CA2027321C - Silane free radiation curable abrasion resistant coatings - Google Patents
Silane free radiation curable abrasion resistant coatingsInfo
- Publication number
- CA2027321C CA2027321C CA 2027321 CA2027321A CA2027321C CA 2027321 C CA2027321 C CA 2027321C CA 2027321 CA2027321 CA 2027321 CA 2027321 A CA2027321 A CA 2027321A CA 2027321 C CA2027321 C CA 2027321C
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- group
- hydrocarbon radical
- monovalent hydrocarbon
- mixture
- mixtures
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Classifications
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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
-
- 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]
-
- 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
Abstract
The present invention relates to coating compositions containing multifunctional acrylate monomers, organic compounds and colloidal silica. Silanes are absent from these coating compositions. Transparent, abrasion resistant coatings result from the cure, either by ultraviolet light or electron beam radiation, of these compositions.
Description
4 2 ~
SILANE FREE RADIATION CURABLE ABRASION RESISTANT COATINGS
This invention relates to a radiation curable protective coating composition. More specifically, it relates to a silane free coating composition which, when applied to a substrate and radiation cured, forms a protective, abrasion resistant, weather resistant, ultraviolet light resistant, transparent coating firmly held thereon. In addition, substrates coated with this composition may be tinted and/or dyed. Current markets for such coatings are well established and will expand as the abrasion resistance and weatherability of these coatings is improved.
The present invention teaches not only that transparent, abrasion resistant coating compositions containing colloidal silica, water miscible hydroxy acrylates and multifunctional acrylates may be prepared, without the use of silanes, but that other specified organic compounds function in place of or in conjunction with, water miscible hydroxy acrylates, such as water immiscible hydroxy acrylates and cyclic ethers.
Accordingly, it is one object of the present invention to provide a silane free abrasion resistant coating for solid substrates. Another object of the present invention is to provide a silane free abrasion resistant coating composition in which aqueous dispersions of colloidal silica may be used. Yet another object of this invention is to provide an electron beam or ultraviolet light radiation curable coating composition for solid substrates which, when applied to a substrate, provide an improved abrasion resistant surface thereon.
7 3 2 ~ Z~
These and other objects are accomplished herein by a silane free radiation curable coating composition comprising:
(A) at least one multifunctional acrylate monomer;
(B) an organic compound selected from the group consisting of:
( i ) acrylic monomers or mixture~ thereof, Relected from the group consisting of H2C=C-COOR
and o CH2=C-C-O-R2-CH-R
R OH
(ii) cyclic ether~ or mixture~ thereof, having the general formula CH2=C-C-O-R -CH- CH2 Il \ /
R O
(iii) mixtures of (i) and (ii);
wherein:
R is a monovalent hydrocarbon radical;
R is hydrogen or a monovalent hydrocarbon radical;
R2 and R4 are selected from an alkyl or alkenyl group having 1 to 10 carbons, an aryl, alkaryl and aralkyl group containing 6 to 10 carbons; any of said groups optionally containing one or more ether oxygen atoms within .
'~ 3 ~ a ~ 7 ~
aliphatic segments thereof and optionally containing one or more functional substituents;
R3 is selected from the group consisting of hydrogen, a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and containing at least one hydroxy - group; and (C) an aqueous dispersion of colloidal silica.
Component (A) of this novel composition comprises at least one acrylate monomer which contains two or more functional groups selected from the group consisting of acryloxy and methacryloxy groups. These multifunctional acrylate monomers may be used singly or in combination with other multifunctional acrylate monomers. Some preferred multifunctional acrylate monomers useable as component (A) include:
diacrylates suchasthefollowing:
1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol dimethacrylate, poly(butanediol) diacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, triethylene glycol diacrylate, triisopropylene glycol diacrylate, polyethylene glycol diacrylate, bisphenol A dimethacrylate, B
~ ~ ~ 7 3 ~ ~
triacrylates of the formulas;
trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol monohydroxy triacrylate, trimethylolpropane triethoxy triacrylate, tetraacrylates of the formulas;
pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, pentaacrylates such as, for example, dipentaerythritol (monohydroxy) pentaacrylate.
These multifunctional acrylate monomers are commercially available from Aldrich Chemical Company, Inc., Milwaukee, Wisconsin.
The second component (B) of this composition comprises an organic compound selected from the group consisting of acrylicmonomers or mixture~ thereof, cyclic ethers or mixtures thereof, and any combination of the above - organic compounds. The acrylic monomers or mixtures thereof, is selected from the group consisting of R
and Il 2 3 CH2=C-C-O-R -CH-R
R OH
wherein:
R is a monovalent hydrocarbon radical;
Rl is hydrogen or a monovalent hydrocarbon radical;
R is selected from an alkyl or alkenyl group having 1 to 10 carbons, an aryl, alkaryl and aralkyl group containing 6 to 10 carbons; any of said groups optionally containing one or more ether oxygen atoms within aliphatic ~, J~.r _ ~ .
~5~ 7 n ~7 3 2 ~
segments thereof and optionally containing one or more functional substituents;
R is selected from the group consisting of hydrogen, a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and containing at least one hydroxy group. The exact nature of the organic portion of R2 is not critical to the operability of this invention, but said organic portion must exclude functionality which would react with either the acryloxy or hydroxy functionality thereon.
In other words, the organic portion of the R2 group serves only as a structure to link the acryloxy functionality thereof with the hydroxy functionality thereof and is preferably chemically inert. In this regard, the term "inert" defines structures which will not interfere with either the radiation curing of the acryloxy functional group or with the hYdroxy functionality. Among the acrylic monomerswhich may be utilized in the present invention are:
J
SILANE FREE RADIATION CURABLE ABRASION RESISTANT COATINGS
This invention relates to a radiation curable protective coating composition. More specifically, it relates to a silane free coating composition which, when applied to a substrate and radiation cured, forms a protective, abrasion resistant, weather resistant, ultraviolet light resistant, transparent coating firmly held thereon. In addition, substrates coated with this composition may be tinted and/or dyed. Current markets for such coatings are well established and will expand as the abrasion resistance and weatherability of these coatings is improved.
The present invention teaches not only that transparent, abrasion resistant coating compositions containing colloidal silica, water miscible hydroxy acrylates and multifunctional acrylates may be prepared, without the use of silanes, but that other specified organic compounds function in place of or in conjunction with, water miscible hydroxy acrylates, such as water immiscible hydroxy acrylates and cyclic ethers.
Accordingly, it is one object of the present invention to provide a silane free abrasion resistant coating for solid substrates. Another object of the present invention is to provide a silane free abrasion resistant coating composition in which aqueous dispersions of colloidal silica may be used. Yet another object of this invention is to provide an electron beam or ultraviolet light radiation curable coating composition for solid substrates which, when applied to a substrate, provide an improved abrasion resistant surface thereon.
7 3 2 ~ Z~
These and other objects are accomplished herein by a silane free radiation curable coating composition comprising:
(A) at least one multifunctional acrylate monomer;
(B) an organic compound selected from the group consisting of:
( i ) acrylic monomers or mixture~ thereof, Relected from the group consisting of H2C=C-COOR
and o CH2=C-C-O-R2-CH-R
R OH
(ii) cyclic ether~ or mixture~ thereof, having the general formula CH2=C-C-O-R -CH- CH2 Il \ /
R O
(iii) mixtures of (i) and (ii);
wherein:
R is a monovalent hydrocarbon radical;
R is hydrogen or a monovalent hydrocarbon radical;
R2 and R4 are selected from an alkyl or alkenyl group having 1 to 10 carbons, an aryl, alkaryl and aralkyl group containing 6 to 10 carbons; any of said groups optionally containing one or more ether oxygen atoms within .
'~ 3 ~ a ~ 7 ~
aliphatic segments thereof and optionally containing one or more functional substituents;
R3 is selected from the group consisting of hydrogen, a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and containing at least one hydroxy - group; and (C) an aqueous dispersion of colloidal silica.
Component (A) of this novel composition comprises at least one acrylate monomer which contains two or more functional groups selected from the group consisting of acryloxy and methacryloxy groups. These multifunctional acrylate monomers may be used singly or in combination with other multifunctional acrylate monomers. Some preferred multifunctional acrylate monomers useable as component (A) include:
diacrylates suchasthefollowing:
1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol dimethacrylate, poly(butanediol) diacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, triethylene glycol diacrylate, triisopropylene glycol diacrylate, polyethylene glycol diacrylate, bisphenol A dimethacrylate, B
~ ~ ~ 7 3 ~ ~
triacrylates of the formulas;
trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol monohydroxy triacrylate, trimethylolpropane triethoxy triacrylate, tetraacrylates of the formulas;
pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, pentaacrylates such as, for example, dipentaerythritol (monohydroxy) pentaacrylate.
These multifunctional acrylate monomers are commercially available from Aldrich Chemical Company, Inc., Milwaukee, Wisconsin.
The second component (B) of this composition comprises an organic compound selected from the group consisting of acrylicmonomers or mixture~ thereof, cyclic ethers or mixtures thereof, and any combination of the above - organic compounds. The acrylic monomers or mixtures thereof, is selected from the group consisting of R
and Il 2 3 CH2=C-C-O-R -CH-R
R OH
wherein:
R is a monovalent hydrocarbon radical;
Rl is hydrogen or a monovalent hydrocarbon radical;
R is selected from an alkyl or alkenyl group having 1 to 10 carbons, an aryl, alkaryl and aralkyl group containing 6 to 10 carbons; any of said groups optionally containing one or more ether oxygen atoms within aliphatic ~, J~.r _ ~ .
~5~ 7 n ~7 3 2 ~
segments thereof and optionally containing one or more functional substituents;
R is selected from the group consisting of hydrogen, a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and containing at least one hydroxy group. The exact nature of the organic portion of R2 is not critical to the operability of this invention, but said organic portion must exclude functionality which would react with either the acryloxy or hydroxy functionality thereon.
In other words, the organic portion of the R2 group serves only as a structure to link the acryloxy functionality thereof with the hydroxy functionality thereof and is preferably chemically inert. In this regard, the term "inert" defines structures which will not interfere with either the radiation curing of the acryloxy functional group or with the hYdroxy functionality. Among the acrylic monomerswhich may be utilized in the present invention are:
J
2-hydroxyethylacrylate 2-hydroxyethylmethacrylate 2-hydroxypropylacrylate 2-hydroxyethylmethacrylate 3-hydroxypropylacrylate 3-hydroxypropylcrotonate 3-hydroxypropylmethacrylate 5-hydroxypentylacrylate 2-hydroxy-3-methacryloxypropylacrylate 2-hydroxy-3-acryloxypropylacrylate 2-hydroxy-3-methacryloxypropylmethacrylate 2-hydroxyethyl 2-octenoate 2-hydroxyethyl 2-pentylacry~ate.
B
-6~ 3 These acrylic monomers are commercially available from Aldrich Chemical Company, Inc., Milwaukee, WI.
The second component (B) ~f this composition may also be a cyclic ether instead of an acrylic monomer or it may be a mixture containing both organic compounds. The cyclic ether and mixtures thereof, has the general formula o CH2=C-C-O-R -CH-CH2 Il \ /
R O
~herein:
Rl is hydrogen or a monovalent hydrocarbon radical;
R is selected from an alkyl or alkenyl group having 1 to 10 carbons, an aryl, alkaryl and aralkyl group containing 6 to 10 carbons; any of said groups optionally containing one or more ether oxygen atoms within aliphatic segments thereof and optionally containing one or more functional substituents. The exact nature of the organic portion of R4 is not critical to the operability of this invention, but said organic portion must exclude functionality which would react with either the acryloxy or epoxy functionality thereon. In other words, the organic portion of the R4 group serves only as a structure to link the acryloxy functionality thereof with the epoxy functionality thereof and is preferably chemically inert. In this regard, the term "inert" defines structures which will not interfere with either the radiation curing of the acryloxy functional group or with the epoxy group. Among the cyclic ether acrylateF, which may ~e utilized in the pre~ent invention are:
glycidylacrylate glycidylmethacrylate ethyleneglycolmonoacrylate ~ a ~ 3 ~ ~
diethyleneglycoldiacrylate triethyleneglycoldiacrylate tetraethyleneglycoldiacrylate trimethylolpropanetriacrylate tetrahydrofurfurylmethacrylate 1-6-Hexanedioldiacrylate.
These cyclic either compounds are commercially available from Aldrich Chemical Company, Inc., Milwaukee, WI.
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 (SiO2) particles in an aqueous or other solvent medium. The colloidal silicas used in this composition are dispersions of submicron size silica (SiO2) particles in an aqueous or in a water/organic solvent mixture. Colloidal silica is available in acid or basic form. Either form may be utilized. An example of satisfactory colloidal silica for use in these coating compositions is ~alco *1034A colloidal silica (Nalco *
1034A),"Nalcdl 1129 colloidal silica ~alcd'1129),"Nalco"2327 colloidal silica ~halco*2327), Nalco 2326 colloidal silica rNalco*2326) and halco 1140 colloidal silica (Nalco 1140), which can be obtained from Nalco Chemical Company, Naperville, IL.
"Nalcd' 1034A has a mean particle size of 20 nm and an SiO2 content of approximately 34% by weight in water with a pH of approximately 3.1. Nalco 1129 has a mean particle size of 20nm and an SiO2 content of approximately 30% by weight in a solution of 40% isopropanol and 30% water. "Nalco"
2327 has a mean particle size of 20nm and an SiO2 content of approximately 40% by weight in water with a pH of approximately 9.3 and ammonium as the stabilizing ion. "Nalco"
2326 has a mean particle size of 5nm and an SiO2 content of approximately 14.5% by weight in water with a pH of ~Trademark A~
~ S~ ?~
approximately 9.0 and ammonium as the stabilizing ion. Nalco 1140 has a mean particle size of 15nm and an SiO2 content of approximately 40% by weight in water with a pH of approximately 9.7 and sodium as the stabilizing ion.
Other additives can be added to the compositions in order to enhance the usefulness of the coatings. For example, leveling agents, ultraviolet light absorbers, hindered amine light stabilizers (HALS), oxygen inhibitors, 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, it being understood that any of these compounds can be used so long as they do not deleteriously effect the radiation curing of the coating composition and do not adversely effect the transparency of the coating.
A particularly desirable additive has been found to be a small amount of a leveling agent. Leveling agents can be used on the substrates to cover surface irregularities and to 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 and hindered amine light stabilizers. UV absorbers and hindered amine light stabilizers act to diminish the harmful effects of UV
radiation on the final cured product and thereby enhance the weatherability or resistance to cracking, yellowing and delamination of the coating. A preferred hindered amine -9- ~ n ~ ~ 3 light stabilizer is bis(l,2,2,6,6-pentamethyl-4-piperidinyl) [3,5-bis(l,l-dimethylethyl-4-hydroxyphenyl)methyl]butyl-propanedioate, available as Tinuvin ~ 144, from CIBA-GEIGY
Corporation, Hawthorne, NY.
For the purpose of the present compositions the following W absorbers and combinations thereof in concentrations of less than 20 weight percent based on the total composition, have been shown to produce desirable results: bis(l,2,2,6,6-pentamethyl-4-piperidinyl)(3,5-bis-(l,l-dimethylethyl 1-4-hydroxyphenyl)methyl)butylpropane-dioate, 2-ethylhexyl-2-cyano-3,3 -diphenylacrylate, 2-hydroxyl-4-n-octoxybenzophenone, 2-(2 -hydroxy-5 -methyl-phenyl)b~nzotriazole, poly(oxy-1,2-ethanediyl), alpha-(3-(3-(2H-benzotriazol-2-yl)-5-(1,1-dimethyl-ethyl)-4-hydroxylphenyl)-1-oxopropyl)-omega-hydroxy and Uvinui ~ D-50 and MS-40, sold by BASF Wyandotte Inc., Parsippa~y, NJ. Concentrations of W absorbers, however, in the range of 1 to 5 percent based on the total weight of the compositi~n are preferred.
Incorporating UV absorbers into the instant composit~ns 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 to be used to cure the composition, the amount of W
absorbers added must be carefully controlled so as not to hinder the cure. This limitation does not exist in the case of electron beam radiation cure.
In the practice of the present invention, the radiation curable compositions can be made by combining the acrylate monomers and organic compounds with a given quantity of alcohol. Generally, the manner in which these components are mixed together is not important. A small amount of a carboxylic acid may, optionally, be added dropwise to the ~"~
-lo~ 73~
mixture. Suitable carboxylic acids include, for example, acetic acid, propionic acid and benzoic acid, etc. The colloidal silica is then added while agitation is applied to the mixture. After allowing the mixture to stand for a period of time, the volatiles may optionally be removed under reduced pressure and/or the mixture may, be filtered.
According to the coating process of the present invention, the above described compositions are coated on a substrate using conventional coating techniques modified as appropriate to the particular substrate. For example, these compositions can be applied to a variety of solid substrates by methods such as roller coating, flow coating, dip coating, spin coating, spray coating and curtain coating. These various methods of coating allow the compositions to be placed on the substrate at variable thicknesses thus allowing a wider range of use of the compositions. Coating thicknesses may vary, but for improved abrasion resistance coating thicknesses of 2-25 microns, preferably about 5 microns, are recommended. The compositions are then cured by either ultraviolet or electron beam radiation.
The compositions may be ultraviolet light cured if one or more photoinitiators is added prior to curing. Oxygen inhibitors, which are materials used in conjunction with photoinitiators that increase their efficiency, may also be added. An example of a preferred oxygen inhibitor is 2-ethylhexyl-para-dimethylaminobenzoate, available as"Uvatone' 8303, from The Upjohn Company, North Haven, CT.
There are no special restrictions on the radical-type photoinitiators as long as they can generate radicals by the absorption of optical energy. Ultraviolet light sensitive photoinitiators or blends of initiators which may be used in the W cure of the present composition include 2-hydroxy-2-methyl-1-phenyl-propan-1-one ~Darocur (R) 1173), J 'J
2 7 3 ~ ~
sold by EM Industries, Inc., Hawthorne, New York, and 2,2-dimethoxy-2-phenyl-acetyl-phenone (Irgacur~ ~ 651), sold by Ciba-Geigy Corporation, Hawthorne, New York. In addition, cationic-type photoinitiators such as'~yracure UVI 6974 or UVI 6990, sold by Union Carbide Corporation, Danbury, CT., may also be used in conjunction with the radical-type photoinitiators. 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.
Alternatively, the coating composition may be electron beam radiation cured. Electron beam sources of various types such as van de Graaff-type, resonance transformer-type, linear-type, dynatron-type and high frequency-type can be used as a source of electron beam.
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 10.0 Mega Rads (MR). A
particularly preferred source of electron beam is one wherein a continuous curtain-like beam is irradiated from linear filaments. Examples of commercially available sources of electron beam are Electro Curtain CB-150 available from Energy Sciences Inc., and NP-ESH 150 available from btto 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 * Trade~nark -12~ 73~
substantially all solid substrates. Substrates which are 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(ethylene 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 ~ , 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, textiles and paper.
The apparatus and testing procedures used for the results shown herein are as follows:
Abrasion resistance was determined according to ASTM Method D-1044 (Tabor Test). The ~nstrument used was a Teledyne Taber 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 ~Trademark 3 ~. ~
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.~ degrees on the average is considered to be haze. The percent haze on the coatings was determined by ASTM Method D1003. A Gardner Haze 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.
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. Thi*s 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.
A steel wool test was conducted 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 l; slight scratching is graded a 2 and heavy scratching is graded a 3.
A pencil test was conducted which is meant to be a qualitative method of determining scratch resistance of a ~Trademark coating. A coated panel is placed on a firm 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 l/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. The 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.
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. All parts and percentages in the examples are on a weight basis.
Example 1 A mixture of 1.73 g of glycidylacrylate, 4.50 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. 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 agitation. The mixture was then allowed to stand for 24 hours, before being filtered through a five micron filter. The filtered sample was flow coated onto a 4 x 4 polycarbonate panel and allowed to air dry for five minutes. The sample was cured by electron beam 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 test results are summarized in Table I.
Example 2 A mixture of 1.89 g of glycidylmethacrylate, 4.34 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. 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 agitation. The mixture was then allowed to stand for 24 hours, before being filtered through a five micron filter. The filtered sample was flow coated onto a 4 x 4 polycarbonate panel and allowed to air dry for five minutes. The sample was cured by electron beam 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 test results are summarized in Table I.
Example 3 A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. 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 agitation. The mixture was then allowed to stand for 24 hours, before being filtered through a five micron filter. The filtered sample was flow coated onto a 4 x 4 polycarbonate panel and allowed to air dry for five minutes. The sample was cured by electron beam under 4MR, _ -16- 79 ~ ~7~
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 test results are summarized in Table I.
Example4 A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. This mixture was allowed to stand for five minutes. Next, 11.24 g of "Nalco" 1034A was added while the mixture underwent agitation. The mixture was then allowed to stand for 24 hours, before being filtered through a five micron filter. The filtered sample was flow coated onto a 4 x 4 polycarbonate panel and allowed to air dry for five minutes. The sample was cured by electron beam 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 test results are summarized in Table I.
Ex~npleS
A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. This mixture was allowed to stand for five minutes. Next, 11.24 g of Nalco 1034A was added while the mixture underwent agitation. To 10.0 g of this mixture was added 0.11 g of 2-Hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur ~ 1173), sold by EM Industries, Inc., Hawthorne, New York. This 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 UV 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 speed of three feet per minute. The test results are summarized in Table I.
Example6 A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. This mixture was allowed to stand for five minutes. Next, 11.24 g of "Nalco" 1034A was added while the mixture underwent agitation. To 10.0 g of this mixture was added 0.11 g of 2-Hydroxy-2-methyl-1-phenyl-propan-1-one (~arocur" ~ 1173), sold by EM Industries, Ine., Hawthorne, New York, and 0.02 g of 2-ethylhexyl-para-dimethylamino-benzoate, (Uvatone" ~ 8303), from The Upjohn Company, North Haven, CT. This 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 UV 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 speed of three feet per minute. The test results are summarized in Table I.
.~
- 18~ ~3 ~ ~
Example 7 A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. This mixture was allowed to stand for five minutes. Next, 11.24 g of "Nalco" 1034A was added while the mixture underwent agitation. To 10.0 g of this mixture was added 0.04 g of "Uvinol" (R) D-50, sold by BASF Wyandotte Inc., Parsippany, NJ. and 0.03 g of "Tinuvin~ (R) 144, from Ciba-Geigy Corporation, Hawthorne, NY. This 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 cured by electron beam 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 test results are summarized in Table I.
Example 8 A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. This mixture was allowed to stand for five minutes. Next, 11.24 g of Nalco 1034A was added while the mixture underwent agitation. To 10.0 g of this mixture was added 0.04 g of "Uvinul" (R) MS-40, sold by BASF Wyandotte Inc., Parsippany, NJ. and 0.03 g of (R) "Tinuvin" 144, from Ciba-Geigy Corporation, Hawthorne, NY. This 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 cured by electron beam 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 test results are summarized in Table I.
Example 9 A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. This mixture was allowed to stand for five minutes. Next, 11.24 g of "Nalco" 1034A was added while the mixture underwent agitation. To 10.0 g of this mixture was added 0.04 g of bisphenol A dimethacrylate, sold by Aldrich Chemical Company, Inc., Milwaukee, WI. and 0.03 g of "Tinuvin"
(R) 144, from Ciba-Geigy Corporation, Hawthorne, NY. This 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 cured by electron beam 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 test results are summarized in Table I.
Example 10 A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 25.23 g of isopropanol, was prepared. This mixture was allowed to stand for five minutes. Next, 12.73 g of "Nalco" 1129 was added while the mixture underwent agitation. The mixture was then allowed to stand for 24 hours, before being filtered through a five micron filter. The filtered sample was flow coated onto a 4 x 4 polycarbonate panel and allowed to air dry for 5 minutes.
The coated polycarbonate sample was cured by electron beam 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 test results are summarized in Table I.
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TABLE I
- Properties of Coated Polycarbonate ADHESION STEELPENCIL ABRASION TEST
Coating Compositions TEST WOOL TEST%H1oo %H500 Example 1 10% 2 B 3.5 12.6 Example 2 100% 2 B 10.1 20.1 Example 3 100% 2 F 1.9 9.0 Example4 100% 2 HB 1.8 7 4 Example5 100% 1 F 0.2 4.7 Example6 100% 2 HB 0.0 3.7 Example7 ~i 100% 2 HB 3.7 11. 3 Example8 100% 2 HB 6.7 12.8 Example9 100% 2 HB 3.2 10.0 ExamplelO 100% 2 HB 0.3 3.2 As the results in Table I clearly indicate, silane free, abrasion resistant coating compositions comprising multifunctional acrylates, specified organic compounds and aqueous colloidal silica may be easily manufactured.
Furthermore, excellent results were obtained whether the coating compositions were cured by ultraviolet light or by electron beam radiation.
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.
B
B
-6~ 3 These acrylic monomers are commercially available from Aldrich Chemical Company, Inc., Milwaukee, WI.
The second component (B) ~f this composition may also be a cyclic ether instead of an acrylic monomer or it may be a mixture containing both organic compounds. The cyclic ether and mixtures thereof, has the general formula o CH2=C-C-O-R -CH-CH2 Il \ /
R O
~herein:
Rl is hydrogen or a monovalent hydrocarbon radical;
R is selected from an alkyl or alkenyl group having 1 to 10 carbons, an aryl, alkaryl and aralkyl group containing 6 to 10 carbons; any of said groups optionally containing one or more ether oxygen atoms within aliphatic segments thereof and optionally containing one or more functional substituents. The exact nature of the organic portion of R4 is not critical to the operability of this invention, but said organic portion must exclude functionality which would react with either the acryloxy or epoxy functionality thereon. In other words, the organic portion of the R4 group serves only as a structure to link the acryloxy functionality thereof with the epoxy functionality thereof and is preferably chemically inert. In this regard, the term "inert" defines structures which will not interfere with either the radiation curing of the acryloxy functional group or with the epoxy group. Among the cyclic ether acrylateF, which may ~e utilized in the pre~ent invention are:
glycidylacrylate glycidylmethacrylate ethyleneglycolmonoacrylate ~ a ~ 3 ~ ~
diethyleneglycoldiacrylate triethyleneglycoldiacrylate tetraethyleneglycoldiacrylate trimethylolpropanetriacrylate tetrahydrofurfurylmethacrylate 1-6-Hexanedioldiacrylate.
These cyclic either compounds are commercially available from Aldrich Chemical Company, Inc., Milwaukee, WI.
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 (SiO2) particles in an aqueous or other solvent medium. The colloidal silicas used in this composition are dispersions of submicron size silica (SiO2) particles in an aqueous or in a water/organic solvent mixture. Colloidal silica is available in acid or basic form. Either form may be utilized. An example of satisfactory colloidal silica for use in these coating compositions is ~alco *1034A colloidal silica (Nalco *
1034A),"Nalcdl 1129 colloidal silica ~alcd'1129),"Nalco"2327 colloidal silica ~halco*2327), Nalco 2326 colloidal silica rNalco*2326) and halco 1140 colloidal silica (Nalco 1140), which can be obtained from Nalco Chemical Company, Naperville, IL.
"Nalcd' 1034A has a mean particle size of 20 nm and an SiO2 content of approximately 34% by weight in water with a pH of approximately 3.1. Nalco 1129 has a mean particle size of 20nm and an SiO2 content of approximately 30% by weight in a solution of 40% isopropanol and 30% water. "Nalco"
2327 has a mean particle size of 20nm and an SiO2 content of approximately 40% by weight in water with a pH of approximately 9.3 and ammonium as the stabilizing ion. "Nalco"
2326 has a mean particle size of 5nm and an SiO2 content of approximately 14.5% by weight in water with a pH of ~Trademark A~
~ S~ ?~
approximately 9.0 and ammonium as the stabilizing ion. Nalco 1140 has a mean particle size of 15nm and an SiO2 content of approximately 40% by weight in water with a pH of approximately 9.7 and sodium as the stabilizing ion.
Other additives can be added to the compositions in order to enhance the usefulness of the coatings. For example, leveling agents, ultraviolet light absorbers, hindered amine light stabilizers (HALS), oxygen inhibitors, 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, it being understood that any of these compounds can be used so long as they do not deleteriously effect the radiation curing of the coating composition and do not adversely effect the transparency of the coating.
A particularly desirable additive has been found to be a small amount of a leveling agent. Leveling agents can be used on the substrates to cover surface irregularities and to 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 and hindered amine light stabilizers. UV absorbers and hindered amine light stabilizers act to diminish the harmful effects of UV
radiation on the final cured product and thereby enhance the weatherability or resistance to cracking, yellowing and delamination of the coating. A preferred hindered amine -9- ~ n ~ ~ 3 light stabilizer is bis(l,2,2,6,6-pentamethyl-4-piperidinyl) [3,5-bis(l,l-dimethylethyl-4-hydroxyphenyl)methyl]butyl-propanedioate, available as Tinuvin ~ 144, from CIBA-GEIGY
Corporation, Hawthorne, NY.
For the purpose of the present compositions the following W absorbers and combinations thereof in concentrations of less than 20 weight percent based on the total composition, have been shown to produce desirable results: bis(l,2,2,6,6-pentamethyl-4-piperidinyl)(3,5-bis-(l,l-dimethylethyl 1-4-hydroxyphenyl)methyl)butylpropane-dioate, 2-ethylhexyl-2-cyano-3,3 -diphenylacrylate, 2-hydroxyl-4-n-octoxybenzophenone, 2-(2 -hydroxy-5 -methyl-phenyl)b~nzotriazole, poly(oxy-1,2-ethanediyl), alpha-(3-(3-(2H-benzotriazol-2-yl)-5-(1,1-dimethyl-ethyl)-4-hydroxylphenyl)-1-oxopropyl)-omega-hydroxy and Uvinui ~ D-50 and MS-40, sold by BASF Wyandotte Inc., Parsippa~y, NJ. Concentrations of W absorbers, however, in the range of 1 to 5 percent based on the total weight of the compositi~n are preferred.
Incorporating UV absorbers into the instant composit~ns 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 to be used to cure the composition, the amount of W
absorbers added must be carefully controlled so as not to hinder the cure. This limitation does not exist in the case of electron beam radiation cure.
In the practice of the present invention, the radiation curable compositions can be made by combining the acrylate monomers and organic compounds with a given quantity of alcohol. Generally, the manner in which these components are mixed together is not important. A small amount of a carboxylic acid may, optionally, be added dropwise to the ~"~
-lo~ 73~
mixture. Suitable carboxylic acids include, for example, acetic acid, propionic acid and benzoic acid, etc. The colloidal silica is then added while agitation is applied to the mixture. After allowing the mixture to stand for a period of time, the volatiles may optionally be removed under reduced pressure and/or the mixture may, be filtered.
According to the coating process of the present invention, the above described compositions are coated on a substrate using conventional coating techniques modified as appropriate to the particular substrate. For example, these compositions can be applied to a variety of solid substrates by methods such as roller coating, flow coating, dip coating, spin coating, spray coating and curtain coating. These various methods of coating allow the compositions to be placed on the substrate at variable thicknesses thus allowing a wider range of use of the compositions. Coating thicknesses may vary, but for improved abrasion resistance coating thicknesses of 2-25 microns, preferably about 5 microns, are recommended. The compositions are then cured by either ultraviolet or electron beam radiation.
The compositions may be ultraviolet light cured if one or more photoinitiators is added prior to curing. Oxygen inhibitors, which are materials used in conjunction with photoinitiators that increase their efficiency, may also be added. An example of a preferred oxygen inhibitor is 2-ethylhexyl-para-dimethylaminobenzoate, available as"Uvatone' 8303, from The Upjohn Company, North Haven, CT.
There are no special restrictions on the radical-type photoinitiators as long as they can generate radicals by the absorption of optical energy. Ultraviolet light sensitive photoinitiators or blends of initiators which may be used in the W cure of the present composition include 2-hydroxy-2-methyl-1-phenyl-propan-1-one ~Darocur (R) 1173), J 'J
2 7 3 ~ ~
sold by EM Industries, Inc., Hawthorne, New York, and 2,2-dimethoxy-2-phenyl-acetyl-phenone (Irgacur~ ~ 651), sold by Ciba-Geigy Corporation, Hawthorne, New York. In addition, cationic-type photoinitiators such as'~yracure UVI 6974 or UVI 6990, sold by Union Carbide Corporation, Danbury, CT., may also be used in conjunction with the radical-type photoinitiators. 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.
Alternatively, the coating composition may be electron beam radiation cured. Electron beam sources of various types such as van de Graaff-type, resonance transformer-type, linear-type, dynatron-type and high frequency-type can be used as a source of electron beam.
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 10.0 Mega Rads (MR). A
particularly preferred source of electron beam is one wherein a continuous curtain-like beam is irradiated from linear filaments. Examples of commercially available sources of electron beam are Electro Curtain CB-150 available from Energy Sciences Inc., and NP-ESH 150 available from btto 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 * Trade~nark -12~ 73~
substantially all solid substrates. Substrates which are 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(ethylene 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 ~ , 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, textiles and paper.
The apparatus and testing procedures used for the results shown herein are as follows:
Abrasion resistance was determined according to ASTM Method D-1044 (Tabor Test). The ~nstrument used was a Teledyne Taber 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 ~Trademark 3 ~. ~
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.~ degrees on the average is considered to be haze. The percent haze on the coatings was determined by ASTM Method D1003. A Gardner Haze 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.
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. Thi*s 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.
A steel wool test was conducted 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 l; slight scratching is graded a 2 and heavy scratching is graded a 3.
A pencil test was conducted which is meant to be a qualitative method of determining scratch resistance of a ~Trademark coating. A coated panel is placed on a firm 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 l/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. The 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.
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. All parts and percentages in the examples are on a weight basis.
Example 1 A mixture of 1.73 g of glycidylacrylate, 4.50 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. 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 agitation. The mixture was then allowed to stand for 24 hours, before being filtered through a five micron filter. The filtered sample was flow coated onto a 4 x 4 polycarbonate panel and allowed to air dry for five minutes. The sample was cured by electron beam 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 test results are summarized in Table I.
Example 2 A mixture of 1.89 g of glycidylmethacrylate, 4.34 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. 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 agitation. The mixture was then allowed to stand for 24 hours, before being filtered through a five micron filter. The filtered sample was flow coated onto a 4 x 4 polycarbonate panel and allowed to air dry for five minutes. The sample was cured by electron beam 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 test results are summarized in Table I.
Example 3 A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. 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 agitation. The mixture was then allowed to stand for 24 hours, before being filtered through a five micron filter. The filtered sample was flow coated onto a 4 x 4 polycarbonate panel and allowed to air dry for five minutes. The sample was cured by electron beam under 4MR, _ -16- 79 ~ ~7~
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 test results are summarized in Table I.
Example4 A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. This mixture was allowed to stand for five minutes. Next, 11.24 g of "Nalco" 1034A was added while the mixture underwent agitation. The mixture was then allowed to stand for 24 hours, before being filtered through a five micron filter. The filtered sample was flow coated onto a 4 x 4 polycarbonate panel and allowed to air dry for five minutes. The sample was cured by electron beam 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 test results are summarized in Table I.
Ex~npleS
A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. This mixture was allowed to stand for five minutes. Next, 11.24 g of Nalco 1034A was added while the mixture underwent agitation. To 10.0 g of this mixture was added 0.11 g of 2-Hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur ~ 1173), sold by EM Industries, Inc., Hawthorne, New York. This 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 UV 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 speed of three feet per minute. The test results are summarized in Table I.
Example6 A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. This mixture was allowed to stand for five minutes. Next, 11.24 g of "Nalco" 1034A was added while the mixture underwent agitation. To 10.0 g of this mixture was added 0.11 g of 2-Hydroxy-2-methyl-1-phenyl-propan-1-one (~arocur" ~ 1173), sold by EM Industries, Ine., Hawthorne, New York, and 0.02 g of 2-ethylhexyl-para-dimethylamino-benzoate, (Uvatone" ~ 8303), from The Upjohn Company, North Haven, CT. This 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 UV 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 speed of three feet per minute. The test results are summarized in Table I.
.~
- 18~ ~3 ~ ~
Example 7 A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. This mixture was allowed to stand for five minutes. Next, 11.24 g of "Nalco" 1034A was added while the mixture underwent agitation. To 10.0 g of this mixture was added 0.04 g of "Uvinol" (R) D-50, sold by BASF Wyandotte Inc., Parsippany, NJ. and 0.03 g of "Tinuvin~ (R) 144, from Ciba-Geigy Corporation, Hawthorne, NY. This 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 cured by electron beam 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 test results are summarized in Table I.
Example 8 A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. This mixture was allowed to stand for five minutes. Next, 11.24 g of Nalco 1034A was added while the mixture underwent agitation. To 10.0 g of this mixture was added 0.04 g of "Uvinul" (R) MS-40, sold by BASF Wyandotte Inc., Parsippany, NJ. and 0.03 g of (R) "Tinuvin" 144, from Ciba-Geigy Corporation, Hawthorne, NY. This 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 cured by electron beam 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 test results are summarized in Table I.
Example 9 A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 51.46 g of isopropanol, was prepared. This mixture was allowed to stand for five minutes. Next, 11.24 g of "Nalco" 1034A was added while the mixture underwent agitation. To 10.0 g of this mixture was added 0.04 g of bisphenol A dimethacrylate, sold by Aldrich Chemical Company, Inc., Milwaukee, WI. and 0.03 g of "Tinuvin"
(R) 144, from Ciba-Geigy Corporation, Hawthorne, NY. This 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 cured by electron beam 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 test results are summarized in Table I.
Example 10 A mixture of 2.07 g of hydroxyethylacrylate, 4.16 g of trimethylolpropanetriacrylate and 25.23 g of isopropanol, was prepared. This mixture was allowed to stand for five minutes. Next, 12.73 g of "Nalco" 1129 was added while the mixture underwent agitation. The mixture was then allowed to stand for 24 hours, before being filtered through a five micron filter. The filtered sample was flow coated onto a 4 x 4 polycarbonate panel and allowed to air dry for 5 minutes.
The coated polycarbonate sample was cured by electron beam 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 test results are summarized in Table I.
-20~ 3 ~ ~
TABLE I
- Properties of Coated Polycarbonate ADHESION STEELPENCIL ABRASION TEST
Coating Compositions TEST WOOL TEST%H1oo %H500 Example 1 10% 2 B 3.5 12.6 Example 2 100% 2 B 10.1 20.1 Example 3 100% 2 F 1.9 9.0 Example4 100% 2 HB 1.8 7 4 Example5 100% 1 F 0.2 4.7 Example6 100% 2 HB 0.0 3.7 Example7 ~i 100% 2 HB 3.7 11. 3 Example8 100% 2 HB 6.7 12.8 Example9 100% 2 HB 3.2 10.0 ExamplelO 100% 2 HB 0.3 3.2 As the results in Table I clearly indicate, silane free, abrasion resistant coating compositions comprising multifunctional acrylates, specified organic compounds and aqueous colloidal silica may be easily manufactured.
Furthermore, excellent results were obtained whether the coating compositions were cured by ultraviolet light or by electron beam radiation.
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.
B
Claims (6)
1. A silane free radiation curable coating composition comprising:
(A) at least one multifunctional acrylate monomer;
(B) an organic compound selected from the group consisting of (i) acrylic monomers or mixtures thereof, selected from the group consisting of and (ii) cyclic ethers or mixtures thereof, having the general formula (iii) mixtures of (i) and (ii);
wherein:
R is a monovalent hydrocarbon radical;
R1 is hydrogen or a monovalent hydrocarbon radical;
R2 and R4 are selected from an alkyl or alkenyl group having 1 to 10 carbons, an aryl, alkaryl and aralkyl group containing 6 to 10 carbons; any of said groups optionally containing one or more ether oxygen atoms within aliphatic segments thereof;
R3 is selected from the group consisting of hydrogen, a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and containing at least one hydroxy group; and (C) an aqueous dispersion of colloidal silica.
(A) at least one multifunctional acrylate monomer;
(B) an organic compound selected from the group consisting of (i) acrylic monomers or mixtures thereof, selected from the group consisting of and (ii) cyclic ethers or mixtures thereof, having the general formula (iii) mixtures of (i) and (ii);
wherein:
R is a monovalent hydrocarbon radical;
R1 is hydrogen or a monovalent hydrocarbon radical;
R2 and R4 are selected from an alkyl or alkenyl group having 1 to 10 carbons, an aryl, alkaryl and aralkyl group containing 6 to 10 carbons; any of said groups optionally containing one or more ether oxygen atoms within aliphatic segments thereof;
R3 is selected from the group consisting of hydrogen, a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and containing at least one hydroxy group; and (C) an aqueous dispersion of colloidal silica.
2. A composition as claimed in claim 1 which additionally contains a carboxylic acid.
3. A composition as claimed in claim 1 which additionally contains one or more materials selected from the group consisting of UV absorbers, hindered amine light stabilizers, photoinitiators and oxygen inhibitors.
4. The product obtained by the cure of the composition of claim 1.
5. A process for preparing a silane free radiation curable coating composition comprising (I) combining (A) at least one multifunctional acrylate monomer;
(B) an organic compound selected from the group consisting of (i) acrylic monomers or mixtures thereof, selected from the group consisting of and (ii) cyclic ethers or mixtures thereof, having the general formula (iii) mixtures of (i) and (ii);
wherein:
R is a monovalent hydrocarbon radical;
R1 is hydrogen or a monovalent hydrocarbon radical;
R2 and R4 are selected from an alkyl or alkenyl group having 1 to 10 carbons, an aryl, alkaryl and aralkyl group containing 6 to 10 carbons; any of said groups optionally containing one or more ether oxygen atoms within aliphatic segments thereof;
R3 is selected from the group consisting of hydrogen, a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and containing at least one hydroxy group; and (II) mixing the product of (I) with (C) an aqueous dispersion of colloidal silica.
(B) an organic compound selected from the group consisting of (i) acrylic monomers or mixtures thereof, selected from the group consisting of and (ii) cyclic ethers or mixtures thereof, having the general formula (iii) mixtures of (i) and (ii);
wherein:
R is a monovalent hydrocarbon radical;
R1 is hydrogen or a monovalent hydrocarbon radical;
R2 and R4 are selected from an alkyl or alkenyl group having 1 to 10 carbons, an aryl, alkaryl and aralkyl group containing 6 to 10 carbons; any of said groups optionally containing one or more ether oxygen atoms within aliphatic segments thereof;
R3 is selected from the group consisting of hydrogen, a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and a monovalent hydrocarbon radical having from 1 to 6 carbon atoms and containing at least one hydroxy group; and (II) mixing the product of (I) with (C) an aqueous dispersion of colloidal silica.
6. A solid substrate having at least one surface coated with the cured composition of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/423,159 US5126394A (en) | 1989-10-18 | 1989-10-18 | Radiation curable abrasion resistant coatings from colloidal silica and acrylate monomer |
| US423,159 | 1989-10-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2027321A1 CA2027321A1 (en) | 1991-04-19 |
| CA2027321C true CA2027321C (en) | 1998-12-01 |
Family
ID=23677875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2027321 Expired - Fee Related CA2027321C (en) | 1989-10-18 | 1990-10-11 | Silane free radiation curable abrasion resistant coatings |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5126394A (en) |
| EP (1) | EP0424006B1 (en) |
| JP (1) | JPH03140371A (en) |
| CA (1) | CA2027321C (en) |
| DE (1) | DE69024316T2 (en) |
| ES (1) | ES2084007T3 (en) |
Families Citing this family (81)
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|---|---|---|---|---|
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Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3986997A (en) * | 1974-06-25 | 1976-10-19 | Dow Corning Corporation | Pigment-free coating compositions |
| JPS5163382A (en) * | 1974-11-29 | 1976-06-01 | Kohkoku Chem Ind | Shinsui bodonseitomakuokeiseisuru hoho |
| DE2927249A1 (en) * | 1978-07-07 | 1980-01-17 | Sinloihi Co Ltd | FINE SPHERICAL POLYMER PARTICLES CONTAINING AN INORGANIC PIGMENT AND / OR A BLACK COLORANT, AND METHOD FOR THE PRODUCTION THEREOF |
| US4436851A (en) * | 1978-11-30 | 1984-03-13 | General Electric Company | Silicone resin coating composition containing an ultraviolet light absorbing agent |
| US4309319A (en) * | 1978-11-30 | 1982-01-05 | General Electric Company | Silicone resin coating composition |
| US4348462A (en) * | 1980-07-11 | 1982-09-07 | General Electric Company | Abrasion resistant ultraviolet light curable hard coating compositions |
| GB2089826B (en) * | 1980-12-18 | 1985-01-03 | Gen Electric | Abrasion resistant ultraviolet light curable hard coating compositions |
| 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 |
| US4575473A (en) * | 1983-05-26 | 1986-03-11 | Union Carbide Corporation | Curable poly(acrylate) molding compositions containing a thermoplastic polymer low profile additive |
| US4557980A (en) * | 1984-08-21 | 1985-12-10 | Martin Processing, Inc. | Radiation curable coating for film structure |
| DE3439482A1 (en) * | 1984-10-27 | 1986-05-07 | Röhm GmbH, 6100 Darmstadt | METHOD FOR COATING SUBSTRATES WITH SCRATCH-RESISTANT, NON-REFLECTIVE COVERS |
| JPS63286409A (en) * | 1987-05-19 | 1988-11-24 | Idemitsu Petrochem Co Ltd | Production of curable resin composition |
| JP2576586B2 (en) * | 1987-08-12 | 1997-01-29 | 日本油脂株式会社 | Method for producing polymer non-aqueous dispersion, polymer non-aqueous dispersion and coating composition |
-
1989
- 1989-10-18 US US07/423,159 patent/US5126394A/en not_active Expired - Fee Related
-
1990
- 1990-10-09 EP EP19900311040 patent/EP0424006B1/en not_active Expired - Lifetime
- 1990-10-09 ES ES90311040T patent/ES2084007T3/en not_active Expired - Lifetime
- 1990-10-09 DE DE1990624316 patent/DE69024316T2/en not_active Expired - Fee Related
- 1990-10-11 CA CA 2027321 patent/CA2027321C/en not_active Expired - Fee Related
- 1990-10-18 JP JP2277921A patent/JPH03140371A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CA2027321A1 (en) | 1991-04-19 |
| DE69024316D1 (en) | 1996-02-01 |
| JPH03140371A (en) | 1991-06-14 |
| EP0424006A3 (en) | 1991-10-16 |
| ES2084007T3 (en) | 1996-05-01 |
| EP0424006B1 (en) | 1995-12-20 |
| EP0424006A2 (en) | 1991-04-24 |
| US5126394A (en) | 1992-06-30 |
| DE69024316T2 (en) | 1996-07-18 |
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