40g HCl (0.05N) and 2960g deionized water was then added to the 5 liter flask. The solution was then heated to reflux. After refluxing for 3 hours, 743g of the solvent was removed by distillation. The product was used "as is" without further purification.
Example 2: coating composition and primer
7.5g of Deionized (DI) water was added dropwise to a stirred solution of 15.0g A-187, 19.3g of dihydro-3- (3- (triethoxysilyl) propyl) -2, 5-furandione silylated polyfunctional anhydride (GF20, Wacker chemical corporation, Adrian, MI) and 140.0g of isopropanol solvent. The mixture was stirred at room temperature overnight. 0.18g of a 10% by weight solution of the leveling agent PA-57(Dow Corning corporation, Midland, MI) in propylene glycol monomethyl ether (PM ether, Ashland Chemical, Columbus, OH) was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing.
The coating composition was applied by flow coating onto 1/4 inch thick polycarbonate panels primed with PR-1180(SDC Technologies, Inc., Anaheim, Calif.). After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from taber test was obtained according to the method set out herein, using a CS-10F wheel, as: the haze after 50 revolutions was 1.7%, and the haze after 200 revolutions was 7.5%. The thickness of the topcoat was 3.5 microns. The formability of the coating on a cylindrical mandrel was evaluated as described herein, and no cracks were observed at a radius of 5 inches.
Example 3: coating composition and primer
8.0g of deionized water was added dropwise to a stirred solution of 17.7g A-187, 15.2g GF20 and 140.0g of isopropanol. The mixture was stirred at room temperature overnight. 0.18g of a 10% by weight solution of PA-57 in PM glycol ether was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing.
The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 2.3%, and the haze after 200 revolutions was 11.4%. The thickness of the topcoat was 3.5 microns. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 4 inches.
Example 4: coating composition and primer
17.0g of deionized water was added dropwise to a stirred solution of 45.0g A-187, 29.0g GF20 and 280.0g of isopropanol. The mixture was stirred at room temperature overnight. 0.37g of a 10% by weight solution of PA-57 in PM glycol ether was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing.
The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 3.1%, and the haze after 200 revolutions was 17.2%. The thickness of the topcoat was 3.2 microns. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 3 inches.
Example 5: coating composition and primer
16.0g of deionized water was added dropwise to a stirred solution of 47.0g A-187, 20.0g GF20 and 280.0g isopropanol. The mixture was stirred at room temperature overnight. 0.36g of a 10% by weight solution of PA-57 in PM glycol ether was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing.
The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 5.3%, and the haze after 200 revolutions was 38.1%. The thickness of the topcoat was 3.1 microns. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 3 inches.
Example 6: coating composition and primer
15.0g of deionized water was added dropwise to a stirred solution of 47.0g A-187, 15.0g GF20 and 260.0g of isopropanol. The mixture was stirred at room temperature overnight. 0.34g of a 10% by weight solution of PA-57 in PM glycol ether was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing.
The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 6.0%, and the haze after 200 revolutions was 59.1%. The thickness of the topcoat was 3.2 microns. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 3 inches.
Example 7: coating composition and primer
14.3g of deionized water was added dropwise to a stirred solution of 30.0g A-187, 38.6g of GF20, and 300.0g of PM glycol ether (PMOH) solvent. The mixture was stirred at room temperature for three days. 0.38g of a 10% by weight solution of PA-57 in PMOH was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing.
The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 3.0%, and the haze after 200 revolutions was 14.0%. The thickness of the topcoat was 3.0 microns. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 3 inches.
Example 8: coating composition and primer
16.2g of deionized water were added dropwise to a stirred solution of 45.0g A-187, 29.0g of GF20 and 300.0g of PM glycol ether (PMOH). The mixture was stirred at room temperature for three days. 0.39g of a 10% by weight solution of PA-57 in PMOH was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing.
The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 4.7%, and the haze after 200 revolutions was 26.7%. The thickness of the topcoat was 3.0 microns. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 3 inches.
Example 9: coating composition and primer
15.8g of deionized water was added dropwise to a stirred solution of 47.2g A-187, 20.3g GF20 and 300.0g PM glycol ether (PMOH). The mixture was stirred at room temperature for three days. 0.38g of a 10% by weight solution of PA-57 in PMOH was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing.
The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 5.8%, and the haze after 200 revolutions was 34.5%. The thickness of the topcoat was 3.0 microns. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 3 inches.
Example 10: coating composition and primer
15.0g of deionized water was added dropwise to a stirred solution of 47.2g A-187, 15.2g GF20 and 265.0g PM glycol ether (PMOH). The mixture was stirred at room temperature for three days. 0.34g of a 10% by weight solution of PA-57 in PMOH was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing.
The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the 50-revolution haze was 6.4%, and the haze after 200 revolutions was 57.2%. The thickness of the topcoat was 3.0 microns. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 3 inches.
Example 11: coating composition and primer
2.7g of deionized water were added dropwise to a stirred solution of 3.8g A-187, 9.7g of GF20 and 55g of isopropanol/PM glycol ether (1: 1). The mixture was stirred at room temperature for three days. 0.08g of a 10% by weight solution of PA-57 in PM glycol ether was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing.
The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 1.6%, and the haze after 200 revolutions was 5.6%. The thickness of the topcoat was 3.2 microns. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 6 inches.
Example 12: coating composition and primer
4.0g of deionized water was added dropwise to a stirred suspension of 15.0g A-187, 1.8g of itaconic acid cross-linking agent and 75.0g of isopropanol. The mixture was stirred at room temperature overnight. 0.10g of 10% by weight solution of PA-57 in PMOH was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing.
The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 13.3%, and the haze after 200 revolutions was 67.2%. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 3 inches.
Example 13: coating composition and primer
4.0g of deionized water was added dropwise to a stirred suspension of 15.0g A-187, 1.4g of succinic anhydride crosslinker and 70.0g of isopropanol. The mixture was stirred at room temperature overnight. 0.10g of a 10% by weight solution of PA-57 in PMOH was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing.
The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 36.2%. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 3 inches.
Example 14: coating composition and primer
4.0g of deionized water was added dropwise to a stirred suspension of 15.0g A-187, 1.4g of succinic anhydride and 70.0g of PM glycol ether (PMOH). The mixture was stirred at room temperature for three days. 0.10g of a 10% by weight solution of PA-57 in PMOH was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing.
The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: haze after 50 revolutions was 42.0%. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 3 inches.
Example 15: coating composition and primer
A mixture of 15.0g of an aqueous trimethoxy (3-oxiranylmethoxy) propyl silane solution HS2926(SIVENTO Inc, Piscataway, N.J.), 9.66g of GF20 and 70.0g of isopropanol was stirred at room temperature overnight. 0.10g of a 10% by weight solution of PA-57 in PM glycol ether was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing. The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 1.0%, and the haze after 200 revolutions was 3.0%. The thickness of the topcoat was 3.0 microns. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 7 inches.
Example 16: coating composition and primer
A mixture of 15.0g HS2926, 9.66g GF20, and 70.0g PM glycol ether was stirred at room temperature overnight. 0.10g of a 10% by weight solution of PA-57 in PM glycol ether was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing. The composition was aged at room temperature for 5 days, followed by coating. The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 1.34%, and the haze after 200 revolutions was 4.19%. The thickness of the topcoat was 3.0 microns. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 7 inches.
Example 17: coating composition and primer
A mixture of 15.0g HS2926, 0.7g succinic anhydride and 30.0g isopropanol was stirred at room temperature overnight. 0.05g of a 10% by weight solution of PA-57 in PMOH was added. After the addition of PA-57, the composition was stirred for an additional 20 minutes to ensure mixing. The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: haze after 25 revolutions was 26.0%. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 3 inches.
Example 18: comparative example coating compositions and primers
Commercial SDC MP1154D (SDC Technologies, inc., analheim, CA), a representative coating described in U.S. patent 6,001,163, was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 0.39%, and the haze after 200 revolutions was 0.78%. The thickness of the topcoat was 3.0 microns. The coated specimens were placed in an oven according to the thermoforming process set forth herein. At 165 ℃, the coating cracked before it could be placed on the cylindrical mandrel.
Example 19: comparative example coating compositions and primers
Commercial SDC MP1193a1(SDC Technologies, inc., analheim, CA), a representative coating described in U.S. patent 6,348,269, was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 0.22%, and the haze after 200 revolutions was 0.47%. The thickness of the topcoat was 5.0 microns. The coated specimens were placed in an oven according to the thermoforming process set forth herein. At 165 ℃, the coating cracked before it could be placed on the cylindrical mandrel.
Example 20: comparative example coating compositions and primers
Commercial SDC TC332(SDC Technologies, inc., Anaheim, CA), a representative coating described in U.S. patent 5,013,608, was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 1.48%, and the haze after 200 revolutions was 3.57%. The thickness of the topcoat was 3.5 microns. The coated specimens were placed in an oven according to the thermoforming process set forth herein. At 165 ℃, the coating cracked before it could be placed on the cylindrical mandrel.
Example 21: antifogging coating composition and primer
1.91g of deionized water was added dropwise to a stirred solution of 4.0g A-187, 5.15g GF20 and 40g PM glycol ether. The mixture was stirred at room temperature overnight. 0.74g of a mixture solution of the surfactant dioctyl sodium sulfosuccinate in ethanol and water (OT-75, Van Waters & Rogers Inc., Kirkland, WA) (75% solids) WAs added. The composition was stirred at room temperature for 2 hours, then aged in a 100 ℃ F. greenhouse for 3 weeks, and then painted.
The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The coating on the surface was stored at 20 ℃ and the coated article was subsequently placed in saturated water vapour at 60 ℃. After 10 seconds the coated article became clear and remained clear for at least 1 minute. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 1.6%, and the haze after 200 revolutions was 9.0%. The thickness of the topcoat was 3.2 microns. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 4 inches.
Example 22: antifogging coating composition and primer
2.11g of deionized water were added dropwise to a stirred solution of 5.88g A-187, 3.79g GF20 and 39.2g PM glycol ether. The mixture was stirred at room temperature overnight. 0.74gOT-75 (75% solids) was added. The composition was stirred at room temperature for 2 hours, then aged at 100F for 3 weeks, and then coated with paint.
The coating composition was applied by flow coating onto an 1/4 inch thick polycarbonate panel primed with PR-1180. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The coating on the surface was stored at 20 ℃ and the coated article was subsequently placed in saturated water vapour at 60 ℃. After 10 seconds the coated article became clear and remained clear for at least 1 minute. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 4.8%, and the haze after 200 revolutions was 33%. The thickness of the topcoat was 3.2 microns. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 4 inches.
Example 23: comparative example anti-fog coating composition and primer
Commercial SDC AF1140(SDC Technologies, inc., analheim, CA) was coated by flow coating onto PR-1180 primer coated 1/4 inch thick polycarbonate panels. After air drying for 30 minutes, the coating was cured at 130 ℃ for 2 hours. The coating on the surface was stored at 20 ℃ and the coated article was subsequently placed in saturated water vapour at 60 ℃. After 10 seconds the coated article became clear and remained clear for at least 1 minute. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 3.20%, and the haze after 200 revolutions was 14.3%. The thickness of the topcoat was 3.1 microns. The formability of the coating on the cylindrical mandrel was evaluated and cracks were observed at radii less than 10 inches.
Example 24: coatings and weatherable primers
30-45% by weight of poly (oxy-1, 2-ethanediyl), α - [3- [3- (2H-benzotriazole (-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxyphenyl) -1-oxopropyl ] - Ω - [3- [3[ (2H-benzotriazole-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxyphenyl ] -1-oxopropoxy ] and 40-55% by weight of poly (oxy-1, 2-ethanediyl), α - [3- [3- (2H-benzotriazole (-2-yl) -5- (1, 1-Dimethylethyl) -4-hydroxyphenyl) -1-oxopropyl ] -omega-hydroxy-, (Tinuvin 1130, Ciba specialty Chemicals Corporation, Tarrytown, NY) was mixed into a commercial PR1180 primer to prepare a weatherable primer. Thus, 6.42g of Tinuvin1130 was added to 150g of PR 1180. The resulting composition was stirred for 4 hours, followed by application of a paint.
The composition was applied as a primer by flow coating a polycarbonate panel 1/4 inches thick. The primer was air dried for 1 hour and then the topcoat of example 7 was applied. The final coating was cured at 130 ℃ for 2 hours. The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 2.0%, and the haze after 200 revolutions was 11%. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 3 inches.
Coatings were evaluated for weatherability using QUV and Weather-O-Meter. In both accelerated weathering testers, the coatings showed no adhesion failure and cracking after 200 hours of exposure to uv light. QUV was operated under UV cycling at 70 ℃ for 8 hours followed by condensation cycling at 50 ℃ for 4 hours. The Weather-O-Meter was operated according to ASTM 155-1.
Example 25: coatings and weatherable primers
3.0g of Tinuvin1130 was added to 150g of PR 1180. The resulting composition was stirred for 4 hours, followed by application of a paint. The composition was applied as a primer by flow coating a polycarbonate panel 1/4 inches thick. The primer was air dried for 1 hour and then the topcoat of example 7 was applied. The final coating was cured at 130 ℃ for 2 hours.
The haze increment from the taber test using a CS-10F wheel was: the haze after 50 revolutions was 2.7%, and the haze after 200 revolutions was 12%. The formability of the coating on the cylindrical mandrel was evaluated and no cracks were observed at a radius of 3 inches.
Coatings were evaluated for weatherability using QUV and Weather-O-Meter. In both accelerated weathering testers, the coatings showed no adhesion failure and cracking after 200 hours of exposure to uv light. QUV was operated under UV cycling at 70 ℃ for 8 hours followed by condensation cycling at 50 ℃ for 4 hours. The Weather-O-Meter was operated according to ASTM 155-1.
It will be understood that various changes may be made without departing from the scope of the invention and are not to be considered limited to what is described in the specification.

Claims (32)

1. A composition which, when applied to a substrate and cured, provides an abrasion resistant formable coating on said substrate, said composition comprising:
an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of at least one of an epoxy functional silane and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein said multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein the molar ratio of the at least one of the epoxy functional silane and the diol functional organopolysiloxane to the multifunctional crosslinker is from about 10: 1 to 1: 10; and
water in an amount sufficient to hydrolyze said epoxy functional silane, said diol functional organopolysiloxane, and said silylated multifunctional crosslinker.
2. The composition of claim 1, wherein the molar ratio of the at least one of the epoxy-functional silane and the diol-functional organopolysiloxane to the multifunctional crosslinker is from about 2: 1 to 1: 2.
3. The composition of claim 1, wherein the coating is formable into a radius of from about 1 inch to less than about 10 inches on a polycarbonate substrate.
4. The composition of claim 1, wherein the coating is formable into a radius of about 3 inches to about 5 inches on a polycarbonate substrate.
5. The composition of claim 1, wherein the coating has a taber value of less than about 10% to less than about 2% after 50 revolutions of the taber wheel.
6. The composition of claim 1, wherein the coating has a taber value of less than about 45% to less than about 15% after 200 revolutions of the taber wheel.
7. The composition of claim 1, wherein the at least one of an epoxy functional silane and a diol functional organopolysiloxane is from about 5 to about 90 percent by weight of the solids of the composition, and wherein the multifunctional crosslinker is from about 10 to about 95 percent by weight of the solids of the composition.
8. The composition of claim 1, wherein the solvent component of the aqueous-organic solvent mixture is from about 40 to about 98% by weight of the composition.
9. The composition of claim 1 wherein the solvent component of the aqueous-organic solvent mixture is selected from the group consisting of ethers, glycols or glycol ethers, ketones, esters, glycol ether acetates, alcohols having the formula ROH, wherein R is an alkyl group containing from 1 to about 10 carbon atoms, and mixtures thereof.
10. The composition of claim 1, wherein the solvent component of the aqueous-organic solvent mixture is selected from the group consisting of compounds having the formula R1-(OR2)x-OR1Wherein x is 0, 1, 2, 3 or 4, R is1Is hydrogen or alkyl containing 1 to about 10 carbon atoms, R2Is an alkylene group containing from 1 to about 10 carbon atoms.
11. The composition of claim 1 wherein said epoxy functional silane is of the formula R3 xSi(OR4)4-xIs shown, in which:
x is an integer 1, 2 or 3;
R3is H, an alkyl group containing from 1 to about 10 carbon atoms and having at least one epoxy functional group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether, and combinations thereof;
R4is H, alkyl containing 1 to about 5 carbon atoms, acetyl, -Si (OR)5)3-yR6 yGroups and combinations thereof, wherein y is an integer of 0, 1, 2 or 3;
R5is H, alkyl containing 1 to about 5 carbon atoms, acetyl OR another-Si (OR)5)3-yR6 yGroups and combinations thereof; and
R6is H, alkyl groups containing 1 to about 10 carbon atoms, functionalized alkyl groups, alkylene groups, aryl groups, alkyl ethers, and combinations thereof.
12. A composition which, when applied to a substrate and cured, provides an abrasion resistant formable coating on said substrate, said composition comprising:
an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein said multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the molar ratio of said diol functional organopolysiloxane to said multifunctional crosslinker is from about 10: 1 to 1: 10; and
water in an amount sufficient to hydrolyze said diol functional organopolysiloxane and said silylated multifunctional crosslinker.
13. The composition of claim 12, wherein the aqueous-organic solvent mixture further comprises hydrolysis products and partial condensates of an epoxy functional silane and the at least one multifunctional crosslinker.
14. A composition which, when applied to a substrate and cured, provides an abrasion resistant formable coating on said substrate, said composition comprising:
an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein said multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the molar ratio of said at least one said epoxy functional silane to said multifunctional crosslinker is from about 10: 1 to 1: 10; and
water in an amount sufficient to hydrolyze the epoxy functional silane and the multifunctional crosslinker, wherein the composition comprises at least one of a tetrafunctional silane, a disilane, and an alkylsilane in an amount insufficient to render the coating on the substrate rigid.
15. The composition of claim 14, wherein the composition comprises at least one of a tetrafunctional silane and a disilane, and wherein the molar ratio of the epoxy-functional silane to the at least one of a tetrafunctional silane and a disilane is at least about 5.5: 1.
16. The composition of claim 14, wherein the aqueous-organic solvent mixture further comprises hydrolysis products and partial condensates of a diol functional organopolysiloxane and the multifunctional crosslinker.
17. The composition of claim 14, wherein:
the tetrafunctional silane has the formula Si (OR)9)4Wherein R is9Is H, alkyl containing 1 to about 5 carbon atoms and ethers thereof, (OR)9) Carboxylic acid group, -Si (OR)10)3Groups and combinations thereof, wherein R10Is H, alkyl containing 1 to about 5 carbon atoms and ethers thereof, (OR)10) Carboxylic acid group OR another-Si (OR)10)3A group wherein:
the disilane has the formula (R)11O)xR12 3-xSi-R13 y-SiR14 3-x(OR15)x(ii) a Wherein x is 0, 1, 2 or 3 and y is 0 or 1; wherein R is12And R14Including H, alkyl groups containing from about 1 to about 10 carbon atoms, functionalized alkyl groups, alkylene groups, aryl groups, alkyl polyether groups, and combinations thereof; wherein R is11And R15Including H, alkyl groups containing from about 1 to about 10 carbon atoms, acetyl, and combinations thereof; wherein if y is 1, then R13Including alkylene groups containing from about 1 to about 12 carbon atoms, alkylene polyethers containing from about 1 to about 12 carbon atoms, aryl groups, alkylene substituted aryl groups, alkylene groups which may contain one or more olefinic bonds, S or O; wherein if x is 0, then R12And R14Including Cl or Br; and wherein if y is 0, then a direct Si-Si bond is present, and wherein:
the alkylsilane has the formula R16 xSi(OR17)4-xWherein x is the number 1, 2 or 3; r16Is H or an alkyl group containing 1 to about 10 carbon atoms, a functionalized alkyl group, an alkylene group, an aryl group, an alkoxy polyether group, and combinations thereof; r17Is H, alkyl groups containing 1 to about 10 carbon atoms, acetyl, and combinations thereof.
18. The composition of claim 14, wherein the composition comprises at least one alkylsilane, and wherein the molar ratio of the epoxy-functional silane to the at least one alkylsilane is at least about 2.5: 1.
19. An article of manufacture, comprising:
a substrate and an abrasion resistant formable coating formed on at least one surface of the substrate by curing a coating composition comprising:
an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of at least one of an epoxy functional silane and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein said multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein the molar ratio of the at least one of the epoxy functional silane and the diol functional organopolysiloxane to the multifunctional crosslinker is from about 10: 1 to 1: 10; and
water in an amount sufficient to hydrolyze said epoxy functional silane, said diol functional organopolysiloxane, and said silylated multifunctional crosslinker.
20. The article of claim 19, wherein said article comprises a shaped article comprising a shaped substrate and said abrasion resistant formable coating formed on at least one surface of said substrate, said coating composition being applied to the substrate, said coating composition being cured, and said substrate subsequently being shaped to form said shaped substrate.
21. The article of claim 19, further comprising at least one primer disposed on at least one surface of the substrate between the substrate and the coating.
22. An article of manufacture, comprising:
a substrate and an abrasion resistant formable coating formed on at least one surface of the substrate by curing a coating composition comprising:
an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein said multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the molar ratio of said diol functional organopolysiloxane to said multifunctional crosslinker is from about 10: 1 to 1: 10; and
water in an amount sufficient to hydrolyze said diol functional organopolysiloxane and said silylated multifunctional crosslinker.
23. An article of manufacture, comprising:
a substrate and an abrasion resistant formable coating formed on at least one surface of the substrate by curing a coating composition comprising:
an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein said multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the epoxy functional silane is present in a molar ratio to said multifunctional crosslinker of from about 10: 1 to 1: 10; and
water in an amount sufficient to hydrolyze said epoxy functional silane and said silylated multifunctional crosslinker, wherein said composition comprises at least one of tetrafunctional silane, disilane, and alkylsilane in an amount insufficient to render said coating on said substrate rigid.
24. The article of claim 23, wherein the coating composition comprises at least one of a tetrafunctional silane and a disilane, and wherein the molar ratio of the epoxy-functional silane to the at least one of the tetrafunctional silane and the disilane is at least about 5.5: 1.
25. The article of claim 23, wherein the coating composition comprises at least one alkylsilane, wherein the molar ratio of the epoxy functional silane to the at least one alkylsilane is at least about 2.5: 1.
26. A method of providing a substantially transparent abrasion resistant formable coating, the method comprising:
applying a coating composition to a substrate; and
curing the coating composition, wherein the coating composition comprises:
an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of at least one of an epoxy functional silane and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein said multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein the molar ratio of the at least one of the epoxy functional silane and the diol functional organopolysiloxane to the multifunctional crosslinker is from about 10: 1 to 1: 10; and
water in an amount sufficient to hydrolyze said epoxy functional silane, said diol functional organopolysiloxane, and said silylated multifunctional crosslinker.
27. The method of claim 26, further comprising the step of shaping the coated substrate.
28. The method of claim 26 further comprising applying a primer to said substrate and subsequently applying said coating composition to said substrate over said primer.
29. A method of providing an abrasion resistant formable coating, the method comprising:
applying a coating composition to a substrate; and
curing the coating composition, wherein the coating composition comprises:
an aqueous-organic solvent mixture comprising hydrolysis products and partial condensates of a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein said multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the molar ratio of said diol functional organopolysiloxane to said multifunctional crosslinker is from about 10: 1 to 1: 10; and
water in an amount sufficient to hydrolyze said diol functional organopolysiloxane and said silylated multifunctional crosslinker.
30. A method of providing an abrasion resistant formable coating, the method comprising:
applying a coating composition to a substrate; and
curing the coating composition, wherein the coating composition comprises:
a hydrolysate and partial condensate hydro-organic solvent mixture comprising an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from the group consisting of multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the epoxy functional silane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to 1: 10; and
water in an amount sufficient to hydrolyze said epoxy functional silane and said silylated multifunctional crosslinker, wherein said composition comprises at least one of tetrafunctional silane, disilane, and alkylsilane in an amount insufficient to render said coating on said substrate rigid.
31. The method of claim 30 wherein the composition comprises at least one of a tetrafunctional silane and a disilane, and wherein the molar ratio of the epoxy-functional silane to the at least one of a tetrafunctional silane and a disilane is at least about 5.5: 1.
32. The method of claim 30 wherein the composition comprises at least one alkylsilane, and wherein the molar ratio of the epoxy-functional silane to the at least one alkylsilane is at least about 2.5: 1.
HK08103105.8A 2004-10-12 2005-10-12 Coating compositions, articles, and methods of coating articles HK1113933A (en)

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