CA2018237C - Radiation curable acryloxyfunctional silicone coating composition - Google Patents
Radiation curable acryloxyfunctional silicone coating composition Download PDFInfo
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- CA2018237C CA2018237C CA002018237A CA2018237A CA2018237C CA 2018237 C CA2018237 C CA 2018237C CA 002018237 A CA002018237 A CA 002018237A CA 2018237 A CA2018237 A CA 2018237A CA 2018237 C CA2018237 C CA 2018237C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
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Abstract
The present invention relates to a silicone coating composition which, when cured on a solid substrate either by ultraviolet or electron beam radiation, provides a transparent abrasion resistant coating firmly adhered thereon. The silicone coating is prepared by reacting in a polar solvent solution at least one multifunctional acrylate monomer with an amino-organofunctional silane to form a Michael adduct and optionally adding an acid to the reaction mixture, and thereafter adding colloidal silica.
Description
~ 2018237 RADIATION CURABLE ACRYLOXYFUNCTIONAL
:>ILICONE COATING COMPOSITION
This invention deals with a siloxane composition used primarily as a transparent coating on solid substrates.
More specifically the composition can be used to coat solid substrates to render such substrates abrasion resistant, weather resistanit, ultraviolet light (UV) resistant and to allow such substrates to be tinted and/or dyed. The compositions of 'this invention when cured on solid substrates especially polyc;arbonate, yield uniform, gel free, glossy surfaces to the coated substrates. Current markets for such coatings are well established and will expand as the abrasion resistance and w~eatherability of these coatings is improved.
The present invention offers significant advantages over many of the known silicone coating compositions in that an amino-organofunctional silane is used instead of the more costly acryloxyfunctional silanes to solubilize and stabilize the colloidal silica.
Amino-organofunctional silanes and siloxanes have been incorporated into coating compositions that are used as adhesion promoters and releasing films but never before has colloidal silica been added to these formulations to provide a silicone coating composition which, when cured on a solid substrate provides a transparent abrasion resistant coating firmly adhered thereon. Fujii et al, U.S. Patent No.
4,603,086 dated July 29, 1986~said patent being assigned to Dai Nippon Insat:su Kabushiki Kaisha; Shin-Etsu Kagaku Kogyo Kabushiki Kaisha, both of Japan, discloses silicone compounds made by reacting a primary amino-organo-functional silane with a di- or multifunctional acrylic compound by a Michael addition reaction. Similarly, U.S. Patent No.
4,697,026 of Chi-long Lee and Michael A. Lutz, issued September 29, 1987, said patent being assigned to Dow Corning Corporation, Midland, Michigan, discloses silicone compounds made by ."'~., --.~Y --~.
:>ILICONE COATING COMPOSITION
This invention deals with a siloxane composition used primarily as a transparent coating on solid substrates.
More specifically the composition can be used to coat solid substrates to render such substrates abrasion resistant, weather resistanit, ultraviolet light (UV) resistant and to allow such substrates to be tinted and/or dyed. The compositions of 'this invention when cured on solid substrates especially polyc;arbonate, yield uniform, gel free, glossy surfaces to the coated substrates. Current markets for such coatings are well established and will expand as the abrasion resistance and w~eatherability of these coatings is improved.
The present invention offers significant advantages over many of the known silicone coating compositions in that an amino-organofunctional silane is used instead of the more costly acryloxyfunctional silanes to solubilize and stabilize the colloidal silica.
Amino-organofunctional silanes and siloxanes have been incorporated into coating compositions that are used as adhesion promoters and releasing films but never before has colloidal silica been added to these formulations to provide a silicone coating composition which, when cured on a solid substrate provides a transparent abrasion resistant coating firmly adhered thereon. Fujii et al, U.S. Patent No.
4,603,086 dated July 29, 1986~said patent being assigned to Dai Nippon Insat:su Kabushiki Kaisha; Shin-Etsu Kagaku Kogyo Kabushiki Kaisha, both of Japan, discloses silicone compounds made by reacting a primary amino-organo-functional silane with a di- or multifunctional acrylic compound by a Michael addition reaction. Similarly, U.S. Patent No.
4,697,026 of Chi-long Lee and Michael A. Lutz, issued September 29, 1987, said patent being assigned to Dow Corning Corporation, Midland, Michigan, discloses silicone compounds made by ."'~., --.~Y --~.
reacting a primary or secondary amino-organofunctional silane with a di- or multifunctional acryl compound by a Michael addition reaction. The uniqueness of the present invention is found in that iit further reacts the products formed from the reaction between an amino-organofunctional silane and multifunctional ac:rylate with dispersions of colloidal silica to yield a transparent abrasion resistant coating with superior properties.
To take advantage of more cost effective materials and improved properties, a new radiation curable coating cro~osition has been discovere<i which, when cured on a solid substrate renders such substrates abrasion resistant, weather resistant, ultraviolet light resistant and allows such substrates to be tinted and/or dyed. The present invention relates to a composition produced by the mixing of colloidal silica with the reaction product of an amino-organofunctional silane and a multifunctional acrylate. The solvent remaining after mixing the components may optionally be removed. In addition, this composition, unlike those of the prior art, may be cured by either ultraviolet light or electron beam radiation.
The comp ~o ~ i t i o n comp r i s a s the product of reaction of (A) at least one multifunctional acrylate monomer;
(B) an amino-organofunctional silane of the formula X$S1 {Q (NHQ' ) bNZH~~a wherein X is selected from alkoxy groups having 1 to 6 carbon atoms;
Q and Q' are the same or different divalent hydrocarbon groups;
Z is hydrogen or monovalent hydrocarbon group;
a is an integer from 1 to 3; and b is an integer from 0 to 6;
--for a time and at a. temperature sufficient to form a Michael adduct therefrom;
adding an acid to the above-resulting solution; and thereafter adding cc>lloidal silica to the above-resulting solution.
This invention also relates to a process for coating solid substrates with the above described compositions which process comprises preparing a solid substrate to receive the inventive composition, contacting the substrate with the inventive composition and thereafter curing the inventive composition on the substrate by either ultraviolet or electron beam radiation.
A third aspect of this invention is a solid substrate coated with a cured composition of this invention.
Component: (A) of this novel composition comprises at least one acryla~te monomer which contains two or more functional groups selected from the group consisting of acryloxy and methac:ryloxy groups. These multifunctional acrylate monomers may be used singly or in combination with other multifunctional acrylate monomers. Some preferred multifunctional acrylate monomers usable as component (A) include:
diacrylates of the formulas;
1,6-hexanediol. diacrylate, 1,4-butanediol. diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene p;lycol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol. dimethacrylate, poly(butanediol) diacrylate, tetraethylene glycol dimethacrylate, --,--~\ , .."'.y 1,3-butylene glycol diacrylate, triethylene glycol diacrylat~e, triisopropylene glycol diacrylate, polyethylene glycol diacrylate, bisphenol A d:Lmethacrylate, triacrylates of they formulas;
trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol monohydroxy triacrylate, trimethylolpropane triethoxy triacrylate, tetraacrylates of the formulas;
pentaerythritol tetraacrylate, di-trimethylo:lpropane tetraacrylate, and pentaacrylates of the formulas;
dipentaerythr:Ltol (monohydroxy) pentaacrylate.
These mu:Ltifunctional acrylate monomers are commercially available from Aldrich Chemical Company, Inc., Milwaukee, Wisconsin. , The second component of this composition (B) comprises an amino-organofunctional silane of the general formula:
XaJSi~Q(NHQ~ )bNZH?4-a wherein R is selected from alkoxy groups having 1-6--carbon atoms;
Q and Q~ are the same or different divalent hydrocarbon groups;
Z is a hydrogen or a monovalent hydrocarbon group;
a is an :integer from 1 to 3; and b is an :integer from 0 to 6.
,... , 2018~3*~
To take advantage of more cost effective materials and improved properties, a new radiation curable coating cro~osition has been discovere<i which, when cured on a solid substrate renders such substrates abrasion resistant, weather resistant, ultraviolet light resistant and allows such substrates to be tinted and/or dyed. The present invention relates to a composition produced by the mixing of colloidal silica with the reaction product of an amino-organofunctional silane and a multifunctional acrylate. The solvent remaining after mixing the components may optionally be removed. In addition, this composition, unlike those of the prior art, may be cured by either ultraviolet light or electron beam radiation.
The comp ~o ~ i t i o n comp r i s a s the product of reaction of (A) at least one multifunctional acrylate monomer;
(B) an amino-organofunctional silane of the formula X$S1 {Q (NHQ' ) bNZH~~a wherein X is selected from alkoxy groups having 1 to 6 carbon atoms;
Q and Q' are the same or different divalent hydrocarbon groups;
Z is hydrogen or monovalent hydrocarbon group;
a is an integer from 1 to 3; and b is an integer from 0 to 6;
--for a time and at a. temperature sufficient to form a Michael adduct therefrom;
adding an acid to the above-resulting solution; and thereafter adding cc>lloidal silica to the above-resulting solution.
This invention also relates to a process for coating solid substrates with the above described compositions which process comprises preparing a solid substrate to receive the inventive composition, contacting the substrate with the inventive composition and thereafter curing the inventive composition on the substrate by either ultraviolet or electron beam radiation.
A third aspect of this invention is a solid substrate coated with a cured composition of this invention.
Component: (A) of this novel composition comprises at least one acryla~te monomer which contains two or more functional groups selected from the group consisting of acryloxy and methac:ryloxy groups. These multifunctional acrylate monomers may be used singly or in combination with other multifunctional acrylate monomers. Some preferred multifunctional acrylate monomers usable as component (A) include:
diacrylates of the formulas;
1,6-hexanediol. diacrylate, 1,4-butanediol. diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene p;lycol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol. dimethacrylate, poly(butanediol) diacrylate, tetraethylene glycol dimethacrylate, --,--~\ , .."'.y 1,3-butylene glycol diacrylate, triethylene glycol diacrylat~e, triisopropylene glycol diacrylate, polyethylene glycol diacrylate, bisphenol A d:Lmethacrylate, triacrylates of they formulas;
trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol monohydroxy triacrylate, trimethylolpropane triethoxy triacrylate, tetraacrylates of the formulas;
pentaerythritol tetraacrylate, di-trimethylo:lpropane tetraacrylate, and pentaacrylates of the formulas;
dipentaerythr:Ltol (monohydroxy) pentaacrylate.
These mu:Ltifunctional acrylate monomers are commercially available from Aldrich Chemical Company, Inc., Milwaukee, Wisconsin. , The second component of this composition (B) comprises an amino-organofunctional silane of the general formula:
XaJSi~Q(NHQ~ )bNZH?4-a wherein R is selected from alkoxy groups having 1-6--carbon atoms;
Q and Q~ are the same or different divalent hydrocarbon groups;
Z is a hydrogen or a monovalent hydrocarbon group;
a is an :integer from 1 to 3; and b is an :integer from 0 to 6.
,... , 2018~3*~
Preferred for this invention are monoamines and diamine:s, that is amines wherein b is 0 or 1. Specific examples of the most preferred amino-organofunctional silanes are:
n-(2-aminoeth.yl-3-aminopropyl)trimethoxysilane 3-aminopropyltriethoxysilane 3-aminopropyltrimethoxysilane, and anilinopropyltrimethoxysilane.
These amino-organofunctional silanes are commercially available from Petrarch Systems, Inc., Bristol, PA.
The amino-organofunctional silane modified multifunctional acrylate compounds of this invention can be prepared by intimately mixing an amino-organofunctional silane compound having at least one primary amine or secondary amine group with an acrylate functional compound as described in component (A). When an amine compound and an acrylate compound are mixed, there is a reaction which produces an acrylate functional compound. This reaction is generally known as the Michael addition reaction. For example, in the reaction between (i) and (ii), a primary or secondary amine functionality of the amino-organofunctional silane undergoes a Michael addition to one or more of the acrylate double bonds of the multifunctional acrylate monomers described in component (A). The resulting product is referred to as an amino-organofunctional silane modified multifunctional acrylate monomer. This reaction occurs at a temperature of from room temperature to 100°C. Heating the mixture increases the rate of the reaction, however, as the temperature of the reaction is increased, the loss of acrylate functionality due to free radical initiated chain reactions also increases. At temperatures above 100°C., considerable loss of the acrylate functionality may occur.
~.,I
n-(2-aminoeth.yl-3-aminopropyl)trimethoxysilane 3-aminopropyltriethoxysilane 3-aminopropyltrimethoxysilane, and anilinopropyltrimethoxysilane.
These amino-organofunctional silanes are commercially available from Petrarch Systems, Inc., Bristol, PA.
The amino-organofunctional silane modified multifunctional acrylate compounds of this invention can be prepared by intimately mixing an amino-organofunctional silane compound having at least one primary amine or secondary amine group with an acrylate functional compound as described in component (A). When an amine compound and an acrylate compound are mixed, there is a reaction which produces an acrylate functional compound. This reaction is generally known as the Michael addition reaction. For example, in the reaction between (i) and (ii), a primary or secondary amine functionality of the amino-organofunctional silane undergoes a Michael addition to one or more of the acrylate double bonds of the multifunctional acrylate monomers described in component (A). The resulting product is referred to as an amino-organofunctional silane modified multifunctional acrylate monomer. This reaction occurs at a temperature of from room temperature to 100°C. Heating the mixture increases the rate of the reaction, however, as the temperature of the reaction is increased, the loss of acrylate functionality due to free radical initiated chain reactions also increases. At temperatures above 100°C., considerable loss of the acrylate functionality may occur.
~.,I
Using a polar solvent also increases the reaction rate .of the Michael addition reaction. Alcohols are the preferred solvents because of their low boiling points and non hazardous properties, and alcohols can easily be removed from the compositions, if desired. Suitable alcohols, for example, include an.y water soluble or water miscible alcohol, for example, methanol, ethanol, propanol, butanol, etc., or ether alcohols, such as ethoxyethanol, butoxyethanol, methoxypropanol, etc. For purposes of the present process, applicant prefers to use isopropanol as a solvent because of its low cost and nonhazardous properties. In addition, to ensure sufficient time for the Michael addition to take place, applicant prefers that the time and temperature the reactants remain in. contact be between six and seventy-two hours at room temperature.
The third. component (C) of this composition comprises silica in. the form of a colloidal dispersion.
Colloidal silica is a dispersion of submicron-sized silica (Si02) particles in. an aqueous or other solvent medium. The colloidal silicas used in this composition are dispersions of submicron size silica (Si02) particles in an aqueous or organic solvent or combination thereof. Colloidal silica is available in acid o~r basic form. Either form may be utilized. An example of satisfactory colloidal silica for use in these c*oating composi* ions is "Nalco ~~~034A colloidal silica (Nalco 1034A.~ , ~~Nalco~~84SS258 colloidal silica rNalco"*
84SS258 ) and~~Nalco~~ 1129 colloidal silica ('Nalco' 1129 ) which can be obtained from Nalco Chemical Company, Naperville,IL.
"Nalco"1034A has a mean particle size of 20 nm and an Si02 content of approximately 34°/ by weight in water with a pH of approximately 3.1. "Nalco"~4SS258 has a mean particle size of 20nm and an Si02 content of approximate*ly 30°/ by weight in a solution of propoxyethanol. ~Nalco~1129 has a * Tradcznark mean particle size of 20nm and an Si02 content of approximately 30o by weight in a solution of 40% 2-Propanol (IPA) and 30o water.
Preferably the amount of colloidal silica employed does not exceed 60% by weight of the sum of the weights of the multifunctional acrylic monomer, amino-organofunctional silane and colloidal silica.
It i_s believed by the inventors herein, that with the addition of colloidal silica, the amino-organofunctional silane modified multifunctional acrylate monomer, undergoes methoxy-hydroxy silane condensation with the collc>idal silica. In other words, the methoxy groups on the modified amino-organofunctional silane are replaced by hydroxy groups which are able to hydrogen bond to the hydroxy groups present on the surface of the roughly spherical colloidal silica particles. As a result, it is believed that the silica particles are encapsulated by the amino-organofunctional silane modified multifunctional acrylate monomers and remain suspended because of the attractive forces between the hydroxy group~~ on the amino-organofunctional silane modified multifunctional acrylate monomers. While not wishing to be bound by any particular mechanism or theory, applicant believes that the encapsulated silica particles are suspended in the mixture because of the van der Waals forces between the acrylate monomers.
Other additives can be added to the compositions i.n order to enhance the usefulness of the coatings. For example, leveling agents, ultraviolet light absorbers, dyes and the like, can be included herein. All of these additives and the use thereof are well known in the art and do not require extensive discussions. Therefore, only a limited number will be referred to, i.t being understood that any of these ,,,:, -8_ compounds can be used so long as they do not deleteriously affect the radiation curing of the coating composition and do not adversely affect the non-opaque character of t:he coating.
A particularly desirable additive has been found to be a small amount for example, up to about 10%
by weight, of a leveling agent. Leveling agents can be used on the substrates to cover surface irregularities and aid in the uniform dispersion of the coating composition. These agents are especially useful in compositions where all the solvent has been removed. For purposes of the present invention, the addition of 0.01 to 5.0 percent: commercial silicone glycol leveling agents, work well to provide the coating composition with desirable flowout and wetting properties.
Also useful as additives to the present coating compositions are UV absorbers. UV absorbers act to diminish the harmful effects of UV radiation on the final cured composition and thereby enhance the weatherability or resistance to cracking, yellowing and delamination of the coating. Incorporating UV absorbers into the instant compositions will permit the curing process regardless of.
whether UV or electron beam radiation is used to cure the composition. However, in the situation where UV
radiation is t.o be used to cure the composition, the amount of UV absorbers added must be carefully controlled so as not to hinder the cure. This limitation does not exist in the ease of electron beam radiation cure.
For the purpose of the present composition, the following UV absorbers and combinations thereof in concentration~~ of less than 20 weight percent based on the total composition, have been shown to produce desirable results: bis(1,2,2,6,6-pentamethyl-4-piperidinyl) (3,5-bis-(1,1-dimethylethyl-1-1-4-C
. ~ 2018237 _g-hydroxyphenyl)methyl)butylpropane-dioate, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, 2-hydroxyl-4-n-octoxybenzophenone, 2-(2'-hydroxy-5-methylphenyl)benzotriazole and poly(oxy-1,2-ethanediyl)-alpha-(3-(3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxylphenyl)-1-oxopropyl)-omega-hydroxy.
Concentration: of UV absorbers, however, in the range of 1 to 5 percent: based on the total weight of the composition are preferred.
In t:he practice of the present invention, the radiation curable compositions can be made by combining the multifunctional acrylate monomer or mixtures thereof with a given quantity of alcohol. Generally, the manner in which these, components are mixed together is not important. The amino-organofunctional silane is added dropwise to the mixture while agitation is applied. The mixture is thE~n stirred at a certain temperature for a sufficient period of time to allow the Michael Addition to take place. At this time, a small amount of acid may, optionally, be: added dropwise to the mixture. Suitable acids include, for example, weak acids such as acetic acid and acrylic acid, etc. and, for example, dilute solutions of t~trong acids such as hydrochloric acid and nitric acid, etc. The acid may comprise, for instance, up to ten percent by weight of acrylic acid. The colloidal silica is then added quickly while vigorous agitation is applied to the mixture. After allowing the mixture to stand for a period of time, the volatiles may optionally be removed by vacuum stripping and/or the mixture may o~>tionally be filtered.
According to the coating process of the present invention, they above described composition is coated on a substrate using conventional coating techniques modified as appropriate to the particular c ..
-9a-substrate. For example, this composition can be applied to a variety of solid substrates by methods such as flow coating, dip coating, spin coating, spray coating or curtain coating. These various methods of coating allow the composition to be placed on the substrate at variable thicknesses thus allowing a wider range of use of the composition. Coating thicknesses may vary, but for C
. Z~ 1 8237 -lo-improved abrasion resistance coating thicknesses of 3-25 microns, preferably about 5 microns, are recommended.
The compositions are then cured by either ultraviolet or electron beam radiation. The compositions may be ~iltraviolet light cured if one or more photoinitiators is added prior to curing. There are no special restrictions on the photoinitiators as long as they can generate radicals by the absorption of optical energy. Ultraviolet light sensitive photoinitiators or blends of initiators used in the UV cure of the present composition include 2-hydroxy-2-"*
methyl-1-phenyl-propan-1-one (Darocur 1173), sold by EM
Chemicals, Hawthorne, New York, and 2,2-dimethoxy-2-phenyl-acetophenone ("I:rgacure 651" ), sold by Ciba-Geigy Corporation, Hawthorne, New York. For purposes of this invention, it has been found that from 0.05 to 5 weight percent based on the total solids in the composition, of the photoinitiators described herein will cause the composition to cure.
Desirable hard, transparent coatings having excellent adhesion can thus be obtained when the composition of this invention is applied to a substrate and exposed to radiation such as that provided by UV lamps.
When the aforementioned photoinitiators are used, these additives are individually mixed with the afore-mentioned amino-organofunctional silane modified multi-functional acrylate monomers a.nd a dispersion of the multifunctional acrylate monomers and colloidal silica.
Alternatively, the coating composition may be electron beam ra.diatian cured. LQw energy electron beam radiation has the advantage over UV cure of decreasing the curing time while increasing the cross link density of the coated sample. Because electron beam radiation has a shorter wavelength than UV radiation, EB radiation penetrates deeper -into a coating sample causing more of the functional groups * Trademark (e~~ch instance) t -i -11- ~_ 2 0 1 8 2 3 7 to react, thus resulting in a greater degree of cross linking in the sample. In addition, nonfunctional groups may also react in the presence of EB radiation therefore further increa:~ing the cross link density of the coating sample. EB cure also allows for an increase in weatherability of the coating because a greater concentration c>f UV absorbers may be added to EB cured compositions than to compositions which are UV cured since the need for photoinitiators is eliminated. UV absorbers function to protect the substrate and the coating from the deleterious effects of ultra-violet light, thus resulting in the greater weatherability of EB radiation cured coated substrates.
Electron beam accelerators of various types such as van de Graaf:f-type, resonance transformer-type, linear-type, dynatron-type and high frequency-type can be used as a source of electron beam. An electron beam having energy of from 50 to 1000 KeV, preferably from 100 to 300 KeV
discharged therefrom may be irradiated in a dose of from 0.1 to 10 Mega Rads; (MR). A particularly preferred source of electron beam i.s one wherein a continuous curtain-like beam is irradiated from linear filaments. Examples of commercially available sources of electron beams are "Electro Curtain CB-150"* available from Energy Sciences Inc. And NP-ESA: 150* available from Otto Durr.
The curable composition obtained in the process of the present invention is coated on the surface of a substrate (e. g., polycarbonate, etc.). After said composition has been ultraviolet light or electron beam treated, a cured coating film is formed.
By choice of the proper formulation and application conditions including the optional use of a leveling agent, the compositions can be applied and will adhere to substantially all solid substrates. Substrates which are * Trademark C
especially contemplated herein are transparent and nontransparent plastics and metals. More particularly, these plastics are synthetic organic polymeric substrates such as acrylic polymers like poly(methylmethacrylate); polyesters, such as poly(eth~ylene terephthalate), poly(butylene ' terephthalate), etc.; polyamides; polyimides; acrylonitrile-styrene copolymers; styrene-acrylonitrile-butadiene copolymers; polyvinyl chloride; butyrates; polyethylene;
polyolefins and the like including modifications thereof.
The compositions of this invention are especially useful as transparent coatings for polycarbonates such as poly(bisphenol-A, carbonate) and those polycarbonates known as "Lexan"(R), sold by General Electric Company, Schenectady, New York; and as coatings for acrylics such as polymethyl-methacrylates. Metal substrates on which the present compositions are: also effective include bright and dull metals like aluminum and bright metallized surfaces like sputtered chromium alloy. Other solid substrates contemplated herein include wood, painted surfaces, leather, glass, ceramics and textiles.
The apparatus and testing procedures used for the results shown hE:rein are as follows:
Adhesion was measured by cross-hatch adhesion. A
series of cross-hatch scribes are made in an area of one square inch with lines to form 1/10 inch squares. This surface is covered with 1.0 inch No. 600"Scotch Brand"*
adhesive tape which is pressed down firmly over the cross-hatched area. The tape is withdrawn from the surface of the substrate with one rapid motion at about a 90° angle.
This action of applying and removing the tape is carried out three times and then the substrate is observed. The number of squares remaining intact on the substrate are reported as a percentage of the total number of squares on the grid.
* Trademark (each instance) r Steel wool testing was done as follows: A two inch square of 0000 steel wool was applied over the face of a 24 oz. hammer and was secured with a rubber band. Coated sample blanks were tested for scratch resistance to 20 double rubs across the center of the sample with the weighted steel wool.
The hammer is held by the end of its handle such that the majority of the pressure on the steel wool comes from the hammer head. The sample is graded according to the amount of scratching produced by the steel wool and hammer. The absence of scratches on the sample is graded a 1; slight scratching is graded a 2 and heavy scratching is graded a 3.
Abrasion resistance was determined according to ASTM Method D-1044, also known as the Taber Test. The instrument used was a"Teledyne"model 503 Taber Abraser with two 250 gram auxiliary weights (500 gram load) for each of the CSlOF abrasive wheels. The acrylic and polycarbonate test panels were subjected to 100 and 500 cycles on the abraser turntable. The percent change in haze which is the criterion for determining the abrasion resistance of the coating is determined by measuring the difference in haze of the unabrased and abrased coatings. Haze is defined as the percentage of transmitted light which, in passing through the sample, deviates. from the incident beam by forward scattering. In this method, only light flux that deviates more than 2.5 degrees on the average is considered to be haze. The percent haze on the coatings w*s determined by ASTM Method D10C13. A Gardner ~~Iaze Meter was used. The haze was calculated by measuring the amount of diffused light, dividing by the amount of transmitted light and multiplying by one hundred.
"Penci.l Testing" was done as follows: This test is meant to be a qualitative method of determining scratch resistance of a coating. A coated panel is placed on a firm * Trademark ,.-.
202823' horizontal surface. A pencil is held firmly against the film at.a 45° angle (point away from the operator) and pushed away from the operator in a 1/4-in. (6.5-mm) stroke. The process is started with the hardest lead pencil and continued down the scale of hardness to the pencil that will not cut into or gouge the film. T'he hardest pencil that will not cut through the film to the substrate for a distance of at least 1/8 in.
(3mm) is reported according to the following scale from Berol Corporation, Brentwood, TN.:
___________softer-____ _____________harder-_____________ 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H,7H,8H,9H
The HB grade is approximately equal to that of a .~~2 pencil.
The F grade is slightly harder and is the one most commonly used. The H grades are harder than that and get progressively harder up through the 9H grade which is very hard. The B grade is softer than the HB grade and get progressively softer through the 6B grade which is very soft.
A "tinting test" was done as follows: Coated samples were tinted using commercially available dyes from Brain Power, Inc., Miami, Fla., U.S.A. The coated samples were tinted using BPI Black ~~4600. The tinting was carried out using an Economy Six Model dye system from BPI. The tinting was carried out at about 93°C. by immersing the coated sample in BPI Lens Preparation for one (1) minute at 90°C. and then into the dye bath for up to 45 minutes. In the tables of the examples the time of immersion is indicated at 5 minutes (5 min.), 15 minutes (15 min.), 25 minutes (25 min.), 35 minutes (35 min.) and 45 minutes (45 min.). The light transmission through the sample was measured using a Gardner Haze Meter, model XL-835 Colorimeter and is reported as % transmission.
,,---15- ' In order that those skilled in the art may better understand how to practice the present invention, the following examples are given by way of illustration and not by way of limitation.
A mixture of 0.2 g of aminopropyltrimethoxysilane, 10.0 g of t-butanol, 1.32 g of hexanedioldiacrylate and 1.32 g of trimethylo7propanetriacrylate was stirred at room temperature for :l8 hours. To this mixture was added 0.62 g of glacial acetic. acid. The mixture was then allowed to stand for five minutes .
Next 3.2 g of ~~lalco~ 1034A was added while the mixture underwent vigorous agitation. The mixture was then allowed to stand for five minutes, before being vacuum stripped at 50°C, under 5 Torr pressure for ten minutes.
The resulting mixture was applied to a 4 x 4 acrylic panel a sing a ~8 wire wound rod and to a 4 x 4 polycarbonate panel by the method of spin coating. Next, each panel was electron beam cured under 4MR 160KeV electron dose at a belt speed of 68 feet per minute under a six inch wide electron beam operated with a 4 milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The compositional ratios and test results are summarized in Table I.
A mixture of 4.38 g of aminopropyltrimethoxysilane, 168.3 g of t-butanol, 22.23 gms of hexanedioldiacrylate and 22.23 g of trimethylolpropanetriacrylate was stirred at room temperature for 72 hours. To 5.0 g of this mixture, 3.75 g of~~Nalco~~'~4SS258 was added while the mixture underwent vigorous agitation. The mixture was then allowed to stand for five minutes, before being vacuum stripped at 30°C. under Torr pressure to reduce the volatile content to 54%.
*Trademark The resulting mixture was then filtered through a 5 micron filter and applied to a 4 x 4 acrylic panel using a ~~8 wire wound rod. The treated panel was then exposed to a flow of air for appro~cimately twenty minutes to remove the remaining solvent.
Next, the panel was electron beam cured under 4MR
160KeV electron dose at a belt speed of 68 feet per minute under a six inch wide electron beam operated with a 4 milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The compositional ratios and test results are summarized in Talble I.
A mixture of 1.01 g of aminopropyltrimethoxysilane, 38.75 g of isopropanol, 5.12 g of hexanedioldiacrylate and 5.12 g of trimet'tiylolpropanetriacrylate was stirred at room temperature for 72 hours. To this mixture was added 0.46 g of glacial acetic acid. The mixture was then allowed to stand for five minutes. Next, 16.58 g of~~Nalco~~1034A was added while the mixture underwent vigorous agitation. The mixture was then allowed to stand for five minutes, before being vacuum stripped at 35°C. and 2mm Hg, until all volatiles were removed. The resulting mixture was spin coated onto a 4 x 4 polycarbonate panel and electron beam cured under 4MR, 160KeV electron dose at a belt speed of 68 feet per minute under a six inch wide electron beam operated with a 4 milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The compositional ratios and test results are summarized in Table I and Table II.
EEA~LE 4 A mixture of 1.01 g of aminopropyltrimethoxysilane, 38.75 g of IPA, 5.12 g of hexanedioldiacrylate and 5.12 g of trimethylolpropanetriacrylate was stirred at room temperature for 72 hours. T'o this mixture was added 0.46 g of glacial acetic acid. The mixture was then allowed to stand for five minutes. Next, :16.58 g of"Nalco"1034A were added while the mixture underwent= vigorous agitation. The mixture was then allowed to stand for five minutes before being vacuum stripped at 35°C. and 2mm Hg, until all volatiles were .
removed. To 2.0 g of the resulting mixture, 0.01 g of~~Dow Corning"(R) 57 leveling agent was added. The mixture was then spin coated onto a 4 x 4 polycarbonate panel and electron beam cured under 4MR, 160KeV electron dose at a belt speed of 68 feet per minute under a six inch wide electron beam operated wit=h a 4 milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The compositional ratios and test results are summarized in Table I and Table II.
A mixture of 1.08 g of aminopropyltrimethoxysilane, 51.46 g of IPA, 1.36 g of hexanedioldiacrylate and 3.79 g of trimethylolpropanetriacrylate was stirred at room temperature for 72 hours. To this mixture was added 0.23 g of glacial acetic acid. The mixture was then allowed to stand for five minutes. Next, :11.24 g of~~Nalco~~1034A was added while the mixture underwent vigorous agitation. The resulting mixture was then filtere<i through a 5 micron filter.
The filtered mixture was flow coated onto a 4 x 4 polycarbonate panel, which was allowed to air dry for 5 minutes. The coa3ted composition was then electron beam cured under 4MR, 160KeV electron dose at a belt speed of 68 feet per minute under a six inch wide electron beam operated with a 4 milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The cornpositional ratios and test results are summarized in Table I.
* Trademark ,.. . ~ 2018237 A mixture of 1.08 g of aminopropyltrimethoxysilane, 25.36 g of IPA, 1.36 g of hexanedioldiacrylate and 3.79 g of trimethylolpropanetriacrylate was stirred at room temperature for 72 hours. To this mixture was added 0.23 g of glacial acetic acid. The mixture was then allowed to stand for five minutes. Next, :L2.73 g of "Nalco"'129 was added while the mixture underwent vigorous agitation. The resulting mixture was then filtered through a 5 micron filter.
The filtered mixture was flow coated onto a 4 x 4 polycarbonate panel, which was allowed to air dry for 5 minutes. The coated composition was then electron beam cured under 4MR, 160KeV electron dose at a belt speed of 68 feet per minute under a six inch wide electron beam operated with a 4 milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The compositional ratios and test results are summarized in Table I.
EEAltPLE 7 A mixture of 1.08 g of aminopropyltrimethoxysilane, 51.46 g of IPA, 1.36 g of hexanedioldiacrylate and 3.79 g of trimethylolpropanetriacrylate was stirred at room temperature for 72 hours. 7.'o this mixture was added 0.23 g of glacial acetic acid. The mixture was then allowed to stand for five minutes. Next, 11.24 g of~Nalcop1034A was added while the mixture underwent vigorous agitation. The mixture was then allowed to stand for five minutes before 0.50 g of DAROCUR*
1173, sold by Et~! Chemicals, Hawthorns, N.Y., and 0.10 g of methyldiethanol;amine were added. The resulting mixture was filtered through a 5 micron filter.
The filtered mixture was flow coated onto a 4 x 4 polycarbonate panel, which was allowed to air dry for 5 minutes. The coated polycarbonate sample was then W cured by passing the sample through a medium pressure mercury vapor arc lamp with an average intensity of 91.56 mW/cm2 at a line * Trademark speed of three feet per minute. The compositional ratios and test results are summarized in Table I.
EaAMPLE 8 A mixture of 1.53 g of anilinopropyltrimethoxy-silane, 51.47 g of IPA, 1.36 g of hexanedioldiacrylate and 0.40 g of bisphenol A dimethacrylate was stirred at room temperature for 72 hours. To this mixture was added 0.23 g of glacial acetic acid. The mixture was then allowed to stand for five minutes. Next, 11.24 g of"Nalco"1034A was added while the mixture underwent vigorous agitation. The mixture was then. flow coated onto a 4 x 4 polycarbonate panel, which was allowed to air dry for 5 minutes. The coated composition was then electron beam cured under 4MR, 160KeV electron dose at a belt speed of 68 feet per minute under a six inch. wide electron beam operated with a 4 milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The compositional ratios and test results are summarized in Table I.
ExAMPLE 9 A mixture of 1.53 g of anilinopropyltrimethoxy-silane, 51.47 g of IPA, 1.36 g of hexanedioldiacrylate and 3.34 g of trimethylolpropanetriacrylate was stirred at room temperature for 72 hours. To this mixture was added 0.23 g of glacial acetic acid. The mixture was then allowed to stand for five minutes. Next, 11.24 g of~~Nalco 1034A was added while the mixture underwent vigorous agitation. The mixture was then. flow coated onto a 4 x 4 polycarbonate panel, which was allowed to air dry for 5 minutes. The coated composition was then electron beam cured under 4MR, 160KeV electron dose at a belt speed of 68 feet per minute under a six inch. wide electron beam operated with a 4 .,..., A
milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The compositional ratios and test results are summarized in Table I.
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H 47 GJ GJ N CJ 07 G1 G! G! 41 r C
N r r r r r r r r r r f0 O G. G. a. G1 a G. G. G. G. a d E E E E E E E E E E <C a E
g ,n ro ~o ~o ~o ro ~o ro ro ro s O X X X X X X X X X X O , U LL!UJ UJ L1JLLJ t1!LLJL1J UJ LLJ OC
201823'7 The results in Table I show, among other things, that the percent c:hange.in haze which is the criterion for determining the abrasion resistance of a coating, is low where amino-organo~functional silanes are used in a composition containing multifunctional acrylates and colloidal silica. Example 5 highlights the fact that an abrasion resistant coating will result whether 'or not the solvent remaining after mixing is removed. In addition, hard abrasion resistant transparent coatings result, regardless of whether electron beam or ultraviolet light radiation is used to cure these compositions.
Table II
LIGHT TRANSMISSION v. DYE BATH TIME
COMPOSITION 0 min. 5 min. 15 min. 25 min. 35 min. 45 min Example 3 88.0 70.1 56.9 50.2 45.4 41.3 Example 4 88.0 67.7 57.4 51.1 45.7 42.4 The results in Table II show that Example 3 and Example 4 become increasingly tinted (transmit less light) as the sample time in the dye bath is increased. ' Many variations will suggest themselves to those skilled in this art in light of the above detailed description. All such obvious modifications are within the full intended scope of the appended claims.
The third. component (C) of this composition comprises silica in. the form of a colloidal dispersion.
Colloidal silica is a dispersion of submicron-sized silica (Si02) particles in. an aqueous or other solvent medium. The colloidal silicas used in this composition are dispersions of submicron size silica (Si02) particles in an aqueous or organic solvent or combination thereof. Colloidal silica is available in acid o~r basic form. Either form may be utilized. An example of satisfactory colloidal silica for use in these c*oating composi* ions is "Nalco ~~~034A colloidal silica (Nalco 1034A.~ , ~~Nalco~~84SS258 colloidal silica rNalco"*
84SS258 ) and~~Nalco~~ 1129 colloidal silica ('Nalco' 1129 ) which can be obtained from Nalco Chemical Company, Naperville,IL.
"Nalco"1034A has a mean particle size of 20 nm and an Si02 content of approximately 34°/ by weight in water with a pH of approximately 3.1. "Nalco"~4SS258 has a mean particle size of 20nm and an Si02 content of approximate*ly 30°/ by weight in a solution of propoxyethanol. ~Nalco~1129 has a * Tradcznark mean particle size of 20nm and an Si02 content of approximately 30o by weight in a solution of 40% 2-Propanol (IPA) and 30o water.
Preferably the amount of colloidal silica employed does not exceed 60% by weight of the sum of the weights of the multifunctional acrylic monomer, amino-organofunctional silane and colloidal silica.
It i_s believed by the inventors herein, that with the addition of colloidal silica, the amino-organofunctional silane modified multifunctional acrylate monomer, undergoes methoxy-hydroxy silane condensation with the collc>idal silica. In other words, the methoxy groups on the modified amino-organofunctional silane are replaced by hydroxy groups which are able to hydrogen bond to the hydroxy groups present on the surface of the roughly spherical colloidal silica particles. As a result, it is believed that the silica particles are encapsulated by the amino-organofunctional silane modified multifunctional acrylate monomers and remain suspended because of the attractive forces between the hydroxy group~~ on the amino-organofunctional silane modified multifunctional acrylate monomers. While not wishing to be bound by any particular mechanism or theory, applicant believes that the encapsulated silica particles are suspended in the mixture because of the van der Waals forces between the acrylate monomers.
Other additives can be added to the compositions i.n order to enhance the usefulness of the coatings. For example, leveling agents, ultraviolet light absorbers, dyes and the like, can be included herein. All of these additives and the use thereof are well known in the art and do not require extensive discussions. Therefore, only a limited number will be referred to, i.t being understood that any of these ,,,:, -8_ compounds can be used so long as they do not deleteriously affect the radiation curing of the coating composition and do not adversely affect the non-opaque character of t:he coating.
A particularly desirable additive has been found to be a small amount for example, up to about 10%
by weight, of a leveling agent. Leveling agents can be used on the substrates to cover surface irregularities and aid in the uniform dispersion of the coating composition. These agents are especially useful in compositions where all the solvent has been removed. For purposes of the present invention, the addition of 0.01 to 5.0 percent: commercial silicone glycol leveling agents, work well to provide the coating composition with desirable flowout and wetting properties.
Also useful as additives to the present coating compositions are UV absorbers. UV absorbers act to diminish the harmful effects of UV radiation on the final cured composition and thereby enhance the weatherability or resistance to cracking, yellowing and delamination of the coating. Incorporating UV absorbers into the instant compositions will permit the curing process regardless of.
whether UV or electron beam radiation is used to cure the composition. However, in the situation where UV
radiation is t.o be used to cure the composition, the amount of UV absorbers added must be carefully controlled so as not to hinder the cure. This limitation does not exist in the ease of electron beam radiation cure.
For the purpose of the present composition, the following UV absorbers and combinations thereof in concentration~~ of less than 20 weight percent based on the total composition, have been shown to produce desirable results: bis(1,2,2,6,6-pentamethyl-4-piperidinyl) (3,5-bis-(1,1-dimethylethyl-1-1-4-C
. ~ 2018237 _g-hydroxyphenyl)methyl)butylpropane-dioate, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, 2-hydroxyl-4-n-octoxybenzophenone, 2-(2'-hydroxy-5-methylphenyl)benzotriazole and poly(oxy-1,2-ethanediyl)-alpha-(3-(3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxylphenyl)-1-oxopropyl)-omega-hydroxy.
Concentration: of UV absorbers, however, in the range of 1 to 5 percent: based on the total weight of the composition are preferred.
In t:he practice of the present invention, the radiation curable compositions can be made by combining the multifunctional acrylate monomer or mixtures thereof with a given quantity of alcohol. Generally, the manner in which these, components are mixed together is not important. The amino-organofunctional silane is added dropwise to the mixture while agitation is applied. The mixture is thE~n stirred at a certain temperature for a sufficient period of time to allow the Michael Addition to take place. At this time, a small amount of acid may, optionally, be: added dropwise to the mixture. Suitable acids include, for example, weak acids such as acetic acid and acrylic acid, etc. and, for example, dilute solutions of t~trong acids such as hydrochloric acid and nitric acid, etc. The acid may comprise, for instance, up to ten percent by weight of acrylic acid. The colloidal silica is then added quickly while vigorous agitation is applied to the mixture. After allowing the mixture to stand for a period of time, the volatiles may optionally be removed by vacuum stripping and/or the mixture may o~>tionally be filtered.
According to the coating process of the present invention, they above described composition is coated on a substrate using conventional coating techniques modified as appropriate to the particular c ..
-9a-substrate. For example, this composition can be applied to a variety of solid substrates by methods such as flow coating, dip coating, spin coating, spray coating or curtain coating. These various methods of coating allow the composition to be placed on the substrate at variable thicknesses thus allowing a wider range of use of the composition. Coating thicknesses may vary, but for C
. Z~ 1 8237 -lo-improved abrasion resistance coating thicknesses of 3-25 microns, preferably about 5 microns, are recommended.
The compositions are then cured by either ultraviolet or electron beam radiation. The compositions may be ~iltraviolet light cured if one or more photoinitiators is added prior to curing. There are no special restrictions on the photoinitiators as long as they can generate radicals by the absorption of optical energy. Ultraviolet light sensitive photoinitiators or blends of initiators used in the UV cure of the present composition include 2-hydroxy-2-"*
methyl-1-phenyl-propan-1-one (Darocur 1173), sold by EM
Chemicals, Hawthorne, New York, and 2,2-dimethoxy-2-phenyl-acetophenone ("I:rgacure 651" ), sold by Ciba-Geigy Corporation, Hawthorne, New York. For purposes of this invention, it has been found that from 0.05 to 5 weight percent based on the total solids in the composition, of the photoinitiators described herein will cause the composition to cure.
Desirable hard, transparent coatings having excellent adhesion can thus be obtained when the composition of this invention is applied to a substrate and exposed to radiation such as that provided by UV lamps.
When the aforementioned photoinitiators are used, these additives are individually mixed with the afore-mentioned amino-organofunctional silane modified multi-functional acrylate monomers a.nd a dispersion of the multifunctional acrylate monomers and colloidal silica.
Alternatively, the coating composition may be electron beam ra.diatian cured. LQw energy electron beam radiation has the advantage over UV cure of decreasing the curing time while increasing the cross link density of the coated sample. Because electron beam radiation has a shorter wavelength than UV radiation, EB radiation penetrates deeper -into a coating sample causing more of the functional groups * Trademark (e~~ch instance) t -i -11- ~_ 2 0 1 8 2 3 7 to react, thus resulting in a greater degree of cross linking in the sample. In addition, nonfunctional groups may also react in the presence of EB radiation therefore further increa:~ing the cross link density of the coating sample. EB cure also allows for an increase in weatherability of the coating because a greater concentration c>f UV absorbers may be added to EB cured compositions than to compositions which are UV cured since the need for photoinitiators is eliminated. UV absorbers function to protect the substrate and the coating from the deleterious effects of ultra-violet light, thus resulting in the greater weatherability of EB radiation cured coated substrates.
Electron beam accelerators of various types such as van de Graaf:f-type, resonance transformer-type, linear-type, dynatron-type and high frequency-type can be used as a source of electron beam. An electron beam having energy of from 50 to 1000 KeV, preferably from 100 to 300 KeV
discharged therefrom may be irradiated in a dose of from 0.1 to 10 Mega Rads; (MR). A particularly preferred source of electron beam i.s one wherein a continuous curtain-like beam is irradiated from linear filaments. Examples of commercially available sources of electron beams are "Electro Curtain CB-150"* available from Energy Sciences Inc. And NP-ESA: 150* available from Otto Durr.
The curable composition obtained in the process of the present invention is coated on the surface of a substrate (e. g., polycarbonate, etc.). After said composition has been ultraviolet light or electron beam treated, a cured coating film is formed.
By choice of the proper formulation and application conditions including the optional use of a leveling agent, the compositions can be applied and will adhere to substantially all solid substrates. Substrates which are * Trademark C
especially contemplated herein are transparent and nontransparent plastics and metals. More particularly, these plastics are synthetic organic polymeric substrates such as acrylic polymers like poly(methylmethacrylate); polyesters, such as poly(eth~ylene terephthalate), poly(butylene ' terephthalate), etc.; polyamides; polyimides; acrylonitrile-styrene copolymers; styrene-acrylonitrile-butadiene copolymers; polyvinyl chloride; butyrates; polyethylene;
polyolefins and the like including modifications thereof.
The compositions of this invention are especially useful as transparent coatings for polycarbonates such as poly(bisphenol-A, carbonate) and those polycarbonates known as "Lexan"(R), sold by General Electric Company, Schenectady, New York; and as coatings for acrylics such as polymethyl-methacrylates. Metal substrates on which the present compositions are: also effective include bright and dull metals like aluminum and bright metallized surfaces like sputtered chromium alloy. Other solid substrates contemplated herein include wood, painted surfaces, leather, glass, ceramics and textiles.
The apparatus and testing procedures used for the results shown hE:rein are as follows:
Adhesion was measured by cross-hatch adhesion. A
series of cross-hatch scribes are made in an area of one square inch with lines to form 1/10 inch squares. This surface is covered with 1.0 inch No. 600"Scotch Brand"*
adhesive tape which is pressed down firmly over the cross-hatched area. The tape is withdrawn from the surface of the substrate with one rapid motion at about a 90° angle.
This action of applying and removing the tape is carried out three times and then the substrate is observed. The number of squares remaining intact on the substrate are reported as a percentage of the total number of squares on the grid.
* Trademark (each instance) r Steel wool testing was done as follows: A two inch square of 0000 steel wool was applied over the face of a 24 oz. hammer and was secured with a rubber band. Coated sample blanks were tested for scratch resistance to 20 double rubs across the center of the sample with the weighted steel wool.
The hammer is held by the end of its handle such that the majority of the pressure on the steel wool comes from the hammer head. The sample is graded according to the amount of scratching produced by the steel wool and hammer. The absence of scratches on the sample is graded a 1; slight scratching is graded a 2 and heavy scratching is graded a 3.
Abrasion resistance was determined according to ASTM Method D-1044, also known as the Taber Test. The instrument used was a"Teledyne"model 503 Taber Abraser with two 250 gram auxiliary weights (500 gram load) for each of the CSlOF abrasive wheels. The acrylic and polycarbonate test panels were subjected to 100 and 500 cycles on the abraser turntable. The percent change in haze which is the criterion for determining the abrasion resistance of the coating is determined by measuring the difference in haze of the unabrased and abrased coatings. Haze is defined as the percentage of transmitted light which, in passing through the sample, deviates. from the incident beam by forward scattering. In this method, only light flux that deviates more than 2.5 degrees on the average is considered to be haze. The percent haze on the coatings w*s determined by ASTM Method D10C13. A Gardner ~~Iaze Meter was used. The haze was calculated by measuring the amount of diffused light, dividing by the amount of transmitted light and multiplying by one hundred.
"Penci.l Testing" was done as follows: This test is meant to be a qualitative method of determining scratch resistance of a coating. A coated panel is placed on a firm * Trademark ,.-.
202823' horizontal surface. A pencil is held firmly against the film at.a 45° angle (point away from the operator) and pushed away from the operator in a 1/4-in. (6.5-mm) stroke. The process is started with the hardest lead pencil and continued down the scale of hardness to the pencil that will not cut into or gouge the film. T'he hardest pencil that will not cut through the film to the substrate for a distance of at least 1/8 in.
(3mm) is reported according to the following scale from Berol Corporation, Brentwood, TN.:
___________softer-____ _____________harder-_____________ 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H,7H,8H,9H
The HB grade is approximately equal to that of a .~~2 pencil.
The F grade is slightly harder and is the one most commonly used. The H grades are harder than that and get progressively harder up through the 9H grade which is very hard. The B grade is softer than the HB grade and get progressively softer through the 6B grade which is very soft.
A "tinting test" was done as follows: Coated samples were tinted using commercially available dyes from Brain Power, Inc., Miami, Fla., U.S.A. The coated samples were tinted using BPI Black ~~4600. The tinting was carried out using an Economy Six Model dye system from BPI. The tinting was carried out at about 93°C. by immersing the coated sample in BPI Lens Preparation for one (1) minute at 90°C. and then into the dye bath for up to 45 minutes. In the tables of the examples the time of immersion is indicated at 5 minutes (5 min.), 15 minutes (15 min.), 25 minutes (25 min.), 35 minutes (35 min.) and 45 minutes (45 min.). The light transmission through the sample was measured using a Gardner Haze Meter, model XL-835 Colorimeter and is reported as % transmission.
,,---15- ' In order that those skilled in the art may better understand how to practice the present invention, the following examples are given by way of illustration and not by way of limitation.
A mixture of 0.2 g of aminopropyltrimethoxysilane, 10.0 g of t-butanol, 1.32 g of hexanedioldiacrylate and 1.32 g of trimethylo7propanetriacrylate was stirred at room temperature for :l8 hours. To this mixture was added 0.62 g of glacial acetic. acid. The mixture was then allowed to stand for five minutes .
Next 3.2 g of ~~lalco~ 1034A was added while the mixture underwent vigorous agitation. The mixture was then allowed to stand for five minutes, before being vacuum stripped at 50°C, under 5 Torr pressure for ten minutes.
The resulting mixture was applied to a 4 x 4 acrylic panel a sing a ~8 wire wound rod and to a 4 x 4 polycarbonate panel by the method of spin coating. Next, each panel was electron beam cured under 4MR 160KeV electron dose at a belt speed of 68 feet per minute under a six inch wide electron beam operated with a 4 milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The compositional ratios and test results are summarized in Table I.
A mixture of 4.38 g of aminopropyltrimethoxysilane, 168.3 g of t-butanol, 22.23 gms of hexanedioldiacrylate and 22.23 g of trimethylolpropanetriacrylate was stirred at room temperature for 72 hours. To 5.0 g of this mixture, 3.75 g of~~Nalco~~'~4SS258 was added while the mixture underwent vigorous agitation. The mixture was then allowed to stand for five minutes, before being vacuum stripped at 30°C. under Torr pressure to reduce the volatile content to 54%.
*Trademark The resulting mixture was then filtered through a 5 micron filter and applied to a 4 x 4 acrylic panel using a ~~8 wire wound rod. The treated panel was then exposed to a flow of air for appro~cimately twenty minutes to remove the remaining solvent.
Next, the panel was electron beam cured under 4MR
160KeV electron dose at a belt speed of 68 feet per minute under a six inch wide electron beam operated with a 4 milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The compositional ratios and test results are summarized in Talble I.
A mixture of 1.01 g of aminopropyltrimethoxysilane, 38.75 g of isopropanol, 5.12 g of hexanedioldiacrylate and 5.12 g of trimet'tiylolpropanetriacrylate was stirred at room temperature for 72 hours. To this mixture was added 0.46 g of glacial acetic acid. The mixture was then allowed to stand for five minutes. Next, 16.58 g of~~Nalco~~1034A was added while the mixture underwent vigorous agitation. The mixture was then allowed to stand for five minutes, before being vacuum stripped at 35°C. and 2mm Hg, until all volatiles were removed. The resulting mixture was spin coated onto a 4 x 4 polycarbonate panel and electron beam cured under 4MR, 160KeV electron dose at a belt speed of 68 feet per minute under a six inch wide electron beam operated with a 4 milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The compositional ratios and test results are summarized in Table I and Table II.
EEA~LE 4 A mixture of 1.01 g of aminopropyltrimethoxysilane, 38.75 g of IPA, 5.12 g of hexanedioldiacrylate and 5.12 g of trimethylolpropanetriacrylate was stirred at room temperature for 72 hours. T'o this mixture was added 0.46 g of glacial acetic acid. The mixture was then allowed to stand for five minutes. Next, :16.58 g of"Nalco"1034A were added while the mixture underwent= vigorous agitation. The mixture was then allowed to stand for five minutes before being vacuum stripped at 35°C. and 2mm Hg, until all volatiles were .
removed. To 2.0 g of the resulting mixture, 0.01 g of~~Dow Corning"(R) 57 leveling agent was added. The mixture was then spin coated onto a 4 x 4 polycarbonate panel and electron beam cured under 4MR, 160KeV electron dose at a belt speed of 68 feet per minute under a six inch wide electron beam operated wit=h a 4 milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The compositional ratios and test results are summarized in Table I and Table II.
A mixture of 1.08 g of aminopropyltrimethoxysilane, 51.46 g of IPA, 1.36 g of hexanedioldiacrylate and 3.79 g of trimethylolpropanetriacrylate was stirred at room temperature for 72 hours. To this mixture was added 0.23 g of glacial acetic acid. The mixture was then allowed to stand for five minutes. Next, :11.24 g of~~Nalco~~1034A was added while the mixture underwent vigorous agitation. The resulting mixture was then filtere<i through a 5 micron filter.
The filtered mixture was flow coated onto a 4 x 4 polycarbonate panel, which was allowed to air dry for 5 minutes. The coa3ted composition was then electron beam cured under 4MR, 160KeV electron dose at a belt speed of 68 feet per minute under a six inch wide electron beam operated with a 4 milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The cornpositional ratios and test results are summarized in Table I.
* Trademark ,.. . ~ 2018237 A mixture of 1.08 g of aminopropyltrimethoxysilane, 25.36 g of IPA, 1.36 g of hexanedioldiacrylate and 3.79 g of trimethylolpropanetriacrylate was stirred at room temperature for 72 hours. To this mixture was added 0.23 g of glacial acetic acid. The mixture was then allowed to stand for five minutes. Next, :L2.73 g of "Nalco"'129 was added while the mixture underwent vigorous agitation. The resulting mixture was then filtered through a 5 micron filter.
The filtered mixture was flow coated onto a 4 x 4 polycarbonate panel, which was allowed to air dry for 5 minutes. The coated composition was then electron beam cured under 4MR, 160KeV electron dose at a belt speed of 68 feet per minute under a six inch wide electron beam operated with a 4 milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The compositional ratios and test results are summarized in Table I.
EEAltPLE 7 A mixture of 1.08 g of aminopropyltrimethoxysilane, 51.46 g of IPA, 1.36 g of hexanedioldiacrylate and 3.79 g of trimethylolpropanetriacrylate was stirred at room temperature for 72 hours. 7.'o this mixture was added 0.23 g of glacial acetic acid. The mixture was then allowed to stand for five minutes. Next, 11.24 g of~Nalcop1034A was added while the mixture underwent vigorous agitation. The mixture was then allowed to stand for five minutes before 0.50 g of DAROCUR*
1173, sold by Et~! Chemicals, Hawthorns, N.Y., and 0.10 g of methyldiethanol;amine were added. The resulting mixture was filtered through a 5 micron filter.
The filtered mixture was flow coated onto a 4 x 4 polycarbonate panel, which was allowed to air dry for 5 minutes. The coated polycarbonate sample was then W cured by passing the sample through a medium pressure mercury vapor arc lamp with an average intensity of 91.56 mW/cm2 at a line * Trademark speed of three feet per minute. The compositional ratios and test results are summarized in Table I.
EaAMPLE 8 A mixture of 1.53 g of anilinopropyltrimethoxy-silane, 51.47 g of IPA, 1.36 g of hexanedioldiacrylate and 0.40 g of bisphenol A dimethacrylate was stirred at room temperature for 72 hours. To this mixture was added 0.23 g of glacial acetic acid. The mixture was then allowed to stand for five minutes. Next, 11.24 g of"Nalco"1034A was added while the mixture underwent vigorous agitation. The mixture was then. flow coated onto a 4 x 4 polycarbonate panel, which was allowed to air dry for 5 minutes. The coated composition was then electron beam cured under 4MR, 160KeV electron dose at a belt speed of 68 feet per minute under a six inch. wide electron beam operated with a 4 milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The compositional ratios and test results are summarized in Table I.
ExAMPLE 9 A mixture of 1.53 g of anilinopropyltrimethoxy-silane, 51.47 g of IPA, 1.36 g of hexanedioldiacrylate and 3.34 g of trimethylolpropanetriacrylate was stirred at room temperature for 72 hours. To this mixture was added 0.23 g of glacial acetic acid. The mixture was then allowed to stand for five minutes. Next, 11.24 g of~~Nalco 1034A was added while the mixture underwent vigorous agitation. The mixture was then. flow coated onto a 4 x 4 polycarbonate panel, which was allowed to air dry for 5 minutes. The coated composition was then electron beam cured under 4MR, 160KeV electron dose at a belt speed of 68 feet per minute under a six inch. wide electron beam operated with a 4 .,..., A
milliamp electron current in a nitrogen atmosphere containing 200 ppm oxygen.
The compositional ratios and test results are summarized in Table I.
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201823'7 The results in Table I show, among other things, that the percent c:hange.in haze which is the criterion for determining the abrasion resistance of a coating, is low where amino-organo~functional silanes are used in a composition containing multifunctional acrylates and colloidal silica. Example 5 highlights the fact that an abrasion resistant coating will result whether 'or not the solvent remaining after mixing is removed. In addition, hard abrasion resistant transparent coatings result, regardless of whether electron beam or ultraviolet light radiation is used to cure these compositions.
Table II
LIGHT TRANSMISSION v. DYE BATH TIME
COMPOSITION 0 min. 5 min. 15 min. 25 min. 35 min. 45 min Example 3 88.0 70.1 56.9 50.2 45.4 41.3 Example 4 88.0 67.7 57.4 51.1 45.7 42.4 The results in Table II show that Example 3 and Example 4 become increasingly tinted (transmit less light) as the sample time in the dye bath is increased. ' Many variations will suggest themselves to those skilled in this art in light of the above detailed description. All such obvious modifications are within the full intended scope of the appended claims.
Claims (37)
1. A composition for forming an abrasion-resistant coating material formulated by the steps comprising:
reacting the following components in a solution of a polar solvent;
at least one multifunctional acrylate monomer;
an amino-organofunctional silane of the formula;
Xa Si{Q(NHQ')b NZH} 4-a wherein X is selected from alkoxy groups having 1 to 6 carbon atoms;
Q and Q' are the same or different divalent hydrocarbon groups;
Z is hydrogen or a monovalent hydrocarbon group;
a is an integer from 1 to 3; and b is an integer from 0 to 6;
for a time and at a temperature sufficient to form a Michael adduct therefrom;
adding an acid to the above-resulting solution;
and thereafter adding colloidal silica to the above-resulting solution.
reacting the following components in a solution of a polar solvent;
at least one multifunctional acrylate monomer;
an amino-organofunctional silane of the formula;
Xa Si{Q(NHQ')b NZH} 4-a wherein X is selected from alkoxy groups having 1 to 6 carbon atoms;
Q and Q' are the same or different divalent hydrocarbon groups;
Z is hydrogen or a monovalent hydrocarbon group;
a is an integer from 1 to 3; and b is an integer from 0 to 6;
for a time and at a temperature sufficient to form a Michael adduct therefrom;
adding an acid to the above-resulting solution;
and thereafter adding colloidal silica to the above-resulting solution.
2. The composition of claim 1 wherein said acid comprises up to about ten percent by weight of acrylic acid.
3. The composition of claim 1, wherein said steps further comprise vacuum stripping said polar solvent after the addition of said colloidal silica.
4. The composition of claim 1 wherein said polar solvent comprises isopropyl alcohol.
5. The composition of claim 1 wherein said multifunctional acrylate monomer is a mixture of hexanedioldiacrylate and trimethylpropanetriacrylate.
6. The composition of claim 1 wherein said colloidal silica is in an aqueous dispersion.
7. The composition of claim 6 wherein said steps further comprise vacuum stripping said polar solvent and water from said composition after the addition of colloidal silica.
8. The composition of claim 1 wherein the colloidal silica does not exceed 60% by weight of the sum of the weights of the multifunctional acrylic monomer, amino-organofunctional silane and colloidal silica.
9. The composition of claim 1 wherein said steps further comprise adding a leveling agent.
10. The composition of claim 9 which contains up to about ten percent by weight of a leveling agent.
11. The composition of claim 9 wherein the leveling agent is a silicone glycol surfactant.
12. The composition of claim 1 wherein said steps further comprise adding one or more UV
absorbers.
absorbers.
13. The composition of claim 12 which contains up to 20% UV absorbers.
14. The composition of claim 12 wherein said UV
absorbers are selected from the group consisting of bis(1,2,2,6,6-pentamethyl-4-piperidinyl)(3,5-bis(1,1-dimethylethyl 1-4'-hydroxyphenyl)methyl)butylpropanedioate, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, 2-hydroxyl-4-n-octoxybenzophenone, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and poly(oxy-1,2-ethanediyl), alpha-(3-(3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxylphenyl)-1-oxopropyl)-omega-hydroxy and combinations thereof.
absorbers are selected from the group consisting of bis(1,2,2,6,6-pentamethyl-4-piperidinyl)(3,5-bis(1,1-dimethylethyl 1-4'-hydroxyphenyl)methyl)butylpropanedioate, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, 2-hydroxyl-4-n-octoxybenzophenone, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and poly(oxy-1,2-ethanediyl), alpha-(3-(3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxylphenyl)-1-oxopropyl)-omega-hydroxy and combinations thereof.
15. The composition of claim 12 where the UV
absorber is poly(oxy-1,2-ethanediyl), alpha-(3-(3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyl-phenyl-1-oxopropyl)-omega-hydroxy.
absorber is poly(oxy-1,2-ethanediyl), alpha-(3-(3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyl-phenyl-1-oxopropyl)-omega-hydroxy.
16. The composition of claim 1 wherein said steps further comprise adding one or more photoinitiators.
17. The composition of claim 16 wherein said photoinitiator is 2,2-dimethoxy-2-phenyl-acetophenone.
18. A composition in accordance with claim 16 wherein the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-propan-1-one.
19. A composition in accordance with claim 1 wherein said multifunctional acrylate monomer is a mixture of hexanedioldiacrylate and bisphenol A
dimethacrylate.
dimethacrylate.
20. A composition in accordance with claim 1 wherein said amino-organofunctional silane is 3-amino-propyltrimethoxy silane.
21. A composition in accordance with claim 1 wherein said amino-organofunctional silane is 3-amino-propyltriethoxy silane.
22. A composition in accordance with claim 1 wherein said amino-organofunctional silane is anilino-propyltrimethoxy silane.
23. A composition in accordance with claim 1 wherein the molar ratio of said multifunctional acrylate monomer to said amino-organofunctional silane is at least 1:1.
24. A composition in accordance with claim 1 wherein said colloidal silica is an acidic aqueous dispersion.
25. A composition in accordance with claim 1 wherein said colloidal silica is dispersed in a solution of 2-propanol and water.
26. A composition in accordance with claim 1 wherein said colloidal silica is dispersed in propoxyethanol.
27. A composition in accordance with claim 1 wherein said acid is acetic acid.
28. A method of coating a surface on a substrate with an abrasion-resistant coating comprising the steps of:
(1) formulating a coating composition by reacting the following components in a solution of a polar solvent:
at least one multifunctional acrylic monomer; and an amino-organofunctional silane of the formula XaSi{Q(NHQ") b NZH}4-a wherein X is selected from alkoxy groups having 1 to 6 carbon atoms;
Q and Q' are the same or different divalent hydrocarbon groups;
Z is hydrogen or a monovalent hydrocarbon group;
a is an integer from 1 to 3; and b is an integer from 0 to 6;
for a time and at a temperature sufficient to form a Michael adduct therefrom;
(2) adding an acid to the above-resulting solution; and (3) adding colloidal silica to the above-resulting solution;
(4) applying the resulting coating composition to the surface of said substrate; and (5) curing the coating composition with radiation.
(1) formulating a coating composition by reacting the following components in a solution of a polar solvent:
at least one multifunctional acrylic monomer; and an amino-organofunctional silane of the formula XaSi{Q(NHQ") b NZH}4-a wherein X is selected from alkoxy groups having 1 to 6 carbon atoms;
Q and Q' are the same or different divalent hydrocarbon groups;
Z is hydrogen or a monovalent hydrocarbon group;
a is an integer from 1 to 3; and b is an integer from 0 to 6;
for a time and at a temperature sufficient to form a Michael adduct therefrom;
(2) adding an acid to the above-resulting solution; and (3) adding colloidal silica to the above-resulting solution;
(4) applying the resulting coating composition to the surface of said substrate; and (5) curing the coating composition with radiation.
29. The method of claim 28 further comprising the steps of:
adding one or more photoinitiators to the coating composition prior to the curing step; and carrying out the curing step by exposing the coating composition to ultraviolet radiation.
adding one or more photoinitiators to the coating composition prior to the curing step; and carrying out the curing step by exposing the coating composition to ultraviolet radiation.
30. The method of claim 28 wherein said curing step is carried out by subjecting the coating composition to electron beam radiation.
31. The method of claim 28 further comprising the step of vacuum stripping the polar solvent from said resulting composition before applying the same to the surface of said substrate.
32. An article of manufacture comprising:
(A) a substrate defining at least one surface;
(b) said at least one surface being coated with an abrasion-resistant coating formulated by:
(1) reacting the following components in a solution of a polar solvent:
at least one multifunctional acrylate monomer;
an amino-organofunctional silane of the formula X a Si{Q(NHQ')b NZH}4-a wherein:
X is selected from alkoxy groups having 1 to 6 carbon atoms;
Q and Q' are the same or different divalent hydrocarbon groups;
Z is hydrogen or a monovalent hydrocarbon group;
a is an integer from 1 to 3; and b is an integer from 0 to 6; for a time and at a temperature sufficient to form a Michael adduct therefrom;
(2) adding an acid to the above-resulting solution; and thereafter (3) adding colloidal silica to the above-resulting solution; and (C) said abrasion-resistant coating being radiation-cured upon said at least one surface.
(A) a substrate defining at least one surface;
(b) said at least one surface being coated with an abrasion-resistant coating formulated by:
(1) reacting the following components in a solution of a polar solvent:
at least one multifunctional acrylate monomer;
an amino-organofunctional silane of the formula X a Si{Q(NHQ')b NZH}4-a wherein:
X is selected from alkoxy groups having 1 to 6 carbon atoms;
Q and Q' are the same or different divalent hydrocarbon groups;
Z is hydrogen or a monovalent hydrocarbon group;
a is an integer from 1 to 3; and b is an integer from 0 to 6; for a time and at a temperature sufficient to form a Michael adduct therefrom;
(2) adding an acid to the above-resulting solution; and thereafter (3) adding colloidal silica to the above-resulting solution; and (C) said abrasion-resistant coating being radiation-cured upon said at least one surface.
33. The article of claim 32 wherein said substrate is transparent.
34. The article of claim 32 wherein said substrate is an acrylic polymer.
35. The article of claim 32 wherein said substrate is a polyester.
36. The article of claim 35 wherein said polyester substrate is selected from the group consisting of: polyethylene terephthalate);
poly(butylene terephthalate); poly(diethylene glycol bis allyl) carbonate; and poly(diphenylolpropane) carbonate.
poly(butylene terephthalate); poly(diethylene glycol bis allyl) carbonate; and poly(diphenylolpropane) carbonate.
37. The article of claim 32 wherein said substrate is a polycarbonate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US37983689A | 1989-07-14 | 1989-07-14 | |
| US379,836 | 1989-07-14 |
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|---|---|
| CA2018237A1 CA2018237A1 (en) | 1991-01-14 |
| CA2018237C true CA2018237C (en) | 2000-05-09 |
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ID=23498910
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002018237A Expired - Lifetime CA2018237C (en) | 1989-07-14 | 1990-06-05 | Radiation curable acryloxyfunctional silicone coating composition |
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|---|---|
| US (2) | US5260350A (en) |
| EP (1) | EP0408047B1 (en) |
| JP (1) | JP2892786B2 (en) |
| KR (1) | KR0154123B1 (en) |
| AU (1) | AU645018B2 (en) |
| CA (1) | CA2018237C (en) |
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| US5214085A (en) * | 1992-02-03 | 1993-05-25 | General Electric Company | Abrasion-resistant coating compositions with improved weatherability |
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| AU4123993A (en) * | 1992-06-25 | 1994-01-06 | General Electric Company | Radiation curable hardcoat compositions |
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| US5677050A (en) * | 1995-05-19 | 1997-10-14 | Minnesota Mining And Manufacturing Company | Retroreflective sheeting having an abrasion resistant ceramer coating |
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| US4455205A (en) * | 1981-06-01 | 1984-06-19 | General Electric Company | UV Curable polysiloxane from colloidal silica, methacryloyl silane, diacrylate, resorcinol monobenzoate and photoinitiator |
| US4486504A (en) * | 1982-03-19 | 1984-12-04 | General Electric Company | Solventless, ultraviolet radiation-curable silicone coating compositions |
| JPH0627196B2 (en) * | 1984-03-12 | 1994-04-13 | 大日本印刷株式会社 | Method for producing radiation curable organosilicon compound |
| US4697026A (en) * | 1986-01-06 | 1987-09-29 | Dow Corning Corporation | Acryl functional silicone compounds |
| US4822828A (en) * | 1987-11-23 | 1989-04-18 | Hoechst Celanese Corporation | Radiation curable coating composition based on a silica/vinyl-functional silanol dispersion |
| CA2023923A1 (en) * | 1989-09-05 | 1991-03-06 | Anthony Revis | Radiation curable transparent coating compositions containing basic colloidal silica |
-
1990
- 1990-06-05 CA CA002018237A patent/CA2018237C/en not_active Expired - Lifetime
- 1990-07-12 KR KR1019900010537A patent/KR0154123B1/en not_active IP Right Cessation
- 1990-07-13 JP JP2184369A patent/JP2892786B2/en not_active Expired - Lifetime
- 1990-07-13 EP EP90113427A patent/EP0408047B1/en not_active Expired - Lifetime
- 1990-07-13 AU AU59040/90A patent/AU645018B2/en not_active Expired
- 1990-07-13 DE DE69027373T patent/DE69027373T2/en not_active Expired - Lifetime
-
1992
- 1992-02-14 US US07/839,007 patent/US5260350A/en not_active Expired - Lifetime
-
1993
- 1993-02-22 US US08/020,036 patent/US5374483A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0408047A3 (en) | 1992-03-04 |
| EP0408047A2 (en) | 1991-01-16 |
| EP0408047B1 (en) | 1996-06-12 |
| DE69027373D1 (en) | 1996-07-18 |
| KR910003052A (en) | 1991-02-26 |
| CA2018237A1 (en) | 1991-01-14 |
| KR0154123B1 (en) | 1998-11-16 |
| US5260350A (en) | 1993-11-09 |
| JP2892786B2 (en) | 1999-05-17 |
| AU645018B2 (en) | 1994-01-06 |
| JPH0356514A (en) | 1991-03-12 |
| US5374483A (en) | 1994-12-20 |
| DE69027373T2 (en) | 1996-11-07 |
| AU5904090A (en) | 1991-01-17 |
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