CA1078266A - Caustic-resistant polymer coatings for glass - Google Patents
Caustic-resistant polymer coatings for glassInfo
- Publication number
- CA1078266A CA1078266A CA258,691A CA258691A CA1078266A CA 1078266 A CA1078266 A CA 1078266A CA 258691 A CA258691 A CA 258691A CA 1078266 A CA1078266 A CA 1078266A
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- CA
- Canada
- Prior art keywords
- copolymer
- glass
- acid
- alpha
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
TITLE
Caustic-Resistant Polymer Coatings For Glass ABSTRACT OF THE DISCLOSURE
Improved caustic-resistant coatings for glass which comprise (1) a primer layer consisting essentially of an epoxy resin containing a curing agent, e.g., poly-amide, amine, etc., and an organofunctional silane either in a single layer or separate layers, in order on the glass, (a) organofunctional silane and (b) epoxy resin, and (2) a copolymer of alpha-olefins of the formula R-CH=CH2, where R is a radical of hydrogen or alkyl radicals having from 1 to 8 carbon atoms, and alpha, beta-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, said copolymer having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions.
Caustic-Resistant Polymer Coatings For Glass ABSTRACT OF THE DISCLOSURE
Improved caustic-resistant coatings for glass which comprise (1) a primer layer consisting essentially of an epoxy resin containing a curing agent, e.g., poly-amide, amine, etc., and an organofunctional silane either in a single layer or separate layers, in order on the glass, (a) organofunctional silane and (b) epoxy resin, and (2) a copolymer of alpha-olefins of the formula R-CH=CH2, where R is a radical of hydrogen or alkyl radicals having from 1 to 8 carbon atoms, and alpha, beta-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, said copolymer having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions.
Description
1078Z~
BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to caustic-resistant coatings for glass, and particularly such coatings which include a primer of a combination of an epoxy resin and an organofunctional silane. The invention has particular-ly valuable utility for providing clear, caustic resistant, adherent coatings for glass containers which strengthen the container and provide a safety factor.
Description of the Prior Art Copolymers of alpha-olefins and alpha, beta-ethylenically unsaturated carboxylic acids when used as coatings for surfaces such as glass bottles, do not change the physical appearance of the bottles. The coatings exhibit good initial adhesion to glass, but the adhesion deteriorates rapidly in the presence of high humidity due to hydrophilicity. Beverage bottles of the returnable type are sterilized in a hot caustic solution (e.g., 5 percent NaOH, 70C.). One or two 15-minute caustic treatments have been found to destroy the adhesion between the glass and the polymers.
In Belgian Patent 822,689, issued May 28, 1975, improved adhesion between glass and ionic copolymers has been achieved by priming the glass with amino- or epoxy functional silane or epoxy resins. About five ~ 15-minute caustic treatments can be tolerated before the - adhesion between glass and the ionic copolymer , deteriorates. Still further improvement in caustic resistance, e.g., 10 to 15 treatments, is achieved by overcoating the ionic copolymer layer with a polymeric, ;' ~ -2-': , ~ . 1078266 hydrophobic protective layer, e.g., nylon.
Wells ~. S. Patent 3,297,186 describes a method of permanently sealing glass surfaces together using an adhesive composition consisting essentially of a major portion of an epoxy resin, a curing agent and a minor amount of an amino-substituted alkylalkoxysilane.
There is no teaching in this patent that a polymer or other nonsilicious material will form a strong caustic-resistent bond to glass via this adhesive.
Kiel U. S. Patent 3,666,539 describes glass coatings having increased permanency of adhesion and capable of being rapidly cured at elevated temperatures.
The coatings consist essentially of at least one carboxyl functional acrylic resin, at least one hydroxyl containing epoxy resin and a small effective amount of an ambi-functional epoxy reactive silane. The coating is said to exhibit permanency of adhesion to a glass surface when soaked in 3 percent by weight aqueous NaOH solution - at 160F. (71C.) for a relatively short period of time.
~ 20 The acrylic compound acts as a curing agent, and the coating provides only poor protection against caustic.
S~MMARY OF THE INVENTION
It has now been found that clear coatings on ; glass, particularly returnable glass bottles, which exhibit improved caustic-resistance to 15-minute treat-ments in 5 percent by wei~ht solution of NaOH at 70 to 80C. comprise, (l) a primer layer consisting essentially of a combination of (A) an organofunctional silane and (B) an epoxy resin containing a curing agent taken from the group consisting of an amine and a :
': ' , 1~'78~6 polyamide compound where (A) and (B) are in a single layer or in individual layers, with the proviso that the silane layer (A) is adjacent the glass and (2) a copoly-meric layer consisting essentially of a copolymer of alpha-ole~ins of the fo~mula R-CH=C~, where R is a radical selected from the class consisting of hydrogen and alkyl radicals having from 1 to 8 carbon atoms, and alpha, beta-ethylenically unsaturated carboxylic a.cids having from 3 to 8 carbon atoms, said copolymeræ having from O
to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions, said metal ions having an ionized valence of from one-to three inclusive when the . unsaturated acid is a monocarboxylic acid and an ionized valence of one when the unsaturated acid is a dicarbox-; ylic acid and said metal ions being selected from the group consisting of uncomplexed and complexed metal ions, . said copolymer being a direct copolymer of the alpha-olefins and the unsaturated carboxylic acid in which the carboxylic acid groups are randomly distributed over all molecules and in which (a) the alpha-olefin content of the copolymer is at least 70 mol percent, based on the alpha-~ olefin-acid copolymer, (b) the unsaturated carboxylic acid content of the copolymer is from 0.2 to 5 mol percent, ~. based on the alpha-olefin-acid copolymer, and (c) any 9, other monomer component copolymerized in said copolymer fJ' being monoethylenically unsaturated and being in an amount ~. of O to 29.8 mol percent, based on the alpha-ole~in-acid copolymer.
.~ DETAILED DESCRIPTION OF THE INVENTION
The improved clear, caustic-resistant coatings , for glass comprise (1) a primer layer consisting '''''; :.. ~_ , .
1078;266 essentially of a combination of (A) an organofunctional silane and (B) an epoxy resin in either a single layer, or in individual layers with the silane layer adjacent the glass; and (2) a copolymeric layer which is more fully described below. A curing agent, e.g., polyamide or amine, is present with the epoxy resin. The primer layer(s) may be applied by any one of a number of well known coating means such as spraying of a liquid dispersion or solution, dipping into a solution or dispersion, fluidized bed powder coating, electrostatic powder spraying, etc. Such coatings meet the standard of resisting delamination for at ~east twelve 15-minute . treatments in 5 percent by weight caustic solution at 70 to 80C.
Suitable silane compounds useful in the primer layer or as a separate layer are organofunctional silanes of the formula: (RO)3Si(CH2)xR~ where RO is a hydrolyzable alkoxy group, R being an alkyl radical of 1 to 4 carbon atoms; Rl is a functional organic group, e.g., /O\ HCl NH2-, CH2-CH-CH2O-, and -NH-CH2CH2-NH-CH2-C6H4-CH=CH2;
and x is a whole number of 1 to 4. Useful silanes are gamma-aminopropyltriethoxy silane, gamma-glycidoxy-; propyltrimethoxy silane and N-vinylbenzylaminoethyl-3-trimethoxysilylpropylamine hydrochloride which is preferred.
Epoxy resins useful in combination with the silane compounds include epichlorohydrin/bisphenol A
- types, epoxy compounds containing one or more oxirane . .
:~ 1078Z66 o . , / \ , rings, CH2-CH , e.g., cycloaliphatic epoxies, etc. The epoxy resihs contain a curing agent. Polyamides and amines are preferred curing agents but acid or anhydride epoxy curing agents are useful. Amine and polyamide curing agents include resin materials such as, for example, primary amine functional acrylic resins. I~hen a reactive polyamide is used, very thin primer coatings, e.g., 0.2 mil (0 .005 mm.) in thickness, perform well. When the epoxy resins contain other type curing agents thicker coatings are necessary (higher percentage of solids in the dispersion). The ratio of epoxy resin to curing agent ranges from 1:1 to 4:1 and perhaps slightly higher.
The concentration range for the aqueous epoxy systems ranges from 7. 5 to 40 percent by weight total solids. The degree of caustic resistance is de-pendent on the concentration (viscosity) of epoxy resin.
Aqueous epoxv systems are preferred over organic solvent systems and powder form for economic reasons. Aqueous epoxy systems are better from pollution and fire hazard standpoints. Small amounts of water soluble organic solvents can be used in the aqueous epoxy systems, how-ever, to enhance the wetting characteristics of the system. Eligible water soluble organic solvents are se-lected to be chemically inert with resoect to other components in the primer systems.
referably the silane compound and epoxy resin , . .
are present in a single layer. Not only is one priming -l operation eliminated but the presence of the silane ~: I
l 3~ compound stabilizes the dispersion viscosity.
,.
, ' .
.
The primer compounds can be applied to the glass surface over a wide range of conditions. For example, the glass, at room temperature, preferably in the form of a bottle, but the glass can be flat or have other shapes, can be sprayed with a dispersion or solution of the primer containing epoxy resin, epoxy curing agent and an organofunctional silane; or the glass can be sprayed with a dispersion or solution of organofunctional silane and, preferably after drying, sprayed with a dispersion or solution of epoxy resin or the epoxy resin can be applied in the form of a powder. The solution tempera-tures range from 20C. up to 70C. or more. The concentration range of the silane compound when present with the epoxy resin is about 0.05 to 5 percent by weight, preferably about 2 percent by weight, based on the total weight of dispersion. When applied separately the organofunctional silane is present in a range of about 0.05 to 10 percent by weight, preferably about 2 percent by weight. A wetting agent, e.g., alcohols and ethers such as methanol, ethanol, diethylene glycol monoethyl ether, etc. and nonionic detergents such as the Igepal~ series sold by General Aniline and Film Company can be used in con-junction with the epoxy dispersions. Other coating tech-niques as previously described are also useful. The primer layer(s) is cured to the gel point which is understood to be to the point of solidification and not complete curing of the primer layer(s). Curing can be conducted by using con-vection air, e.g., 5 to 8 minutes at 205C. or 60 to 120 - seconds in an infrared oven with the surface of the quartz ; 30 heaters at 788C. The cured primer layer(s) can range in ~~" ~(~78'~;6 thickness from 0.1 to 3.0 mils (0.003 to o.o8 mm. ) .
Additives can be used in con~unction with the epoxy resin to extend the uncured pot life of the epoxy resln system. Additives eligible for use in practlce of this invention include acetic acid and metal salts which form a complex with the epoxy curing agents. Water soluble zinc salts are preferred and zinc chloride is most pre-ferred, because epoxy resinæ cured in the presence of zinc salts are not discolored and because the use of zinc salts provides an epoxy dispersion of increased viscosity more suitably adapted as a coating composition. The zinc salts are used in an amount of about 5 to 50 percent by weight and, preferably, about 15 to 30 percent by weight, of the amount of curing agent in the epoxy system.
Onto the cured primed surface of the glass is placed a copolymer of alpha-olefins, preferably an ionic ~; copolymer powder. The copolymers can be O to 100 percent neutralized with metal ions. Also use~ul is a blend o~
such copolymer powder and a nylon powder. Preferred copolymers are described in U.S. Patent 3,264,272. The copolymers may be applied in the form of a powder of 100 mesh or finer particles. Preferably the particles which make up the powder are in the form of spherlcal-shaped particles having an average diameter of 10 to 100 microns and are characterized by having a surface that is rough and is covered with hemispherical-shaped bumps about 0.1 micron in diameter at the base. The unique, spherical-- shaped particles can be prepared by a method described in ;~ U.S. Patent No. 3,933,954.
",~..1~, ~
` `-``` 1~78;~
, Illustrati~e o~ the polymers are copolymers of alpha-ole~ins of the formula R-CH= ~ , where R i8 hydrogen or an alkyl radical of 1 to 8 carbon atoms; and alpha, beta-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and, optionally, a noethylenlcally unsaturated monomer. Suitable olefins include ethylene, propylene, butene-l, pentene-l, hexene-l, heptene-l, 3-methylbutene-1, 4~methylpentene-1, etc. The preferred olefin ~s ethylene. Although polymers o~
ole~ins having higher carbon nu~bers can be employed in the pre~ent invention, they are not materials which are readily obtained or a~ailable. The concentration of the alpha-ole~in is at least 70 mol percent in the co~olymer and is preferably greater than 80 mol percent. Exa~ples of alpha, beta-ethylenically unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ltaconic acid, maleic acid, fumaric acid, monoesters Or said dicarboxylic acids, such as methyl hgdrogen maleate, methyl hydrogen fumarate, ethyl hydrogen ~umarate and maleic anhydride. Although maleic anhydrlde is not a carboxylic acid in that it haB no hydrogen attached to the carboxyl groups, it can be considered an acid ~or the purposes of the pxesent invention because of its chemical reactivity being that o~ an acid. Similarly~
other alpha, beta~m~noethylenically unsaturated anhydrides o~ carboxylic acids can be employed. The preferred unsaturæted carboxylic acids are methacrylic and ,; .
acrylic aclds. As indicated, the concentrat~on of acldic monomer ln the copolymer is from 0.2 mol percent to 5.0 mol percent.
,... .
. _9 _ ~078;~66 me copolymer base need not necessarily comprise a two component polymer. Thus, although the olefin content of the copolymer should be at least 70 mol percent, more than one ole M n can be employed to provide the hydrocarbon nature of the copolymer base. Additionally, other copolymerizable monoethylenically un~aturated monomer~, illustrative member~ of whlch are mentioned below in this and the following paragraph, can be s employed in combination with the olefin and the carboxylic acid comonomer. The scope of base copolymer~ suitable ; for use in the present invent~on is illustrated by the ~ollowing two component examples: ethylene/acrylic acid ~-. copolymers, ethylene/methacrylic acid copolymers, ethylene/
itaconic acid copolymers, ethylene/methyl hydrogen maleate copolymeræ, and ethylene/maleic acid copolymers, etc.
~xamples of tri-component copolymers include: ethylene/
acryl~c acid/methyl methacrylate copolymers, ethylene/
methacrylic acid/ethyl acrylate copolymer~, ethylene/
itaconic acid/methyl methacrylate copolymers, ethylene/
methyl hydrogen maleate/ethyl acrylate copolymers, ; eth~lene/methacrylic acid/vinyl acetate copolymers~
ethylene/acrylic acid/vinyl alcohol copolymers, ethylene/propylene/acrylic acld copolymers, ethylene/
styrene/acryl~c acid copolymers, ethylene/methacryl~c acld/acrylonitrile copolymers, ethylene/iumaric acid/
vinyl methyl ether copolymeræ, ethylene/vinyl ehloride/
acrylic acid copolymers, ethylene/vinylidene chloride/
acrylic acid copolymers, ethylene/vinyl fluoride/methacrylic ; acid copolymer~, and ethylene/chlorotrifluoroethylene/
methacryl~c acid copolymers.
~ `
, ~
-07B;~66 Other particularly preferred third monomerlc components are the alkyl esters of an alpha, beta-ethylenically unsaturated carboxylic acid of 3 to 8 carbon atoms where the alkyl radical has 4 to 18 carbon atoms. Particularly preferred are the terpolymers obtained from the copolymerization of ethylene, methacrylic acid and alkyl esters of methacrylic and/or acrylic acid with butanol.
The concentration of the third optional component ls 0.2 to 25 mol percent, based on the weight -of copolymer, pre~erablg from 1 to 10 mol percent.
Representative examples of the third component include n-butyl acrylate, isobutyl acrylate, secondary butyl -acrylate, tertiary butgl acrylate, n-butyl methacrylate, b isobutyl methacrylate, sec-butyl methacryla~e, t~butyl methacrylate, n~pentyl acrylate, n-pentyl methacrylate, isopentyl acrylate, isopentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethyl-hexyl acrylate,
BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to caustic-resistant coatings for glass, and particularly such coatings which include a primer of a combination of an epoxy resin and an organofunctional silane. The invention has particular-ly valuable utility for providing clear, caustic resistant, adherent coatings for glass containers which strengthen the container and provide a safety factor.
Description of the Prior Art Copolymers of alpha-olefins and alpha, beta-ethylenically unsaturated carboxylic acids when used as coatings for surfaces such as glass bottles, do not change the physical appearance of the bottles. The coatings exhibit good initial adhesion to glass, but the adhesion deteriorates rapidly in the presence of high humidity due to hydrophilicity. Beverage bottles of the returnable type are sterilized in a hot caustic solution (e.g., 5 percent NaOH, 70C.). One or two 15-minute caustic treatments have been found to destroy the adhesion between the glass and the polymers.
In Belgian Patent 822,689, issued May 28, 1975, improved adhesion between glass and ionic copolymers has been achieved by priming the glass with amino- or epoxy functional silane or epoxy resins. About five ~ 15-minute caustic treatments can be tolerated before the - adhesion between glass and the ionic copolymer , deteriorates. Still further improvement in caustic resistance, e.g., 10 to 15 treatments, is achieved by overcoating the ionic copolymer layer with a polymeric, ;' ~ -2-': , ~ . 1078266 hydrophobic protective layer, e.g., nylon.
Wells ~. S. Patent 3,297,186 describes a method of permanently sealing glass surfaces together using an adhesive composition consisting essentially of a major portion of an epoxy resin, a curing agent and a minor amount of an amino-substituted alkylalkoxysilane.
There is no teaching in this patent that a polymer or other nonsilicious material will form a strong caustic-resistent bond to glass via this adhesive.
Kiel U. S. Patent 3,666,539 describes glass coatings having increased permanency of adhesion and capable of being rapidly cured at elevated temperatures.
The coatings consist essentially of at least one carboxyl functional acrylic resin, at least one hydroxyl containing epoxy resin and a small effective amount of an ambi-functional epoxy reactive silane. The coating is said to exhibit permanency of adhesion to a glass surface when soaked in 3 percent by weight aqueous NaOH solution - at 160F. (71C.) for a relatively short period of time.
~ 20 The acrylic compound acts as a curing agent, and the coating provides only poor protection against caustic.
S~MMARY OF THE INVENTION
It has now been found that clear coatings on ; glass, particularly returnable glass bottles, which exhibit improved caustic-resistance to 15-minute treat-ments in 5 percent by wei~ht solution of NaOH at 70 to 80C. comprise, (l) a primer layer consisting essentially of a combination of (A) an organofunctional silane and (B) an epoxy resin containing a curing agent taken from the group consisting of an amine and a :
': ' , 1~'78~6 polyamide compound where (A) and (B) are in a single layer or in individual layers, with the proviso that the silane layer (A) is adjacent the glass and (2) a copoly-meric layer consisting essentially of a copolymer of alpha-ole~ins of the fo~mula R-CH=C~, where R is a radical selected from the class consisting of hydrogen and alkyl radicals having from 1 to 8 carbon atoms, and alpha, beta-ethylenically unsaturated carboxylic a.cids having from 3 to 8 carbon atoms, said copolymeræ having from O
to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions, said metal ions having an ionized valence of from one-to three inclusive when the . unsaturated acid is a monocarboxylic acid and an ionized valence of one when the unsaturated acid is a dicarbox-; ylic acid and said metal ions being selected from the group consisting of uncomplexed and complexed metal ions, . said copolymer being a direct copolymer of the alpha-olefins and the unsaturated carboxylic acid in which the carboxylic acid groups are randomly distributed over all molecules and in which (a) the alpha-olefin content of the copolymer is at least 70 mol percent, based on the alpha-~ olefin-acid copolymer, (b) the unsaturated carboxylic acid content of the copolymer is from 0.2 to 5 mol percent, ~. based on the alpha-olefin-acid copolymer, and (c) any 9, other monomer component copolymerized in said copolymer fJ' being monoethylenically unsaturated and being in an amount ~. of O to 29.8 mol percent, based on the alpha-ole~in-acid copolymer.
.~ DETAILED DESCRIPTION OF THE INVENTION
The improved clear, caustic-resistant coatings , for glass comprise (1) a primer layer consisting '''''; :.. ~_ , .
1078;266 essentially of a combination of (A) an organofunctional silane and (B) an epoxy resin in either a single layer, or in individual layers with the silane layer adjacent the glass; and (2) a copolymeric layer which is more fully described below. A curing agent, e.g., polyamide or amine, is present with the epoxy resin. The primer layer(s) may be applied by any one of a number of well known coating means such as spraying of a liquid dispersion or solution, dipping into a solution or dispersion, fluidized bed powder coating, electrostatic powder spraying, etc. Such coatings meet the standard of resisting delamination for at ~east twelve 15-minute . treatments in 5 percent by weight caustic solution at 70 to 80C.
Suitable silane compounds useful in the primer layer or as a separate layer are organofunctional silanes of the formula: (RO)3Si(CH2)xR~ where RO is a hydrolyzable alkoxy group, R being an alkyl radical of 1 to 4 carbon atoms; Rl is a functional organic group, e.g., /O\ HCl NH2-, CH2-CH-CH2O-, and -NH-CH2CH2-NH-CH2-C6H4-CH=CH2;
and x is a whole number of 1 to 4. Useful silanes are gamma-aminopropyltriethoxy silane, gamma-glycidoxy-; propyltrimethoxy silane and N-vinylbenzylaminoethyl-3-trimethoxysilylpropylamine hydrochloride which is preferred.
Epoxy resins useful in combination with the silane compounds include epichlorohydrin/bisphenol A
- types, epoxy compounds containing one or more oxirane . .
:~ 1078Z66 o . , / \ , rings, CH2-CH , e.g., cycloaliphatic epoxies, etc. The epoxy resihs contain a curing agent. Polyamides and amines are preferred curing agents but acid or anhydride epoxy curing agents are useful. Amine and polyamide curing agents include resin materials such as, for example, primary amine functional acrylic resins. I~hen a reactive polyamide is used, very thin primer coatings, e.g., 0.2 mil (0 .005 mm.) in thickness, perform well. When the epoxy resins contain other type curing agents thicker coatings are necessary (higher percentage of solids in the dispersion). The ratio of epoxy resin to curing agent ranges from 1:1 to 4:1 and perhaps slightly higher.
The concentration range for the aqueous epoxy systems ranges from 7. 5 to 40 percent by weight total solids. The degree of caustic resistance is de-pendent on the concentration (viscosity) of epoxy resin.
Aqueous epoxv systems are preferred over organic solvent systems and powder form for economic reasons. Aqueous epoxy systems are better from pollution and fire hazard standpoints. Small amounts of water soluble organic solvents can be used in the aqueous epoxy systems, how-ever, to enhance the wetting characteristics of the system. Eligible water soluble organic solvents are se-lected to be chemically inert with resoect to other components in the primer systems.
referably the silane compound and epoxy resin , . .
are present in a single layer. Not only is one priming -l operation eliminated but the presence of the silane ~: I
l 3~ compound stabilizes the dispersion viscosity.
,.
, ' .
.
The primer compounds can be applied to the glass surface over a wide range of conditions. For example, the glass, at room temperature, preferably in the form of a bottle, but the glass can be flat or have other shapes, can be sprayed with a dispersion or solution of the primer containing epoxy resin, epoxy curing agent and an organofunctional silane; or the glass can be sprayed with a dispersion or solution of organofunctional silane and, preferably after drying, sprayed with a dispersion or solution of epoxy resin or the epoxy resin can be applied in the form of a powder. The solution tempera-tures range from 20C. up to 70C. or more. The concentration range of the silane compound when present with the epoxy resin is about 0.05 to 5 percent by weight, preferably about 2 percent by weight, based on the total weight of dispersion. When applied separately the organofunctional silane is present in a range of about 0.05 to 10 percent by weight, preferably about 2 percent by weight. A wetting agent, e.g., alcohols and ethers such as methanol, ethanol, diethylene glycol monoethyl ether, etc. and nonionic detergents such as the Igepal~ series sold by General Aniline and Film Company can be used in con-junction with the epoxy dispersions. Other coating tech-niques as previously described are also useful. The primer layer(s) is cured to the gel point which is understood to be to the point of solidification and not complete curing of the primer layer(s). Curing can be conducted by using con-vection air, e.g., 5 to 8 minutes at 205C. or 60 to 120 - seconds in an infrared oven with the surface of the quartz ; 30 heaters at 788C. The cured primer layer(s) can range in ~~" ~(~78'~;6 thickness from 0.1 to 3.0 mils (0.003 to o.o8 mm. ) .
Additives can be used in con~unction with the epoxy resin to extend the uncured pot life of the epoxy resln system. Additives eligible for use in practlce of this invention include acetic acid and metal salts which form a complex with the epoxy curing agents. Water soluble zinc salts are preferred and zinc chloride is most pre-ferred, because epoxy resinæ cured in the presence of zinc salts are not discolored and because the use of zinc salts provides an epoxy dispersion of increased viscosity more suitably adapted as a coating composition. The zinc salts are used in an amount of about 5 to 50 percent by weight and, preferably, about 15 to 30 percent by weight, of the amount of curing agent in the epoxy system.
Onto the cured primed surface of the glass is placed a copolymer of alpha-olefins, preferably an ionic ~; copolymer powder. The copolymers can be O to 100 percent neutralized with metal ions. Also use~ul is a blend o~
such copolymer powder and a nylon powder. Preferred copolymers are described in U.S. Patent 3,264,272. The copolymers may be applied in the form of a powder of 100 mesh or finer particles. Preferably the particles which make up the powder are in the form of spherlcal-shaped particles having an average diameter of 10 to 100 microns and are characterized by having a surface that is rough and is covered with hemispherical-shaped bumps about 0.1 micron in diameter at the base. The unique, spherical-- shaped particles can be prepared by a method described in ;~ U.S. Patent No. 3,933,954.
",~..1~, ~
` `-``` 1~78;~
, Illustrati~e o~ the polymers are copolymers of alpha-ole~ins of the formula R-CH= ~ , where R i8 hydrogen or an alkyl radical of 1 to 8 carbon atoms; and alpha, beta-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and, optionally, a noethylenlcally unsaturated monomer. Suitable olefins include ethylene, propylene, butene-l, pentene-l, hexene-l, heptene-l, 3-methylbutene-1, 4~methylpentene-1, etc. The preferred olefin ~s ethylene. Although polymers o~
ole~ins having higher carbon nu~bers can be employed in the pre~ent invention, they are not materials which are readily obtained or a~ailable. The concentration of the alpha-ole~in is at least 70 mol percent in the co~olymer and is preferably greater than 80 mol percent. Exa~ples of alpha, beta-ethylenically unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ltaconic acid, maleic acid, fumaric acid, monoesters Or said dicarboxylic acids, such as methyl hgdrogen maleate, methyl hydrogen fumarate, ethyl hydrogen ~umarate and maleic anhydride. Although maleic anhydrlde is not a carboxylic acid in that it haB no hydrogen attached to the carboxyl groups, it can be considered an acid ~or the purposes of the pxesent invention because of its chemical reactivity being that o~ an acid. Similarly~
other alpha, beta~m~noethylenically unsaturated anhydrides o~ carboxylic acids can be employed. The preferred unsaturæted carboxylic acids are methacrylic and ,; .
acrylic aclds. As indicated, the concentrat~on of acldic monomer ln the copolymer is from 0.2 mol percent to 5.0 mol percent.
,... .
. _9 _ ~078;~66 me copolymer base need not necessarily comprise a two component polymer. Thus, although the olefin content of the copolymer should be at least 70 mol percent, more than one ole M n can be employed to provide the hydrocarbon nature of the copolymer base. Additionally, other copolymerizable monoethylenically un~aturated monomer~, illustrative member~ of whlch are mentioned below in this and the following paragraph, can be s employed in combination with the olefin and the carboxylic acid comonomer. The scope of base copolymer~ suitable ; for use in the present invent~on is illustrated by the ~ollowing two component examples: ethylene/acrylic acid ~-. copolymers, ethylene/methacrylic acid copolymers, ethylene/
itaconic acid copolymers, ethylene/methyl hydrogen maleate copolymeræ, and ethylene/maleic acid copolymers, etc.
~xamples of tri-component copolymers include: ethylene/
acryl~c acid/methyl methacrylate copolymers, ethylene/
methacrylic acid/ethyl acrylate copolymer~, ethylene/
itaconic acid/methyl methacrylate copolymers, ethylene/
methyl hydrogen maleate/ethyl acrylate copolymers, ; eth~lene/methacrylic acid/vinyl acetate copolymers~
ethylene/acrylic acid/vinyl alcohol copolymers, ethylene/propylene/acrylic acld copolymers, ethylene/
styrene/acryl~c acid copolymers, ethylene/methacryl~c acld/acrylonitrile copolymers, ethylene/iumaric acid/
vinyl methyl ether copolymeræ, ethylene/vinyl ehloride/
acrylic acid copolymers, ethylene/vinylidene chloride/
acrylic acid copolymers, ethylene/vinyl fluoride/methacrylic ; acid copolymer~, and ethylene/chlorotrifluoroethylene/
methacryl~c acid copolymers.
~ `
, ~
-07B;~66 Other particularly preferred third monomerlc components are the alkyl esters of an alpha, beta-ethylenically unsaturated carboxylic acid of 3 to 8 carbon atoms where the alkyl radical has 4 to 18 carbon atoms. Particularly preferred are the terpolymers obtained from the copolymerization of ethylene, methacrylic acid and alkyl esters of methacrylic and/or acrylic acid with butanol.
The concentration of the third optional component ls 0.2 to 25 mol percent, based on the weight -of copolymer, pre~erablg from 1 to 10 mol percent.
Representative examples of the third component include n-butyl acrylate, isobutyl acrylate, secondary butyl -acrylate, tertiary butgl acrylate, n-butyl methacrylate, b isobutyl methacrylate, sec-butyl methacryla~e, t~butyl methacrylate, n~pentyl acrylate, n-pentyl methacrylate, isopentyl acrylate, isopentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethyl-hexyl acrylate,
2-ethyl-hexyl methacrylate, stearyl acrylate, stearyl methacrylate, n-butyl ethacrylate, 2-ethyl hexyl ethacrylate. Also, the third component includes mono- and di-esters of 4 to 8 carbon atom dicarboxylic acid such aæ n-butyl hydrogen maleate, sec~butyl hydrogen maleate, isobutyl hydrogen maleate, t-butyl hydrogen maleate, 2-ethyl hexyl hydrogen maleate, stearyl hydrogen maleate, n-butyl hydrogen fumarate, sec-butyl hydrogen fumarate~ isobutyl hydrogen fumarate, t-butyl hydrogen fumarate, 2-ethyl hexyl hydrogen fumarate, stearyl hydrogon fumarate, n-butyl fumarateg sec-butyl ~umarate, i~obuty~ fumarate, t-butyl ~umarate, 2-ethyl ,; -11-.,.
. ~
''' ' ' ' :` 1078266 hexyl fumarate, stearyl fumarate, n-butyl maleate, sec-butyl maleate, isobutyl maleate, t-butyl maleate, 2-ethyl hexyl maleate, stearyl maleate. The preferred alkyl esters contain alkyl yroups of 4 to 8 carbon atoms. The most preferred contain 4 carbon atoms in the alkyl ester group. Representative examples of the most preferred esters are n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate.
The copolymers may also, after polymerization but prior to any ionic crosslinking, be further modified by various reactions to result in polymer modifications which do not interfere with the ionic crosslinking.
~alogenation of an olefin acid copolymer is an example of such polymer modification.
The preferred base copolymers, however, are those obtained by the direct copolymerization of ethylene with a monocarboxylic acid comonomer.
Metal ions which are suitable in forming the ionic copolymers employed in the present invention can be divided into two categories, uncomplexed metal ions and complexed metal ions. In the uncomplexed metal ions the valence of the ion corresponds to the valence of the metal. These metal ions are obtained from the commonly known and used metal salts. The complexed metal ions are , those in which the metal is bonded to more than one type of salt group, at least one of which is ionized and at least one of which is not. Since the formation of the ionic copolymers requires only one ionized valence state, it will be apparent that such complexed metal ions are equally well suited in the present invention. The term "metal ion having one or more ioni~ed valence states"
- means a metal ion having the general formula Me+nXm, where n is the ionic charge and is at least one, X is a nonionized group and n+m equal the valence of the metal. The utility of complexed metal ions employed in the formation of ionic copolymers corresponds in their ionized valences to those of the uncomplexed metal ions.
The monovalent metals are, of course, excluded from the class of complexed metal ions but higher valent metals may be included depending on how many metal valences are complexed and how many can be ionized. The preferred metal ions are those in which all but one metal valences are complexed and one is readily ionized. Such compounds are in particular the mixed salts of very weak salts, such as oleic and stearic acid, with ionizable acids, such as formic and acetic acid.
The uncomplexed metal ions which are suitable in forming the ionic copolymers useful in the present in-vention, therefore comprise for the alpha-olefin-mono-carboxylic acid copolymers, mono-, di- and trivalent ions of metals in Groups I, II, III, IV-A and VIII of the Periodic Table of Elements (see page 392, Handbook of Chemistry and Physics, Chemical Rubber Publishing Co., 37th ed.). Uncomplexed monovalent metal ions of the metals in the stated groups are also suitable in forming the ionic copolymers with copolymers of olefins and ethylenically unsaturated dicarboxylic acids. Suitable monovalent metal ions are Na+, K+, Li+, Cs+, Ag+, Hg+ and Cu+. Suitable divalent metal ions are Be+2, Mg+2, Ca+2, ,;
;,,, ..
-` 1078266 Sr 2, Ba+2, Cu+2, Cd+2, Hg+2, Sn+2 pb+2 Fe+2 Co+2 Ni+2 and Zn+2. Suitable trivalent metal ions are Al+3, Sc+3, Fe+3 and Y+3.
The preferred metal ions, regardless of the nature of the base copolymer are Na+ and Zn+2. These metals are preferred because they result in ionic co-polymers having the best combination of improvement in solid state properties with retention of melt fabricability. It is not essential that only one metal ion be employed in the formation of the ionic copolymers and more than one metal ion may be preferred in certain applications.
While it is not necessary that the copolymers be neutralized, preferably they are neutralized in the range of 10 to 50 percent. It has been found that co-polymeric layers comprising 100 percent neutralized copolymers are also useful. The fully neutralized copolymeric layers may be applied as such or may result from caustic treatment of glass bottles coated with a ;~ 20 partially neutralized copolymeric layer.
~ The melt index of the copolymer ranges from 0.1 - g./10 minutes to 500 g./10 minutes, preferably 10 to 150 g./10 minutes.
The nylon powder used in the blend with copolymers of alpha-olefins to improve abrasion and ; heat resistance can be prepared from polycaprolactam (6-nylon), polyhexamethylene adipamide (66-nylon), polyhexamethylene sebacamide (610-nylon), polyhexa-- methylene dodecamide, as well as similar aliphatic polycarbonamides. The nylons must be capable of being :
melted to form the protective layer, thus the lower melting nylons are particularly useful. Crystal Clad¢i3 nylon powder sold by General Mills is useftll. This nylon is prepared from hexamethylene diamine, sebacic acid and another component which is believed to be a linoleic dimer or trimer.
The blend of copolymer and nylon powder can be prepared by dry blending the components to form a homogeneous mixture. Melt blending the copolymer and nylon resins prior to the production of the powder results in a powder useful to form coatings with properties equal to or superior to those produced from the dry blend. In general 60 to 90 parts hy weight of ., .
copolymer powder are blended with 10 to 40 parts by weight of nylon powder. A preferred blend is 80 parts by weight copolymer powder and 20 parts by weight of nylon powder.
The copolymer powder or blend with nylon powder can be placed on the primed surface by conventional electrostatic powder coating equipment. For flat glass objects, such as microscopic slides used in laboratory testing, the powder can be applied in such a manner that a cloud of powder falls or is sprinkled onto the glass held essentially horizontal. The copolymer powder or blend thereof is fused by convection heating or -infrared radiation heating above the fusing pOillt to form continuous coatings, 4 to 12 mils (0.1 to 0.3 mm.), preferably 8 to 10 mils (0.2 to 0.25 mm.) in thickness.
The fused ionic copolymer coating is desirably of such thickness to retain 90 to 100 percent of the glass ~78Z~;6 ., .
fragments when a bottle pressured to 60 psig (4.22 kg./
sq. cm.) is dropped 4 feet (1.22 m.) onto a metal slab.
While the coating thickness can vary, it is desirable to keep it as thin as possible to obtain the desired results.
A nylon protective layer can optionally be present on the copolymer layer. In forming the protective layer a nylon powder can be applied and fused over the layer of copolymer, or a nylon film may be laminated to the copolymer layer. It is desirable that the protective layer be clear and abrasive and heat resistant. Thickness of the protective layer is in the order of 1.5 to 2.0 mils (0.04 to 0.05 mm.).
The present invention has particular utility in providing returnable glass bottles for carbonated beverages which are stronger and more resistant to fracture on impact than glass alone and which, in case of fracture, provide a valuable safety factor by retaining the broken gIass. The coatings in their preferred embodiments exhibit excellent resistance to hot caustic treatment solutions used to sterilize returnable glass bottles. The coatings of the present invention are also useful on other glass items such as fluorescent light bulbs, and protective screens for television tubes.
~ EXAMPLES OF THE INVENTION
;~ The following Examples furtller illustrate the invention. All percentages are by weight unless otherwise indicated. The caustic solution is a 5 percent solution at 80C. unless otherwise indicated.
1~378~66 '' EXA~IE 1 Glass slides were primed with N-vinylbenzyl-aminoethyl-3-trimethoxysilylpropylamine hydrochloride, Dow Corning silane QZ-85069*J by dipping in a 2 percent aqueous dispersion at ambient temperature for 30 seconds followed by air drying. me primed glass slide~ were dipped in an acetone solution of an epoxy resin of the formula:
/0 ~ C~ OH
CH2 -cH2~o-c6H4-c-c6E4-o-cH2-cH-cH23n i CH3 ~ where n is in the range of 1 to 20, Genepoxy~ 205 General - Mills Co., containing a reactive polyamide containing ex-cess amine groups as a curing agentJ Versamid~ 5201 HR 65 General Mills Co. Total solids in the acetone solution were 55 percent and the epoxy resin/curing agent weight ratio was 1.4:1Ø The epoxy/curing agent coating was ;; cured by maintaining the slides under an infrared radiation quartz heater manufactured by Hugo N. Cahnman Associates, Ine., Model ES-10 (1000 wattsJ 240 volts) for about 7 minutes. While still hot the slides were dipped in an ionic copolymer powder of a 24 percent sodium neutralized copolymer of ethylene with 11 percent methacrylic acid having a melt index o~ 20.4 g./10 minutes (ASTM D-1238, Condltion E) having a ~olume average particle size of 37 microns dete~mined by a Quantimet Image Analyzing ,~'! Computer- The ionic copolymer was prepared as described P! in Example 1 of U.S. Patent 3,933,954, issued January 20, ;~ 1976. The powder was then fused by placing the slides under a horizontally mounted quartz heater for `
~denctes trade mark ~:, --= ., r about 60 seconds. The ionic copolymer coating was about 8 mils (0.20 mm) thick. The coated slides were treated by placing them in caustic solution for fifteen minute periods. The three-layer coating was still tenaciously bonded to the glass after 41 fifteen-minute periods.
The above procedure was repeated except that the epoxy layer was omitted and the ionic copolymer coating was top coated with about a 3-mil (0.08 mm.) thick layer of nylon powder, Crystal Clad~ EP~2100 General Mills Company and believed to be a 610/636 copolymer. The glass slides withstood thirteen periods of the caustic solution.
The procedure of paragraph one above was repeated except that the silane layer was omitted. After the epoxy layer was cured, it delaminated from the glass slide after only one fifteen-minute period in caustic solution.
The procedure of paragraph one above was re-peated except that the layer of ionic copolymer was omitted. After the epoxy layer was cured, it withstood -;
62 fifteen-minute periods in caustic solution.
The procedure of paragraph one above was repeated except that in lieu of the epoxy layer the silane-treated slides were dipped in about a 12 percent chloroform solution of a low molecular weight polyamide ;
derived from a reaction of dimer acid (aliphatic, dibasic acid produced by the polymerization of un-saturated fatty acids), Emerz~ 1537, Emory Industries, air dried and coated with ionic copolymex powder. In two fifteen-minute periods in caustic solution (70C.) the ionic copolymer layer delaminated from the polyamide -layer, the polyamide layer was tenaciously bonded to the glass after 20 fifteen-minute periods in the caustic solution.
Glass slides were primed with the silane described in Example 1 and were air dried. The slides ; were then dipped in an aqueous solution of epoxy resin of the formula:
O\ CH3 OH
CH2-CH-C~I2~O-C6H4-C-C6H4-o CH2 C 2~n ` CH3 where n is in the range of 1 to 20, General Mills Co. TS~
679~, 50 percent solids dispersion, containing a reac-tive polyamide containing excess amine groups as a cur-ing agent, Versamid3 5501 General Mills Co. Total solids in the dispersion were adjusted to 15 percent.
The epoxy/curing agent weight ratio was 1.4:1Ø The ; epoxy layer was cured by maintaining the slides under j 20 the quartz heater described in Example 1 for 2 minutes.
The slides were then dipped in the ionic copolymer powder described in Example 1 and the powder fused as described in that Example. The coated slides withstood at least 36 fifteen-minute periods in the hot caustic solution of Example 1.
The above procedure was repeated except that the ionic copolymer described in Example 1 was replaced with an unneutralized acid copolymer powder having a melt ' index of 10g./10 minutes and containing 9.0 percent ,~ 30 methacrylic acid. The glass slides withstood at least .. --19--, ' ' ~
~ 1078Z66 20 fifteen-minute periods in the caustic solution without delamination.
The above procedure was repeated except that the silane primer layer was omitted. The glass slides withstood only two fifteen-minute periods in the caustic solution before delamination of the ionic copolymer layer.
Glass slides were primed with the silane described in Example 1 and were air dried. The slides were preheated under the quartz heater of Example 1 for about 15 seconds and dipped in epoxy powder, Vitralon~
80-1005, Pratt and Lambert Company. The powder was cured under the quartz heater for about 2 minutes. The thick-ness of the epoxy layer was about 1.0 mil (0.025 mm.).
The slides were then dipped in the ionic copolymer powder described in that Example. The coated slides withstood at least 49 fifteen-minute periods in the caustic solution of Example 1 without sign of delamination.
The above procedure was repeated except that the silane primer layer was omitted. The glass slides withstood four fifteen-minute periods in the caustic solution before delamination of the ionic copolymer layer.
--Glass slides were primed with the silane ; described in Example 1 and were air dried. The slides were then primed with an aqueous dispersion of an epoxy resin of the formula:
; 30 ~ -20--~ 1078266 , O CH OH
;~ / \ , 3 CH2-CH-CH2~O-C6H4-C-C6H4 O CH2 C 2~n where n is in the range of 1 to 20, TSX 679 General Mills Co., containing as the curing agent a modified amine A-100~, General Mills Company which is a ketone blocked amine of ,, ~ Rl ~ .
, the formula -R-N=C \ and a molecular weight of ~" \R2 ' 10 about 1100; functionality of about 4; equivalent weight ,~ of about 275; blocking agent: methyl isobutyl ketone.
' Total solids for the dispersion was adjusted to 16.6 percent and the epoxy-curing agent ratio was 1.26 to 1Ø
~` The epoxy layer was cured under a horizontally xi mounted quartz heater by maintaining the slides under ;, the heater for 2 minutes. The slides were then dipped /~ in the ionic copolymer powder described in Example 1 and `~, the powder fused as described in that Example. The coated slides withstood at least 2~ fifteen-minute periods in the hot caustic solution of Example 1 without sign of delamination.
;
The above procedure was repeated except that the curing agent was omitted in the aqueous epoxy dispersion. The epoxy resin was adjusted to 10 percent ~ and the epoxy layer was cured for greater than 6 minutes `l under the quartz heater described in Example 1. The final ionic copolymer coated slides showed signs of delamination after four fifteen-minute periods in the ' hot caustic solution.
.:, ," O
,~ , ;
:.
~ 1078Z~;6 .
Glass beverage bottles (Coca Cola returnable bottles No. 53201) were primed with the silane described in Example l and were air dried. The bottles were dipped in the aqueous solution of epoxy resin as described . in Example 2. The total solids of the epoxy resin solution was adjusted to 25 percent and the epoxy/curing agent ratio was 2.0 to lØ The epoxy layer was cured in a convection air oven for 7 minutes at about 205C.
, lO The bottles were coated with the ionic copolymer as described in Example l, and the powder was fused as described in that Example. Cuts were made in the bottle coatings to simulate extreme bottle abuse. The bottles withstood 40 fifteen-minute periods in the caustic solution (70C.) of Example l. After each period the bottles were abused in an American Glass Research bottle line simulator.
Glass beverage bottles described in Example 5 were primed with gamma-aminopropyltriethoxysilane, ~ -- NH2-(CH213-Si-(OC2H5)3 A-llO0~ manufactured by Union Carbide by dipping the bottles in a 2 percent aqueous solution for 30 seconds at ambient temperature and were air dried. The bottles were dipped in the epoxy ) ~
i, dispersion described in Example 5 and cured as described in that Example. The bottles were preheated to 177C.
~ in a convection air oven and coated with the ionic -~ copolymer powder described in Example l using a Gema~
:. .
electrostatic spray gun (60 kilovolts), Interrad
. ~
''' ' ' ' :` 1078266 hexyl fumarate, stearyl fumarate, n-butyl maleate, sec-butyl maleate, isobutyl maleate, t-butyl maleate, 2-ethyl hexyl maleate, stearyl maleate. The preferred alkyl esters contain alkyl yroups of 4 to 8 carbon atoms. The most preferred contain 4 carbon atoms in the alkyl ester group. Representative examples of the most preferred esters are n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate.
The copolymers may also, after polymerization but prior to any ionic crosslinking, be further modified by various reactions to result in polymer modifications which do not interfere with the ionic crosslinking.
~alogenation of an olefin acid copolymer is an example of such polymer modification.
The preferred base copolymers, however, are those obtained by the direct copolymerization of ethylene with a monocarboxylic acid comonomer.
Metal ions which are suitable in forming the ionic copolymers employed in the present invention can be divided into two categories, uncomplexed metal ions and complexed metal ions. In the uncomplexed metal ions the valence of the ion corresponds to the valence of the metal. These metal ions are obtained from the commonly known and used metal salts. The complexed metal ions are , those in which the metal is bonded to more than one type of salt group, at least one of which is ionized and at least one of which is not. Since the formation of the ionic copolymers requires only one ionized valence state, it will be apparent that such complexed metal ions are equally well suited in the present invention. The term "metal ion having one or more ioni~ed valence states"
- means a metal ion having the general formula Me+nXm, where n is the ionic charge and is at least one, X is a nonionized group and n+m equal the valence of the metal. The utility of complexed metal ions employed in the formation of ionic copolymers corresponds in their ionized valences to those of the uncomplexed metal ions.
The monovalent metals are, of course, excluded from the class of complexed metal ions but higher valent metals may be included depending on how many metal valences are complexed and how many can be ionized. The preferred metal ions are those in which all but one metal valences are complexed and one is readily ionized. Such compounds are in particular the mixed salts of very weak salts, such as oleic and stearic acid, with ionizable acids, such as formic and acetic acid.
The uncomplexed metal ions which are suitable in forming the ionic copolymers useful in the present in-vention, therefore comprise for the alpha-olefin-mono-carboxylic acid copolymers, mono-, di- and trivalent ions of metals in Groups I, II, III, IV-A and VIII of the Periodic Table of Elements (see page 392, Handbook of Chemistry and Physics, Chemical Rubber Publishing Co., 37th ed.). Uncomplexed monovalent metal ions of the metals in the stated groups are also suitable in forming the ionic copolymers with copolymers of olefins and ethylenically unsaturated dicarboxylic acids. Suitable monovalent metal ions are Na+, K+, Li+, Cs+, Ag+, Hg+ and Cu+. Suitable divalent metal ions are Be+2, Mg+2, Ca+2, ,;
;,,, ..
-` 1078266 Sr 2, Ba+2, Cu+2, Cd+2, Hg+2, Sn+2 pb+2 Fe+2 Co+2 Ni+2 and Zn+2. Suitable trivalent metal ions are Al+3, Sc+3, Fe+3 and Y+3.
The preferred metal ions, regardless of the nature of the base copolymer are Na+ and Zn+2. These metals are preferred because they result in ionic co-polymers having the best combination of improvement in solid state properties with retention of melt fabricability. It is not essential that only one metal ion be employed in the formation of the ionic copolymers and more than one metal ion may be preferred in certain applications.
While it is not necessary that the copolymers be neutralized, preferably they are neutralized in the range of 10 to 50 percent. It has been found that co-polymeric layers comprising 100 percent neutralized copolymers are also useful. The fully neutralized copolymeric layers may be applied as such or may result from caustic treatment of glass bottles coated with a ;~ 20 partially neutralized copolymeric layer.
~ The melt index of the copolymer ranges from 0.1 - g./10 minutes to 500 g./10 minutes, preferably 10 to 150 g./10 minutes.
The nylon powder used in the blend with copolymers of alpha-olefins to improve abrasion and ; heat resistance can be prepared from polycaprolactam (6-nylon), polyhexamethylene adipamide (66-nylon), polyhexamethylene sebacamide (610-nylon), polyhexa-- methylene dodecamide, as well as similar aliphatic polycarbonamides. The nylons must be capable of being :
melted to form the protective layer, thus the lower melting nylons are particularly useful. Crystal Clad¢i3 nylon powder sold by General Mills is useftll. This nylon is prepared from hexamethylene diamine, sebacic acid and another component which is believed to be a linoleic dimer or trimer.
The blend of copolymer and nylon powder can be prepared by dry blending the components to form a homogeneous mixture. Melt blending the copolymer and nylon resins prior to the production of the powder results in a powder useful to form coatings with properties equal to or superior to those produced from the dry blend. In general 60 to 90 parts hy weight of ., .
copolymer powder are blended with 10 to 40 parts by weight of nylon powder. A preferred blend is 80 parts by weight copolymer powder and 20 parts by weight of nylon powder.
The copolymer powder or blend with nylon powder can be placed on the primed surface by conventional electrostatic powder coating equipment. For flat glass objects, such as microscopic slides used in laboratory testing, the powder can be applied in such a manner that a cloud of powder falls or is sprinkled onto the glass held essentially horizontal. The copolymer powder or blend thereof is fused by convection heating or -infrared radiation heating above the fusing pOillt to form continuous coatings, 4 to 12 mils (0.1 to 0.3 mm.), preferably 8 to 10 mils (0.2 to 0.25 mm.) in thickness.
The fused ionic copolymer coating is desirably of such thickness to retain 90 to 100 percent of the glass ~78Z~;6 ., .
fragments when a bottle pressured to 60 psig (4.22 kg./
sq. cm.) is dropped 4 feet (1.22 m.) onto a metal slab.
While the coating thickness can vary, it is desirable to keep it as thin as possible to obtain the desired results.
A nylon protective layer can optionally be present on the copolymer layer. In forming the protective layer a nylon powder can be applied and fused over the layer of copolymer, or a nylon film may be laminated to the copolymer layer. It is desirable that the protective layer be clear and abrasive and heat resistant. Thickness of the protective layer is in the order of 1.5 to 2.0 mils (0.04 to 0.05 mm.).
The present invention has particular utility in providing returnable glass bottles for carbonated beverages which are stronger and more resistant to fracture on impact than glass alone and which, in case of fracture, provide a valuable safety factor by retaining the broken gIass. The coatings in their preferred embodiments exhibit excellent resistance to hot caustic treatment solutions used to sterilize returnable glass bottles. The coatings of the present invention are also useful on other glass items such as fluorescent light bulbs, and protective screens for television tubes.
~ EXAMPLES OF THE INVENTION
;~ The following Examples furtller illustrate the invention. All percentages are by weight unless otherwise indicated. The caustic solution is a 5 percent solution at 80C. unless otherwise indicated.
1~378~66 '' EXA~IE 1 Glass slides were primed with N-vinylbenzyl-aminoethyl-3-trimethoxysilylpropylamine hydrochloride, Dow Corning silane QZ-85069*J by dipping in a 2 percent aqueous dispersion at ambient temperature for 30 seconds followed by air drying. me primed glass slide~ were dipped in an acetone solution of an epoxy resin of the formula:
/0 ~ C~ OH
CH2 -cH2~o-c6H4-c-c6E4-o-cH2-cH-cH23n i CH3 ~ where n is in the range of 1 to 20, Genepoxy~ 205 General - Mills Co., containing a reactive polyamide containing ex-cess amine groups as a curing agentJ Versamid~ 5201 HR 65 General Mills Co. Total solids in the acetone solution were 55 percent and the epoxy resin/curing agent weight ratio was 1.4:1Ø The epoxy/curing agent coating was ;; cured by maintaining the slides under an infrared radiation quartz heater manufactured by Hugo N. Cahnman Associates, Ine., Model ES-10 (1000 wattsJ 240 volts) for about 7 minutes. While still hot the slides were dipped in an ionic copolymer powder of a 24 percent sodium neutralized copolymer of ethylene with 11 percent methacrylic acid having a melt index o~ 20.4 g./10 minutes (ASTM D-1238, Condltion E) having a ~olume average particle size of 37 microns dete~mined by a Quantimet Image Analyzing ,~'! Computer- The ionic copolymer was prepared as described P! in Example 1 of U.S. Patent 3,933,954, issued January 20, ;~ 1976. The powder was then fused by placing the slides under a horizontally mounted quartz heater for `
~denctes trade mark ~:, --= ., r about 60 seconds. The ionic copolymer coating was about 8 mils (0.20 mm) thick. The coated slides were treated by placing them in caustic solution for fifteen minute periods. The three-layer coating was still tenaciously bonded to the glass after 41 fifteen-minute periods.
The above procedure was repeated except that the epoxy layer was omitted and the ionic copolymer coating was top coated with about a 3-mil (0.08 mm.) thick layer of nylon powder, Crystal Clad~ EP~2100 General Mills Company and believed to be a 610/636 copolymer. The glass slides withstood thirteen periods of the caustic solution.
The procedure of paragraph one above was repeated except that the silane layer was omitted. After the epoxy layer was cured, it delaminated from the glass slide after only one fifteen-minute period in caustic solution.
The procedure of paragraph one above was re-peated except that the layer of ionic copolymer was omitted. After the epoxy layer was cured, it withstood -;
62 fifteen-minute periods in caustic solution.
The procedure of paragraph one above was repeated except that in lieu of the epoxy layer the silane-treated slides were dipped in about a 12 percent chloroform solution of a low molecular weight polyamide ;
derived from a reaction of dimer acid (aliphatic, dibasic acid produced by the polymerization of un-saturated fatty acids), Emerz~ 1537, Emory Industries, air dried and coated with ionic copolymex powder. In two fifteen-minute periods in caustic solution (70C.) the ionic copolymer layer delaminated from the polyamide -layer, the polyamide layer was tenaciously bonded to the glass after 20 fifteen-minute periods in the caustic solution.
Glass slides were primed with the silane described in Example 1 and were air dried. The slides ; were then dipped in an aqueous solution of epoxy resin of the formula:
O\ CH3 OH
CH2-CH-C~I2~O-C6H4-C-C6H4-o CH2 C 2~n ` CH3 where n is in the range of 1 to 20, General Mills Co. TS~
679~, 50 percent solids dispersion, containing a reac-tive polyamide containing excess amine groups as a cur-ing agent, Versamid3 5501 General Mills Co. Total solids in the dispersion were adjusted to 15 percent.
The epoxy/curing agent weight ratio was 1.4:1Ø The ; epoxy layer was cured by maintaining the slides under j 20 the quartz heater described in Example 1 for 2 minutes.
The slides were then dipped in the ionic copolymer powder described in Example 1 and the powder fused as described in that Example. The coated slides withstood at least 36 fifteen-minute periods in the hot caustic solution of Example 1.
The above procedure was repeated except that the ionic copolymer described in Example 1 was replaced with an unneutralized acid copolymer powder having a melt ' index of 10g./10 minutes and containing 9.0 percent ,~ 30 methacrylic acid. The glass slides withstood at least .. --19--, ' ' ~
~ 1078Z66 20 fifteen-minute periods in the caustic solution without delamination.
The above procedure was repeated except that the silane primer layer was omitted. The glass slides withstood only two fifteen-minute periods in the caustic solution before delamination of the ionic copolymer layer.
Glass slides were primed with the silane described in Example 1 and were air dried. The slides were preheated under the quartz heater of Example 1 for about 15 seconds and dipped in epoxy powder, Vitralon~
80-1005, Pratt and Lambert Company. The powder was cured under the quartz heater for about 2 minutes. The thick-ness of the epoxy layer was about 1.0 mil (0.025 mm.).
The slides were then dipped in the ionic copolymer powder described in that Example. The coated slides withstood at least 49 fifteen-minute periods in the caustic solution of Example 1 without sign of delamination.
The above procedure was repeated except that the silane primer layer was omitted. The glass slides withstood four fifteen-minute periods in the caustic solution before delamination of the ionic copolymer layer.
--Glass slides were primed with the silane ; described in Example 1 and were air dried. The slides were then primed with an aqueous dispersion of an epoxy resin of the formula:
; 30 ~ -20--~ 1078266 , O CH OH
;~ / \ , 3 CH2-CH-CH2~O-C6H4-C-C6H4 O CH2 C 2~n where n is in the range of 1 to 20, TSX 679 General Mills Co., containing as the curing agent a modified amine A-100~, General Mills Company which is a ketone blocked amine of ,, ~ Rl ~ .
, the formula -R-N=C \ and a molecular weight of ~" \R2 ' 10 about 1100; functionality of about 4; equivalent weight ,~ of about 275; blocking agent: methyl isobutyl ketone.
' Total solids for the dispersion was adjusted to 16.6 percent and the epoxy-curing agent ratio was 1.26 to 1Ø
~` The epoxy layer was cured under a horizontally xi mounted quartz heater by maintaining the slides under ;, the heater for 2 minutes. The slides were then dipped /~ in the ionic copolymer powder described in Example 1 and `~, the powder fused as described in that Example. The coated slides withstood at least 2~ fifteen-minute periods in the hot caustic solution of Example 1 without sign of delamination.
;
The above procedure was repeated except that the curing agent was omitted in the aqueous epoxy dispersion. The epoxy resin was adjusted to 10 percent ~ and the epoxy layer was cured for greater than 6 minutes `l under the quartz heater described in Example 1. The final ionic copolymer coated slides showed signs of delamination after four fifteen-minute periods in the ' hot caustic solution.
.:, ," O
,~ , ;
:.
~ 1078Z~;6 .
Glass beverage bottles (Coca Cola returnable bottles No. 53201) were primed with the silane described in Example l and were air dried. The bottles were dipped in the aqueous solution of epoxy resin as described . in Example 2. The total solids of the epoxy resin solution was adjusted to 25 percent and the epoxy/curing agent ratio was 2.0 to lØ The epoxy layer was cured in a convection air oven for 7 minutes at about 205C.
, lO The bottles were coated with the ionic copolymer as described in Example l, and the powder was fused as described in that Example. Cuts were made in the bottle coatings to simulate extreme bottle abuse. The bottles withstood 40 fifteen-minute periods in the caustic solution (70C.) of Example l. After each period the bottles were abused in an American Glass Research bottle line simulator.
Glass beverage bottles described in Example 5 were primed with gamma-aminopropyltriethoxysilane, ~ -- NH2-(CH213-Si-(OC2H5)3 A-llO0~ manufactured by Union Carbide by dipping the bottles in a 2 percent aqueous solution for 30 seconds at ambient temperature and were air dried. The bottles were dipped in the epoxy ) ~
i, dispersion described in Example 5 and cured as described in that Example. The bottles were preheated to 177C.
~ in a convection air oven and coated with the ionic -~ copolymer powder described in Example l using a Gema~
:. .
electrostatic spray gun (60 kilovolts), Interrad
3 Corporation. The ionic copolymer powder was fused by ., .
, , ... . . . . .
, ' ' .' ' ' , ,,'' : '. : ~' '' ' ' , - - :- ~ .
- -` 1078266 post heating the bottles in the infrared oven described in Example 1 for about 45 seconds. The coatings were about 8 mils (0.2 mm.) thick. The bottles withstood 30 fifteen-minute periods in the caustic solution of Example 1 followed each time in the AGR line simulator of Example 5 without any signs of delamination.
The above procedure was repeated except that the epoxy layer was omitted. After undergoing seven -caustic treatments (70C.) as indicated above, coatings on 50 percent of the bottles delaminated from the glass, especially in the neck area.
The procedure described in the first paragraph of this Example except that the silane was a 2.0 percent !, .
aqueous dispersion as described in Example l and the epoxy layer was omitted. After undergoing nine caustic ` treatments (70~C.) as indicated above in paragraph 1 of this Example, coatings on 50 percent of the bottles delaminated from the glass, especially in the neck area. ~ -Glass beverage bottles as described in Example 5 were primed with the silane described in Example 1 and were air dried. The bottles were dipped in the aqueous solution of epoxy resin as described in Example 2 -. except that the total solids (epoxy and curing agent) was adjusted to 7.5 percent. The epoxy/curing agent ratio was 2 to 1. The epoxy layer was cured in an infrared radiation oven described in Example 1 for about one minute. The bottles were then coated with the ionic copolymer powder as described in Example 6. After thirteen fifteen-minute periods in the caustic solution ,..... .:
(70C.) some signs of delamination appeared in the neck ;
area of the bottles.
Glass beverage bottles as described in Example 5 were dipped in an aqueous epoxy dispersion as described in Example 2 containing about 2.0 percent silane as described in Example 1. The dispersion was adjusted to contain about 7.5 percent epoxy resin and curing agent.
The epoxy/curing agent ratio was 2:1. The epoxy layer .. . .
was cured as described in Example 7 followed by coating with ionic copolymer powder as described in Example 6.
After thirteen fifteen-minute periods in caustic solution (70C.) some signs of delamination appeared in the , neck area of the bottles.
~! Glass beverage bottles as described in Example .~ 5 were primed and cured as described in Example 7 except that the aqueous epoxy dispersion contained silane ~ described in Example l; the total solids was 15 percent .j epoxy and curing agent and 2 percent silane. After '-~ coating the bottles as described in Example 6, the bottles ., .
;,~ survived 24 fifteen-minute periods in caustic solution (70C.) with no observable delamination.
The above procedure was repeated except that the , epoxy dispersion was adjusted to 20 percent epoxy plus curing agent and 2 percent silane. The bottles survived 24 fifteen-minute periods in the caustic solution (70C.) with no observable delamination.
;- The procedure of paragraph one of this Example was repeated except that the epoxy dispersion was adjusted .
,, . ~ , :: . . ......................................... :
- . . : ... . . .
~ ~`` 1078Z66 to an epoxy/curing agent ratio of 1.4 to 1 (7.5 percent epoxy plus curing agent and 2 percent silane). The bottles survived 28 fifteen-minute periods in the caustic solution (70C.) with no observable delamination.
~, EXAMPLE 10 Glass beverage bottles as described in Example 5 were primed with the silane as described in Example 1 and were air dried. The bottles were dipped in an aqueous epoxy dispersion containing an epoxy compound of the formula:
HOC~I CH2OH
CH2-CH-CH2-0~ C~- O-CH2-CH-~CH2 ~pogen~ 401 containing an epoxy curing agent 242 manu-factured by M and T Chemical Company. The dispersion was adjusted to contain 40 percent epoxy plus the curing agent. The epoxy/curing agent ratio was 1.25 to 1Ø
The epoxy layer was cured as described in Example 7.
The bottles were coated with the ionic copolymer as described in Example 6. The bottles survived 20 f ~ fifteen-minute periods in the caustic solution (70C.) with no observable delamination.
The above procedure was repeated except that the epoxy dispersion was adjusted to contain 35 percent epoxy plus the curing agent. The epoxy/curing agent ratio was 1.25 to 1Ø Some delamination of the coatings ,, in the neck area of the bottles was noted after 12 ~, fifteen-minute caustic treatment (70C.) periods.
"
Glass beverage bottles were coated using an . - ~ -' - ' - -: : ' .~--` 1078266 aqueous dispersion of 34.96 parts of liquid epoxy resin solution designated as Genepoxy~ 37 OH 55, General Mills Company; 3.85 parts of silane designated as Dow Silane ~-6032~, Dow Chemical Company; 4.81 parts of a reactive polyamid curing agent designated as Versamid~ 125, General Mills Company; 0.71 parts of glacial acetic acid; 3.67 parts of diethylene glycol monoethyl ether as a wetting agent;
and 52 parts of water. The epoxy/curing agent weight ratio was 4:1 and the total solids in the dispersion were about 25 percent. The epoxy was cured as described in Example 5.
The bottles were coated with ionic copolymer as described in Example 1, and the powder was fused as described in Example 1.
-- .
Glass beverage bottles were coated using an : aqueous dispersion of 28.27 parts of the epoxy of the pre-, vious example; 3.60 parts of the silane of the previous example; 5.91 parts of the epoxy curing agent of the pre-vious example 0.56 parts of zinc chloride; 4.92 parts of ~ 20 diethylene glycol monoethyl ether; and 56.74 parts of water.
; The epoxy/curing agent weight ratio was 2.63:1 and the total ,~ solids in the dispersion were about 23.5 percent. The epoxy was applied and fused as described in Example 11.
Glass beverage bottles were coated using an aqueous dispersion of 40.7 parts of the epoxy of Example 11;
3.8 parts of the silane of Example 11; 46.6 parts of a , primary amine of functional acrylic resin epoxy curing - agent such as that material designated as Dow XD-7080, .
; 30 Dow Chemical Company; and 44.2 parts of water. The . ~ .
,,~ -26-, . .
.. . .
i~ ~
~. .. .
epoxy/curing agent weight ratio was 2:1 and the total solids in the dispersion were about 35 percent. The epoxy . was cured and the ionic copolymer was applied and fused as described in Example 7.
, '~ 10 . ~
.~
,, .
'~' '',~, ~
.
,, , , I .
~ ~' '., .
' :. ~- - . , , ., ', .. .
- : . . . .
, , ... . . . . .
, ' ' .' ' ' , ,,'' : '. : ~' '' ' ' , - - :- ~ .
- -` 1078266 post heating the bottles in the infrared oven described in Example 1 for about 45 seconds. The coatings were about 8 mils (0.2 mm.) thick. The bottles withstood 30 fifteen-minute periods in the caustic solution of Example 1 followed each time in the AGR line simulator of Example 5 without any signs of delamination.
The above procedure was repeated except that the epoxy layer was omitted. After undergoing seven -caustic treatments (70C.) as indicated above, coatings on 50 percent of the bottles delaminated from the glass, especially in the neck area.
The procedure described in the first paragraph of this Example except that the silane was a 2.0 percent !, .
aqueous dispersion as described in Example l and the epoxy layer was omitted. After undergoing nine caustic ` treatments (70~C.) as indicated above in paragraph 1 of this Example, coatings on 50 percent of the bottles delaminated from the glass, especially in the neck area. ~ -Glass beverage bottles as described in Example 5 were primed with the silane described in Example 1 and were air dried. The bottles were dipped in the aqueous solution of epoxy resin as described in Example 2 -. except that the total solids (epoxy and curing agent) was adjusted to 7.5 percent. The epoxy/curing agent ratio was 2 to 1. The epoxy layer was cured in an infrared radiation oven described in Example 1 for about one minute. The bottles were then coated with the ionic copolymer powder as described in Example 6. After thirteen fifteen-minute periods in the caustic solution ,..... .:
(70C.) some signs of delamination appeared in the neck ;
area of the bottles.
Glass beverage bottles as described in Example 5 were dipped in an aqueous epoxy dispersion as described in Example 2 containing about 2.0 percent silane as described in Example 1. The dispersion was adjusted to contain about 7.5 percent epoxy resin and curing agent.
The epoxy/curing agent ratio was 2:1. The epoxy layer .. . .
was cured as described in Example 7 followed by coating with ionic copolymer powder as described in Example 6.
After thirteen fifteen-minute periods in caustic solution (70C.) some signs of delamination appeared in the , neck area of the bottles.
~! Glass beverage bottles as described in Example .~ 5 were primed and cured as described in Example 7 except that the aqueous epoxy dispersion contained silane ~ described in Example l; the total solids was 15 percent .j epoxy and curing agent and 2 percent silane. After '-~ coating the bottles as described in Example 6, the bottles ., .
;,~ survived 24 fifteen-minute periods in caustic solution (70C.) with no observable delamination.
The above procedure was repeated except that the , epoxy dispersion was adjusted to 20 percent epoxy plus curing agent and 2 percent silane. The bottles survived 24 fifteen-minute periods in the caustic solution (70C.) with no observable delamination.
;- The procedure of paragraph one of this Example was repeated except that the epoxy dispersion was adjusted .
,, . ~ , :: . . ......................................... :
- . . : ... . . .
~ ~`` 1078Z66 to an epoxy/curing agent ratio of 1.4 to 1 (7.5 percent epoxy plus curing agent and 2 percent silane). The bottles survived 28 fifteen-minute periods in the caustic solution (70C.) with no observable delamination.
~, EXAMPLE 10 Glass beverage bottles as described in Example 5 were primed with the silane as described in Example 1 and were air dried. The bottles were dipped in an aqueous epoxy dispersion containing an epoxy compound of the formula:
HOC~I CH2OH
CH2-CH-CH2-0~ C~- O-CH2-CH-~CH2 ~pogen~ 401 containing an epoxy curing agent 242 manu-factured by M and T Chemical Company. The dispersion was adjusted to contain 40 percent epoxy plus the curing agent. The epoxy/curing agent ratio was 1.25 to 1Ø
The epoxy layer was cured as described in Example 7.
The bottles were coated with the ionic copolymer as described in Example 6. The bottles survived 20 f ~ fifteen-minute periods in the caustic solution (70C.) with no observable delamination.
The above procedure was repeated except that the epoxy dispersion was adjusted to contain 35 percent epoxy plus the curing agent. The epoxy/curing agent ratio was 1.25 to 1Ø Some delamination of the coatings ,, in the neck area of the bottles was noted after 12 ~, fifteen-minute caustic treatment (70C.) periods.
"
Glass beverage bottles were coated using an . - ~ -' - ' - -: : ' .~--` 1078266 aqueous dispersion of 34.96 parts of liquid epoxy resin solution designated as Genepoxy~ 37 OH 55, General Mills Company; 3.85 parts of silane designated as Dow Silane ~-6032~, Dow Chemical Company; 4.81 parts of a reactive polyamid curing agent designated as Versamid~ 125, General Mills Company; 0.71 parts of glacial acetic acid; 3.67 parts of diethylene glycol monoethyl ether as a wetting agent;
and 52 parts of water. The epoxy/curing agent weight ratio was 4:1 and the total solids in the dispersion were about 25 percent. The epoxy was cured as described in Example 5.
The bottles were coated with ionic copolymer as described in Example 1, and the powder was fused as described in Example 1.
-- .
Glass beverage bottles were coated using an : aqueous dispersion of 28.27 parts of the epoxy of the pre-, vious example; 3.60 parts of the silane of the previous example; 5.91 parts of the epoxy curing agent of the pre-vious example 0.56 parts of zinc chloride; 4.92 parts of ~ 20 diethylene glycol monoethyl ether; and 56.74 parts of water.
; The epoxy/curing agent weight ratio was 2.63:1 and the total ,~ solids in the dispersion were about 23.5 percent. The epoxy was applied and fused as described in Example 11.
Glass beverage bottles were coated using an aqueous dispersion of 40.7 parts of the epoxy of Example 11;
3.8 parts of the silane of Example 11; 46.6 parts of a , primary amine of functional acrylic resin epoxy curing - agent such as that material designated as Dow XD-7080, .
; 30 Dow Chemical Company; and 44.2 parts of water. The . ~ .
,,~ -26-, . .
.. . .
i~ ~
~. .. .
epoxy/curing agent weight ratio was 2:1 and the total solids in the dispersion were about 35 percent. The epoxy . was cured and the ionic copolymer was applied and fused as described in Example 7.
, '~ 10 . ~
.~
,, .
'~' '',~, ~
.
,, , , I .
~ ~' '., .
' :. ~- - . , , ., ', .. .
- : . . . .
Claims (14)
1. A clear caustic-resistant coating for glass which comprises (1) a primer layer consisting essentially of a combination of (A) an organofunctional silane, and (B) an epoxy resin containing a curing agent taken from the group consisting of an amine and a polyamide compound where (A) and (B) are in a single layer or in individual layers, with the proviso that the silane layer (A) is adjacent the glass, and (2) a copolymeric layer consisting essentially of a copolymer of alpha-olefins of the formula R-CH=CH2, where R is a radical selected from the class consisting of hydrogen and alkyl radicals having from 1 to 8 carbon atoms, and alpha, beta-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, said copolymers having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions, said metal ions having an ionized valence of from one to three inclusive when the unsaturated acid is a monocarboxylic acid and an ionized valence of one when the unsaturated acid is a di-carboxylic acid and said metal ions being selected from the group consisting of uncomplexed and complexed metal ions, said copolymer being a direct copolymer of the alpha-olefins and the unsaturated carboxylic acid in which the carboxylic acid groups are randomly distributed over all molecules and in which (a) the alpha-olefin content of the copolymer is at least 70 mol percent, based on the alpha-olefin-acid copolymer, and (b) the unsaturated carboxylic acid content of the copolymer is from 0.2 to 5 mol percent, based on the alpha-olefin-acid copolymer, other monomer components copolymerized in said copolymer being monoethylenically unsaturated and being in an amount of from 0 to 29.8 mol percent, based on the alpha-olefin-acid copolymer.
2. A coating according to Claim 1 wherein (A) and (B) are present in a single layer.
3. A coating according to Claim 1 wherein (A) and (B) are present in separate layers, the layer containing (A) being adjacent the glass.
4. A coating according to Claim 1 wherein the silane primer is a compound of the formula (RO)3Si(CH2)xR1, where R is an alkyl of 1 to 4 carbon atoms; R1 is NH2-, and ; and x is 1 to 4.
5. A coating according to Claim 4 wherein the silane is N-vinylbenzylaminoethyl-3-trimethoxysilylpropyl-amine hydrochloride.
6. A coating according to Claim 1 wherein the epoxy resin is taken from the group consisting of epichlorohydrin/bisphenol A types and epoxy compounds containing 1 to 20 oxirane rings, .
7. A coating according to Claim 1 wherein the epoxy resin curing agent is a polyamide containing excess amine groups.
8. A coating according to Claim 1 wherein the epoxy resin curing agent is an amine.
9. A coating according to Claim 1 wherein the polymeric layer is an ionic copolymer having from 10 to 50 percent of the carboxylic acid groups ionized by neutralization with metal ions.
10. A coating according to Claim 9 wherein the ionic copolymer is an ethylene/methacrylic acid ionic copolymer.
11. A coating according to Claim 1 wherein the copolymer is an unneutralized ethylene/methacrylic acid copolymer.
12. Returnable beverage bottles coated with the coating of Claim 1.
13. Returnable beverage bottles coated with the coating of Claim 2.
14. Returnable beverage bottles coated with the coating of Claim 9.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60366175A | 1975-08-11 | 1975-08-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1078266A true CA1078266A (en) | 1980-05-27 |
Family
ID=24416408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA258,691A Expired CA1078266A (en) | 1975-08-11 | 1976-08-09 | Caustic-resistant polymer coatings for glass |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5227412A (en) |
| AU (1) | AU1664876A (en) |
| BE (1) | BE845040A (en) |
| CA (1) | CA1078266A (en) |
| DE (1) | DE2636157A1 (en) |
| FR (1) | FR2320914A1 (en) |
| IT (1) | IT1065935B (en) |
| NL (1) | NL7608935A (en) |
| SE (1) | SE7608921L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11292911B2 (en) | 2018-08-17 | 2022-04-05 | Evonik Operations Gmbh | Aqueous, storage-stable composition containing N-benzyl-substituted N-(2-aminoethyl)-3-aminopropylsiloxane hydrochlorides, processes for production thereof and use thereof |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0001148B1 (en) * | 1977-09-07 | 1981-09-30 | Chemische Werke Hüls Ag | Method of coating glass surfaces |
| JPS5950188B2 (en) * | 1979-07-18 | 1984-12-06 | 麒麟麦酒株式会社 | Composition for shielding scratches on glass containers |
| DE2941105C2 (en) * | 1978-10-14 | 1982-04-08 | Kirin Beer K.K. | Use of a polysiloxane composition for coating glass objects, in particular for covering scratches on glass bottles |
| US4396655A (en) * | 1982-03-08 | 1983-08-02 | Owens-Illinois, Inc. | Method of sealing a glass container with a thin membrane closure |
| FR2625450B1 (en) * | 1988-01-05 | 1992-05-07 | Corning Glass Works | ARTICLE PROVIDED WITH AN ADHESIVE COATING HAVING IMPROVED SUBSTRATE AUDIT AND DURABILITY, ITS MANUFACTURE AND COMPOSITION IMPLEMENTED |
| DE68917288T2 (en) * | 1989-03-08 | 1995-02-09 | Corning Inc | Process for producing colored glass or glass-ceramic articles with a non-stick coating, compositions used in these processes and articles thus obtained. |
| ES2060797T3 (en) * | 1989-03-08 | 1994-12-01 | Corning Inc | ARTICLE PROVIDED WITH AN ANTI-STICK COATING, WITH ADHESION TO THE SUBSTRATE AND WITH MODIFIED DURABILITY, ITS MANUFACTURING AND COMPOSITION PROCEDURE USED. |
| DE4233021A1 (en) * | 1992-10-01 | 1994-04-07 | Huels Chemische Werke Ag | Organosilane polycondensates |
| FR2738241B1 (en) * | 1995-09-01 | 1998-03-20 | Vetrotex France Sa | REINFORCING GLASS WIRES AND CORROSIVE RESISTANT COMPOSITES |
-
1976
- 1976-08-06 AU AU16648/76A patent/AU1664876A/en not_active Expired
- 1976-08-09 CA CA258,691A patent/CA1078266A/en not_active Expired
- 1976-08-10 IT IT26203/76A patent/IT1065935B/en active
- 1976-08-10 FR FR7624401A patent/FR2320914A1/en active Granted
- 1976-08-10 BE BE169688A patent/BE845040A/en unknown
- 1976-08-10 SE SE7608921A patent/SE7608921L/en unknown
- 1976-08-11 JP JP51095011A patent/JPS5227412A/en active Pending
- 1976-08-11 NL NL7608935A patent/NL7608935A/en not_active Application Discontinuation
- 1976-08-11 DE DE19762636157 patent/DE2636157A1/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11292911B2 (en) | 2018-08-17 | 2022-04-05 | Evonik Operations Gmbh | Aqueous, storage-stable composition containing N-benzyl-substituted N-(2-aminoethyl)-3-aminopropylsiloxane hydrochlorides, processes for production thereof and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2320914B3 (en) | 1979-05-04 |
| BE845040A (en) | 1977-02-10 |
| IT1065935B (en) | 1985-03-04 |
| DE2636157A1 (en) | 1977-03-03 |
| AU1664876A (en) | 1978-02-09 |
| NL7608935A (en) | 1977-02-15 |
| SE7608921L (en) | 1977-02-12 |
| FR2320914A1 (en) | 1977-03-11 |
| JPS5227412A (en) | 1977-03-01 |
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| MKEX | Expiry |