ARTICLE, COMPOSITION OF COATING, AND, METHOD

专利摘要:
coating composition, article, and method the present invention provides a polymer, which is a polyether polymer, for use in coating compositions. containers are also provided comprising the polymer and methods of making such containers. the invention additionally provides powder coating compositions including polymer, which are useful in a variety of coating end uses, including, for example, valve and pipe coating.
公开号:BR112013020026A2
申请号:R112013020026-0
申请日:2012-02-07
公开日:2020-01-07
发明作者:Niederst Jeffrey；H. Evans Richard；Romagnoli Kevin；Howard Killilea T.；S. Von Maier Mark
申请人:Valspar Sourcing, Inc.；
IPC主号:

专利说明:

"ARTICLE, COMPOSITION OF COATING, AND, METHOD"
REFERENCE TO RELATED REQUESTS
This application claims the benefits of US provisional patent application 61 / 440,085 filed on February 7, 2011 and entitled COATING COMPOSITION FOR CONTAINERS AND OTHER ARTICLES AND METHODS OF COATING, and US provisional patent application 61 / 579,072 on December 22, 2011 and entitled COATING COMPOSITION FOR CONTAINERS AND OTHER ARTICLES AND METHODS OF COATING, each of which is incorporated herein in its entirety as a reference.
BACKGROUND
The application of coatings on metals to delay or inhibit corrosion is well established. This is particularly true in the area of packaging containers such as metal cans for food and drinks. Coatings are typically applied inside these containers to prevent the contents from coming into contact with the metal in the container. Contact between the metal and the packaged product can cause corrosion of the metal container, which can contaminate the packaged product. This is particularly true when the contents of the container are chemically aggressive in nature. Protective coatings are also applied inside the food and beverage containers to prevent corrosion in the free space of the container between the food product fill line and the lid of the container.
Packaging coatings preferably need to be capable of high-speed application to the substrate, in addition to providing the necessary properties, when hardened, to perform well for this demanding purpose. For example, the coating should be safe for contact with food, not adversely affect the flavor of the beverage or packaged food product, have excellent adhesion to the substrate, resist staining and other coating defects such as bursts, fog and / or blistering, and resist degradation over long periods of time, even when exposed to harsh environments. In addition, the coating must generally be able to maintain adequate film integrity during container manufacture, and be able to withstand conditions process to which the container can be subjected during the product packaging process.
Various coatings have been used as internal protective coatings for cans, including poly (vinyl chloride) based coatings and epoxy based coatings incorporating bisphenol A (BPA). Each of these types of flooring, however, has possible disadvantages. For example, the recycling of materials containing poly (vinyl chloride) or related vinyl polymers containing halide can be problematic. There is also a desire by some to reduce or eliminate certain BPA-based compounds commonly used to formulate epoxy coatings in contact with food.
What the market needs is an improved binder system for use in coatings, such as packaging coatings.
SUMMARY
This invention provides a polymer useful in a variety of applications such as, for example, a polymer binder in a coating composition. The polymer preferably includes one or more segments having two or more aryl or heteroaryl groups in which each aryl or heteroaryl group includes an oxygen atom attached to the ring and a substituent group (preferably a bulky substituent group) attached to the ring preferably in one ortho or goal position relative to the oxygen atom. An example of such a segment is: -O-Ar- (R ² ) _n -Ar-O-, in which
Ar represents an aryl or heteroaryl group, preferably having at least one R ¹ group attached to the ring in an ortho or meta position relative to the oxygen atom shown, which preferably belongs to an ether bond, and in which R, R , and n are as defined herein for formula (I). In preferred embodiments, the polymer is a polyether polymer.
In preferred embodiments, the polymer includes one or more segments, and even more preferably a plurality of segments, of the formula below (I):
(HVv (R ¹ V (H), (R ²
(R ¹ ).
, Formula (I) where:
each pair of oxygen atoms shown in formula (I) is preferably present in an ether or ester bond, more preferably an ether bond;
H denotes a hydrogen atom, if present;
each R ¹ is independently an atom or group, preferably having an atomic weight of at least 15 daltons, each of the phenylene groups shown in formula (I) preferably including at least one R ¹ bonded to the ring in a ortho or goal position relative to the oxygen atom;
v is independently 1 to 4;
w is 4;
R, if present, is preferably a divalent group;
n is 0 or 1, with the proviso that if n is 0, the phenylene groups shown in formula (I) can join with each other to form a fused ring system (for example, a substituted naphthalene group), in whose case w is 3 (instead of 4); and with two or more groups R ¹ and / or R ^{2 being} able to come together to form one or more cyclic groups.
The segment of formula (I) preferably includes at least one R ¹ which is capable of causing steric hindrance to a hydroxyl group of phenol. More preferably, each phenylene group shown in formula (I) includes at least one such group R ¹ . Such preferred R ¹ groups are sufficiently bulky so that when located in an ortho or para position (more typically an ortho position) relative to a hydroxyl phenol group, the R ¹ group causes sufficient steric impediment to reduce accessibility and / or the reactivity of such a phenol hydroxyl group.
In preferred embodiments, one or both of the following are true: (i) at least one R ¹ is attached to each phenylene ring shown in formula (I) in an ortho position relative to the oxygen atom shown and (ii) at least one R ¹ attached to the ring in an ortho or target position relative to the oxygen atom shown includes one or more carbon atoms. Non-limiting examples of R ¹ groups include groups having at least one carbon atom, a halogen atom, a sulfur-containing group, or any other suitable group preferably having an atomic weight of at least 15 daltons which is preferably substantially non-reactive with a epoxy group. Other organic groups are presently preferred, with organic groups that are free of halogen atoms being particularly preferred.
Although the polymer of the present invention can have any suitable backbone chemistry, in preferred embodiments the polymer is a polyether polymer.
The polymer preferably does not include any structural units derived from bisphenol A (BPA) or BPA diglycidyl ether (BADGE).
In preferred embodiments, the polymer also includes pendent hydroxyl groups (e.g., secondary hydroxyl groups) and, more preferably, one or more -CH ₂ -CH (OH) -CH2- segments, which are preferably derived from an oxirane and are located in a polymer main chain.
The present invention also provides a coating composition that includes the polymer described herein, more preferably a polyether polymer described herein. The coating composition preferably includes at least a film-forming amount of the polymer and can optionally include one or more additional polymers. The coating composition is useful in coating a variety of substrates, including as an internal or external coating on packaging containers or portions thereof. In preferred embodiments, the coating composition is useful as a coating for contacting food on a beverage or food container. In preferred embodiments, the coating composition is at least substantially free of BPA or mobile BADGE, and most preferably is completely free of BPA or BADGE. The coating composition can also be useful in a variety of other end uses, including, for example, coatings for valves and fittings, especially valves and fittings for use with drinking water; tubes for transporting liquids, especially drinking water tubes; and liquid storage tanks, specifically drinking water tanks, such as steel riveted water tanks.
In one embodiment, the coating composition of the present invention is a powder coating composition that preferably includes a base powder, formed, at least in part, from the polymer of the present invention. The coating composition can include one or more optional ingredients in the particles of the base powder and / or in a separate particle. Such optional ingredients may include, for example, crosslinker, curing accelerator, color pigment, filler, flow additives, etc.
The present invention also provides packaging articles that have a coating composition of the present invention applied to a surface of the packaging article. In one embodiment, the packaging article is a container such as a beverage or food container, or a portion thereof (for example, a twist and pull closure lid, beverage can end, food can end, etc.), wherein at least a portion of an inner surface of the container is coated with a coating composition described herein that is suitable for prolonged contact with a beverage or food product or other packaged product.
In one embodiment, a method of preparing a container that includes an inner liner is provided for contacting the food of the present invention. The method includes: providing a coating composition described herein that includes a polymer binder and optionally a liquid carrier; and applying the coating composition to at least a portion of a surface of a substrate before or after the formation of the substrate within a container or portion thereof having the coating composition positioned on an internal surface. Typically, the substrate is a metallic substrate, although the coating composition can be used to coat other substrate materials if desired.
In one embodiment, a method of forming beverage or food cans, or a portion thereof, is provided, which includes: applying a coating composition described herein to a metallic substrate (for example, applying the coating composition to the metallic substrate in the form of thin sheet or flat coil), harden the coating composition, and transform the substrate into a beverage or food can or a portion thereof.
In certain embodiments, transforming the substrate into an article includes transforming the substrate into an end of the can or a body of the can. In certain embodiments, the article is a two-piece drawn food can, three-piece food can, food can end, stamped and drawn drink or food can, drink can end, twist closure lid and take out, and the like. Suitable metal substrates include, for example, steel or aluminum.
In certain embodiments, a packaging container is provided which has: (a) a coating composition of the present invention positioned on at least a portion of an internal or external surface of the container and (b) a product packaged within the same as a food, drink, cosmetic, or medicinal product.
The summary of the present invention set out above is not intended to describe each embodiment or implementation of the present invention. The following description more particularly exemplifies the illustrative modalities. In various parts of this application, guidance is provided through lists of examples, examples of which can be used in various combinations. In each instance, the reported list serves only as a representative group and should not be interpreted as an exclusive list. Except where otherwise noted, the structural representations included herein are not intended to indicate any specific stereochemistry and are intended to include all stereoisomers.
Definitions
As used here, the term organic group means a hydrocarbon group (with optional elements other than carbon and hydrogen, such as oxygen, nitrogen, sulfur, and silicon) that is classified as an aliphatic group, a cyclic group, or a combination of groups aliphatic and cyclic (for example, alkaryl and aralkyl groups). The term cyclic group means a closed ring hydrocarbon group that is classified as an alicyclic group or an aromatic group, both of which may include heteroatoms. The term alicyclic group means a cyclic hydrocarbon group having properties resembling those of aliphatic groups.
The term aryl group (for example, an arylene group) refers to a closed aromatic ring or closed aromatic ring system such as phenylene, naphthylene, biphenylene, flurenylene and indenyl, and also heteroarylene groups (i.e., a ring or hydrogen system) aromatic or similar to aromatic in which one or more of the atoms in the ring is an element other than carbon (eg nitrogen, oxygen, sulfur, etc.)). Suitable heteroaryl groups include fiiryl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazoyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, benzofuranyl, benzothiophilyl, benzylol, benzazol, benzazol, benzazol, benzazol, benzazol, benzazol isoxazolyl, isothiazolyl, purinyl, quinazolinyl, pyrazinyl, 1oxidopyridyl, pyridazinyl, triazinyl, tetrazinyl, oxadiazolyl, thiadiazolyl and so on. When such groups are divalent, they are typically called arylene or heteroarylene groups (for example, furylene, pyridylene, etc.)
A group that can be the same or different is called something independently.
A substitution is anticipated in the organic groups of the compounds of the present invention. As a way of simplifying the discussion and mention of certain terminology used throughout this application, the terms group and portion are used to distinguish between the chemical species that allow substitution or that can be replaced and those that do not or cannot be replaced. Thus, when the term group is used to describe a chemical substituent, the chemical material described includes the unsubstituted group and the group with O atoms,
N, Si, or S, for example, in the chain (such as in an alkoxy group) as well as carbonyl groups or other conventional substitution. When the term portion is used to describe a chemical or substituting compound, only an unsubstituted chemical material should be included. For example, the phrase alkyl group is intended to include not only pure open saturated alkyl hydrocarbon substituents, such as methyl, ethyl, propyl, t-butyl, and the like, but also alkyl substituents containing additional substituents known in the art, such as hydroxyl, alkoxy, alkylsulfonyl, halogen atoms, cyan, nitro, amino, carboxyl, etc. Thus, an alkyl group includes ether, haloalkyl, nitroalkyl, carboxyalkyl, hydroxyalkyl, sulfoalkyl, etc. groups. On the other hand, the phrase alkyl portion is limited to the inclusion of pure open saturated alkyl hydrocarbon substituents, such as methyl, ethyl, propyl, t-butyl, and the like. For use in the present invention, the term group is intended to refer to both the specific portion and the broader class of substituted and unsubstituted structures that includes the portion.
The term polyhydric phenol as used herein refers broadly to any compound having one or more aryl or heteroaryl groups (more typically one or more phenylene groups) and at least two hydroxyl groups attached on the same or different aryl or heteroaryl ring. Thus, for example, hydroquinone and 4,4'-biphenol are both considered to be polyhydric phenols. For use in the present invention, polyhydric phenols typically have six carbon atoms in an aryl ring, although it is contemplated that aryl or heteroaryl groups that have rings of other sizes can be used.
The term phenylene, for use in the present invention, refers to an aryl group of six carbon atoms (for example, as in a benzene group) that can have any substituent groups (including, for example, hydrogen atoms, halogens, hydrocarbon groups, oxygen atoms, hydroxyl groups, etc.). Thus, for example, the following aryl groups are each phenylene rings: -CéHr, -C ₆ H ₃ (CH ₃ ) -, and -C6H (CH ₃ ) 2C1-.
In addition, for example, each of the aryl rings of a naphthalene group is phenylene rings.
The term substantially free (a) of a particular mobile compound means that the mentioned polymer and / or composition (a) contains less than 100 parts per million (ppm) of the mentioned mobile compound. The term essentially free (a) of a particular mobile compound means that the mentioned polymer and / or composition (a) contains less than 5 parts per million (ppm) of the mentioned mobile compound. The term completely free (a) of a particular mobile compound means that the mentioned polymer and / or composition (a) contains less than 20 parts per billion (ppb) of the mentioned mobile compound.
The term mobile means that the compound can be extracted from the cured coating when a coating (typically ~ 1 mg / cm) is exposed to a test medium for some defined set of conditions, depending on the end use. An example of these test conditions is the exposure of the cured coating to HPLC grade acetonitrile for 24 hours at 25 ° C. If the aforementioned phrases are used without the term mobile (for example, substantially free of BPA) then the mentioned polymer and / or composition contains less than the aforementioned amount of the compound, whether it is the mobile compound in the coating or attached to a constituent of the coating.
The term estrogenic activity refers to the ability of a compound to mimic hormone-like activity through interaction with an endogenous estrogen receptor, typically a human endogenous estrogen receptor.
The term food contact surface refers to the substrate surface of a container (typically an internal surface of a beverage or food container) that is in contact with, or is intended to contact, a beverage or food product. food. For example, an internal surface of a metallic substrate of a beverage or food container, or a portion thereof, is a surface in contact with food even if the internal metal surface is coated with a polymeric coating composition.
The term crosslinker refers to a molecule capable of forming a covalent bond between polymers or between two different regions of the same polymer.
The term about, when used in the context of a coating applied to a surface or substrate, includes coatings applied directly or indirectly to the surface or substrate. In this way, for example, a coating applied to a primer layer that covers a substrate constitutes a coating applied to the substrate.
Unless otherwise indicated, the term polymer includes both homopolymers and copolymers (for example, polymers of two or more different monomers). Similarly, except where otherwise noted, the use of a term designating a class of polymer such as, for example, polyether is intended to include both homopolymers and copolymers (for example, polyether ester copolymers).
The terms comprise and variations thereof do not have a limiting meaning when those terms appear in the description and claims.
The terms preferentially and preferably refer to modalities of the invention that can provide certain benefits, under certain circumstances. However, other modalities may also be preferred, under the same or different circumstances. In addition, the mention of one or more preferred modalities does not imply that other modalities are not useful, and is not intended to exclude other modalities from the scope of the invention.
For use in the present invention, one, one, o, a, at least one, at least one, one or more and one or more are used interchangeably. Therefore, for example, a coating composition comprising a polyether can be interpreted to mean that the coating composition includes one or more polyethers.
In the present invention, mentions of number ranges with extremes include all numbers contained within this range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc. .). In addition, the description of a range includes all the sub-ranges included within the broadest range (for example, 1 to 5 describes 1 to 4, 1.5 to 4.5, 4 to 5, etc.).
DETAILED DESCRIPTION OF THE ILLUSTRATIVE MODALITIES
In one aspect, the present invention provides a coating composition that includes a polymer, more preferably a binder polymer, and even more preferably a polyether binder polymer. Although the following discussion mainly highlights the end uses of coating, it is considered that the polymer of the present invention, and also its intermediates, may be useful in a variety of other end uses, for example, in adhesives or composites.
The coating compositions of the present invention preferably include at least a film-forming amount of the polymer described herein. In addition to the polymer, the coating composition can also include one or more additional ingredients such as, for example, a crosslinker, a liquid carrier, and any other suitable optional additives. Although any suitable curing mechanism can be used, thermoset coating compositions are preferred. In addition, although coating compositions that include a liquid carrier are presently preferred, it is envisaged that the polymer of the present invention may be of use in solid coating application techniques such as, for example, powder coating.
The coating compositions of the present invention can be useful in a variety of coating end uses, and especially in packaging coating end uses. The preferred coating compositions of the present invention exhibit a superior combination of coating attributes such as good flexibility, good substrate adhesion, good chemical resistance and corrosion protection, good manufacturing properties, and a smooth, bubble-free, regular coating appearance other application-related defects. In preferred embodiments, the coating composition is suitable for use as an adhesive packaging coating and, more preferably, as an adhesive coating on an internal and / or external surface of a beverage or food container. Thus, in preferred embodiments, the coating composition is suitable for us as a coating in contact with food. It is also considered that the coating composition may be useful in the end uses of cosmetic packaging or medical packaging coating, and as a coating in contact with a particular medication (for example, as an inner coating of a dose inhaler can. measure commonly called an MDI container). It is also considered that the coating composition may be useful in coating applications in which the coated substrate will contact body fluids, for example, as an inner coating of a blood vial.
In preferred embodiments, the polymer of the present invention, which is preferably a polyether polymer, includes one or more segments of the formula below (I):
Formula (I) where:
each pair of oxygen atoms shown in formula (I) is preferably present in an ether or ester bond, more preferably an ether bond;
H denotes a hydrogen atom, if present;
each R ¹ is preferably independently an atom or group preferably having an atomic weight of at least 15 daltons which is preferably substantially non-reactive with an epoxy group;
v is independently 1 to 4;
w is 4;
each of the phenylene groups shown in formula (I) includes at least one R ¹ bonded to the ring preferably in an ortho or meta position relative to the oxygen atom;
R, if present, is preferably a divalent group;
n is 0 or 1, with the proviso that if n is 0, the phenylene groups shown in formula (I) can optionally join to form a fused ring system (for example, a substituted naphthalene group) in which case w is 3 (instead of 4); and two or more groups R and / or R can optionally join to form one or more cyclic groups.
In preferred embodiments, each R and R, if present, are preferably non-reactive with an oxirane group at a temperature less than about 200 ° C.
As shown in formula (I) above, the segment includes a pair of phenylene groups (and can optionally include one or more phenylene groups or other additional aryl or heteroaryl groups). Although aryl groups having an aromatic ring with six carbon atoms are presently preferred, it is envisaged that any other suitable aryl or heteroaryl may be used in place of the phenylene groups shown in formula (I). As shown in formula (I) above, the substituent groups (i.e., -O-, H, R, and R) of each phenylene group can be located at any position on the ring relative to each other, although in preferred embodiments at least one R ¹ is positioned on the ring immediately adjacent to the oxygen atom. In other embodiments in which other aryl or heteroarylene groups are used in place of the phenylene groups shown in formula (I), it is considered that the same would remain true for the substituent groups of such other aryl or heteroarylene groups.
In preferred embodiments, R ¹ is attached to the phenylene ring at a carbon atom immediately adjacent to the carbon atom to which the shown oxygen atom is attached. In other words, R ¹ is preferably located in an ortho position on the ring relative to the oxygen atom. In some embodiments, an R ¹ is located immediately adjacent to oxygen on either side. That is, in some modalities, an R ¹ is located in each ortho position in the ring relative to the oxygen atom. Although there is no intention to be bound by any theory, it is believed that the positioning of one or more R ¹ groups in an ortho position relative to the oxygen atom shown in formula (I) can be beneficial, for example, in the case of the monomer which is used to prepare the segment of formula (I) is not fully reacted in polymer. Such an unreacted monomer could potentially migrate out of a cured coating composition including the polymer. The benefits of R ¹ with respect to a lack of appreciable estrogenic activity in certain such potential migrants are discussed in more detail below.
Although it is not intended to be bound by any theory, it is believed that a polyhydric phenol compound is less likely to exhibit appreciable estrogenic activity if the one or more hydroxyl groups present in each aryl ring (typically phenol hydroxyl groups) they are sterically prevented by one or more other aryl ring substituents, compared to a similar polyhydric phenol compound having hydrogen atoms present in each ortho position. It is believed that it may be preferable to have substituent groups positioned in each ortho position relative to the hydroxyl groups mentioned above to provide an optimal steric effect to reduce the accessibility and / or reactivity of the hydroxyl group. While it is preferred to position the substituent groups in one or both ortho positions, a bulky substituent group (s) located in one or both of the meta positions can also provide the desired effect.
Preferred R ¹ groups are sufficiently bulky to provide an adequate level of steric hindrance for the hydroxyl groups mentioned above to achieve the desired effect. To avoid any ambiguity, the term group when used in the context of R ¹ groups refers to both individual atoms (for example, a halogen atom) or molecules (that is, two or more atoms). The optimal chemical constituents, size, and / or configuration (for example, linear, branched, etc.) of one or more R ¹ groups can depend on a variety of factors, including, for example, the location of the R ¹ group in the group aryl.
Preferred segments of formula (I) include one or more R ¹ groups having an atomic weight of at least 15 daltons. In some embodiments, the segments of formula (I) include one or more R ¹ groups having an atomic weight of at least 25, at least 40, or at least 50. Although the maximum suitable size of R ^{1 is} not particularly limited, typically it will be less than 500 daltons, more typically less than 100 daltons, and even more typically less than 60 daltons. Non-limiting examples of R ¹ groups include groups having at least one carbon atom (e.g., organic groups), halogen atoms, sulfur-containing groups, or any other suitable group that is preferably substantially non-reactive with an epoxy group.
In the presently preferred embodiments, one or more R ¹ groups from each phenylene group includes at least one carbon atom, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 4 carbon atoms. R ¹ will typically be a saturated or unsaturated hydrocarbon group, more typically saturated, which may optionally include one or more heteroatoms other than carbon or hydrogen atoms (e.g., N, O, S, Si, a halogen atom, etc.). ). Examples of suitable hydrocarbon groups may include substituted or unsubstituted: alkyl groups (for example, methyl, ethyl, propyl, butyl groups, etc., including their isomers), alkenyl groups, alkynyl groups, alicyclic groups, aryl groups, or combinations thereof .
In certain preferred embodiments, each phenylene group shown in formula (I) includes at least one R ¹ alkyl group. As discussed above, any suitable isomer can be included. Thus, for example, a linear butyl group can be used or a branched isomer such as an isobutyl group or a tert-butyl group. In one embodiment, a tert-butyl group (and more preferably a tert-butyl moiety) is a preferred R ¹ group.
As previously mentioned, it is considered that R ¹ may include one or more cyclic groups. In addition, R ¹ can form a cyclic or polycyclic group with one or more other R ¹ and / or R ^{2 groups} .
In some embodiments, one or both of the phenylene groups shown in formula (I) includes an R ¹ located ortho to oxygen which is a halogen atom, more preferably a higher molecular weight halogen such as bromine or iodine. However, in preferred embodiments, the segment of formula (I) does not include any halogen atoms. In addition, in the presently preferred embodiments, the polymer including one or more segments of formula (I) is preferably free of halogen atoms.
R ² is present or absent in the segment of formula (I) depending on whether n is 0 or 1. When R is absent, either (i) a carbon atom of one phenylene ring is covalently bonded to a carbon atom of the other phenylene ring (which occurs when w is 4) or (ii) the phenylene group shown in formula (I) comes together to form a fused ring system (which occurs when w is 3 and the two phenylene groups are then fused). In some embodiments, R ² (or the ring-ring covalent bond if R is absent) is preferably attached to at least one, and more preferably both, the phenylene rings in a relative (i.e., position 1,4) position to the oxygen atom shown in formula (I). A modality of the segment of formula (I), in which n is 0 and w = 3 in such a way that the two phenylene groups have joined to form a naphthalene group, is shown below:
_and
R can be any suitable divalent group including, for example, carbon-containing groups (which may optionally include heteroatoms such as, for example, N, O, S, Si, a halogen atom, etc.), sulfur-containing groups (including, for example, example, a sulfur atom), oxygen-containing groups (including, for example, an oxygen atom, a ketone group, etc.), nitrogen-containing groups, or a combination thereof.
* *2
In preferred embodiments, R is present and is typically an organic group containing less than 15 carbon atoms, more typically 1 to 10 carbon atoms. R will typically be a saturated or unsaturated hydrocarbon group, more typically a saturated alkyl group. In some embodiments, R may include one or more cyclic groups, which may be aromatic or alicyclic and may optionally include heteroatoms. The one or more optional cyclic groups of R may be present, for example, (i) in a chain connecting the two phenylene groups shown in formula (I) and / or (ii) in a pendant group linked in a chain connecting the two phenylene groups.
The atomic weight of the group R of formula (I), if present, can be any suitable atomic weight, although in preferred embodiments, R has an atomic weight less than about 500 daltons, more preferably less than about 200 daltons, even more preferably less than 150 daltons, and optimally less than 100 daltons.
In some embodiments, R includes a carbon atom that is attached to a carbon atom of each of the phenylene groups shown in formula (I). For example, R may have a structure of formula -C (RR) - in which R and R are each independently a hydrogen atom, a halogen atom, an organic group, a sulfur-containing group, a nitrogen-containing group, or any other suitable group that is preferably substantially non-reactive with an epoxy group, and wherein R and R can optionally join to form a cyclic group. In one embodiment, R is a divalent methylene group (ie, -CH ₂ -).
The oxygen atom of a phenylene ring shown in formula (I) can be positioned on the ring in any position relative to R (or relative to the other phenylene ring if R is absent). In some embodiments, the oxygen atom (which is preferably an '2 · ether oxygen) and R are located relative to each other in positions for.
The segments of formula (I) can be of any suitable size. Typically, the segments of formula (I) will have an atomic weight less than 1,000, preferably less than 600, more preferably less than 400 daltons. More typically, the segments of formula (I) will have an atomic weight of about 250 to about 400 daltons.
In preferred embodiments, the substituted phenylene groups of formula (I) are symmetrical to each other. Stated otherwise, the substituted phenylene groups are preferably formed from the same 5-phenol compound, thereby resulting in the same substituent groups on each ring located at the same ring positions. An example of a compound having symmetric phenylene groups is provided below.
An example of a compound having phenylene groups that are not symmetrical is shown below, in which a methyl group is in a meta position on one ring and an ortho position on the other.
In preferred embodiments, the polymer of the present invention includes a plurality of segments of formula (I), which are preferably dispersed throughout the polymer main chain, more preferably a polyether main chain. In preferred embodiments, the segments of formula (I) constitute a substantial portion of the total polymer mass. Typically, the segments of formula (I) constitute at least 10 weight percent (% by weight), preferably at least 30 weight percent, more preferably at least 40 weight percent, even more preferably at least 50 weight percent, and optimally at least 55% by weight of the polymer.
The weight percentage of segments of formula (I) in the polymer of the present invention may be below the amounts cited above in certain situations, and may even be substantially below. As an example, the concentration of segments of formula (I) may be outside the range mentioned above if the polymer of the present invention, which is preferably a polyether polymer, includes additional components of large molecular weight as may occur, for example, when the polymer is a copolymer such as an acrylic-containing copolymer (for example, an acrylic-polyether copolymer formed by graft of acrylic into a polyether polymer of the present invention). In such embodiments, the weight percentage of segments of formula (I) present in the polymer is preferably as described above (i.e., 2 10% by weight, 2 30% by weight, 2 40% by weight, 2 50% by weight , 2 55% by weight), based on the weight percentage of segments of formula (I) relative to the total polyether fraction of the polymer (although the total weight of the non-polyether portions such as acrylic portions is not considered) . In general, the total polyether fraction of the polymer can be calculated based on the total weight of polyhydroxy and polyhydric phenol reagents (for example, polyphenols and / or polyhydric diphenols) incorporated in the polymer.
Depending on the specific embodiment, the polymer of the present invention can be amorphous or semi-crystalline.
The polymer can include branching, if desired. In preferred embodiments, however, the polymer of the invention is a linear or substantially linear polymer.
If desired, the polymer backbone can include growth bonds in steps (e.g., condensation bonds) other than ether bonds (i.e., in addition to, or in place of, ether bonds) such as, for example, amide bonds , carbonate bonds, ester bonds, urea bonds, urethane bonds, etc. Thus, for example, in some embodiments, the main chain may include both ester and ether bonds.
The polymer of the present invention preferably includes hydroxyl groups. In preferred embodiments, the polymer includes a plurality of hydroxyl groups attached on the main chain. In preferred embodiments, polyether portions of the main polymer chain include secondary hydroxyl groups distributed along the main chain. Preferred secondary hydroxyl groups are present in CH ₂ -CH (OH) -CH ₂ - segments, which are preferably derived from an oxirane group. Such segments can be formed, for example, via reaction of an oxirane group and a hydroxyl group (preferably a hydroxyl group of a polyhydric phenol). In some embodiments, the CH ₂ CH (OH) -CH ₂ - segments are attached to each of the preferred ether oxygen atoms of the formula (I) segments.
The polymer backbone of the present invention can include any suitable end groups, including, for example, epoxy and / or hydroxyl groups (for example, a hydroxyl group attached to an aryl or heteroaryl ring).
In preferred embodiments, the polymer of the present invention is formed using reagents that include at least one polyepoxide compound, more typically at least one diepoxide compound. Although any suitable ingredients can be used to form the polymer, in the presently preferred embodiments, the polymer is formed via reaction of ingredients that include: (a) one or more polyepoxides, more preferably one or more diepoxides, and (b) one or more polyols, more preferably one or more polyhydric phenols, and even more preferably one or more dihydric phenols. The polymer is preferably derived from ingredients including a diepoxide that has one or more hindered aryl or heteroaryl groups, and more preferably one or more hindered phenylene groups described herein (for example, as shown in formula (I)).
While it is envisaged that the segments of formula (I) can be incorporated into the polymer using ingredients other than a compound of a polyepoxide compound, in preferred embodiments some or all of the segments of formula (I) are incorporated into the polymer using a polyepoxide compound, and more preferably a diepoxide compound. The polyepoxide compound can be enhanced to form a binder polymer, more preferably a polyether binder polymer, of a suitable molecular weight using any suitable extender or combinations of extenders. As discussed above, polyhydric phenols, and dihydric phenols in particular, are preferred extenders. Examples of other suitable extenders may include polyacids (and diacids in particular) or phenol compound having both a phenol hydroxyl group and a carboxylic group (for example, parahydroxybenzoic acid and / or parahydroxyphenylacetic acid). The conditions for such reactions are generally performed using standard techniques that are known to the person skilled in the art, or that are exemplified in the Examples Section.
The epoxy groups (also commonly called oxirane groups) of the polyepoxide compound can be attached to the compound via any suitable bond, including, for example, ether-containing bonds or ester-containing bonds. Glycidyl ethers of polyhydric phenols and glycidyl esters of polyhydric phenols are preferred polyepoxide compounds, with diglycidyl ethers being particularly preferred.
A preferred polyepoxide compound for use in incorporating segments of formula (I) into the polymer of the present invention is shown in formula (II) below:
Formula (II)
R ¹ , R ² , n, v, and w are as described above for formula (I);
each of the phenylene groups shown in formula (II) includes at least one R ¹ which is preferably attached to the ring in a position immediately adjacent to the oxygen atom (i.e., ortho);
s is 0 to 1, more preferably 1;
R, if present, is a divalent group, more preferably a divalent organic group; and preferably each R ⁴ is independently a hydrogen atom, a halogen atom, or a hydrocarbon group that can include one or more hetero atoms; more preferably each R ⁴ is a hydrogen atom.
R is typically a hydrocarbyl group, which can optionally include one or more heteroatoms. Preferred hydrocarbyl groups include groups having one to four carbon atoms, with methylene groups being particularly preferred. In some embodiments, R includes a carbonyl group. In such an embodiment, R includes a carbonyl group that is attached to the oxygen atom shown in formula (II) (for example, as in an ester bond).
In the presently preferred embodiments, R ⁴ is a hydrogen atom.
The preferred polyepoxide compounds of formula (II) are non-mutagenic. A useful test for assessing mutagenicity is the in vivo mammalian assay known as the in vivo alkaline single cell gel electrophoresis assay (called the comet assay). The method is described in: Tice, R.R.The single cell gel / comet assay: a microgel electrophoretic technique for the detection of DNA damage and repair in individual cells. Environmental Mutagenesis. Eds. Phillips, D.H and Venitt, S. Bios Scientific, Oxford, UD, 1995, pp. 315-339. A negative test result in the comet assay indicates that a compound is not mutagenic.
In some embodiments, the polyepoxide compound of formula (II) is formed via epoxidation of a diphenol compound (for example, via a condensation reaction using epichlorohydrin or any other suitable material). Such a diphenol compound is shown in figure 1 2 (III) below, in which R, R, n, v, and w are as in formula (I):
(HV _v (R ² ) n (H) wV
HO
OH (R ¹ V (R ¹ ) v Formula (III)
Preferred compounds of formula (III) do not exhibit appreciable estrogenic activity. Preferably appreciably non-estrogenic compounds exhibit a degree of estrogen agonist activity, in a competent human estrogen receptor assay in vitro, which is less than that displayed by genestein in the assay, and more preferably less than that displayed by 4 , 4 '- (propane-2,2-diyl) diphenol in the assay. Compounds such as 4,4'methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'methylenebis (2, 6-dimethylphenol), 4,4'-butylidenobis (2-t-butyl-5-methylphenol), and 4,4 '- (ethane-1,2-di-yl) bis (2,6-dimethylphenol) do not exhibit appreciable estrogenic activity in a suitable in vitro assay whose results, as is known, are directly correlated with the results of the MCF-7 cell proliferation assay (MCF-7 assay) through analysis of common reference compounds. The MCF-7 assay is a useful test to assess whether a polyhydric phenol compound is appreciably non-estrogenic. The test
MCF-7 uses MCF-7 WS 8 cells to measure whether and to what extent a substance induces cell proliferation via estrogen receptor-mediated routes (ER, estrogen receptor). The method is generally described in
NICEATM Pre-Screen Evaluation of the In Vitro Endocrine Disruptor Assay,
National Toxicology Program Interagency Center for the Evaluation of
Alternative Toxicological Methods (NICEATM). Examples of appreciably non-estrogenic polyhydric phenols include polyhydric phenols that when tested using the MCF-7 assay exhibit a Relative Proliferative Effect (RPE) that has a logarithmic value 10 (at base 10) less than about -2 .0, more preferably less than about -3.0, and even more preferably less than about -4.0.
The RPE, which is specifically defined in the MCF-7 reference mentioned above, is the ratio between the highest cell yield obtained with the test compound in the MCF-7 test and that obtained with 17-beta-estradiol in the MCF- 7 multiplied by 100. A table is provided below including several polyhydric compounds of formula (III) and their logarithmic RPE values provided for in the MCF-7 test.
Polyhydric compound of formula (III) Reference compound in RPE Log17p-estradiol2.00 -1.85 4,4 '- (propane-2,2-di-yl) bis (2,6-dimethylphenol) -2.2 4,4'-methylenebis (2,6-dimethylphenol) about -4 4,4 '- (1,2-di-yl ethane) bis (2,6dimethylphenol) in the range of -2 to -3 4,4'-butylidenobis (2-t-butyl-5-methylphenol) in the range of -3 to -5 4,4'-methylenebis (2,6-di-t-butylphenol) in the range of -3.5 to -5 2,2'-methylenebis (4-methyl-6-t-butylphenol in the range of -4 to -5 4,4 '- (ethane-1,2-di-yl) bis (2,6dimethylphenol) in the range of -4 to -5 Tetrabromobisphenol A * less than -5
* A bromine is located in each ortho position.
A diphenol having no appreciable estrogenic activity can be beneficial if some residual, unreacted diphenol may be present in an uncured coating composition. Although the rest of the scientific data does not indicate that the presence, in cured coatings, of very small amounts of residual diphenols that have estrogenic activity in an in vitro recombinant cellulose assay represents a concern for human health, the use of diphenols that do not have appreciable estrogenic activity in such an assay may however be desirable from the point of view of public perception. Thus, in preferred embodiments, the polymer of the present invention is preferably formed using polyhydric phenol compounds that do not exhibit appreciable estrogenic activity in the MCF-7 test.
Although there is no intention to link to any theory, as previously discussed, it is believed that the presence of substituting groups (that is, a group other than a hydrogen atom) in one or more of the ortho and / or goal positions of each phenylene ring of the compound of formula (III), relative to the hydroxyl group of phenol of each ring, can reduce or effectively eliminate any estrogenic activity. It is believed that the inhibition / elimination of estrogenic activity may be attributable to one or both of the following: (a) steric impediment of the phenol hydroxyl group and / or (b) the compound that has a higher molecular weight due to the presence of one or more substituent groups. Substitution in one or both ortho positions of each phenylene ring is presently preferred because ortho substitution is believed to provide the highest steric hindrance to the hydroxyl group.
Preferred compounds of formula (III) include the diphenol compounds mentioned below (with the chemical name indicated below each structure.
4,4 '-Methylenebis (2,6-di-t-butylphenol);
2,2'-Methylenobis (4-ethyl-6-t-butylphenol)
4.4 ’-Butilidenobis (2-t-butyl-5-methylphenol)
2,2'-Methylenobis (6- (1-methyl-cyclohexyl) -4-methylphenol)
2,2 ’-Methylenobi s (6-t-butyl-4-methyl phenol)
4,4’-Isopropylidenobis (2,6-dimethylphenol)
4.4 ’-Methylenebis (2,6-dimethylphenol)
2,2 ’-Methylenobi s (4-methyl-6-t-butylphenol)
The compounds of formula (III) below can also be used in certain embodiments if desired.
4,4 '- (Ethane-1,2-di-yl) bis (2,6-dimethylphenol)
4,4’-Isobutylidenobis (2-t-butyl-5-methylphenol)
4.4 ’-Isopropylidenobis (2-methylphenol)
4,4’-Isopropylidenobis (2-isopropylphenol)
4.4 ’-Isopropylidenobis (2-phenylphenol)
2,5-Di-t-butylhydroquinone
4,4’-Cyclohexylidenobis (2-methylphenol)
4,4’-Cyclohexylidenobis (2, b-dimethylphenol)
In certain embodiments, bis (4-hydroxy-3-methylphenyl) methane can be used if desired, which is shown below.
The diphenol compounds of formula (III) can be converted to a diepoxide using any suitable process and materials. The use of epichlorohydrin in the epoxidation process is presently preferred. As an example, below is a diepoxide formed via an epoxidation with 4,4'-methylenebis (2,6-di-tbutylphenol) epichlorohydrin.
Numerous diepoxides have been successfully generated using various diphenol compounds of formula (III), and polyether polymers have been successfully produced from them. In general, it is much more difficult to correctly form a polyether polymer (using reasonable process conditions and time) using, as a diphenol component, a compound of formula (III) substituted in the ortho-ring positions. For example, the inventors have found that using conventional industrial processes it is difficult to effectively react 4,4'-methylenebis (2,6-di-t-butylphenol) with the diepoxide monomer to form a polyether polymer. (Somewhat surprisingly, however, diphenol compounds such as 4,4'methylenebis (2,6-di-t-butylphenol) can experience a condensation reaction with epichlorohydrin to form a diepoxide that is reactive with di-phenols. conventional water sources that are not substituted in ortho or meta positions.) Although it is not intended to be bound by theory, it is believed that the hydroxyl groups of such diphenol compounds are generally not accessible enough to react efficiently with a group oxirane of a diepoxide monomer and form an ether bond. However, it is considered that a hindered diphenol compound of formula (III) can be selected so that the hydroxyl groups are sufficiently sterically prevented so that the compound does not exhibit appreciable estrogenic activity, while the hydroxyl groups are still sufficiently accessible. that the compound can react with a diepoxide and develop molecular weight under reasonable conditions and process times (for example, less than 24 hours of reaction time at a reaction temperature less than about 240 ° C).
In certain preferred embodiments, the diphenol compound of formula (III) is substituted at one or both ortho ring positions of each phenylene group shown with an R ¹ group that includes from 1 to 4 carbon atoms, more preferably from 1 to 4 3 carbon atoms, and even more preferably 1 to 2 carbon atoms. In some embodiments, substituted or unsubstituted methyl groups are ortho-preferred R ¹ groups, with the methyl moiety (i.e., -CH ₃ ) being particularly preferred. Although it is not intended to be bound by any theory, it has been observed that the presence of ortho large substituent groups can sometimes affect the efficiency by which certain diphenol compounds of formula (III) are converted to diepoxides using epichlorohydrin and, in addition , the efficiency by which the resulting diepoxide can be improved in a polyether polymer having segments of formula (I).
Any suitable polyhydric phenol can be used to increase the molecular weight of polyepoxides of formula (II) to form polyether polymers. However, the use of bisphenol A is not preferred. Preferred polyhydric phenols are dihydric phenols that are free of bisphenol A and preferably do not exhibit appreciable estrogenic activity. In certain preferred embodiments, a polyhydric phenol is used which has a higher molecular weight than that of bisphenol A (i.e., greater than about 228 grams / mol).
Examples of dihydric phenols suitable for use in forming the polyether polymer include the compounds of the formula below (IV):
HO-Ar- (Y _u -Ar) _t -OH, where:
each Ar is independently an aryl group or heteroaryl group, more preferably a phenylene group (and typically an unsubstituted phenylene group, i.e., -C ₆ H4-);
Y, if present, is a divalent group;
u is independently 0 or 1; and t is independently 0 or 1.
In some embodiments, Y includes one or more cyclic groups (for example, alicyclic and / or aromatic groups), which can be monocyclic or polycyclic groups (for example, a divalent: Norman, Norbomen, Tricyclodecane, Bicycle group [4.4.0] dean, or isosorbide, or a combination thereof).
In some embodiments, Y includes one or more ester bonds. For example, in some embodiments, Y is a segment -R ⁶ WZR ⁵ -ZR ⁶ W-, where: R ⁵ is a divalent organic group; each R ⁶ , if present, is independently a divalent organic group; each Z is independently an ester bond which can be of any directionality (i.e., -C (O) -O- or -OC (O) -; and each w is independently 0 or 1. In such an embodiment, R ⁵ includes at least one divalent cyclic group such as a divalent polycyclic group, a divalent aryl or heteroaryl group (for example, a substituted or unsubstituted phenylene group) or a divalent alicyclic group (for example, a cyclohexane or cyclohexene group substituted or unsubstituted) such as, for example, any of those described here. In one embodiment, Y is -R ⁶ WC (O) -OR ⁵ -OC (O) -R ⁶ w-. Another discussion of suitable segments containing ester bonds and materials for incorporating such segments into the polymer of the invention is provided in published US application No. 2007/0087146 by Evans et al. and in published international application No. WO 2011/130671 by Niederst et al.
If present, Y typically has a molecular weight less than about 500, and more typically less than about 300.
Examples of suitable dihydric phenols include hydroquinone, catechol, p-tert-butylcatechol, resorcinol, 1,1-bis (4-hydroxyphenyl) -
3,3,5-trimethyl-cyclohexane, 1,1-di (4-hydroxyphenyl) -cyclohexane, dihydroxynaphthalene, biphenol, or a mixture thereof.
As an example, a compound of formula (IV) containing cyclic group can be formed by reacting (a) a suitable amount (for example, about 2 moles) of compound A having a hydroxyl group of phenol and a carboxylic acid or another group containing active hydrogen with (b) a suitable amount (for example, about 1 mol) of a difunctional or higher compound B having one or more cyclic groups (monocyclic and / or polycyclic) and two or more groups containing active hydrogen capable of reacting with the active hydrogen containing group of compound A. Examples of preferred compounds A include 4-hydroxyphenylacetic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, and their derivatives or mixtures thereof. Examples of preferred B compounds include cyclic group-containing diols such as cyclohexanedimethanol (CHDM); tricyclodecanedimethanol (TCDM); naic acid and / or anhydride; one of anhydrous polycyclic sugar such as isosorbide, isomanide, or isoidide; and derivatives or mixtures thereof. In some embodiments, the cyclic group can be formed after the reaction of compounds A and B. For example, a Diels-Alder reaction (using, for example, cyclopentadiene as a reagent) could be used to incorporate an unsaturated bicyclic group such as a norbomenous group in compound B, in which case compound B in its unreacted form would need to include at least one non-aromatic carbon-carbon double bond in order to participate in the Diels-Alder reaction. For further discussion of suitable materials and techniques related to such Diels-Alder reactions see, for example, published international requests for numbers WO 2010/118356 by Skillman et al. and WO 2010/118349 by Hayes et al.
An additional example of a suitable compound B is provided below:
Some examples of dihydric phenol compounds containing cyclic group are provided below. These compounds are discussed in more detail in the previously cited published international application of WO 2011/130671 by Niederst et al.

If desired, one or more comonomers and / or cooligomers can be included in the reagents used to generate the polymer of the present invention. Some non-limiting examples of such materials include adipic acid, azelaic acid, terephthalic acid, isophthalic acid, and combinations thereof. The comonomers and / or cooligomers can be included in an initial reaction mixture of polyepoxide and polyhydric phenol and / or can be post-reacted with the resulting polyether oligomer or polymer. In the presently preferred embodiments, a comonomer and / or cooligomer is not used to produce a polyether polymer of the present invention.
The preferred polymers of the present invention can be prepared in a variety of molecular weights. The polyether polymers of the present invention have a numerical average molecular weight (Mn) of at least 2,000, more preferably at least 3,000, and even more preferably at least 4,000. The molecular weight of the polyether polymer can be as high as is necessary for the desired application. Typically, however, the Mn of the polyether polymer, when adapted for use in a liquid coating composition, will not exceed about 10,000. In embodiments in which the polymer of the present invention is a copolymer, such as a polyether-acrylic copolymer, although the molecular weight of the polyether polymer is typically in the ranges mentioned above, the molecular weight of the total polymer may be higher than the one previously mentioned. Typically, however, such copolymers will have an Mn less than about 20,000.
The advance of the molecular weight of the polymer can be intensified by the use of a catalyst in the reaction of a diepoxide with one or more enhancing comonomers, such as, for example, a polyhydric phenol of formula (IV). Typical catalysts useful in advancing the molecular weight of the epoxy material of the present invention include amines, hydroxides (e.g., potassium hydroxide), phosphonium salts, and the like. A currently preferred catalyst is a phosphonium catalyst. The phosphonium catalyst useful in the present invention is preferably present in an amount sufficient to facilitate the desired condensation reaction.
Alternatively, epoxy-terminated polymers of the present invention can be reacted with fatty acids to form polymers that have unsaturated reactive groups (e.g., oxidizable by air), or with acrylic acid or methacrylic acid to form free radical-curable polymers.
The advance of the molecular weight of the polymer can also be enhanced by reacting a hydroxyl or epoxy-terminated polymer of the present invention with a suitable acid (such as adipic acid).
As discussed above, in certain preferred embodiments, the coating composition of the present invention is suitable for use in forming a food contact packaging coating. For the purpose of exhibiting an appropriate balance of coating properties for use as a food contact packaging coating, including adequate corrosion resistance when in prolonged contact with packaged beverage or food products that may be of a corrosive nature, the The polymer of the present invention preferably has a glass transition temperature (Tg) of at least 60 ° C, more preferably at least 70 ° C, and even more preferably at least 80 ° C. In preferred embodiments, Tg is less than 150 ° C, more preferably less than 130 ° C, and more preferably even less than 110 ° C. Tg can be measured via differential scanning calorimetry (DSC) using the methodology described in the test methods section. In preferred embodiments, the polymer is a polyether polymer exhibiting a Tg according to the aforementioned Tg values.
Although it is not intended to be bound by any theory, it is believed that it is important for the polymer to exhibit a Tg such as that described above in applications where the coating composition will be in contact with beverage or food products during processing high temperature retort (for example, at temperatures at or above about 100 ° C and sometimes accompanied by pressures above atmospheric pressure), and particularly when retorting beverage or food products that are of a more natural nature. chemically aggressive. It is considered that, in some embodiments, such as, for example, in which the coating composition is intended for use as an external varnish on a beverage or food container, the Tg of the polymer may be less than that described above (for example, example, as low as about 30 ° C) and the coating composition can still exhibit an appropriate balance of properties in end use.
Although it is not intended to be bound by any theory, it is believed that the inclusion of a sufficient number of aryl and / or heteroaryl groups (typically phenylene groups) in the binder polymer of the present invention is an important factor in achieving coating performance suitable for packaging coatings for contact with food, especially when the product to be packaged is a so-called drink or food product that is difficult to preserve. Sauerkraut is an example of a product that is difficult to maintain. In preferred embodiments, aryl and / or heteroaryl groups constitute at least 20% by weight, more preferably at least 30% by weight, and even more preferably at least 45% by weight of the polyether polymer, based on the total weight of aryl groups. and heteroaryl in the polymer relative to the weight of the polyether polymer. The upper concentration of aryl / heteroaryl groups is not particularly limited, but preferably the amount of such groups is configured so that the Tg of the polyether polymer does not exceed the previously discussed Tg ranges. The total amount of aryl and / or heteroaryl groups in the polyether polymer will typically constitute less than about 80% by weight, more preferably less than about 70% by weight, and even more preferably less than 60% by weight of the polyether polymer. The total amount of aryl and / or heteroaryl groups in the polyether polymer can be determined based on the weight of monomer containing aryl or heteroaryl incorporated in the polyether polymer and the weight fraction of such monomer that constitutes aryl or heteroaryl groups. In embodiments in which the polymer is a polyether copolymer (for example, a polyether acrylic copolymer), the weight fraction of aryl or heteroaryl groups in the copolymer polyether polymer portion (s) will generally be as described above, although the weight fraction relative to the total weight of the copolymer may be less.
Preferred aryl or heteroaryl groups include less than 20 carbon atoms, more preferably less than 11 carbon atoms, and even more preferably less than 8 carbon atoms. The aryl or heteroaryl groups preferably have at least 4 carbon atoms, more preferably at least 5 carbon atoms, and even more preferably at least 6 carbon atoms. Substituted or unsubstituted phenylene groups are preferred aryl or heteroaryl groups. Thus, in preferred embodiments, the polyether fraction of the polymer includes an amount of phenylene groups according to the amounts mentioned above.
The polymers of the present invention can be applied to a substrate as part of a coating composition that includes a liquid carrier. The liquid carrier can be water, organic solvent, or mixtures of several of these liquid carriers. Consequently, the liquid coating compositions of the present invention can be either water-based or solvent-based systems. Examples of suitable organic solvents include glycol-ethers, alcohols, aliphatic or aromatic hydrocarbons, dibasic esters, ketones, and the like, and combinations thereof. Preferably, such vehicles are selected to provide a polymer dispersion or solution for further formulation.
It is envisaged that a polyether polymer of the present invention can replace any conventional epoxy polymer present in a packaging coating composition known in the art. Thus, for example, the polyether polymer of the present invention can replace, for example, a polymer containing BPA / BADGE from an acrylic / epoxy latex coating system, a polymer containing BPA / BADGE from a base epoxy coating system solvent, etc.
The amount of binder polymer of the present invention included in the coating compositions can vary widely depending on a variety of considerations such as, for example, the method of application, the presence of other film-forming materials, whether the coating composition is a water based system. water-based or solvent-based, etc. For liquid-based coating compositions, however, the binder polymer of the present invention will typically constitute at least 10% by weight, more typically at least 30% by weight, and even more typically at least 50% by weight of the coating composition. , based on the total weight of resin solids in the coating composition. For such liquid-based coating compositions, the binder polyether polymer will typically constitute less than about 90% by weight, less than about 80% by weight, and even more typically less than about 70% by weight of the coating composition, based on the total weight of resin solids in the coating composition.
In one embodiment, the coating composition is an organic solvent-based composition preferably having at least 20% by weight of non-volatile components (i.e., solids), and more preferably at least 30% by weight of non-volatile components. . In one embodiment, the coating composition is an organic solvent-based composition preferably having no more than 40% by weight of non-volatile components (i.e., solids), and more preferably not more than 30% by weight of components non-volatile. For this embodiment, the non-volatile film-forming components preferably include at least 50% by weight of the polymer of the invention, more preferably at least 55% by weight of the polymer, and even more preferably at least 60% by weight of the polymer. For this embodiment, the non-volatile film-forming components preferably include not more than 95% by weight of the polymer of the invention, and more preferably not more than 85% by weight of the polymer.
In one embodiment, the coating composition of the present invention is a solvent-based system that includes no more than a minimum amount of water (for example, less than 2% by weight of water), if any.
In one embodiment, the coating composition is a water-based composition preferably having at least 15% by weight non-volatile components (i.e., solids). In one embodiment, the coating composition is a water-based composition preferably having no more than 50% by weight of non-volatile components (i.e., solids), and more preferably not more than 40% by weight of non-volatile components volatile. For this embodiment, the non-volatile film-forming components preferably include at least 5% by weight of the polymer of the present invention, more preferably at least 25% by weight of the polymer, even more preferably at least 30% by weight of the polymer, and optimally at least 40% by weight of the polymer. For this embodiment, the non-volatile film-forming components preferably include not more than 70% by weight of the polymer of the present invention, and more preferably not more than 60% by weight of the polymer.
If a waterborne system is desired, techniques can be used such as those described in ^the patents US No 3943187; 4,076,676; 4,247,439; 4,285,847; 4,413,015; 4,446,258; 4,963,602; 5,296,525; 5,527,840; 5,830,952; 5,922,817; and published US patent application No. 2004/0259989. The water-based coating system of the present invention can optionally include one or more organic solvents, which will typically be selected to be water miscible. The liquid carrier system of water-based coating compositions will typically include 50% by weight of water, more typically at least 75% by weight of water, and in some embodiments more than 90% by weight or 95% by weight of water . Any suitable medium can be used to make the polymer of the invention water miscible. For example, the polymer may include an appropriate amount of saline groups such as ionic or cationic salt groups to make the water miscible polymer (or groups capable of forming such saline groups). Basic or neutralized acid groups are preferred saline groups.
In one embodiment, a water-dispersible polymer can be formed from preformed polymers (for example, (a) an oxirane-functional polymer, such as, for example, a polyether polymer, preferably having at least one segment of formula (I ) and (b) an acid-functional polymer such as, for example, an acid-functional acrylic polymer) in the presence of a tertiary amine.
In another embodiment, a water-dispersible polymer can be formed from an oxirane-functional polymer (more preferably a polyether polymer) preferably having at least one segment of formula (I) which is reacted with ethylenically unsaturated monomers to form an acid-polymer functional, which can then be neutralized, for example, with a tertiary amine. Thus, for example, in an embodiment, a water - dispersible polymer preferably having at least one segment of formula (I) may be formed in accordance with acrylic polymerization techniques of US patents ^Nos 4,285,847 and / or 4,212. 781, which describe techniques for grafting functional acidic acrylic groups (for example, via the use of benzoyl peroxide) into epoxy polymers. In another embodiment, acrylic polymerization can be carried out by reacting ethylenically unsaturated monomers with unsaturation present in the polymer preferably containing at least one segment of formula (I). See, for example, US patent No. 4,517,322 and / or published patent application No. 2005/0196629 for examples of such techniques.
In another embodiment, a water-dispersible polymer can be formed having the ELA structure, in which E is an epoxy portion of the polymer formed from a polyether polymer described herein, A is a polymerized acrylic portion of the polymer, and L is a portion of bond that covalently bonds E in A. Such a polymer can be prepared, for example, from (a) a polyether polymer described herein preferably having about two epoxy groups, (b) an unsaturated bonding compound preferably having (i ) either conjugated carbon-carbon double bonds or a carbon-carbon triple bond and (ii) a functional group capable of reacting with an epoxy group (for example, a carboxylic group, a hydroxyl group, an amino group, a starch group , a mercapto group, etc.). Preferred bonding groups include 12 or less carbon atoms, with sorbic acid being an example of such a preferred bonding compound. The acrylic portion preferably includes one or more salt groups or salt-forming groups (for example, acidic groups such as present in α, β-ethylenically unsaturated carboxylic acid monomers). Such polymers can be formed, for example, using a polyether polymer of the present invention free of BPA and BADGE in combination with the materials and techniques described in US Patent No. 5,830,952.
In some embodiments, the coating composition of the present invention is substantially free of acrylic (for example, it includes less than about 1% by weight of polymerized acrylic monomers).
If desired, an acid-functional polymer can be combined with a tertiary amine to at least partially neutralize it prior to reaction with an oxiran-functional polymer preferably having at least one segment of formula (I).
In another embodiment, a polymer preferably containing segments of formula (I) and including -CH ₂ -CH (OH) CH ₂ - segments, which are derived from an oxirane, is reacted with an anhydride. This provides acidic functionality which, when combined with an amine or other suitable base to neutralize at least partially the acidic functionality, is dispersible in water.
A coating composition of the present invention can also include other optional ingredients that do not adversely affect the coating composition or a resulting cured coating composition. Such optional ingredients are typically included in a coating composition to improve the aesthetics of the composition; to facilitate the manufacture, processing, handling, and application of the composition; and to further improve a specific functional property of a coating composition or a cured coating composition resulting therefrom. For example, the composition that includes a polymer of the present invention can optionally include crosslinkers, fillers, catalysts, lubricants, pigments, surfactants, dyes, colorants, toners, extenders, anticorrosion agents, flow control agents, thixotropic agents, dispersing agents , antioxidants, oxygen scavenging materials, adhesion promoters, light stabilizers, and mixtures thereof, as required to provide the desired film properties. Each optional ingredient is preferably included in an amount sufficient to serve its intended purpose, but not in an amount that would adversely affect a resulting coating composition or cured coating composition.
Preferred compositions are substantially free of mobile BPA and BADGE, and most preferably essentially free of these compounds, and most preferably completely free of these compounds. The coating composition is also preferably substantially free of bound BPA and BADGE, most preferably essentially free of these compounds, and optimally completely free of these compounds. In addition, the preferred compositions are also substantially free, more preferably essentially free, and most preferably completely free of: bisphenol S, bisphenol F, and diglycidyl ether of bisphenol F or bisphenol S.
It has been found that coating compositions using the aforementioned polymer-containing compositions can be formulated using one or more optional curing agents (i.e., crosslinking resins, sometimes called crosslinkers). The choice of the specific crosslinker typically depends on the specific product being formulated. For example, some coating compositions are highly colored (for example, golden colored coatings). These coatings can typically be formulated using crosslinkers which in themselves tend to be yellowish in color. In contrast, white coatings are, in general, formulated using non-yellowing crosslinkers, or only a small amount of a yellowing crosslinker.
Preferred curing agents are substantially free of mobile BPA and BADGE and, more preferably, completely free of bound BPA and BADGE. Suitable examples of such curing agents are hydroxyl-reactive curing resins such as phenolic plastics, amino plastics, blocked or unblocked isocyanates, or mixtures thereof.
Phenolic plastic resins include condensation products from aldehydes with phenols. Formaldehyde and acetaldehyde are preferable aldehydes. Various phenols can be used such as phenol, cresol, p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol, cyclopentylphenol, and compounds of formula (III).
Suitable amine plastic resins are aldehyde condensation products such as formaldehyde, acetaldehyde, crotonaldehyde, and benzaldehyde with substances containing an amino or starch group such as urea, melamine, and benzoguanamine. Examples of suitable amino-crosslinking resins include, but are not limited to, benzoguanamine-formaldehyde resins, melamine-formaldehyde resins, etherified melamine-formaldehyde resins, and urea-formaldehyde resins.
Examples of other generally suitable curing agents are aliphatic, cycloaliphatic or aromatic di, tri or polyvalent blocked or unblocked isocyanates, such as hexamethylene diisocyanate, cyclohexyl-1,4-diisocyanate, and the like. Some other non-limiting examples of generally suitable blocked isocyanates include isophorone diisocyanate isomers, dicyclohexyl methane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, tetramethylxylene diisocyanate xylylene isocyanate, and mixtures thereof. In some embodiments, blocked isocyanates are used which have a Μη of at least about 300, more preferably at least about 650 and, most preferably, at least about 1.00.
Blocked polymeric isocyanates are useful in certain embodiments. Some examples of suitable blocked polymeric isocyanates include a diisocyanate biuret or isocyanurate, a trifunctional trimer, or a mixture thereof. Examples of suitable blocked polymeric isocyanates include TRIXENE BI 7951, TRIXENE BI 7984, TRIXENE BI 7963, TRIXENE BI 7981 (TRIXENE MATERIALS are available from Baxenden Chemicals, Ltd., Accrington, Lancashire, England), DESMODUR BL 3175A, DESMODUR BL3272, DESMODUR BL3272, DESMODUR BL3272 BL3370, DESMODUR BL 3475, DESMODUR BL 4265, DESMODUR PL 340, DESMODUR VP LS 2078, DESMODUR VP LS 2117, and DESMODUR VP LS 2352 (DESMODUR MATERIALS are available from Bayer Corp., Pittsburgh, PA, USA), or combinations thereof . Examples of suitable trimers may include a trimerization product prepared from, on average, three diisocyanate molecules or a trimer prepared from, on average, three moles of diisocyanate (eg, HMDI) reacted with a mole of another compound, such as a triol (for example, trimethylolpropane).
The level of agent (i.e., crosslinker) used will typically depend on the type of curing agent, the time and temperature of roasting, the molecular weight of the binder polymer, and the desired coating properties. If used, the crosslinker is typically present in an amount of up to 50% by weight, preferably up to 30% by weight, and more preferably up to 15% by weight. If used, a crosslinker is preferably present in an amount of at least 0.1% by weight, more preferably at least 1% by weight, and even more preferably at least 1.5% by weight. These weight percentages are based on the total weight of the resin solids in the coating composition.
A coating composition of the present invention can also include other optional polymers that do not adversely affect the coating composition or a resulting cured coating composition. Such resulting polymers are typically included in a coating composition as a filler material, although they can also be included, for example, as a binder polymer, a crosslinker or to provide desirable properties. One or more optional polymers (for example, charge polymers) can be included in an amount sufficient to serve the purpose for which they are intended, but not in an amount such as to adversely affect a resulting coating composition or cured coating composition.
Such additional polymeric materials can be non-reactive, and therefore simply function as fillers. Such optional non-reactive filler polymers include, for example, polyesters, acrylics, polyamides, polyethers, and novolacs. Alternatively, such additional monomers or polymeric materials can be reactive with the other components of the composition (for example, an acid-functional or unsaturated polymer). If desired, reactive polymers can be incorporated into the compositions of the present invention, to provide additional functionality for a variety of purposes, including crosslinking or dispersing the polymer of the present invention in water. Examples of such reactive polymers include, for example, polyesters, acrylics, polyamides, and functionalized polyethers. Preferred optional polymers are substantially free or essentially free of mobile BPA and BADGE, and more preferably completely free of mobile or bonded compounds.
A preferred optional ingredient is a catalyst to increase the curing speed. Examples of catalysts include, but are not limited to, strong acids (eg, phosphoric acid, dodecylbenzenesulfonic acid (DDB SA, dodecylbenzene sulphonic acid), available as CYCAT 600 from Cytec), methanesulfonic acid (MSA, methane sulfonic acid), para-toluenesulfonic acid (pTSA, p-toluene sulfonic acid), dinonylnaphthalene disulfonic acid (DNNDSA, dinonylnaphthalene disulfonic acid), and triflic acid); quaternary ammonium compounds; phosphorus compounds; and tin, titanium, and zinc compounds. Specific examples include, but are not limited to, a tetraalkylammonium halide, a tetraalkyl- or tetra-arylphosphonium iodide or acetate, tin octoate, zinc octoate, triphenylphosphine, and similar catalysts known to those skilled in the art. If used, a catalyst will preferably be present in an amount of at least 0.01% by weight and, more preferably, at least 0.1% by weight, based on the weight of the non-volatile material in the coating composition. If used, a catalyst will preferably be present in an amount not greater than 3% by weight and, more preferably, not greater than 1% by weight, based on the weight of the non-volatile material in the coating composition .
Another useful optional ingredient is a lubricant (for example, a wax), which facilitates the manufacture of manufactured metal articles (for example, closure systems and / or food and beverage can ends) by giving lubricity to thin substrate plates coated metal. Non-limiting examples of suitable lubricants include, for example, natural waxes such as carnauba wax or lanolin wax, polytetrafluoroethane (PTFE) lubricants and polyethylene. If used, a lubricant is preferably present in the coating composition in an amount of at least 0.1% by weight, and preferably not more than 2% by weight, and more preferably, not more than 1% by weight, based on the total weight of non-volatile material in the coating composition.
Another useful optional ingredient is a pigment, such as titanium dioxide. If used, a pigment is present in the coating composition in an amount of not more than 70% by weight, more preferably not more than 50% by weight, and even more preferably not more than 40% by weight, based in the total weight of solids in the coating composition.
Surfactants can optionally be added to the coating composition to aid in the flow and wetting of the substrate. Examples of surfactants include, but are not limited to, polyethers and nonylphenol salts and similar surfactants known to those skilled in the art. If used, a surfactant will preferably be present in an amount of at least 0.01% by weight and, more preferably, at least 0.1% by weight, based on the weight of the resin solids. If used, a surfactant is preferably present in an amount of no more than 10% by weight, and more preferably, no more than 5% by weight, based on the weight of resin solids.
The coating composition of the present invention can be present as a layer of a monolayer coating system or one or more layers of a multilayer coating system. The coating composition can be used as a base coat, an intermediate coat, a top coat, or a combination thereof. The thickness of the coating for a particular layer and the total coating system will vary depending on the coating material used, the substrate, the method of applying the coating, and the purpose of the coated article. Monolayer and multilayer coil coating systems include one or more layers formed from a coating composition of the present invention may have any suitable general coating thickness, but will typically have an overall average dry coating thickness of about 2 to about 60 micrometers, and more typically about 3 to about 12 micrometers.
The coating composition of the present invention can be applied to a substrate before, or after, the substrate is transformed into an article (such as, for example, a beverage or food container or a portion thereof). In one embodiment, a method is provided that includes: applying a coating composition described herein to a metallic substrate (for example, applying the composition to the metallic substrate in the form of a thin sheet or flat coil), hardening the composition, and transforming (by for example, via stamping) the substrate in a packaging container or a portion thereof (for example, a beverage or food can or a portion thereof). For example, riveted beverage can ends having a cured coating of the present invention on a surface thereof can be formed in such a process. In another embodiment, the coating composition is applied to a metallic can of beverage or preformed food, or a portion thereof. For example, in some embodiments, the coating composition is spray-applied to an internal surface of a preformed beverage or food can (for example, as typically occurs with two-piece beverage cans).
After applying the coating composition to a substrate, the composition can be cured using a variety of processes, including, for example, oven roasting using conventional or conventional methods, or any other method that provides a high temperature suitable for curing the coating. The curing process can be carried out in different or combined stages. For example, substrates can be dried at room temperature to leave the coating compositions in a largely uncrosslinked state. The coated substrates can then be heated to fully cure the compositions. In certain examples, the coating compositions of the present invention can be dried and cured in one step.
Curing conditions will vary depending on the method of application and the intended purpose. The curing process can be carried out at any suitable temperature, including, for example, oven temperatures in the range of about 100 ° C to about 300 ° C, and more typically from about 177 ° C to about 250 ° C . If the metal coil is the substrate to be coated, curing of the applied coating composition can be conducted, for example, by heating the coated metal substrate over a suitable period of time to a peak metal temperature (PMT, peak metal temperature) preferably greater than about 177 ° C (350 ° F). Most preferably, the coated metal coil is heated for a suitable period of time (e.g., about 5 to 900 seconds) to a PMT of at least about 218 ° C (425 ° F).
The coating compositions of the present invention are particularly useful for coating metallic substrates. The coating compositions can be used to coat packaging items as a container for food or drinks, or a portion thereof. In preferred embodiments, the container is a food or beverage can and the surface of the container is the surface of a metallic substrate. The polymer can be applied to a metallic substrate before or after the substrate is transformed into a can (for example, two-piece cans, three-piece cans) or their portions, either a can end or a can body. The preferred polymers of the present invention are suitable for use in situations of contact with food and can be used inside such cans. They are particularly useful inside the bodies or ends of two-piece or three-piece cans.
The coating compositions of the present invention may be suitable, for example, for spray coating, coil coating, wash coating, lamination coating, and side junction coating (e.g., food can side junction coating). A more detailed discussion of these application methods is provided below. It is contemplated that the coating compositions of the present invention can be suitably used in each of these application methods discussed further below, including the end uses associated therewith.
The spray coating includes introducing the coated composition into a preformed packaging container. Typical preformed packaging containers for spray coating include food cans, beer and beverage containers, and the like. The spraying process preferably uses a spraying nozzle capable of uniformly coating the inside of the preformed packaging container. The sprayed preformed container is then subjected to heat to remove any residual vehicles (for example, water or solvents) and harden the coating.
Coil coating is described as the coating of a continuous coil composed of a metal (for example, steel or aluminum). Once coated, the coating coil is subjected to a short thermal, ultraviolet, and / or electromagnetic curing cycle for a hardening process (eg drying and curing) of the coating. Coil coatings provide metal-coated substrates (for example, steel and / or aluminum) that can be made from formed articles, such as two-piece stretched food cans, three-piece food cans, food can ends, cans stamped and drawn, ends of beverage cans, and the like.
An impregnation coating is commercially described as the outer coating of cans in two stamped and drawn parts (D&I) with a thin layer of protective coating. The exterior of these D&I cans is coated by washing by passing the cans in two preformed D&I pieces under a coating composition curtain. The cans are inverted, that is, the open end of the can is down when passing through the curtain. This curtain of the cladding composition resembles a waterfall. Once these cans pass through this coating composition curtain, the liquid coating material effectively lines the outside of each can. The excess coating is removed using an air knife. Once the desired amount of coating is applied to the outside of each can, each can is passed through a thermal, ultraviolet, and / or electromagnetic curing oven to harden (for example, dry and cure) the coating. The residence time of the coated can inside the curing oven is typically from 1 minute to 5 minutes. The curing temperature inside this oven will typically be in the range of 150 ° C to 220 ° C.
A laminate coating is described as coating separate parts from a variety of materials (for example, steel or aluminum) that have been pre-cut into square or rectangular sheets. Typical dimensions of these blades are approximately one square meter. Once coated, each slide is cured. Once hardened (for example, dried and cured), the sheets of the coated substrate are collected and prepared for subsequent manufacture. Lamination coatings produce coated metallic substrate (for example, steel or aluminum) that can be successfully transformed to make formed articles, such as two-piece food cans, three-piece food cans, food can end, cans stamped and drawn, end of the beverage can (including, for example, end of the riveted beverage can having a rivet for fixing the pull tab on it), and the like.
A side junction coating is described as applying a powder coating or spraying a liquid coating over the welded area of formed three-piece food cans. When three-piece food cans are being prepared, a rectangular piece of the coated substrate is transformed into a cylinder. The formation of the cylinder becomes permanent due to the welding on each side of the rectangle through thermal welding. Once welded, each can may typically need a coating layer, which protects the exposed weld from subsequent corrosion or other effects of the contained food. The coatings that work in this function are called side joining strips. Typical side junction strips are applied by spraying and cured quickly through residual heat from the welding operation in addition to a small thermal, ultraviolet, and / or electromagnetic oven.
Other commercial coating application and curing methods are also contemplated, for example, electrocoating, extrusion coating, lamination, powder coating, and the like.
In certain preferred embodiments, the coating composition of the present invention is capable of exhibiting one or more (and in some embodiments all) the following coating properties: a fog resistance, corrosion resistance, stain resistance, and / or adhesion on metallic substrate of at least 8, more preferably at least 9, and optimally 10 (10 being perfect), when subjected to the test described below in example 5 using 3% by weight acetic acid in deionized water in place of the Aggressive Food Product.
The polymer of the present invention can be used in powder coating applications for use in forming an adherent polymeric coating. Thus, in some embodiments, the coating composition of the present invention is a powder coating composition that preferably does not include a liquid carrier (although it may include trace amounts of organic solvent or waste water). The powder coating composition is preferably in the form of a finely divided, free flowing powder. In preferred embodiments, the powder composition is a thermosetting powder composition that forms a thermoset coating when properly cured. The discussion that follows refers to the powder composition modalities of the present invention.
The powder coating composition of the present invention can be particularly useful in end uses in which a coated substrate is intended for contacting substances for human consumption or intimate contact with humans. For example, powder coating compositions can be used to coat: surfaces of beverage or food containers, cosmetic containers, or medicinal containers; valve and connection surfaces, including surfaces intended to contact drinking water or other consumable liquids; pipe surfaces, including internal surfaces of water pipes or other liquid transport pipes; and tank surfaces, including internal surfaces of water tanks such as riveted steel tanks. For powder coatings that will contact drinking water, the cured powder coating composition should preferably comply with ANSI / NSF standard 61. Some examples of connections include articles for use in liquid transport systems (for example, for use in transport of drinking water) such as connectors (for example threaded or flanged connectors), elbow joints, flow dividers (for example, T connections, etc.), backflow preventers, pipe end caps, and the like.
The powder coating composition preferably includes at least a film-forming amount of the polymer of the present invention, which in preferred embodiments is a polyether polymer having segments of formula (I). In order to favor the stability of the powder coating composition during storage before use, a polymer of the present invention is preferably selected which has a Tg of at least about 40 ° C, more preferably at least about 50 ° C , and even more preferably at least about 60 ° C. The powder coating composition preferably includes at least about 50% by weight, more preferably at least 70% by weight, and even more preferably at least 90% by weight of the polymer of the present invention, based on the solids of total resin.
Powder coating compositions typically use binder polymers having a different molecular weight (typically a lower molecular weight) than liquid packaging coating compositions for use on metal beverage or food cans. When used in powder coating compositions, the polymer of the present invention preferably has a numerical average molecular weight (Mn) of at least about 1,000, more preferably at least about 1,200, and even more preferably at least about 1,500. In such applications, the polymer of the present invention preferably has an Mn less than about 6,000, more preferably less than about 5,000, and even more preferably less than about 4,000.
The powder coating composition preferably includes at least one base powder which includes the polymer of the present invention. The base powder can additionally include one or more optional ingredients, which can include any suitable ingredients described herein. The base powder preferably includes the polymer of the present invention as a major component on a weight basis, and most preferably includes at least 50% by weight of the polymer. In some embodiments, the polymer of the present invention comprises all or substantially all of the base powder.
The particles of the base powder can be of any suitable size. Preferably, the particles of the base powder exhibit a particle size of 1 micrometer to about 200 micrometers, more preferably from about 10 to about 150 micrometers.
The base powder can exhibit any suitable particle size distribution. The average particle size of the base powder is preferably at least about 20 micrometers, more preferably at least about 30 micrometers, and even more preferably at least about 40 micrometers. In preferred embodiments, the average particle size is less than about 150 micrometers, more preferably less than about 100 micrometers, and even more preferably less than about 60 micrometers. The average particle sizes referred to in this paragraph mean the average particle sizes expressed on a volume basis, which can be determined, for example, via laser diffraction.
The powder compositions of the present invention can also contain one or more other optional ingredients. The optional ingredients preferably do not adversely affect powder compositions or articles formed therefrom. Such optional ingredients can be included, for example, to improve aesthetics; to facilitate the manufacture, processing and / or handling of powder compositions or articles formed from them; and / or to further improve a specific property of the powder compositions or articles formed therefrom. Each optional ingredient is preferably included in an amount sufficient to serve its intended purpose, but not in such an amount as to adversely affect a powdered composition or cured coating resulting therefrom. The one or more optional ingredients can be present in the same particle or in a particle different from the polymer of the present invention, or a combination thereof. In preferred embodiments, one or more optional ingredients are present in the particles of the base powder together with the polymer of the present invention. If present in particles other than those of the base powder, the particles of the optional (optional) ingredient (s) preferably have a particle size in the general particle size range of the base powder.
The powder compositions preferably include one or more optional curing agents (i.e., crosslinkers). Suitable curing agents can include phenolic crosslinkers, preferably phenolic crosslinkers free of diciandiamide BPA, which can be optionally substituted; carboxyl-functional compounds such as, for example, carboxyl-functional polyester resins or acrylic carboxyl-functional resins; and their combinations. The powder composition can include any suitable amount of one or more crosslinkers. In some embodiments, the crosslinker is present in the powder composition in an amount of up to about 15% by weight, preferably up to about 10% by weight, and more preferably up to about 5% by weight, based on the total weight of the powder coating composition. If used, the crosslinker is preferably present in an amount of at least about 0.1% by weight, more preferably at least about 0.5% by weight, and even more preferably at least about 1% by weight, with based on the total weight of the powder coating composition.
An optional curing accelerator may be present in the powder coating composition to facilitate curing. When used, the powder coating composition typically includes from about 0.1% by weight to about 3% by weight of one or more curing accelerators. 2 Methylimidazole is an example of a preferred curing accelerator. Other suitable curing accelerators may include imidazoles, phosphonium salts, tertiary amines, quaternary ammonium salts, anhydrides, polyamides, aliphatic amines, epoxy resin-amine adducts, and combinations thereof.
The powder coating composition can optionally include one or more flow control agents to improve the flow, wetting and / or leveling properties of the cured film. If used, flow control agents are typically present in an amount of about 0.01% by weight to about 5% by weight, more typically from about 0.2% by weight to about 2% by weight , based on the total weight of the powder coating composition. Examples of suitable flow control agents include polyacrylates such as poly (2-ethylhexyl acrylate) and various 2-ethylhexyl acrylate copolymers.
The powder coating composition can optionally include one or more fluidizing agents to facilitate the preparation of a free flowing powder composition. If used, the fluidizing agent is typically present in an amount of about 0.01% by weight to about 5% by weight, more typically from about 0.05% by weight to about 0.5% by weight, based on the total weight of the powder coating composition. Suitable fluidizing agents include, for example, pyrolyzed silicas of a suitable particle size. Such fluidizing agents can preferably be added after the melt mixing process, such as in the extruded flake before or after milling.
Inorganic filler and / or organic pigment can optionally be included in the powder coating compositions. Examples of such suitable materials include calcium silicates such as, for example, wollastonite; barium sulphate; calcium carbonate; mica; baby powder; silica; iron oxide; titanium dioxide; carbon black; phthalocyanines; chromium oxide; and their combinations.
Powder coating compositions can be prepared via any suitable methods. In one embodiment, some or all of the ingredients are mixed together fused, which can be accomplished using conventional single screw or double screw screw extruders. The temperature of the melt mixing step is preferably controlled to avoid any appreciable crosslinking. Typically, a melt mixing temperature is selected such that the temperature of the melt mixture does not exceed about 100 ° C to about 150 ° C. The ingredients can optionally be pre-mixed before mixing the melt. After mixing the melt and cooling, the resulting mixture, which is typically an extrudate, can be processed into powder using conventional milling techniques. The resulting ground powder can be optionally sieved to remove falling particles outside the desired particle size range. The powder can optionally be mixed with one or more additional powders to form the finished powder coating composition. For example, in some embodiments, the ground powder can be combined with a fluidizing agent either before or after the optional sifting.
Powder coating compositions can be applied to the substrate using any suitable method. Typically, the substrate is a metallic substrate (e.g., cast iron, steel, etc.), which can be uncoated metal or can be optionally pre-treated and / or painted with background paint. One such suitable method is the application of electrostatic spraying of charged powder onto the substrate. Alternatively, the substrate can be applied, for example, by immersing the substrate in a fluidized powder bed. In a preferred embodiment, the powder is applied to the heated substrate that has been heated to between 190 ° C and 240 ° C. Upon contact with the heated metallic substrate, the powder melts, reacts, and forms a continuous coating that is preferably smooth and uniform. In another embodiment, the powder is applied to a substrate close to room temperature and the powder-coated substrate is then heated to a temperature sufficient to cause the powder to melt, react, and form a continuous coating that is preferably smooth and uniform. .
The melting and curing (i.e., crosslinking) of the powder composition can be carried out in combined or separate heating steps. In the presently preferred embodiments, a combined heating step is used in which the powder coating composition is heated to a temperature sufficient to both melt the powder and to cure the resulting continuous coating. The roasting temperature and the duration of the roasting process will vary depending on a variety of factors, including, for example, end use. For the purposes of curing the coating, the roasting temperature is typically at least about 150 ° C, and more typically at least about 200 ° C. In general, a lower cure temperature can be used if a longer cure time is used. The curing temperature will typically not exceed about 240 ° C. The curing time can vary, for example, from about 30 seconds to about 30 minutes, depending on the curing temperature and end use.
The thickness of the cured powder coating will vary depending on the specific end use. However, typically the cured powder coating will have an average coating thickness in the range of 25 to about 1,500 micrometers, and more typically about 50 to about 500 micrometers. In some embodiments, an average coating thickness in the range of about 125 to about 300 micrometers is used.
MODALITIES
Some additional non-limiting embodiments are provided below to further exemplify the present invention.
Mode 1: A polymer, more preferably a polyether polymer having one or more segments of the formula (I) below:
Formula (I) where:
each pair of oxygen atoms shown in formula (I) is preferably present in an ether or ester bond, more preferably an ether bond;
H denotes a hydrogen atom, if present;
each R ¹ is independently an atom or group preferably having an atomic weight of at least 15 daltons, each of the phenylene groups shown in formula (I) preferably including at least one R ¹ attached to the ring in an ortho position or target relative to the oxygen atom;
v is independently 1 to 4;
w is 4;
R, if present, is preferably a divalent group;
n is 0 or 1, with the proviso that if n is 0, the phenylene groups shown in formula (I) can join with each other to form a fused ring system (for example, a substituted naphthalene group), in whose case w is 3;
two or more groups R and / or R can join to form one or more cyclic groups; and the polymer is preferably free of BPA or BADGE.
Mode 2: A polyether polymer that is the reaction product of ingredients including:
, Formula (II) where:
2
R, R, n, v, and w are as described above for formula (i);
each of the phenylene groups shown in formula (I) includes at least one R ¹ that is preferably attached to the ring in an ortho or meta position relative to the oxygen atom shown, more preferably an ortho position;
s is 0 to 1;
R, if present, is a divalent group, more preferably a divalent organic group; and preferably each R ⁴ is independently a hydrogen atom, a halogen atom, or a hydrocarbon group that can include one or more hetero atoms.
Mode 3: A coating composition comprising the polymer of modalities 1 or 2 (preferably in at least one film-forming amount) and one or more optional ingredients selected from a crosslinker and a liquid carrier.
Mode 4: An article (preferably a packaging article, more preferably a beverage or food container or a portion thereof) having a substrate (preferably a metallic substrate), with the coating composition of mode 3 being applied over at least a portion of the substrate.
Mode 5: A method comprising: providing a substrate (preferably a metallic substrate) and applying the mode 3 coating composition on at least a portion of the substrate.
Mode 6: A polymer, a coating composition, an article, or a method of any previous modality, the polymer and / or the coating composition being at least partially free of BPA or BADGE.
Mode 7: A polymer, coating composition, article, or method of any previous modality, each of the phenylene groups shown in formula (I) or formula (II) having at least one R ¹ ortho or target ( relative to the oxygen shown) which is an organic group, more preferably an organic group that includes 1 to 4 carbon atoms, even more preferably 1 to 2 carbon atoms.
Mode 8: A polymer, coating composition, article, or method of any previous modality, each of the phenylene groups shown in formula (I) or formula (II) having at least one R ¹ ortho or target (relative to the oxygen shown) which is independently a group selected from methyl groups, ethyl groups, propyl groups, substituted or unsubstituted butyl groups, or an isomer thereof.
Mode 9: A polymer, coating composition, article, or method of any previous modality, with each phenylene group shown in formula (I) or formula (II) including R ¹ s attached to the ring in both ortho positions relative to the oxygen atom shown.
Mode 10: A polymer, coating composition, article, or method of any previous modality, the segment of formula (I) being derived from 4,4'-methylenebis (2,6-di-t-butylphenol); 2,2'-methylenebis (4-methyl-6-t-butylphenol); 4,4'-methylenebis (2,6dimethylphenol); 4,4'-butylidenobis (2-t-butyl-5-methylphenol), a derivative thereof, or a diepoxide thereof (more preferably a diglycidylether).
Mode 11: A polymer, coating composition, article, or method of any previous modality, each phenylene group shown in formula (I) or formula (II) includes at least one R ¹ attached to the ring in one position ortho relative to the oxygen atom shown.
Mode 12: A polymer, a coating composition, an article, or a method of any previous modality, being 1.
Mode 13: A polymer, coating composition, article, or method of any previous modality, where n is 1 and R ² has an atomic mass less than 500, more preferably less than 200, even more preferably less than 100.
Mode 14: A polymer, coating composition, article, or method of any previous modality, where R is an organic group containing less than 15 carbon atoms, more preferably 1 to 10 carbon atoms, and in certain modalities 1 to 2 carbon atoms.
Modality 14.5: A polymer, a coating composition, an article, or a method of any previous modality, where n is 1 and R is an organic group of the formula -C (R R) -, in which R
Q and R are each independently a hydrogen atom, a halogen atom, an organic group, a sulfur-containing group, a nitrogen-containing group, or any other suitable group that is preferably substantially non-reactive with an epoxy group, and in which R and R can optionally join to form a cyclic group.
Mode 15: A polymer, a coating composition, an article, or a method of any previous modality, the polymer (preferably a polyether polymer) includes one or more pendant hydroxyl groups attached on the carbon atoms of the main chain.
Mode 16: A polymer, coating composition, article, or method of any previous modality, the main chain of the polymer including -CH ₂ -CH (OH) -CH ₂ - segments.
Mode 17: A polymer, coating composition, article, or method of any previous modality, with the segments -CH ₂ -CH (OH) -CH ₂ - being linked in each of the ether oxygen atoms shown in formula (I).
Modality 18: A polymer, coating composition, article, or method of any previous modality, with the polymer (preferably a polyether polymer) having a
Tg of at least 60 ° C, more preferably at least 70 ° C, even more preferably at least 80 ° C.
Mode 19: A polymer, coating composition, article, or method of any previous modality, with aryl or heteroaryl groups (more typically phenylene groups) constituting at least 20% by weight of the polyether polymer, based on total weight of aryl and heteroaryl groups present in the polymer relative to the weight of the polymer.
Mode 20: A polymer, coating composition, article, or method of any previous modality, the polymer comprising a plurality of segments of formula (I) and, in some embodiments, includes at least: 1% by weight , 5% by weight, 10% by weight, 20% by weight, 30% by weight, or 50% by weight of the segments of formula (I).
Mode 21: A polymer, coating composition, article, or method of any previous embodiment, the polymer being a polyether polymer and the polyether polymer (or the polyether polymer fraction of a copolymer such as a polyether-acrylic copolymer) includes at least 20% by weight, at least 30% by weight, or at least 50% by weight of segments of formula (I).
Modality 22: A polymer, coating composition, article, or method of any of the above embodiments, the polymer and / or coating composition being at least substantially free of acrylic (that is, including less than than 1% by weight of polymerized acrylic monomers, if any).
Mode 23: A polymer, coating composition, article, or method of any previous modality, the polymer comprising a plurality of segments of the formula below (IV):
-O-Ar- (Y _U -Ar) _t -Oem that:
each Ar is preferably a phenylene group, more preferably an unsubstituted phenylene group;
u is independently 0 or 1;
t is independently 0 or 1;
Y, if present, is a divalent group; and the two oxygen atoms are preferably each ether oxygen.
Mode 24: A polymer, coating composition, article, or method of mode 23, where Y is a divalent organic group having a molecular weight less than 500.
Mode 25: A polymer, coating composition, article, or method of modalities 24 or 25, with the segment of formula (IV) having a higher molecular weight than that of bisphenol A.
Mode 26: A polymer, a coating composition, an article, or a method of any of the modes 23 to 25 where yours are each 1 and Y _u includes one or more ester bonds.
Modality 27: A polymer, coating composition, article, or method of any of the modalities 23 to 26, where Y includes one or more monocyclic or polycyclic groups.
Modality 28: A polymer, coating composition, article, or method of any prior modality, the polymer comprising a polyether polymer which is a reaction product of ingredients including (i) a polyepoxide having a formula segment (I) or a polyepoxide compound of formula (II) and (ii) a polyhydric phenol.
Mode 28.5: A polymer, coating composition, article, or method of mode 28, one or more (and most preferably all) of the following are true:
(a) the polyepoxide of (i) is formed from a polyhydric phenol that does not exhibit appreciable estrogenic activity (for example, when tested using the MCF-7 assay it preferably exhibits an RPE having a logarithmic value less than about - 2.0);
(b) the polyepoxide of (i) does not exhibit mutagenicity or any other inappropriate genotoxicity (that is, the polyepoxide is non-genotoxic, for example, in the comet assay); and (c) polyhydric phenol from (ii) does not exhibit appreciable estrogenic activity.
Mode 29: A polymer, coating composition, article, or method of mode 28, with polyhydric phenol having the formula:
HO — Ar— (R ⁵ ) w — ZR ⁶ —Z— (R ⁵ ) w —Ar — OH where:
each Ar is independently a divalent aryl group or divalent heteroaryl group (more typically a substituted or unsubstituted phenylene group);
each R ⁵ , if present, is independently a divalent organic group;
R ⁶ is a divalent organic group;
each Z is independently an ester bond of any directionality (i.e., -C (O) -O- or -O-C (O) -) and each w is 0 or 1.
Modality 30: A polymer, a coating composition, an article, or a method of any previous modality, the polymer having an Mn of 2,000 to 20,000.
Mode 31: A coating composition, an article, or a method of any previous embodiment, the coating composition, in total weight of resin solids, including at least 5% by weight or 10% by weight of the polyether polymer .
Mode 32: A coating composition, an article, or a method of any previous modality, the coating composition being a coating for contact with food.
Mode 33: A coating composition, an article, or a method of any previous embodiment, the coating composition being one of: a solvent-based coating composition or a water-based coating composition.
Mode 34: A coating composition, an article, or a method of any previous embodiment, the coating composition being a water-based coating composition that is at least substantially free of acrylic.
Mode 3 5: A method of any preceding mode, the substrate being transformed into a packaging container or a portion thereof (for example, a beverage or food container or a portion thereof) after application of the coating composition.
Modality 36: A method or article of any previous modality, the coated article comprising a metallic beverage or food container, a cosmetic container, a pharmaceutical container, or a portion thereof (for example, a can end) having the coating composition applied to one or more of: an outer surface or an inner surface (ie, for contact with product).
Mode 37: A coating composition, an article, or a method of any of the modalities 1 to 32, 35, e36, the coating composition comprising a powder coating composition.
Mode 38: The item or item 37, the item being an item for transporting or storing drinking water (for example, a water valve, water connection, water pipe, a riveted steel tank for water or a panel for use within it, etc.).
The segments of formula (I) and compounds of formulas (II) or (III) in which each of the phenylene groups shown includes one or two ortho X groups (relative to the oxygen atom shown) are presently preferred. To further illustrate such structures, below is a table illustrating some non-limiting combinations of one or more X and R ortho for a given phenylene group. The table is not limiting _t 2 with respect to the position in the ring of R (for example, ortho, meta, para), although typically R is located in a position for relative to the oxygen atom. The columns entitled Ortho Position A and Ortho Position B indicate the group present in each ortho position of the phenylene group (assuming that R is not located in an ortho position). Positions A or B can be any ortho position relative to the oxygen atom shown. If R is located in an ortho position of the phenylene group, then the group listed in the Ortho Position B column will not be present. Typically, the phenylene groups in a given segment of formula (I) or compound of formula (II) or (III) will be symmetrical relative to the second phenylene group such that the same ortho group (as outlined in the orthoA or B position column ) is located on each ring in the same ortho position.
The table below is also intended as a listing of independent examples of X or R ² , as well as examples of combinations of X and R (regardless of whether X is ortho or target relative to the oxygen atom, if other X are present in a specific phenylene group, or if one or more X are the same in both phenylene groups). This additional purpose is the reason for the additional qualifier or X in the caption of the first column.
Ortho Position A (or X) Ortho Position B IV Butila Hydrogen 2-Butylidene Butila Methyl 2-Butylidene Butila Ethyl 2-Butylidene Butila Propyl 2-Butylidene Butila Isopropyl 2-Butylidene Butila Butila 2-Butylidene Ethyl Hydrogen 2-Butylidene Ethyl Methyl 2-Butylidene Ethyl Ethyl 2-Butylidene Isopropyl Hydrogen 2-Butylidene Isopropyl Methyl 2-Butylidene Isopropyl Ethyl 2-Butylidene Isopropyl Propyl 2-Butylidene Isopropyl Isopropyl 2-Butylidene Methyl Hydrogen 2-Butylidene Methyl Methyl 2-Butylidene Propyl Hydrogen 2-Butylidene Propyl Methyl 2-Butylidene Propyl Ethyl 2-Butylidene Propyl Propyl 2-Butylidene sec-Butila Hydrogen 2-Butylidene sec-Butila Methyl 2-Butylidene sec-Butila Ethyl 2-Butylidene sec-Butila Propyl 2-Butylidene sec-Butila Isopropyl 2-Butylidene sec-Butila Butila 2-Butylidene sec-Butila sec-Butila 2-Butylidene terc-Butila Hydrogen 2-Butylidene terc-Butila Methyl 2-Butylidene terc-Butila Ethyl 2-Butylidene terc-Butila Propyl 2-Butylidene terc-Butila Isopropyl 2-Butylidene terc-Butila Butila 2-Butylidene terc-Butila sec-Butila 2-Butylidene terc-Butila terc-Butila 2-Butylidene
Ortho Position A (or X) Ortho Position B go Butila Hydrogen Butylene Butila Methyl Butylene Butila Ethyl Butylene Butila Propyl Butylene Butila Isopropyl Butylene Butila Butila Butylene Ethyl Hydrogen Butylene Ethyl Methyl Butylene Ethyl Ethyl Butylene Isopropyl Hydrogen Butylene Isopropyl Methyl Butylene Isopropyl Ethyl Butylene Isopropyl Propyl Butylene Isopropyl Isopropyl Butylene Methyl Hydrogen Butylene Methyl Methyl Butylene Propyl Hydrogen Butylene Propyl Methyl Butylene Propyl Ethyl Butylene Propyl Propyl Butylene sec-Butila Hydrogen Butylene sec-Butila Methyl Butylene sec-Butila Ethyl Butylene sec-Butila Propyl Butylene sec-Butila Isopropyl Butylene sec-Butila Butila Butylene sec-Butila sec-Butila Butylene terc-Butila Hydrogen Butylene terc-Butila Methyl Butylene terc-Butila Ethyl Butylene terc-Butila Propyl Butylene terc-Butila Isopropyl Butylene terc-Butila Butila Butylene terc-Butila sec-Butila Butylene terc-Butila terc-Butila Butylene
Ortho Position A (or X) Ortho Position B lU Butila Hydrogen Cyclohexylidene Butila Methyl Cyclohexylidene Butila Ethyl Cyclohexylidene Butila Propyl Cyclohexylidene Butila Isopropyl Cyclohexylidene Butila Butila Cyclohexylidene Ethyl Hydrogen Cyclohexylidene Ethyl Methyl Cyclohexylidene Ethyl Ethyl Cyclohexylidene Isopropyl Hydrogen Cyclohexylidene Isopropyl Methyl Cyclohexylidene Isopropyl Ethyl Cyclohexylidene Isopropyl Propyl Cyclohexylidene Isopropyl Isopropyl Cyclohexylidene Methyl Hydrogen Cyclohexylidene Methyl Methyl Cyclohexylidene Propyl Hydrogen Cyclohexylidene Propyl Methyl Cyclohexylidene Propyl Ethyl Cyclohexylidene Propyl Propyl Cyclohexylidene sec-Butila Hydrogen Cyclohexylidene sec-Butila Methyl Cyclohexylidene sec-Butila Ethyl Cyclohexylidene sec-Butila Propyl Cyclohexylidene sec-Butila Isopropyl Cyclohexylidene sec-Butila Butila Cyclohexylidene sec-Butila sec-Butila Cyclohexylidene terc-Butila Hydrogen Cyclohexylidene terc-Butila Methyl Cyclohexylidene terc-Butila Ethyl Cyclohexylidene terc-Butila Propyl Cyclohexylidene terc-Butila Isopropyl Cyclohexylidene terc-Butila Butila Cyclohexylidene terc-Butila sec-Butila Cyclohexylidene terc-Butila terc-Butila Cyclohexylidene
Ortho Position A (or X) Ortho Position BButila Hydrogen Cyclopentylidene Butila Methyl Cyclopentylidene Butila Ethyl Cyclopentylidene Butila Propyl Cyclopentylidene Butila Isopropyl Cyclopentylidene Butila Butila Cyclopentylidene Ethyl Hydrogen Cyclopentylidene Ethyl Methyl Cyclopentylidene Ethyl Ethyl Cyclopentylidene Isopropyl Hydrogen Cyclopentylidene Isopropyl Methyl Cyclopentylidene Isopropyl Ethyl Cyclopentylidene Isopropyl Propyl Cyclopentylidene Isopropyl Isopropyl Cyclopentylidene Methyl Hydrogen Cyclopentylidene Methyl Methyl Cyclopentylidene Propyl Hydrogen Cyclopentylidene Propyl Methyl Cyclopentylidene Propyl Ethyl Cyclopentylidene Propyl Propyl Cyclopentylidene sec-Butila Hydrogen Cyclopentylidene sec-Butila Methyl Cyclopentylidene sec-Butila Ethyl Cyclopentylidene sec-Butila Propyl Cyclopentylidene sec-Butila Isopropyl Cyclopentylidene sec-Butila Butila Cyclopentylidene sec-Butila sec-Butila Cyclopentylidene terc-Butila Hydrogen Cyclopentylidene terc-Butila Methyl Cyclopentylidene terc-Butila Propyl Cyclopentylidene terc-Butila Isopropyl Cyclopentylidene terc-Butila Butila Cyclopentylidene terc-Butila sec-Butila Cyclopentylidene terc-Butila terc-Butila Cyclopentylidene Butila Hydrogen Ethylidene
Ortho Position A (or X) Ortho Position B IT Butila Methyl Ethylidene Butila Ethyl Ethylidene Butila Propyl Ethylidene Butila Isopropyl Ethylidene Butila Butila Ethylidene Ethyl Hydrogen Ethylidene Ethyl Methyl Ethylidene Ethyl Ethyl Ethylidene Isopropyl Hydrogen Ethylidene Isopropyl Methyl Ethylidene Isopropyl Ethyl Ethylidene Isopropyl Propyl Ethylidene Isopropyl Isopropyl Ethylidene Methyl Hydrogen Ethylidene Methyl Methyl Ethylidene Propyl Hydrogen Ethylidene Propyl Methyl Ethylidene Propyl Ethyl Ethylidene Propyl Propyl Ethylidene sec-Butila Hydrogen Ethylidene sec-Butila Methyl Ethylidene sec-Butila Ethyl Ethylidene sec-Butila Propyl Ethylidene sec-Butila Isopropyl Ethylidene sec-Butila Butila Ethylidene sec-Butila sec-Butila Ethylidene terc-Butila Hydrogen Ethylidene terc-Butila Methyl Ethylidene terc-Butila Ethyl Ethylidene terc-Butila Propyl Ethylidene terc-Butila Isopropyl Ethylidene terc-Butila Butila Ethylidene terc-Butila sec-Butila Ethylidene terc-Butila terc-Butila Ethylidene Butila Hydrogen Isopropylidene
Ortho Position A (or X) Ortho Position B K2 Butila Methyl Isopropylidene Butila Ethyl Isopropylidene Butila Propyl Isopropylidene Butila Isopropyl Isopropylidene Butila Butila Isopropylidene Ethyl Hydrogen Isopropylidene Ethyl Methyl Isopropylidene Ethyl Ethyl Isopropylidene Isopropyl Hydrogen Isopropylidene Isopropyl Methyl Isopropylidene Isopropyl Ethyl Isopropylidene Isopropyl Propyl Isopropylidene Isopropyl Isopropyl Isopropylidene Methyl Hydrogen Isopropylidene Methyl Methyl Isopropylidene Propyl Hydrogen Isopropylidene Propyl Methyl Isopropylidene Propyl Ethyl Isopropylidene Propyl Propyl Isopropylidene sec-Butila Hydrogen Isopropylidene sec-Butila Methyl Isopropylidene sec-Butila Ethyl Isopropylidene sec-Butila Propyl Isopropylidene sec-Butila Isopropyl Isopropylidene sec-Butila Butila Isopropylidene sec-Butila sec-Butila Isopropylidene terc-Butila Hydrogen Isopropylidene terc-Butila Methyl Isopropylidene terc-Butila Ethyl Isopropylidene terc-Butila Propyl Isopropylidene terc-Butila Isopropyl Isopropylidene terc-Butila Butila Isopropylidene terc-Butila sec-Butila Isopropylidene terc-Butila terc-Butila Isopropylidene Butila Hydrogen Methylidene
Ortho Position A (or X) Ortho Position B iV Butila Methyl Methylidene Butila Ethyl Methylidene Butila Propyl Methylidene Butila Isopropyl Methylidene Butila Butila Methylidene Ethyl Hydrogen Methylidene Ethyl Methyl Methylidene Ethyl Ethyl Methylidene Isopropyl Hydrogen Methylidene Isopropyl Methyl Methylidene Isopropyl Ethyl Methylidene Isopropyl Propyl Methylidene Isopropyl Isopropyl Methylidene Methyl Hydrogen Methylidene Methyl Methyl Methylidene Propyl Hydrogen Methylidene Propyl Methyl Methylidene Propyl Ethyl Methylidene Propyl Propyl Methylidene sec-Butila Hydrogen Methylidene sec-Butila Methyl Methylidene sec-Butila Ethyl Methylidene sec-Butila Propyl Methylidene sec-Butila Isopropyl Methylidene sec-Butila Butila Methylidene sec-Butila sec-Butila Methylidene terc-Butila Hydrogen Methylidene terc-Butila Methyl Methylidene terc-Butila Ethyl Methylidene terc-Butila Propyl Methylidene terc-Butila Isopropyl Methylidene terc-Butila Butila Methylidene terc-Butila sec-Butila Methylidene terc-Butila terc-Butila Methylidene Butila Hydrogen Propylidene
Ortho Position A (or X) Ortho Position B El Butila Methyl Propylidene Butila Ethyl Propylidene Butila Propyl Propylidene Butila Isopropyl Propylidene Butila Butila Propylidene Ethyl Hydrogen Propylidene Ethyl Methyl Propylidene Ethyl Ethyl Propylidene Isopropyl Hydrogen Propylidene Isopropyl Methyl Propylidene Isopropyl Ethyl Propylidene Isopropyl Propyl Propylidene Isopropyl Isopropyl Propylidene Methyl Hydrogen Propylidene Methyl Methyl Propylidene Propyl Hydrogen Propylidene Propyl Methyl Propylidene Propyl Ethyl Propylidene Propyl Propyl Propylidene sec-Butila Hydrogen Propylidene sec-Butila Methyl Propylidene sec-Butila Ethyl Propylidene sec-Butila Propyl Propylidene sec-Butila Isopropyl Propylidene sec-Butila Butila Propylidene sec-Butila sec-Butila Propylidene terc-Butila Hydrogen Propylidene terc-Butila Methyl Propylidene terc-Butila Ethyl Propylidene terc-Butila Propyl Propylidene terc-Butila Isopropyl Propylidene terc-Butila Butila Propylidene terc-Butila sec-Butila Propylidene terc-Butila terc-Butila Propylidene Butila Hydrogen Trimethyl-cyclohexylidene
Ortho Position A (or X) Ortho Position B R; Butila Methyl Trimethyl-cyclohexylidene Butila Ethyl Trimethyl-cyclohexylidene Butila Propyl Trimethyl-cyclohexylidene Butila Isopropyl Trimethyl-cyclohexylidene Butila Butila T rimethyl-cyclohexylidene Ethyl Hydrogen Trimethyl-cyclohexylidene Ethyl Methyl Trimethyl-cyclohexylidene Ethyl Ethyl Trimethyl-cyclohexylidene Isopropyl Hydrogen Trimethyl-cyclohexylidene Isopropyl Methyl Trimethyl-cyclohexylidene Isopropyl Ethyl Trimethyl-cyclohexylidene Isopropyl Propyl Trimethyl-cyclohexylidene Isopropyl Isopropyl Trimethyl-cyclohexylidene Methyl Hydrogen Trimethyl-cyclohexylidene Methyl Methyl T rimethyl-cyclohexylidene Propyl Hydrogen Trimethyl-cyclohexylidene Propyl Methyl Trimethyl-cyclohexylidene Propyl Ethyl Trimethyl-cyclohexylidene Propyl Propyl Trimethyl-cyclohexylidene sec-Butila Hydrogen Trimethyl-cyclohexylidene sec-Butila Methyl Trimethyl-cyclohexylidene sec-Butila Ethyl Trimethyl-cyclohexylidene sec-Butila Propyl Trimethyl-cyclohexylidene sec-Butila Isopropyl Trimethyl-cyclohexylidene sec-Butila Butila T rimethyl-cyclohexylidene sec-Butila sec-Butila T rimethyl-cyclohexylidene terc-Butila Hydrogen Trimethyl-cyclohexylidene terc-Butila Methyl Trimethyl-cyclohexylidene terc-Butila Ethyl Trimethyl-cyclohexylidene terc-Butila Propyl T rimethyl-cyclohexylidene terc-Butila Isopropyl Trimethyl-cyclohexylidene terc-Butila Butila Trimethyl-cyclohexylidene terc-Butila sec-Butila Trimethyl-cyclohexylidene terc-Butila terc-Butila Trimethyl-cyclohexylidene Butila Hydrogen Acetophenone
Ortho Position A (or X) Ortho Position B El Butila Methyl Aceto phenona Butila Ethyl Acetophenone Butila Propyl Acetophenone Butila Isopropyl Acetophenone Butila Butila Acetophenone Ethyl Hydrogen Acetophenone Ethyl Methyl Acetophenone Ethyl Ethyl Acetophenone Isopropyl Hydrogen Acetophenone Isopropyl Methyl Acetophenone Isopropyl Ethyl Acetophenone Isopropyl Propyl Acetophenone Isopropyl Isopropyl Acetophenone Methyl Hydrogen Acetophenone Methyl Methyl Acetophenone Propyl Hydrogen Acetophenone Propyl Methyl Acetophenone Propyl Ethyl Acetophenone Propyl Propyl Acetophenone sec-Butila Hydrogen Acetophenone sec-Butila Methyl Acetophenone sec-Butila Ethyl Acetophenone sec-Butila Propyl Acetophenone sec-Butila Isopropyl Acetophenone sec-Butila Butila Acetophenone sec-Butila sec-Butila Acetophenone terc-Butila Hydrogen Acetophenone terc-Butila Methyl Acetophenone terc-Butila Ethyl Acetophenone terc-Butila Propyl Acetophenone terc-Butila Isopropyl Acetophenone terc-Butila Butila Acetophenone terc-Butila sec-Butila Acetophenone terc-Butila terc-Butila Acetophenone Butila Hydrogen Benzophenone
Ortho Position A (or X) Ortho Position B IT Butila Methyl Benzophenone Butila Ethyl Benzophenone Butila Propyl Benzophenone Butila Isopropyl Benzophenone Butila Butila Benzophenone Ethyl Hydrogen Benzophenone Ethyl Methyl Benzophenone Ethyl Ethyl Benzophenone Isopropyl Hydrogen Benzophenone Isopropyl Methyl Benzophenone Isopropyl Ethyl Benzophenone Isopropyl Propyl Benzophenone Isopropyl Isopropyl Benzophenone Methyl Hydrogen Benzophenone Methyl Methyl Benzophenone Propyl Hydrogen Benzophenone Propyl Methyl Benzophenone Propyl Ethyl Benzophenone Propyl Propyl Benzophenone sec-Butila Hydrogen Benzophenone sec-Butila Methyl Benzophenone sec-Butila Ethyl Benzophenone sec-Butila Propyl Benzophenone sec-Butila Isopropyl Benzophenone sec-Butila Butila Benzophenone sec-Butila sec-Butila Benzophenone terc-Butila Hydrogen Benzophenone terc-Butila Methyl Benzophenone terc-Butila Ethyl Benzophenone terc-Butila Propyl Benzophenone terc-Butila Isopropyl Benzophenone terc-Butila Butila Benzophenone terc-Butila sec-Butila Benzophenone terc-Butila terc-Butila Benzophenone
Testing methods
Except where otherwise noted, the following test methods have been used in the examples that follow.
Differential scanning calorimetry
The samples for the differential scanning calorimetry (DSC) test were prepared by first applying the liquid resin composition to aluminum foil panels. The panels were then baked in a Fisher Isotemp electric oven for 20 minutes at 149 ° C (300 ° F) to remove volatile materials. After cooling to room temperature, the samples were scraped off the panels, weighed in standard sample vessels and analyzed using the standard DSC heating-cooling-heating method. The samples were equilibrated to 60 ° C, then heated at 20 ° C per minute to 200 ° C, cooled to -60 ° C, and then heated again at 20 ° C per minute to 200 ° C. Glass transitions and melting points were calculated from the thermogram of the last heating cycle. The glass transition was measured at the tipping point of the transition and the melting point was measured at the maximum peak of the melting peak.
Accession
The adhesion test is performed to assess whether the coating compositions adhere to the coated substrate. The adhesion test was performed according to ASTM D 3359 - test method B, using SCOTCH 610 tape (available from 3M Company of Saint Paul, Minnesota, USA). Adhesion is generally rated on a scale of 0-10 in which a rating of 10 indicates no adhesion failure, a rating of 9 indicates that 90% of the coating remains adhered, a rating of 8 indicates that 80% of the coating remains adhered , and so on. Adhesion rates of 10 are typically desired for commercially viable coatings.
Fog resistance
Fog resistance measures the ability of a coating to withstand the attack of various solutions. Typically, fog is measured by the amount of water absorbed in a coated film. When the film absorbs water, it usually becomes cloudy or appears white. Fog is generally measured visually using a scale of 0-10 in which a rating of 10 indicates no fog and a rating of 0 indicates complete bleaching of the film. mist ratings of at least 7 are typically desired for commercially viable coatings and, optimally, 9 or more.
Corrosion
Corrosion is a measure of the coating's ability to withstand a corrosive / acidic environment. It is usually measured on a scale of 0 to 10. A 0 indicates that the coating is completely corroded, observed by the formation of bubbles or blistering of the film in all areas. A 10 indicates that the coating remains unmodified as before its subjection to the environment. corrosive.
Stain resistance
Stain resistance is a measure of a coating's ability to resist staining by a means. It is usually measured on a scale of 0 to 10. A 0 indicates that the coating is completely stained with a complete color change of the film observed in all areas. A 10 indicates that the color of the coating remains unchanged as before it was subjected to the stain-causing environment
Pencil scratch hardness
This test measures the hardness of a cured coating. Pencil scratch hardness was assessed using ASTM D3363, with the test performed against metal grains. The data is reported in the form of the last successful pencil before the film broke. Thus, for example, if a coating does not break when tested with a 2H pencil, but if it does break when tested with a 3H pencil, the coating is reported as having a 2H pencil scratch hardness.
Metal display
This test measures the ability of a coated substrate to maintain its integrity when it undergoes the formulation processes necessary to produce an article manufactured as a beverage can end. It is a measurement of the presence or absence of cracks or fractures at the formed end. The terminal is typically placed in a receptacle filled with an electrolyte solution. The receptacle is inverted to expose the end surface to the electrolyte solution. The amount of electrical current that passes through the end is then measured. If the coating remains intact (without cracks or fractures) after manufacture, a minimum current will pass through the end.
For the present evaluation, the ends of a fully converted riveted standard size drink can 202 were exposed for a period of approximately 4 seconds to an electrolyte solution comprised of 1% by weight of NaCl in deionized water. The evaluated coating was present on the inner surface of the beverage can end. Metal exposure was measured using WACO Enamel Rater II (available from Wilkens-Anderson Company, Chicago, IL, USA) with an output voltage of 6.3 Volts. The electrical current measured in milliamps is reported. End continuities were tested initially and then after the ends were subjected to a boiling solution of Dowfax detergent (Dowfax product is available from Dow Chemical) for 60 minutes. After cooling and drying, the milliamperes of current passing through the end were measured again.
Preferred coatings of the present invention initially conduct less than 10 milliamps (mA) when tested as described above, more preferably less than 5 mA, most preferably less than 2 mA, and ideally less than 1 mA. After
Dowfax, the preferred coatings gave continuities less than mA, more preferably less than 10 mA, and even more preferably less than 5 mA.
Solvent resistance
The extent of curing or crosslinking of a coating is measured as a resistance to solvents, such as meethyl ethyl ketone (MEK) (available from Exxon, Newark, NJ, USA). This test is performed as described in ASTM D 5402-93. The number of double wipes is recorded (ie, a back and forth movement). This test is commonly called MEK Resistance.
EXAMPLES
The following examples are offered to assist in understanding the present invention and are not to be considered as limiting its scope. Except where otherwise noted, all parts and percentages are expressed in weight. The constructions mentioned were evaluated by the tests in the following way:
Example 1 Ortho-substituted diphenol diepoxides
Batch I: 4,4'-methylenebis (2,6-di-tert-butylphenol) diglycidyl-ether
A solution of 4,4'-methylenebis (2,6-di-t-butylphenol) (500 grams, 1.076 moles obtained from Albemarle Corporation) in anhydrous dimethylformamide (1.5 liters) was cooled to -10 ° C and a sodium ether-pentoxide solution (374 grams, 3.23 moles) in anhydrous dimethylformamide (1.5 liters) was added in drops at -10 to -5 ° C. The mixture was stirred for 30 minutes at -10 ° C. Epichlorohydrin (1.9 liters, 24.2 moles) was added via addition funnel at -10 to -5 ° C. The solution was allowed to warm to room temperature and was then heated for 16 hours at 75 to 82 ° C. After cooling to room temperature, the mixture was added in cold tap water (12 liters). Ethyl acetate (5 liters) was added to the mixture, which was stirred for 10 minutes and separated. The aqueous layer was extracted again with additional ethyl acetate (3 liters). The combined ethyl acetate extracts were washed twice with brine (2x6 liters), dried with anhydrous sodium sulfate (600 grams), and filtered. The solvent was evaporated under reduced pressure to give 887 grams of crude product as a purple oil. The crude product was dissolved in toluene (600 milliliters) and passed over a layer of silica gel (1.4 kg), and eluted with a mixture of toluene and heptane (8 parts of toluene to 2 parts heptane). Fractions containing the product were combined and evaporated under reduced pressure. The product was mostly the desired diepoxide (756 grams, yellow oil that crystallizes over time), with a little monopoxide present. The purified material (756 grams) was dissolved at 70 ° C in 2-propanol (2.3 liters) and then allowed to cool to room temperature overnight. The flask was kept in an ice-water bath for 3 hours, filtered and the solids were washed three times with cold 2-propanol (3 x 400 milliliters). The obtained solid was dried under high vacuum at room temperature to give the final product as a white solid (371 grams having an HPLC purity of 95.2%, and a yield of 60%). The epoxy index of the final product was 0.367 equivalent per 100 grams. The resulting 4,4'-methylenebis diglycidyl ether (2,6di-t-butylphenol) was tested using the appropriate genotoxicity assays (for example, Ames II assay) and was found to be non-genotoxic.
Batch II: 4,4'-butylidenobis (2-t-butyl-5methylphenol) diglycidyl-ether)
A batch of 20 grams of 4,4'-butylidenobis diglycidyl-ether (2-t-butyl-5-methylphenol) was prepared by reacting epichlorohydrin with 4,4'-butylidenobis (2-t-butyl-5-methylphenol) . Multiple purification steps were required to obtain a suitably pure batch.
The purified batch showed an epoxy index of 0.402 equivalent per 100 grams. The resulting 4,4'-butylidenobis diglycidyl-ether (2-t-butyl-5-methylphenol) was tested using suitable genotoxicity assays (for example, Ames II assay) and found to be non-genotoxic.
Batch III: 4,4'-methylenebis (2,6dimethylphenol) diglycidyl-ether
4,4'-Methylenebis (2,6-dimethylphenol) (32 grams, 0.125 moles), epichlorohydrin (140 milliliters, 1.79 moles), and 2-propanol (150 milliliters) were heated to 80 ° C in a oil. Sodium hydroxide (12.5 grams, 0.313 moles) in water (20 milliliters) was added in portions over 5 minutes. The purple solution was heated for 2 hours at 80 ° C. The mixture was cooled to room temperature, filtered, and concentrated on a rotary evaporator at a temperature of about 30-40 ° C. The remaining oil was mixed with dichloromethane (50 milliliters) and heptane (100 milliliters) and allowed to stir for 30 minutes at room temperature. The salts were removed by filtration and the filtrate was concentrated on a rotary evaporator at 30-40 ° C. The remaining oil was dried under high vacuum at room temperature until a constant weight was obtained. The crude product was crystallized twice in methanol (250 milliliters) and dried under high vacuum at room temperature until a constant weight was obtained. The batch generated 4,4'-methylenebis (2,6-dimethylphenol) diglycidyl-ether (28 grams, 60% yield) as a white solid. The epoxy index was 0.543 equivalent per 100 grams.
The diphenols used to prepare the diglycidyl ethers of each of the I-III batches were tested for estrogenic activity by an external toxicology laboratory using an appropriate assay whose results, as known, can be directly related to the MCF-7 assay based on common reference compounds.
Example 2 Dihydrous phenol adducts
Batch I: Dihydric phenol adduct of 1 mol 4.8bis (hydroxymethyl) tricyclol5.2.1.01decane with 2 moles of 3hydroxybenzoic acid
In a 4-neck round-bottom flask equipped with a mechanical stirrer, a water-cooled condenser on top of a Dean-Stark collector, and a thermocouple connected to a heating control device and a heating blanket were added 249.24 parts of tricyclodecane dimethanol or TCDM (from OXEA), 350.76 parts of 3-hydroxybenzoic acid (from Aldrich), and 0.6 part of a polymerization catalyst. Stirring and heating started and it took 4 hours until the batch reached 230 ° C. The batch was heated at 230 ° C for an additional 4 hours, at which time about 43 parts of water were collected and the acid number was 2.0 mg KOH / gram. At this time, heating was discontinued until the batch reached 120 ° C, at which point the batch was discharged. The material was a solid at room temperature that could be broken up.
Batch II: Adduct of 1 mol 4.8-dihydric phenol (hydroxymethyl) tricycle [5.2.1.01decane with 2 moles of 4-hydroxyphenylacetic acid
In a 4-neck round-bottom flask equipped with a mechanical stirrer, a water-cooled condenser on top of a Dean-Stark collector, and a thermocouple connected to a heating control device and a heating blanket were added 235.3 parts of TCDM (from OXEA), 364.7 parts of 4-hydroxyphenylacetic acid (from Aceto), and 0.65 parts of polymerization catalyst. Stirring and heating were initiated and it took 7 hours until the batch reached 230 ° C. The batch was heated at 230 ° C for an additional 8 hours, at which point a total of 40 parts of water were collected and the acid number was 1.8 milligrams of KOH / gram. At this time, heating was discontinued until the batch reached 120 ° C, at which point the batch was discharged. The material was a sticky semi-solid at room temperature.
Batch III: 1 mol 1,4-cyclohexanedimethanol (CHDM) phenol adduct with 2 moles of 3-hydroxybenzoic acid
In a 4-neck round-bottom flask equipped with a mechanical stirrer, a water-cooled condenser on top of a Dean-Stark collector, and a thermocouple connected to a heating control device and a heating blanket were added 228.6 parts of the CHDM-90 product (Eastman's 90% cyclohexane dimethanol in water),
394.2 parts of 3-hydroxybenzoic acid (from Aceto), and 0.6 part of polymerization catalyst. Stirring and heating started and it took 4 hours until the batch reached 230 ° C. The batch was heated at 230 ° C for an additional 8 hours, at which time 70 parts of water were collected and the acid number was 1.6 milligrams of KOH / gram. At this time, heating was discontinued until the batch reached 120 ° C, at which point the batch was discharged. The material was a solid at room temperature that could be broken up.
Batch IV: 1 mol 1,4-cyclohexanedimethanol (CHDM) phenol adduct with 2 moles of 4-hydroxyphenylacetic acid
In a 4-neck round-bottom flask equipped with a mechanical stirrer, a water-cooled condenser on top of a Dean-Stark collector, and a thermocouple connected to a heating control device and a heating blanket were added 214.3 parts of the CHDM-90 product, 407.1 parts of 4-hydroxyphenylacetic acid (from Aceto), and 0.6 part polymerization catalyst. Stirring and heating were started and it took 4 hours until the batch reached 230 ° C. The batch was heated at 230 ° C for a further 6 hours, at which time 65 parts of water were collected and the acid number was 3.0 milligrams of KOH / gram.
At this time, heating was stopped until the batch reached
120 ° C, when the batch was unloaded. The material was a solid at room temperature that could be broken up.
Example 3 Polyether polymers
As indicated in table 1 below, 15 different polyether polymers (i.e., batches 1 to 15) were prepared by perfecting various diepoxides (DGE in table 1) of example 1 with several diphenols of example 2.
The following general procedure was used to prepare each of the 1-10 batch polyether polymers in table 1: In a 4-neck round-bottom flask equipped with a mechanical stirrer, a water-cooled condenser, and a thermocouple connected to a a heating control device and a heating blanket were added example diepoxide 1, batch I (ie, 4,4'methylenebis diglycidyl ether (2,6-di-t-butylphenol)) and a specified amount of a diphenol of example 2, 0.1% part of CATALYST 1201 polymerization catalyst (from Shell), and an amount of methylisobutyl ketone (from Ashland) suitable for preparing a batch with 95% by weight of solids. Stirring and heating were started and it took until the batch became homogeneous and reached the temperature indicated in table 1. The batch was kept at that temperature until the target epoxy index (EV, epoxy value) was reached. At this point, heating was discontinued and cyclohexanone (from Ashland) was slowly added until the percentage by weight of solids (or percentage by weight of non-volatile material) indicated in table 1 was reached. The batch was discharged when the room temperature was below 70 ° C. As indicated in Table 1 below, all polymers from experiments 1-10 exhibited good molecular weight development and high Tg.
The aforementioned methodology can also be used to formulate polyether polymers using the diepoxides of example 1, batch
II, III, and IV.
Table 1
Batela da Ex. 1 DGE Parts by weight Diphenol Parts by weight Reaction Temp (° C) Target EV EV Act NV Mn Mw Tg (° C) 1 Batch I 45.3 Ex. 2, Batch I 29.7 120 0.036 0.036 45.6 4,280 10,780 91 2 Batch I 44.3 Ex. 2, BatchII 30.7 120 0.036 0.034 41.7 4,240 15,680 82 3 Batch I 47.4 Ex. 2, Batch III 27.6 120 0.036 0.032 40.4 5,200 15,330 94 4 Batch I 46.2 Ex. 2, Batch IV 28.8 120 0.036 0.034 43.3 5,560 17,800 82 5 Batch I 46 Ex. 2, BatchIII 29 120 0.02 0.18 30.9 7,380 29,540 99 6 Batch I 45.2 Ex. 2, Batch III 29.8 120 0.01 0.007 31.2 5,870 28,620 97 7 Batch I 145.4 Ex. 2, Batch IV 94.6 120 0.032 0.032 42.8 5,230 14,970 80 8 Batch I 142.3 Ex. 2, Batch IV 97.7 120 0.021 0.021 41.9 6,460 26,900 82 9 Batch I 203 HQ ’ 36.96 160 0.032 0.032 40.8 4,700 10,650 100 10 Batch I 201.8 HQ ’ 38.2 160 0.021 0.019 40.4 6,100 14,280 105 11 Batch II 339.2 HQ ’ 60.8 160 0.028 0.029 40.8 5,700 13,280 98 12 Batch II 244.5 Ex. 2, Batch IV 155.5 130 0.028 0.027 41.0 3,800 8,320 82 13 Batch II 250.8 Ex. 2, BatchIII 149.2 130 0.028 0.028 40.8 6,130 17,570 91 14 Batch III 63.2 HQ ’ 16.8 160 0.035 0.033 39.3 5,400 12,900 95 15 Batch III 41.9 Ex. 2, Batch III 38.1 130 0.029 0.023 42.2 7,600 48,900 90
* HQ stands for hydroquinone.
** NV represents% by weight of non-volatile material.
Example 4 Coating compositions
The polyether polymer compositions of example 3, batch 2 and example 3, batch 4 were each diluted to a non-volatile content of 35% by weight using cyclohexanone. Then 20 wt% 10 (solids on solids) phenolic crosslinker was added, followed by 0.1 wt% H3PO4 (solids on solids) added as a 10% butanol solution. Thus, two polyether formulations were obtained: phenolic 80:20 catalyzed by acid. The coating composition formulated using example 3, batch 2 is called here example 4, 15 batch 1, while the coating composition formulated using example 3, batch 4 is called here example 4, batch 2.
Example 5: Coated substrate
The above two coating compositions, together with an industry standard BPA-based polyether coating composition, were each applied to both 75 # tin plate (ETP) and tin-free steel (TFS). Coatings were applied with appropriately sized wire bar applicators to obtain coatings having a dry film thickness of 0.69-0.78 mg / cm (4.55.0 milligrams / square inch (msi, milligrams / square-inch)). The coated metal samples were then baked for 12 minutes in a gas-heated oven to ~ 206 ° C (403 ° F). Clean 202 size food can ends were formed from the resulting coated plates. Each can end was subjected to a reverse impact of 1.58 Nm (14-inch-pound force) in the center of the uncoated side of the can end. The can ends were then immersed in two different aggressive food products (ie, Aggressive Food Products 1 and 2 in table 2) having an initial temperature of 82 ° C (180 ° F) and stored for 2 weeks at ~ 49 ° C (120 ° F). After 2 weeks, the can ends were removed from the food product, washed with water, and evaluated for adhesion, corrosion, stain, and mist. The results are shown in table 2 below. The coating compositions of example 4 exhibited coating properties equal to or better than those of the industry standard epoxy coating.
Table 2
Coating composition Commercial control Batch example 1 4, Batch example 2 4, ETPAggressive Food Product1 Adhesion / mist 10/10 10/10 10/10 Stain / Corrosion 10/10 10/10 10/10 Aggressive Food Product
2 Adhesion / Mist 10/10 10/10 10/10 Stain / Corrosion 10/10 10/10 10/10 TFS Aggressive Food Product 1 Adhesion / Mist 10/10 10/10 10/10 Stain / Corrosion 10/10 10/10 10/10 Aggressive Food Product2 Adhesion / Mist 10/10 10/10 10/10 Stain / Corrosion 9/10 10/10 10/10
Example 6: Water-dispersible polyether polymers
Batch 1:
In a 4-neck round-bottom flask equipped with a mechanical stirrer, a nitrogen inlet to maintain a nitrogen atmosphere, a water-cooled condenser, and a thermocouple connected to a heating control device and a heating blanket were added 65.34 parts of example 1 diepoxide, batch III (ie 4,4'-methylenebis (2,6-dimethylphenol) diglycidyl ether), 17.61 parts of hydroquinone, 0.054 part CATALYST 1201 (from Shell ), 0.305 part of sorbic acid, and 1.96 parts of ethylcarbitol.This mixture was heated with stirring to 125 ° C, allowed to heat (exotherm) to 152 ° C, then it was heated 155 ° C for 4 hours until the index of epoxy was 0.025 eq / 100 g A water dispersible polymer was then produced using a mixture of styrene, ethyl acrylate, methyl methacrylate, acrylic acid, and methacrylic acid in combination with a binding compound according to the teachings ofUS Patent No. 5,830,952, with the polyether polymer used above in place of the polyether polymer taught in US Patent No. 5,830,952. The water dispersible polymer gave an aqueous dispersion having a non-volatile content of about 40% and an acid number of 15-45 mg KOH / gram.
The resin was formulated in a finished aqueous formulation in the same manner as a commercial epoxy polymer based on BPA and BADGE and baked on a chrome treated aluminum substrate for 60 seconds at 241 ° C (465 ° F) for a film thickness 1.09 mg / cm (7 msi). The properties of the cured coating including example resin 6, batch 1 were similar to those of the commercial control epoxy coating. Table 4 below illustrates some of the coating properties of the coating of example 6, batch 1 in relation to the control coating.
Table 3
Coating Metal display (ma) Retort in water Dl Double MEK smears Pencil scratch hardness Before boiling Dowfax After boiling Dowfax Mist (W / V) “ Adhesion (W / V) * BADGE / BPA control 0.2 0.9 10/10 10/10 20-50 4H Example6,Batch 1 0.1 3.1 10/10 10/10 20-50 3H
* Coated aluminum strips were placed in a pressure cooker filled with deionized water and processed for 90 minutes at 121 ° C (at 250 ° F). Next, the coated strips were classified for mist and adhesion both in the area where the coated strip was immersed in the liquid (W) and in the area where the strip was in contact with the vapor phase (V).
Batch 2:
In a 4-neck round-bottom flask equipped with a mechanical stirrer, a nitrogen inlet to maintain a nitrogen atmosphere, a water-cooled condenser, and a thermocouple connected to a heating control device and a heating blanket were added 59.96 parts of Example 1, batch II diepoxide (ie 4,4'-butylidenobis diglycidyl ether (2-t-butyl-5-methylphenol)), 0.08 part
CATALYST CATALYST 1201, and 2.22 parts of xylene. This mixture was stirred and heated to 130 ° C and maintained for 3 hours, at which time the epoxy index was 0.034 equivalent per 100 grams. 25.05 parts of butylcelosolve were added, followed by 10.53 parts of primary amyl alcohol and 14.47 parts of n-butanol while the temperature was stabilized at 120 ° C. A premixture of methacrylic acid, styrene, and benzoyl peroxide was then added while maintaining the temperature. At the end of the addition, the addition device was washed with butylcelosolve. After maintaining the temperature for 2 hours after the end of the feeding, deionized water was added and the temperature was stabilized at 90 ° C. A pre-mix at room temperature of deionized water and dimethylethanolamine was added over time and the batch was maintained, followed by subsequent additions of deionized water. The resulting aqueous dispersion had a non-volatile content of about 20% and an acid number of 80-120 mg KOH / gram.
A finished formulation was prepared by mixing the water-based resin of example 6, batch 2 with a solution consisting of suitable amounts of phenolic resin based on phenol, phenolic resin based on t-butylphenol, and organic solvent. This was followed by an additional dilution with organic solvent and deionized water to give a spray coating having a Ford cup No. 4 viscosity of 20 seconds and a non-volatile content of about 20%. This finished water-based formulation was sprayed onto ETP cans stretched and smoothed for food and baked for 3.5 minutes at 218 ° C (425 ° F), giving a cured coating having a dry film weight of 275 milligrams per can . When tested against a similar control coating based on BADGE / BPA, the coating properties of the coating formulated using the example resin 6, batch 2 were similar, including resistance to corrosion.
Example 7- Preparation of solid resin from the advance of diglycidyl ether with hydroquinone
A reaction flask equipped with a mechanical stirrer, thermocouple, nitrogen inlet and vacuum outlet was loaded with 900.0 parts of the diglycidyl ether described in example 1, batch II, having a titrated epoxy index of 0.376 (equivalent in weight) epoxide = 266) (3,383 equivalents). The contents were carefully heated under nitrogen until completely melted, then stirring was started and 0.80 part of ethyltriphenylphosphonium iodide catalyst was added, followed by 124.0 parts of hydroquinone (2.252 equivalents). Heating was continued under a reduced pressure of approximately 6.67 kPa (50 torr) (to reduce the level of residual moisture or other residual volatiles) to a temperature of 130 ° C, then heating was continued under atmospheric pressure. When the temperature reached 140 ° C, external heating was discontinued and the reaction was allowed to warm up (exotherm). Over a period of approximately 25 minutes, the reaction temperature rose to a peak exotherm temperature of 181 ° C. The contents were kept for an additional 90 minutes at 180 ° C, then they were discharged into shallow aluminum trays and allowed to cool to form a friable solid. The product had a titrated epoxide equivalent of 952 (theoretical = 907), and a melt viscosity of 19.3 P (150 ° C, 900 RPM, Brookfield CAP 2000).
Example 8 - Preparation of cyclohexanedimethanol bis (3-hydroxybenzoate)
A reaction flask equipped with a mechanical stirrer, thermocouple, nitrogen inlet, and a Dean-Stark collector under a reflux condenser was charged with 259.6 parts of 1,4-cyclohexanedimethanol (CHDM, 1.8 moles). Stirring was started under a nitrogen atmosphere, and
497.2 parts of 3-hydroxybenzoic acid (3.6 mol), 3.4 parts of toluenesulfonic acid monohydrate (0.018 mol), and 200 parts of xylene were added successively. The contents were gradually heated to reflux and the esterification water was collected as a bottom layer in the Dean-Stark collector. After approximately 12 hours at 145-150 ° C, approximately 94% of the theoretical amount of water had been collected, and additional water collection in the collector had ceased. Most of the xylene was removed at room pressure, and then a vacuum was gradually applied while maintaining the product at 150 ° C. When a minimum release of volatiles at approximately 6.67 kPa (50 torr) was observed, the product was discharged into a shallow aluminum tray and allowed to cool to room temperature.
Example 9 - Preparation of solid resin from diglycidyl ether advance with CHDM bis (3-hydroxybenzoate)
A reaction flask equipped with a mechanical stirrer, thermocouple, nitrogen inlet, and vacuum outlet was loaded with 750.0 parts of the diglycidyl ether described in example 1, batch II having a titrated epoxy index of 0.376 (equivalent in weight of epoxide = 266) (2,819 epoxide equivalents), followed by 315.0 parts of the CHDM bis (3-hydroxybenzoate) which were prepared according to the procedure of example 8 (calculated theoretical phenolic equivalent weight of 192.2) (1,639 equivalent), and 1.30 parts of ethyltriphenylphosphonium iodide catalyst. The contents were gradually heated until completely melted at about 90 ° C, then stirring was started and the pressure was reduced to approximately 6.67 kPa (50 torr) for the purpose of removing residual volatiles. Heating was continued to a temperature of 140 ° C, at which point external heating was discontinued. The reaction was allowed to warm up (exotherm), and the vacuum was stopped as soon as the temperature reached 145 ° C. The exotherm continued over the course of approximately 30 minutes to a peak temperature of 158 ° C. The temperature set point was increased to 160 ° C and the product was kept for an additional 2 hours before unloading. The final product had an epoxide titrated weight equivalent of 1.016 (theoretical value 903) and a melt viscosity of 39.0 P (150 ° C, 900 RPM, Brookfield CAP 2000).
Examples 10 to 12 - Preparation of powder coatings
The solid resins of examples 7 and 9 were broken down to a smaller flake size using a high intensity paddle mixer (Reos Incorporated, Cleveland, Ohio, USA) for two cycles of 10 seconds each at approximately 1,000 revolutions-per-minute (RPM ). The reams were then combined with the additional ingredients listed in table 4. The composition shown in example 10 is a comparative example based on a conventional commercially available BPA-based epoxy resin. All amounts in Table 4 are expressed in parts by weight.
Table 4
Ingredient Comparative example 10 Example 11 Example 12 Epon 2004 900.0 Epoxy refinement of example 7900.0Epoxy refinement of example 9 900.0 DYHARD 100S 27.0 27.0 27.0 2-methylimidazole 2.0 2.0 2.0 ESCAT 60 10.0 10.0 10.0 RESIFLOW PF-67 13.0 13.0 13.0 Red iron oxide R2899 42.0 42.0 42.0 VANSIL W-20 325.0 325.0 325.0
Additional explanation of certain ingredients included in table 4 is provided below. EPON 2004 is a conventional BPA-based epoxy resin available from Hexion, Columbus, OH, USA. Dyhard 100S is a micronized grade of diciandiamide treated with flow agent
100 dry silica-based, available from Alzchem, Trostberg, Germany. Dyhard MI is a micronized form of 2-methylimidazole available from Alzchem. Resiflow PF-67 is a polyacrylate based flow control agent available from Estron Chemical, Calvert City, KY, USA. Escat 60 is an alkylimidazole on a silica vehicle, available from Estron Chemical, Calvert City, KY, USA. Red iron oxide R2899 was obtained from Rockwood Pigments, Beltsville, MD, USA. Vansil W-20 is a wollastonite pigment available from R.T. Vanderbilt Company, Norwalk, CT, USA.
The ingredients in Table 4 were mixed dry in a Reos high intensity paddle mixer for two cycles of ten seconds each at approximately 1000 RPM. After dry mixing, the samples were extruded in a Coperion ZSK-30 extruder operating at approximately 200 RPM with temperature set points of 90 ° C in zone 1 and 110 ° C in zone 2. The extrudate was discharged through rollers cooled, and the resulting solid flake was ground in a Mikropul Bantam laboratory mill and then sieved through a 94 mesh sieve.
Samples of the finished powder coatings were electrostatically sprayed at approximately 70 kilovolts onto 0.5 mm thick cold-rolled steel panels and baked for 30 minutes at 220 ° C. The film properties were as shown in the table
5. The test method for impact resistance can be found in ASTM D2794.
101
Table 5
test Comparative example 10 Example 11 Example 12 Accession 9 9 10 Pencil scratch hardness 3H 3H 3H Impact resistance (direct) 9.04 Nm (80 inch-pounds force) 9.04 Nm (80 inch-pounds force) 9.04 Nm (80 inch-pounds force) Solvent resistance (double scrubbing with MEK) 50 20 50
Example 13: Powder coating composition
The powder compositions as described in examples 10 to 12 are repeated except that diciandiamide is increased to 36 parts and the accelerators are replaced with triphenylphosphine.
Example 14: Powder coating composition
The powder compositions as described in examples 10 to 12 are repeated except that diciandiamide is increased to 36 parts and the accelerators are replaced by Curezol C17Z accelerator (available from Air Products, Allentown, PA, USA).
The complete description of all patents, patent applications, publications, and electronically available material cited in the present invention are hereby incorporated by reference. The detailed description and examples mentioned above were offered only for the sake of clarity of understanding. No unnecessary limitations should be inferred from them. The invention is not limited to the exact details shown and described, since variations obvious to the person skilled in the art will be included in the invention defined by the claims. The invention illustratively described herein can be suitably practiced, in some embodiments, in the absence of any element that is not specifically described herein.

权利要求:
Claims (22)
[1]
1. Article, characterized by the fact of understanding:
a packaging container, or a portion thereof, having:
a metallic substrate;
a coating composition that is substantially free of bisphenol A or diglycidyl ether of bisphenol A applied to at least a portion of the metallic substrate, the coating composition comprising:
a polyether polymer that includes one or more segments of the formula below (I):

[2]
2. Article according to claim 1, characterized by the fact that each phenylene group shown in formula (I) includes R ¹ s attached to the ring in both ortho positions relative to the ether oxygen atom.
[3]
3. Article according to claim 1 or 2, characterized by the fact that:
each of at least one R ¹ attached to the rings of the phenylene groups shown in an ortho position is independently selected from an organic group or a sulfur-containing group; and each R ¹ is free of halogen atoms.
[4]
4. An article according to any one of claims 1 to
3, characterized by the fact that each of the at least one R ¹ bonded on the rings of the phenylene groups shown is an organic group containing one or two carbon atoms.
[5]
5. Article according to any one of claims 1 to
4, characterized by the fact that n is 1 and R ² is an organic group having from 1 to 10 carbon atoms, and the ether oxygen atom of each phenylene group shown in formula (I) is located in a relative position to R ² .
[6]
6. Article according to claim 1, characterized by the fact that n is 1 and the segment of formula (I) has an atomic weight less than 600 daltons.
[7]
7. Article according to any one of claims 1 to
6, characterized by the fact that n is 1 and R ² is a divalent methylene group.
[8]
8. Article according to any one of claims 1 to
7, characterized by the fact that the polyether polymer includes one or more segments of formula (I) derived from one or more of: 4,4'-methylenebis (2,6-di-t-butylphenol) diglycidyl ether , 2,2'-methylenebis diglicidyl-ether (4methyl-6-t-butylphenol), 4,4'-methylenebis diglicidyl-ether (2,6-dimethylphenol), 4,4 'diglycidyl-ether -butylidenobis (2-t-butyl-5-methylphenol), or a derivative thereof.
[9]
9. Article according to any one of claims 1 to
8, characterized by the fact that:
the segments -CH ₂ -CH (OH) -CH ₂ - are attached to each of the oxygen atoms shown in formula (I); and the polyether polymer has a glass transition temperature of at least 70 ° C prior to curing of the coating composition.
[10]
10. Article according to any one of claims 1 to
9, characterized by the fact that the polyether polymer comprises a reaction product of reagents including a polyepoxide and a polyhydric phenol.
[11]
11. Article according to claim 10, characterized in that the polyepoxide comprises a diglycidyl ether that includes a segment of formula (I).
[12]
12. Article according to any one of claims 1 to
11, characterized by the fact that the packaging container, or its portion, is a beverage or food container, or its portion.
[13]
13. Coating composition, characterized by the fact that it comprises:
at least 10 weight percent, based on the total resin solids of the coating composition, of a polyether polymer having a numerical average molecular weight of at least 2,000 that includes:
one or more segments of the formula below (I):

[14]
Coating composition according to claim 13, characterized in that the polyether polymer comprises a reaction product of ingredients including:
a diglycidyl ether compound including a segment of formula (I), and a polyhydric phenol.
[15]
Coating composition according to claim 14, characterized in that the diglycidyl ether compound is non-genotoxic and is derived from a dihydric phenol that exhibits a relative proliferative effect value log in the proliferation assay. MCF7 cell less than -2.0.
[16]
A coating composition according to claim 14, characterized in that the diglicidyl-ether compound comprises 4,4'-methylenebis (2,6-di-t-butylphenol) diglicidyl-ether, diglicidyl- 2,2'-methylenebis ether (4-methyl-6-t-butylphenol), 4,4'-methylenebis diglicidyl ether (2,6-dimethylphenol), 4,4'-butylidene diglicidyl ether (2-tbutyl-5-methylphenol), or a derivative or a mixture thereof.
[17]
Coating composition according to any one of claims 13 to 16, characterized in that it is a solvent-based coating composition, wherein the segments of formula (I) constitute at least 30 weight percent of the polymer of polyether, based on the weight of the polyether polymer and not considering any other oligomers or polymers that may optionally be attached to the polyether polymer.
[18]
Coating composition according to any one of claims 13 to 16, characterized in that the coating composition is water-based, wherein the segments of formula (I) constitute at least 30 weight percent of the polymer of polyether, based on the weight of the polyether polymer and not considering any other oligomers or polymers that may optionally be attached to the polyether polymer.
[19]
19. Method, characterized by the fact of understanding:
providing a metallic substrate, and applying the coating composition, as defined in any one of claims 13 to 18, on at least a portion of the substrate.
[20]
20. Method according to claim 19, characterized in that it additionally comprises: causing the metallic substrate to be transformed into a beverage or food container, or its portion.
[21]
21. An article according to any one of claims 1 to 12, characterized in that the coating composition has an overall average dry coating thickness of about 3 to about 12
5 micrometers.
[22]
22. An article according to any one of claims 1 to 12 or 21, characterized in that the polyhydric phenol comprises hydroquinone, catechol, p-tert-butylcatechol, resorcinol or a mixture thereof.

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WO2021097308A1|2019-11-14|2021-05-20|Swimc Llc|Metal packaging powder coating compositions, coated metal substrates, and methods|

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WO2021102229A1|2019-11-21|2021-05-27|Swimc Llc|Two-part epoxy compositions for adherent coatings of storage articles|

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KR102110817B1|2020-02-12|2020-05-13|주식회사다원시스템|Water tank with excellent corrosion and thermal resistance|

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CN113185894A|2021-04-29|2021-07-30|甘肃西部邦奇装饰材料科技有限公司|Toughening type steel bar anticorrosion powder coating and preparation method thereof|

法律状态:
2020-01-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-02-04| B25A| Requested transfer of rights approved|Owner name: ENGINEERED POLYMER SOLUTIONS, INC. (US) |

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2020-02-27| B25A| Requested transfer of rights approved|Owner name: THE VALSPAR CORPORATION (US) |

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2020-03-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-03-10| B25A| Requested transfer of rights approved|Owner name: THE SHERWIN-WILLIAMS COMPANY (US) |

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2020-04-07| B25A| Requested transfer of rights approved|Owner name: THE SHERWIN-WILLIAMS HEADQUARTERS COMPANY (US) |

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2020-04-22| B25A| Requested transfer of rights approved|Owner name: SWIMC LLC (US) |

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2020-09-08| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-12-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-02| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/02/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161440085P| true| 2011-02-07|2011-02-07|

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US61/440,085|2011-02-07|

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US61/440085|2011-02-07|

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US201161579072P| true| 2011-12-22|2011-12-22|

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US61/579,072|2011-12-22|

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US61/579072|2011-12-22|

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PCT/US2012/024193|WO2012109278A2|2011-02-07|2012-02-07|Coating compositions for containers and other articles and methods of coating|BR122015001646-0A| BR122015001646B1|2011-02-07|2012-02-07|COATING COMPOSITION, ARTICLE, AND, METHOD|