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Patent US20040116596 - Latex particles having incorporated image stabilizers - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA composition and method of associating stabilizer functionalities with latex particulates is provided. The composition can comprise a latex particulate configured for inclusion in an ink-jet ink to provide improved humidfastness of an image printed by the ink-jet ink, wherein the latex particulate has...http://www.google.com/patents/US20040116596?utm_source=gb-gplus-sharePatent US20040116596 - Latex particles having incorporated image stabilizersAdvanced Patent SearchPublication numberUS20040116596 A1Publication typeApplicationApplication numberUS 10/322,032Publication dateJun 17, 2004Filing dateDec 17, 2002Priority dateDec 17, 2002Also published asCN1508202A, CN100365078C, DE60331402D1, EP1431339A1, EP1431339B1, US7358301, US8148461, US20080070038Publication number10322032, 322032, US 2004/0116596 A1, US 2004/116596 A1, US 20040116596 A1, US 20040116596A1, US 2004116596 A1, US 2004116596A1, US-A1-20040116596, US-A1-2004116596, US2004/0116596A1, US2004/116596A1, US20040116596 A1, US20040116596A1, US2004116596 A1, US2004116596A1InventorsKent Vincent, Sivapackia GanapathiappanOriginal AssigneeKent Vincent, Sivapackia GanapathiappanExport CitationBiBTeX, EndNote, RefManReferenced by (6), Classifications (13), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetLatex particles having incorporated image stabilizers
US 20040116596 A1Abstract
A composition and method of associating stabilizer functionalities with latex particulates is provided. The composition can comprise a latex particulate configured for inclusion in an ink-jet ink to provide improved humidfastness of an image printed by the ink-jet ink, wherein the latex particulate has a molecular weight from 10,000 Mw to 10,000,000 Mw, and has a particle size from 10 nm to 2 μm; and an image stabilizer configured for improving durability of the image, wherein the image stabilizer is bound to or otherwise associated with the latex particulate. The method can comprise the steps of coupling a polymerizable monomer with a stabilizing agent reactive with the polymerizable monomer, thereby forming a stabilizer precursor-containing monomer; polymerizing the stabilizer-containing monomer to form a latex particulate; and decoupling the stabilizing agent from the latex particulate. Images(10) Claims(22)
What is claimed is: 1. A method of associating stabilizer functionalities with latex particulates, comprising: (a) forming a stabilizer precursor-containing monomer by coupling a polymerizable monomer with a stabilizing agent reactive with the polymerizable monomer; (b) polymerizing the stabilizer precursor-containing monomer to form a stabilizer precursor-containing latex particulate; and (c) decoupling the stabilizer precursor-containing latex particulate to form an associated latex particulate and stabilizing agent. 2. A method as in claim 1, wherein the polymerizable monomer comprises an isocyanate group. 3. A method as in claim 2, wherein the stabilizing agent comprises a —NH, —SH, —OH, or —CH functionality, and the coupling occurs by reaction between the isocyanate moiety and the —NH, —SH, —OH, or —CH functionality, thereby blocking the isocyanate moiety and the —NH, —SH, —OH, or —CH functionality from interfering with the polymerizing step. 4. A method as in claim 3, wherein the stabilizing agent further comprises an electron-withdrawing group attached to the functionality. 5. A method as in claim 1, wherein the polymerizable monomer includes a vinylic functionality. 6. A method as in claim 5, wherein the polymerizable monomer that includes the vinylic functionality is as follows: where R is H or an electron withdrawing group. 7. A method as in claim 1, wherein the stabilizer precursor-containing monomer is provided by a condensation reaction between a vinyl isocyanate and a hindered amine stabilizing agent. 8. A method as in claim 1, wherein the step of polymerizing includes random polymerization of the polymerizable monomer with at least one additional monomer. 9. A method as in claim 1, wherein the decoupling is by the use of a member selected from the group consisting of heat, added water, and combinations thereof. 10. A method as in claim 1, wherein the decoupling produces a stabilizing moiety covalently bound to the latex particulate. 11. A method as in claim 1, wherein the decoupling causes the stabilizing agent to become entrapped in the latex particulate. 12. A method as in claim 1, further comprising the step of crosslinking the latex particulate. 13. A latex particulate for providing improved image durability in ink-jet printing applications, comprising: (a) a latex particulate configured for inclusion in an ink-jet ink to provide improved humidfastness of an image printed by the ink-jet ink, said latex particulate having a molecular weight from 10,000 Mw to 10,000,000 Mw, and having a particle size from 10 nm to 2 μm; and (b) an image stabilizer configured for improving image durability of the image, said image stabilizer associated with the latex particulate. 14. A latex particulate as in claim 13, wherein the image stabilizer includes a stabilizing moiety covalently bound to the latex particulate. 15. A latex particulate as in claim 13, wherein the image stabilizer includes a stabilizing agent entrapped within the latex particulate. 16. A latex particulate as in claim 13, wherein the image stabilizer includes both a stabilizing moiety covalently bound to the latex particulate, and a stabilizing agent entrapped within the latex particulate. 17. A latex particulate as in claim 13, wherein the image stabilizer bound to the latex particulate is prepared in-situ, after polymerization of the latex particulate. 18. A latex particulate as in claim 14, wherein the stabilizing moiety comprises an amine functionality. 19. A latex particulate as in claim 15, wherein the stabilizing agent is selected from the group consisting of alkylated monophenols, alkylthiomethylphenols, hydroquinones, tocopherols, hydroxylated thiodiphenyl ethers, alkylidenebisphenols, hydroxybenzylated malonates, aromatic hydroxybenzyl compounds, triazine compounds, benzylphosphonates, acylaminophenols, phenol esters, amides, hindered amines, oxamides, and phenol triazines. 20. A latex particulate as in claim 13, wherein the image stabilizer is selected from the group consisting of free-radical inhibitors, anti-oxidants, anti-ozonants, ultraviolet absorbers, and combinations thereof. 21. A latex particulate as in claim 13, wherein the latex particulate includes multiple monomers being randomly polymerized. 22. A latex particulate as in claim 13, wherein the latex particulate is crosslinked.
FIELD OF THE INVENTION [0001] The present invention relates generally to ink-jet printing. More particularly, the present invention relates to color stabilization for latex-based inks, coatings, and/or paints. BACKGROUND OF THE INVENTION [0002] Computer printer technology has evolved to a point where very high-resolution images can be transferred to various types of media, including paper. One particular type of printing involves the placement of small drops of a fluid ink onto a media surface in response to a digital signal. Typically, the fluid ink is placed or jetted onto the surface without physical contact between the printing device and the surface. Within this general technique, the specific method that the ink-jet ink is deposited onto the printing surface varies from system to system, and can include continuous ink deposit and drop-on-demand. [0003] With regard to continuous printing systems, inks used are typically based on solvents such as methyl ethyl ketone and ethanol. Essentially, continuous printing systems function as a stream of ink droplets that are ejected and directed by a printer nozzle. The ink droplets are directed additionally with the assistance of an electrostatic charging device in close proximity to the nozzle. If the ink is not used on the desired printing surface, the ink is recycled for later use. With regard to drop-on-demand printing systems, the ink-jet inks are typically based upon water and solvents such as glycols. Essentially, with these systems, ink droplets are propelled from a nozzle by heat or by a pressure wave such that all of the ink droplets ejected are used to form the printed image. [0004] There are several reasons that ink-jet printing has become a popular way of recording images on various media surfaces, particularly paper. Some of these reasons include low printer noise, capability of high-speed recording, and capability of multi-color recording. Additionally, these advantages can be obtained at a relatively low price to consumers. [0005] Though there has been great improvement in ink-jet printing technology, as described previously, there are still improvements that can be made in many areas. Poor color durability has partially been alleviated by the incorporation of stabilizer molecules, or photo-stabilizers, into ink-jet inks. However, ink-jet ink chemistry itself as well as ink-jet ink/print media interaction have both contributed to the separation of colorant, i.e., dyes and/or pigments, and photo-stabilizers upon printing. With respect to ink-jet ink chemistry, the majority of commercial ink-jet inks are water-based. Thus, their constituents are generally water-soluble, as in the case with many photo-stabilizers and dyes, or water dispersible, as in the case with pigments. Furthermore, ink-jet inks have low viscosity (typically 5 cps or less) to accommodate high frequency jetting and firing chamber refill processes common to ink-jet pens. The high jetting shear force imposed on the ink can cause an initial separation of a dye, another liquid vehicle component, and/or a photo-stabilizer components of the ink-jet ink. Further, with respect to the relationship between a photo-stabilizer-containing ink-jet ink and a print media sheet, e.g., porous coated media sheet, additional and more permanent separation of the ink-jet ink components can occur chromatographically as the ink-jet ink penetrates the media surface. Thus, there exists challenges related to utilizing photo-stabilizers as effectively as possible within ink-jet ink formulations. [0006] In addition to color and general image fade, ink-jet prints have also been known for poor durability when exposed to water or high humidity. This results from the use of water-soluble and water dispersible colorants within the water-based ink. There has been great improvement in the area of water durability of ink-jet inks through incorporation of certain ink-jet compatible latex polymers. The latex can consist of small micron or submicron hydrophobic polymeric particles of high molecular weight that are dispersed in the aqueous ink-jet ink. When printed as part of an ink-jet ink, a latex component of the ink can form a film on a media surface, entrapping and protecting the colorant within the hydrophobic print film. SUMMARY OF THE INVENTION [0007] It has been recognized that it would be advantageous to develop ink-jet ink compositions that exhibit improved color and water durability. Specifically, it would be advantageous to provide stabilizer-bound latex particulates for use in ink-jet ink formulations, such that the benefits of the presence of the latex can be realized, and the stabilizers bound to the latex particulates can be used to improve image durability as well as to prevent colorant-stabilizer separation. [0008] In one aspect, the invention provides a method of associating stabilizer functionalities with latex particulates. The method can comprise the step of forming a stabilizer precursor-containing monomer by coupling a polymerizable monomer with a stabilizing agent reactive with the polymerizable monomer. After forming the stabilizer precursor-containing monomer, the step of polymerizing the stabilizer precursor-containing monomer to form a stabilizer precursor-containing latex particulate, and decoupling the stabilizer precursor-containing latex particulate to form an associated latex particulate and stabilizing agent can be carried out. In one embodiment, the polymerizable monomer can comprise an isocyanate group. Further, the stabilizing agent can comprise a —NH, —SH, or —OH, or —CH functional group, and the coupling can occur by a reaction between the isocyanate group and the —NH, —SH, —OH, or —CH functionality, thereby blocking the isocyanate group and the —NH, —SH, —OH, or —CH functionality from interfering with the polymerizing step. The decoupling can produce a stabilizing moiety covalently bound to the latex particulate, and/or the stabilizing agent can become entrapped in the latex particulate. [0009] In an alternative embodiment, a latex particulate for providing improved image durability such as humidfastness and lightfastness in ink-jet printing applications can include latex-bound stabilizer particulates. Specifically, the composition can include a latex particulate configured for inclusion in an ink-jet ink to provide improved humidfastness of an image printed by the ink-jet ink, wherein the latex particulate has a molecular weight from 10,000 Mw to 10,000,000 Mw, and has a particle size from 10 nm to 2 μm. The latex particulate can also include an image stabilizer configured for improving durability of the image, wherein the image stabilizer is bound to the latex particulate. By bound, the image stabilizer can either be a stabilizing moiety covalently bound to the latex particulate, and/or the image stabilizer can be a stabilizing agent entrapped within the latex particulate. [0010] Additional features and advantages of the invention will be apparent from the detailed description that follows which illustrates, by way of example, features of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S) [0011] Before the present invention is disclosed and described, it is to be understood that this invention is not limited to the particular process steps and materials disclosed herein because such process steps and materials may vary somewhat. It is also to be understood that the terminology used herein is used for the purpose of describing particular embodiments only. The terms are not intended to be limiting because the scope of the present invention is intended to be limited only by the appended claims and equivalents thereof. [0012] It must be noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. [0013] As used herein, “effective amount” refers to the minimal amount of a substance or agent, which is sufficient to achieve a desired effect. For example, an effective amount of a “liquid vehicle” is the minimum amount required for use in an ink composition or a fixer composition of the present invention, while maintaining properties in accordance with embodiments of the present invention. [0014] As used herein, “liquid vehicle” refers to the fluid in which colorants and stabilizer-bound latex particulates or colloids are dispersed to form ink-jet inks in accordance with the present invention. Many liquid vehicles and vehicle components are known in the art. Typical ink vehicles can include a mixture of a variety of different agents, such as surfactants, solvents, co-solvents, buffers, biocides, sequestering agents, viscosity modifiers, surface-active agents, and water. [0015] “Colorant” can include dyes and/or pigments. Dyes are typically water soluble and are therefore desirable for use in many embodiments. However, pigments can also be used in other embodiments. Pigments that can be used include self-dispersed pigments and polymer dispersed pigments. Self-dispersed pigments included those that have been chemically surface modified with a charge or a polymeric grouping. This chemical modification aids the pigment in becoming and/or substantially remaining dispersed in a liquid vehicle. The pigment can also be a polymer-dispersed pigment that utilizes a dispersant (which can be a polymer or an oligomer, or a surfactant) in the liquid vehicle and/or in the pigment that utilizes a physical coating to aid the pigment in becoming and/or substantially remaining dispersed in a liquid vehicle. [0016] “Image stabilizer” or simply “stabilizer” can be any molecule or functional moiety that acts to stabilize printed images, such as ink-jet printed images. These image stabilizers are particularly effective in increasing image durability of printed ink components, including ink colorants. Typically, image stabilizers can act as free-radical inhibitors, anti-oxidants, anti-ozonants, and/or ultraviolet absorbers. [0017] “Stabilizer-bound latex particulate(s)” refers to one or more image-stabilizers that are chemically or physically associated or entrapped within a hydrophobic polymeric particle(s) of high molecular weight. The latex particulate itself can be from 10 nm to 2 μm in size (or from 100 nm to 400 nm, in another embodiment) and can have a weight average molecular weight from about 10,000 Mw to 10,000,000 Mw (or from about 30,000 Mw to 3,000,000 Mw, in another embodiment). Typically, the stabilizer-bound latex particulate(s) can be present in a colorant-containing liquid vehicle at from 0.5% to 10% by weight to form an ink-jet ink in accordance with principles of the present invention. Additionally, stabilizer-bound latex particulate(s) can be polymerized alone, or can be randomly polymerized with other monomers. Further, crosslinking can be present as well. [0018] “Stabilizing moiety” refers to functional groups that provide image stabilization properties. Such moieties can be covalently attached to the latex particulate, or can be an image-stabilizing portion of a stabilizing agent. Amines attached to the latex particulate directly or through a spacer grouping are an example of a stabilizing moiety. [0019] “Stabilizing agent” refers to compositions that can act as image stabilizer. In one embodiment, the stabilizing agent can be bound to a latex particulate by entrapment within the particulate, not by covalent attachment. Alternatively, a stabilizing agent can be attached to a latex particulate. [0020] “Precursor” includes organic groups that can be attached to a polymerizable or vinylic monomer during free-radical polymerization, but do not substantially interfere with the polymerization process. However, precursors can also be readily separated after polymerization to form a stabilizing agent and/or a stabilizing moiety. [0021] “Image durability” refers to the ability of a printed image to resist change over time or in response to environmental challenges. Such durability factors include but are not limited to lightfastness, humidfastness, gas fade resistance, heat resistance, waterfastness and smearfastness. [0022] With these definitions in mind, the present invention can include a method of associating stabilizer functionalities with latex particulates. The method can comprise forming a stabilizer precursor-containing monomer by coupling a polymerizable monomer (such as a monomer comprising a vinylic functionality) with a stabilizing agent reactive with the polymerizable monomer, thereby forming a stabilizer precursor-containing monomer. In one embodiment, after coupling, the steps of polymerizing the stabilizer precursor-containing monomer to form a stabilizer precursor-containing latex particulate, and subsequently decoupling the stabilizer precursor within the latex particulate to form an associated latex particulate and stabilizing agent can be carried out. Optionally, multiple monomers can be used and randomly polymerized therein, and crosslinking can be carried out. [0023] With this method, the polymerizable monomer can comprise an isocyanate moiety in one embodiment. Therefore, when the stabilizing agent comprises a —NH, —SH, or —OH functionality, and the coupling occurs by reaction between the isocyanate moiety and the —NH, —SH, —OH, or —CH functionality, the isocyanate moiety and the —NH, —SH, —OH, or —CH functionality are blocked from interfering with the polymerizing step. The stabilizing agent, optionally, can further comprise an electron-withdrawing group attached to the functionality. Additionally, the step of polymerizing can include random polymerization of the polymerizable monomer with at least one additional monomer. Decoupling can be carried out by the use of heat and/or water in some embodiments. [0024] The decoupling can produce a stabilizing moiety covalently bound to the latex particulate. In another embodiment, the decoupling can cause the stabilizing agent to become entrapped in the latex particulate. In another embodiment, both can occur. [0025] A stabilizer-bound latex particulate is also provided for improving image durability such as humidfastness and lightfastness in ink-jet printing applications. The stabilizer-bound latex particulate can comprise a latex particulate configured for inclusion in an ink-jet ink to provide improved humidfastness of an image printed by the ink-jet ink, wherein the latex particulate has a molecular weight from 10,000 Mw to 10,000,000 Mw, and has a particle size from 10 nm to 2 μm. Further, an image stabilizer configured for improving durability of the image can be bound to the latex particulate. In one embodiment, the image stabilizer can be a stabilizing moiety covalently bound to the latex particulate. In another embodiment, the image stabilizer can include a stabilizing agent entrapped within the latex particulate. In another embodiment, the image stabilizer can include both a stabilizing moiety covalently bound to the latex particulate, and a stabilizing agent entrapped within the latex particulate. [0026] As will be described in greater detail below, the image stabilizer bound to the latex particulate can be prepared in-situ, after polymerization of the latex particulate, thereby alleviating problems associated with image stabilizer interference with free-radical polymerization. The stabilizer-bound latex particulate can include multiple monomers being randomly polymerized, and/or can be crosslinked. [0027] The association of an image stabilizer and a latex particle can be highly desirable, as a resultant print film or coating can associatively combine a colorant and the stabilizer. Prior to the present invention, the combining of a latex particle and a stabilizer has been difficult, as the preparative chemistry of latex particles are often incompatible with stabilizing agents and/or stabilizing moieties. For example, small micron or submicron latex particles are most successfully formed by free radical emulsion polymerization of vinylic monomers. Conversely, image stabilizers are typically designed to quench such free radicals. Thus, the addition of stabilizers to an ink composition containing a latex monomer mix, with efficacies and proportions necessary to substantially effect print color stability, can prevent appropriate monomer polymerization. [0028] To provide an example, the presence of surface amines on latex particles can be highly desirable for association with certain molecules, such as many dyes and stabilizing salts. The high nucleophilicity of primary and secondary amines can allow preferential surface reactions in a latex aqueous solution without adverse competition with water. However, a clean and effective means of producing a primary or secondary amine on a free radical polymerized latex particle has not been previously demonstrated, particularly in the ink-jet ink arts. For example, vinylic monomers having primary and secondary amines are highly unstable. Further, amines readily react with vinyls through Michael addition, destroying the ability of the monomers to polymerize properly. [0029] Polyvinyl amines are typically prepared commercially by polymerization of vinyl formamide, with subsequent acid reduction to a polyvinyl ammonium salt. A similar product may be prepared through polymerization of a salted vinylic amine monomer. Neither monomer, however, is particularly useful for latex polymerization, as each is sufficiently water soluble to prevent inclusion in the organic phase of the emulsion that forms the latex particle. Alternatively, monomers containing an alkylchloride functionality may be freely polymerized and subsequently aminated with ammonia or amine solvents to form latex amines. Such amination, however, sequentially forms higher classes of amines (in the order primary, secondary, tertiary and ammonium salt) in which each successive step crosslinks the latex, vitiating its ability to form desired protective films over ink-jet produced images. [0030] A goal of many ink and paint films is long-term color durability under a variety of ambient lighting conditions. Commercial free-radical inhibitors, anti-oxidants, anti-ozonants, and other stabilizers are commonly added to ink and paint formulations to extend the color life of incorporated dyes and pigments. When chemically associated with the colorant, such stabilizers have been known to appreciably retard color degradation by blocking free-radical and/or oxidative reactions that cause color and polymer degradation. [0031] The present invention provides a novel means to incorporate significant photo stabilizing function to latex particles. This can be done without detriment to latex polymerization chemistry and process. Specifically, a novel monomer having a stabilizer precursor can be polymerized as part of an overall latex particle monomer mix. The precursor that can be used has little or no free radical quenching properties. Therefore, the precursor does not substantially disrupt the formation of latex particles. Once the particle polymerization reaction has occurred, the latex can further be processed, such as by adding heat and/or water, to generate (or regenerate) the stabilizer from the precursor in-situ. The stabilizer may be chemically bonded to the latex polymer, e.g., stabilizing moiety, and/or may be entrapped within the latex particle, e.g., stabilizing agent. By these compositions, systems, and methods, the colorant and stabilizer can associate within a print film as the latex coagulates during the drying of the print film. [0032] An illustrative example in accordance with an embodiment of the present invention is provided in Formulas 1a-1d below: [0033] Formulas 1a-1d above show an example of a general reaction sequence of monomer preparation, free-radical polymerization, and latex in-situ stabilizer generation of this invention. In Formula 1a, 2-isocyanatoethyl methacrylate (Aldrich) is the vinylic isocyanate (1). The stabilizing agent (2) is 4-hydroxy methylbenzoate prepared through the condensation of 4-hydroxy benzoic acid (Aldrich) and methanol. In Formula 1b, the isocyanate and phenol stabilizer are reacted to form a weak carbamate (3). Through the reaction, the isocyanate and stabilizer functionalities are mutually reacted out in the formation of the carbamate, allowing the resultant methacrylate monomer to freely enter into free radical polymerization with other unspecified monomers to form the desired latex polymer, shown in Formula 1c. The brackets indicate the location of polymerization, which can be with other monomers, such as to form a randomly polymerized copolymer. The portion of the composition that is protected from polymerization by the carbamate bond can be referred to as the precursor. The resultant latex (which includes the precursor) is subsequently heated to unblock the isocyanate which immediately reacts with water in the latex solution to form a primary amine stabilizing moiety (4), liberating carbon dioxide as shown in Formula 1d. Additionally, the stabilizer precursor moiety separation regenerates the added stabilizing agent (2) of Formula 1a (which becomes trapped within the latex particle). Carbon dioxide is liberated as a by-product. [0034] The composition formed as shown in Formula 1d provides two photo-stabilizing functionalities. First, a primary amine stabilizing moiety is formed that is covalently attached or covalently bound to the latex particle. Second, 4-hydroxy benzoic acid stabilizing agent is regenerated and becomes entrapped within, but not covalently attached to, the latex particulate. The precursor is in a form that protects both of these functionalities during polymerization, and upon the addition of water and heat, both functionalities are liberated and bound to the latex particulate. In this embodiment, rather than having a single functionality present that acts as a stabilizer, two types of image stabilizers are generated in-situ that can affect long-term image durability properties of an ink-jet ink, other ink, or paint in which the composition is used. Though Formulas 1a-1d above provide an illustrative example of the present invention, other embodiments are possible, some of which will be described herein. [0035] In more general terms, a precursor composition can comprise a vinylic isocyanate reacted with a phenol, thiophenol, or amine functional stabilizing agent (such as a hindered amine light stabilizer). In general, such reactions form weak carbamate, thiocarbamate, or urea-type bonds, respectively, that are readily dissociated at elevated temperature to regenerate the stabilizing agent and the isocyanate. If water is added, the regenerated isocyanate can then immediately react with water entrapped within an aqueous latex particle to form a primary amine stabilizing moiety and carbon dioxide. The water reaction can be dominant, and can force a stoichiometric conversion of the precursor to a desired stabilizer. The generated amine-stabilizing moiety can act both as a potent free-radical quencher, and as a reactive group that allows covalent latex surface attachment of other moieties, such as a colorant, as well as surface cation generation. Additionally, such a reaction allows a stabilizer to form within a latex reaction bath, without harmful reaction bi-products. [0036] In one embodiment, a vinylic precursor that can be used includes that shown in Formula 2 below: [0037] where R can be H, or preferably, R can be an electron withdrawing group (in addition to the phenyl ring) such as an ester. [0038] Stabilizing agents used alone, or in conjunction with dyes, are known in the ink-jet ink arts. For example, U.S. Pat. No. 5,892,037, which is incorporated herein by reference, provides a list of stabilizers that can be used. Such known stabilizers include, but are not limited to alkylated monophenols, alkylthiomethylphenols, hydroquinones, tocopherols, hydroxylated thiodiphenyl ethers, alkylidenebisphenols, hydroxybenzylated malonates, aromatic hydroxybenzyl compounds, triazine compounds, benzylphosphonates, acylaminophenols, phenol esters, amides, hindered amines, oxamides and phenol triazines. More generally, suitable stabilizing agents can include free radical inhibitors, antioxidants, and/or antiozonants containing one, and alternatively more than one functional amine, phenol, or thiophenol. Some phenol stabilizers that can be used include alkylated monophenols such as 3,5 di-terbutyl phenol and phenolic esters such as 4-hydroxy methylbenzoate. Some amines that can be used include sterically hindered amines such as 2,2,6,6 tetramethyl piperidine and diisopropylamine. In general, any stabilizing agent having a stabilizing functional group (e.g. —NH, —SH, —OH, —CH) that is reactive with an isocyanate is within the scope of this invention. [0039] Examples of common isocyanate blocking agents (including blocking agents that are also stabilizing agents) that can be used in accordance with the present invention can include phenols, thiophenols, pyridinols, oximes, amides, imides, imidazoles, pyrazoles, triazoles, and amines. In each of these examples, isocyanate is blocked through a reaction with an —OH, —SH, or —NH group on the blocking agent. Certain acidic methylene compounds, such as malonic esters, are also used and can block through the reaction with its —CH group, e.g., HO2CCH2—CH—(OH)CO2H. The general isocyanate blocking reaction is provided as Formula 3 below: —N═C═O+HG-→—NHC(O)G- Formula 3 [0040] where G represents an oxygen, sulfur, nitrogen, or carbon atom. [0041] As would be known by one skilled in the art, the reactive groups —NH and —CH are each missing valence groups as represented. It is to be understood that —NH will include an additional valence group, and —CH will include two additional valence groups. The dash (-) indicates the functionality it is associated with is part of a larger molecule. For example, —N═C═O can be included as part of CH2═CH(CH3)(O)OCH2CH2N═C═O, such as shown in Formula 1a. Additionally, in one example, HG- can be part of 4-hydroxy methylbenzoate, also shown in Formula 1a. Only the blocking reaction portion of the composition is shown in Formula 3. This reaction is reversible at elevated temperature to unblock the isocyanate. The unblocking temperature is determined, in large part, by the chemistry of the blocking agent, and can usually be from 70� C. to 200� C. Blocked isocyanates are most commonly used in polymeric systems, wherein the isocyanate is blocked until the polymer is cast, then unblocked at elevated temperature to crosslink the polymer with reactive groups, e.g. hydroxides, positioned along the polymer. In many instances, a crosslinking reaction is significantly inhibited by competition from the blocking agent to re-react with the unblocked isocyanate. [0042] The present invention provides the use of blocked isocyanates, as many isocyanate blocking agents have stabilizer functionality. Phenols, thiophenols, and hindered amines, are each isocyanate blocking agents and potent stabilizing agents. Furthermore, more potent stabilizing agents tend to have lower isocyanate unblocking temperatures. For example, para-substituted phenols show lowered unblocking temperatures and improved color stabilization as such a substituent tends to be more electron withdrawing. Hindered amines also have lower unblocking temperatures and good color stabilization properties by comparison to non-hindered amines. Para substituted phenols, such as hydroxy benzoic esters, and hindered amines, such as 2,2,6,6-tetramethylpiperidine, are two of the more potent known stabilizers used in the industry, and can be used in accordance with the present invention. [0043] In the state shown in Formula 3, the isocyanate is blocked from hindering a polymerization reaction of a latex particulate, and further, the added stabilizing agent is also blocked from hindering the polymerization of the latex particulate. Thus, in the state shown by the reaction product of Formula 3, a stabilizer precursor can be said to be formed (which can be decoupled after polymerization to form active stabilizer moieties). [0044] The present invention disrupts the ability of a stabilizing agent to re-react with the unblocked isocyanate through formation of an amine, a second potent stabilizer. By adding heat and water to the reaction product of Formula 3, an amine (—NH2) is formed that is covalently bound to a polymerized latex particulate, and the stabilizing agent is regenerated to be entrapped by the latex particulate. A possible reaction scheme for this process can be given by Formula 4 below: —NHC(O)G-+H2O+ΔT→—NH2+HG-+CO2 Formula 4 [0045] where G represents an oxygen, sulfur, nitrogen, or carbon atom, and ΔT represents added heat that is sufficient to separate the precursor as shown, but not great enough to denature at least one of the image stabilizers. Again, a dash (—) indicates the functionality it is associated with is part of a larger molecule. In the above reaction scheme, water can be introduced, in this case, by unblocking an isocyanate while the free-radical polymerized latex particles are dispersed in water solution, such as within a latex reaction bath. Water can then be absorbed throughout the latex particle, and can be more abundant and more mobile than the stabilizer. Once unblocked, i.e., precursor portion decoupled, the isocyanate can immediately react with water to form the amine, thereby vitiating the ability of the blocking agent to re-block. While not wishing to be bound by a particular reaction mechanism theory, it is believed that elimination of the competitive re-block reaction lowers the effective unblocking temperature of the isocyanate for some blocking agents. Higher unblocking energy could, otherwise, be required to drive the reaction equilibrium toward the unblocked condition and to mobilize the stabilizing agent away from the unblocked isocyanate. [0046] In another embodiment of the present invention, unlike that shown in Formulas 1a to 4, the isocyanate and stabilizer product may include no vinylic functionality, or other polymerizable functionality whatsoever. In this instance, a stabilizer blocked isocyanate can be dissolved or dispersed in a monomer mix, and does not participate in the free-radical polymerization of the latex. Instead, the stabilizer can simply be entrapped within the latex particle. Such a stabilizer blocked isocyanate can be represented by the example provided by the reaction product of dodecyl isocyanate and 2,2,6,6-tetramethylpiperidine. When unblocked, such as by adding heat to a polymerized latex particulate, the stabilizer blocked isocyanate can form dodecyl amine and the same 2,2,6,6-tetramethylpiperidine, both of which are sufficiently hydrophobic to remain entrapped within the latex particle. [0047] In another embodiment, either or both the isocyanate and stabilizing agent reactant molecules can have, optionally, a vinylic functionality. In general, even more stabilizer-blocked isocyanate can be incorporated into a latex particle when the stabilizer-blocked isocyanate participates in the latex polymerization reaction. In the present invention, vinylic functionality is generally defined as a chemical group capable of entering free radical polymerization. Such a chemical group is exemplified by, but not limited to, acrylates, styrenes, vinyl ethers, and other ethylene reactive moieties. In the instance in which the stabilizer monomer contains only one vinylic group, the polymerized monomer will unblock to form a polymer-attached amine or polymer attached stabilizing agent, depending on which entity is more directly attached to the vinyl group. The remaining entity will not be chemically bonded within the latex particle, and can either be entrapped within the latex polymer matrix or leach out of the latex, depending on solubility. [0048] When both the isocyanate and stabilizing agent reactants each have an attached vinyl group, the reaction product can form a dimer or multimer allowing monomer polymerization across multiple polymer strands. The polymerized precursor-containing stabilizer monomer can unblock to form a polymer-attached amine and a second polymer attached stabilizing moiety (which can be an attached stabilizing agent). Still further, a multi-functional isocyanate or multi-functional stabilizing agent may be used. For example, two vinylic isocyanates may be reacted to a single di-functional stabilizing agent, such as hydroquinone. [0049] In one embodiment, a vinylic isocyanate of the present invention can have a general structure, which is illustrated as Formula 5 below: R1(R2)C═C(R3)R4N═C═O Formula 5 [0050] where R1, R2, and R3 can independently be hydrogen, phenyl, 1-20 carbon substituted or unsubstituted alkyl, substituted or unsubstitued aryl, or halogen; and R4 can comprise an electron withdrawing group, such as an ester, ether, or phenyl ring, attached to the unsaturated carbon. Optionally, though not shown, a linkage or spacer grouping can be attached between the R4 and the isocyanate. As is well known in the chemical art, the R1-4 elements define the vinyl group, fundamentally represented by the double bonded carbon atoms. It is well known in the art that the electron-withdrawing group is used to increase free radical reactivity of an unsaturated carbon-carbon double bond. It is further well known in the art that moieties other that those given for R1-4 can be used without departing from the teachings of this invention. Vinylic isocyanates are well known in the art and include, for example, 2-isocyanatoethyl methacrylate and vinyl isocyanate. In the case of vinyl isocyante, the isocyanate is directly attached to the unsaturated carbon (eliminating R4). [0051] In general, the reaction of the vinylic isocyanate and a stabilizing agent forms a weak carbamate, thiocarbamate, or urea, depending on whether the stabilizing agent is a phenol, thiophenol, or amine compound, respectively. There are many stabilizer molecules having phenol, thiophenol, or amine groups capable of forming such reaction products with isocyanates. The choice of stabilizing agent can be made based upon resultant stabilizer monomer solubility in a latex monomer mix, hydrophobicity, reaction and unblocking temperatures, and stabilizing agent efficiency for a particular application. [0052] In some embodiments, the reaction temperature that forms a stabilizing agent can be designed to be sufficiently low to avoid untimely polymerization of the vinyl group. If too high for a desired reaction, the temperature can be lowered by incorporation of certain catalysts such as tertiary amines or organotin compounds. Likewise, the unblocking temperature, or the temperature at which the stabilizing agent and isocyanate are regenerated, can be kept below the boiling point of water to allow stabilizing agent regeneration in a latex reaction bath. Again, catalysts such as tertiary amines or organotin compounds can be used for this purpose. Catalysts and catalyst concentrations for altering the blocking and unblocking temperature of isocyanates and blocking agents are well known in the art. Examples of suitable cataylsts include dibutyltin dilaurate and triethylamine. Such catalysts can be added to a reaction mixture at from 0.05%-1.0% by weight concentration. In another embodiment, the unblocking temperature may be selected at a higher temperature, requiring that the stabilizer be regenerated under less optimum conditions, e.g. after print film formation. Stabilizing agent hydrophobicity can be considered to assure that the stabilizing agent does not leach out of the latex particle or print film. [0053] Many variations of the teachings of this invention are possible. The precursor monomer, for example, may optionally comprise multiple vinyl functionality to bond the regenerated stabilizing agent to the latex polymer. In such an embodiment, a stabilizing agent-containing vinylic functionality can be used. A dimer produced through the reaction of a vinylic isocyanate and the reaction product of a vinylic acid chloride (e.g. acryloyl chloride) and 2,2,6,6-tetramethyl-4-piperidinol is an example of such multiple vinyl functionality. In this case, the dimer serves to crosslink adjacent polymer strands during latex particle formation. The crosslink is broken upon subsequent heating to form primary amine and stabilizer side chains on the prior crosslinked polymer strands. In another embodiment, the precursor-containing monomer can comprise the reaction product of a vinylic stabilizing agent and a non-vinylic isocyanate (e.g. dodecyl isocyanate). In each example, the stabilizer monomer polymerizes during latex formation and forms stabilizing agent and amine functional entities during post-latex formation heating. [0054] As describe previously, the present invention provides a unique means to incorporate primary amines within latex chemistry. This provides a unique ability to additionally react these in-situ-formed primary amines to form alternate amine types and functional couplings. Alternate amine types include, for example, latex surface salts for particle dispersion, and hindered amine stabilization. [0055] The following examples typify this element of the invention. Surface amines can be salted by addition of certain acids, such as hydrochloric, nitric or carboxylic acid, to the reaction bath. In such reactions, a primary amine can be readily converted to its ammonium salt form. Latex amines can be reacted with alkyl halides to form secondary and hindered amines. For example, primary amines may be reacted with 2-chloropropane to produce hindered amine stabilizer. Hindered amines are believed to be regenerative free-radical scavengers. The amine reactant can then be introduced into the monomer mix or infused through the latex particle through soaking. Surface amines can be, for example, used to attach steric stabilizers to the latex. For example, a poly(ethylene glycol) acrylate may be introduced into the latex solution and reacted to the latex surface through the condensation (Michael addition) reaction of the acrylate and surface amine. [0056] In any of the above-described embodiments, the unblocking reaction can optionally take place at any time after latex polymerization, including after the latex is printed, cast, or otherwise coated. For example, regenerated isocyanate can be used to crosslink the latex print film in a more conventional sense for added durability. In this instance, a monomer (or monomers) containing moieties reactive with isocyanates (e.g. alcohols such as in hydroxyethyl acrylate monomer) can be employed in the monomer mix. This embodiment departs from the concept of simultaneous formation of stabilizer that is used to protect the print film against oxidative degradation. [0057] For some applications, it can be desirable to create latex polymers having covalently attached amines wherein stabilizer functionality is not necessary. In such instances, the stabilizers described above may be substituted by a common isocyanate blocking agent. A common example of such an isocyanate blocking agent is methylethyl ketoxime. This embodiment provides that the blocked isocyanate is used to produce an in-situ amine within the latex after free-radical latex polymerization. [0058] The present invention has benefit to a wide range of latex polymer applications for which color and polymer stability against photo-oxidation and free-radical degradation are desired. Such applications include, but are not limited to inks, paints, and coatings. If used in an ink, such as an ink-jet ink, the stabilizer-bound latex particulates can be incorporated with a colorant and an appropriate ink-vehicle to provide an improved ink-jet ink composition. It is further noted that the teachings of the present invention can extend beyond latex polymers and can include, for example, all polymer systems formed through free-radical polymerization of monomers. This includes water-based and solvent-based polymer systems and solid plastic polymers (e.g. polyacrylates, polystyrenes). The isocyanate blocked stabilizers in plastic polymers can be unblocked to regenerate the stabilizer when molded or extruded at the high flow temperature of the plastic. Plastic products formed from such plastics (e.g. toys, furniture, windows) may be given extended life against discoloration and structural deterioration through the incorporation of the blocked stabilizers of the present invention.
EXAMPLES [0059] The following examples illustrate embodiments of the invention that are presently known. Thus, these examples should not be considered as limitations of the present invention, but are merely in place to teach how to make the best-known compositions of the present invention based upon current experimental data. As such, a representative number of compositions and their method of manufacture are disclosed herein. Example 1 [0060] A control latex was formed using a monomer emulsion of 102.5 g methyl methacrylate (Aldrich), 120.0 g hexyl acrylate (Aldrich), 25 g mono-methylacryloyloxyethyl succinate (Aldrich), 2.5 g ethylene glycol dimethacrylate (Aldrich), and 1.0 g isooctylthioglycolate (Avecia) mixed and sheared gently with 85 g water and 20.8 g Rhodafac™ (Rhodia). A reaction bath containing 725 g water was heated to 90� C. To the reaction bath, 0.87 g potassium persulfate dissolved in 100 g water was added dropwise at a rate of 3 ml/min with stirring. The monomer emulsion was subsequently added to the reaction bath dropwise over a period of 30 minutes. The reaction mixture was maintained at 90� C. for 2 hours and allowed to cool down. When cooled to 50� C., the reaction mixture was buffered to pH 8.5 through the addition of 23 g of 17.5% potassium hydroxide solution. The reaction mixture was filtered with a 200 mesh filter to obtain stable polymer latex particles with an average particle size of 230 nm. Example 2 [0061] The composition of Example 1 was duplicated with the addition of 4-hydroxy benzoic acid, a very potent stabilizer, to the monomer mix. A monomer premix was formed with 4.25 g methyl methacrylate, 4.25 g hexyl acrylate, 1.0 g mono-methacryloyloxyethyl succinate, 0.1 g ethylene glycol dimethacrylate, 0.4 g hyroxybenzoic acid, and the premix was emulsified in 7 g water with 0.25 g Rhodafac. The reaction bath consisted of 30 g water with 0.05 g potassium persulfate initiator. Following the addition of the monomer emulsion, the reaction mixture was maintained at 90� C. for 1.5 hour and allowed to cool to ambient temperature. No latex was formed. Example 3 [0062] A stabilizer monomer was synthesized from the condensation reaction of isocyanatoethyl methacrylate and 4-hydroxy methylbenzoate (the ester form of the stabilizer used in Example 2). About 12 g methyl hydroxybenzoate was dissolved in 5 ml of dichloromethane. To this solution, 15 ml of isocyanatoethyl methacrylate (Aldrich) and 1 ml of triethylamine was added. The reaction mixture was stirred at room temperature for 16 hours. The product mixture was washed with hexane to remove unreacted isocyanate. About 23.5 g of stabilizer monomer was produced. Example 4 [0063] A latex composition comprising 85% methyl methacrylate and 15% of the stabilizer monomer of Example 3 was prepared. An emulsion was prepared by mixing 5.66 g of methyl methacrylate and 1.0 g of the stabilizer monomer in 1.3 g water containing 0.5 g of Rhodafac RS710. The separately prepared water bath contained 20 ml water with 0.07 g potassium persulfate stirred at 90� C. The monomer emulsion was added over 30 minutes to the bath and the reaction mixture stirred at 90� C. for one hour, then cooled to ambient temperature to obtain the latex. The latex particle size was 178 nm. The isocyanate blocked the free-radical quenching function of the stabilizer. Example 5 [0064] The hydroxy methyl benzoate stabilizer of Example 4 was regenerated in-situ within the formed latex by heating the latex at 75� C. for 2.5 hours in the presence of triethylamine catalyst. About 13 g of the latex obtained in Example 4 was mixed with 80 mg triethylamine. The latex mixture was then heated for 2.5 hours at 75� C. Regeneration of the hydroxy methylbenzoate stabilizing agent and creation of the primary amine stabilizing moiety was confirmed by IR spectroscopy and ninhydrin solution analysis. Cleavage of the carbamate blocking group was found to be complete and stoichiometric via NMR analysis. [0065] While the invention has been described with reference to certain preferred embodiments, those skilled in the art will appreciate that various modifications, changes, omissions, and substitutions can be made without departing from the spirit of the invention. It is therefore intended that the invention be limited only by the scope of the appended claims.
Referenced byCiting PatentFiling datePublication dateApplicantTitleUS7402617 *Feb 6, 2003Jul 22, 2008Hewlett-Packard Development Company, L.P.Low bulk density, low surface dielectric constant latex polymers for ink-jet ink applicationsUS7544418Jul 31, 2006Jun 9, 2009Hewlett-Packard Development Company, L.P.Polymer-encapsulated pigments and associated methodsUS7705070Jul 14, 2006Apr 27, 2010Hewlett-Packard Development Company, L.P.Ink-jet compatible latexesUS8246754 *Sep 25, 2009Aug 21, 2012Hewlett-Packard Development Company, L.P.Process for removing ink from printed substrateUS20080182932 *Jan 25, 2007Jul 31, 2008Zhang-Lin ZhouBiocatalytic polymerization of anti-oxidant-modified latex particulatesUS20110073134 *Sep 25, 2009Mar 31, 2011Krzysztof NaukaProcess for removing ink from printed substrate* Cited by examinerClassifications U.S. Classification524/775International ClassificationB41J2/01, C08K5/00, C08K9/10, C09D11/00, B41M5/00, C08F20/36Cooperative ClassificationC08K9/10, C09D11/30, C08K5/005, Y10T428/2989European ClassificationC09D11/30, C08K5/00P6Legal EventsDateCodeEventDescriptionSep 23, 2011FPAYFee paymentYear of fee payment: 4May 18, 2010CCCertificate of correctionJun 18, 2003ASAssignmentOwner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P., COLORADFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;REEL/FRAME:013776/0928Effective date: 20030131Owner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P.,COLORADOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;US-ASSIGNMENT DATABASE UPDATED:20100203;REEL/FRAME:13776/928Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;US-ASSIGNMENT DATABASE UPDATED:20100330;REEL/FRAME:13776/928Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;US-ASSIGNMENT DATABASE UPDATED:20100406;REEL/FRAME:13776/928Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;US-ASSIGNMENT DATABASE UPDATED:20100413;REEL/FRAME:13776/928Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;US-ASSIGNMENT DATABASE UPDATED:20100420;REEL/FRAME:13776/928Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;US-ASSIGNMENT DATABASE UPDATED:20100504;REEL/FRAME:13776/928Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;US-ASSIGNMENT DATABASE UPDATED:20100518;REEL/FRAME:13776/928Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;REEL/FRAME:13776/928Owner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P.,COLORADOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;US-ASSIGNMENT DATABASE UPDATED:20100203;REEL/FRAME:13776/928Effective date: 20030131Owner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P.,COLORADOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;US-ASSIGNMENT DATABASE UPDATED:20100406;REEL/FRAME:13776/928Effective date: 20030131Owner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P.,COLORADOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;REEL/FRAME:13776/928Effective date: 20030131Owner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P.,COLORADOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;US-ASSIGNMENT DATABASE UPDATED:20100420;REEL/FRAME:13776/928Effective date: 20030131Owner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P.,COLORADOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;US-ASSIGNMENT DATABASE UPDATED:20100413;REEL/FRAME:13776/928Effective date: 20030131Owner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P.,COLORADOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;REEL/FRAME:013776/0928Effective date: 20030131Owner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P.,COLORADOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;US-ASSIGNMENT DATABASE UPDATED:20100518;REEL/FRAME:13776/928Effective date: 20030131Owner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P.,COLORADOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;US-ASSIGNMENT DATABASE UPDATED:20100504;REEL/FRAME:13776/928Effective date: 20030131Owner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P.,COLORADOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;US-ASSIGNMENT DATABASE UPDATED:20100330;REEL/FRAME:13776/928Effective date: 20030131Feb 21, 2003ASAssignmentOwner name: HEWLETT-PACKARD COMPANY, COLORADOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:VINCENT, KENT;GANAPATHIAPPAN, SIVAPACKIA;REEL/FRAME:013759/0043Effective date: 20021213RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services


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Patent US5254205 - Wafer binding method and apparatus - Google Patents
The present invention relates to a method and an apparatus for automatically binding a silicon wafer to a carrier plate. In the binding method of the present invention, the wafer is positioned underneath the carrier plate and then lifted and bonded to the carrier plate, at or below atmospheric pressure:...http://www.google.com/patents/US5254205?utm_source=gb-gplus-sharePatent US5254205 - Wafer binding method and apparatus
Publication number US5254205 A
Application number US 07/800,833
Also published as DE69119367D1, DE69119367T2, EP0488267A2, EP0488267A3, EP0488267B1, US5310441
Publication number 07800833, 800833, US 5254205 A, US 5254205A, US-A-5254205, US5254205 A, US5254205A
Inventors Yukio Tsutsumi, Tatsumi Matsumoto, Keisuke Takahashi, Mitsuzi Koyama
Patent Citations (10), Non-Patent Citations (2), Referenced by (33), Classifications (30), Legal Events (4)
Wafer binding method and apparatus
US 5254205 A
1. A wafer binding apparatus comprising:
a binding unit which binds said wafer to said carrier plate;
a first carrier means which supplies a carrier plate to said binding unit,
a second carrier means which supplies said wafer to said binding unit, and
a third carrier means which carries said carrier plate bonded to said wafer from said binding unit,
wherein said binding unit comprises:
a carrier plate support means which supports said carrier plate,
a wafer support means, located on the under side of said carrier plate support means, which supports said wafer, and
a wafer transportation means which raises said wafer, supported by said support means, up until contacting the under surface of said carrier plate,
wherein in the interval between said first carrier means and said binding unit, a rolling means is provided for flipping the sides of said carrier plate.
2. A wafer binding apparatus according to claim 1 wherein the upper surface of said wafer and said carrier plate to be bonded to the upper surface of said wafer are placed under reduced pressure and after said wafer is raised and bonded to the under surface of said carrier plate, pressure is raised by said binding unit.
3. A wafer binding apparatus according to claim 1 wherein:
said first carrier means transports said carrier plate with the surface to be bonded to said wafer facing upwards, and
said second carrier means transports said wafer with the surface to be bonded to said carrier plate facing upwards.
4. A wafer binding apparatus according to claim 2 wherein:
5. A wafer binding apparatus according to claim 1 wherein on the transportation path of said second carrier means a washing means is provided comprising:
a first washing unit which shoots out onto the surface of said wafer, at a high pressure, a washing liquid, and
a second washing unit which adds high frequency wave oscillations to a washing liquid and then shoots said washing liquid with added high frequency wave oscillations out onto the surface of said wafer.
6. A wafer binding apparatus according to claim 2 wherein on the transportation path of said second carrier means a washing means is provided comprising:
However, the minimum line width of the integrated circuit (IC) used in the silicon monocrystal is 1 μm. Additionally, when trying to form a circuit using optical lithography, due to the shallow depth of focus, a wafer possessing a satisfactory flatness is required. In order to obtain this desired wafer, improvements in both the polishing process as well as in the controlling of the carrier plate flatness are being carried out. There exist additional problems however, during the bonding, in the thickness and the thickness distribution of the wax layer: the wax layer thickness can be no greater than 1 μm. Furthermore, there were also drawbacks in that refuse was entering into the space in between the carrier plate and the wafer as well as air bubbles were being left behind creating unwanted "dimples" on the surface of the wafer following the polishing. Deterioration of the ability to flatten the carrier plate also was a point of concern.
Through this kind of organization, there is no air disturbance on the binding face because the binding of the wafer and the carrier plate can be performed under reduced pressure. Consequently, the occurrence of air bubbles on the binding face can be prevented and even if the aperture of the wafer is large, the occurrence of dimples is reduced. Additionally as previously mentioned, the binding is carried out under reduced pressure conditions such that the binding face is not disturbed by the air. Moreover, since normal pressure is returned to slowly, uniform pressure is more effectively applied and the thickness of the wax becomes uniform. Furthermore, there is no rolling about of the wafer surface to which has been applied and the adhesion of refuse is rare so the undesirable occurrence of dimples is reduced and consequently, a wafer with a desirable flatness can be obtained.
FIG. 6 is an enlarged plane view of one part of the wafer carrier.
FIG. 10 is a side view of the fixed frame and the moving frame.
In other words, wafer carrier 5 supports wafer 6 through wafer supporting part 51 at a position above diaphragm 41 and facing the upper surface of diaphragm 41. Wafer carrier 5 supports carrier plate 7 by carrier plate supporting plane 52 at a position between wafer carrier 5 and upper surface of wafer 6 at a fixed space interval. In connection with the explanation on pressboard 3 and cover 21 it should by mentioned that pressboard 3 which is pressed against the upper surface of carrier plate 7, which is attached to the upper part of wafer carrier 5, is installed such that it can move up and down. In the present invention there is n need for putting positive pressure on pressboard 3, and the rising of plate 7 can be prevented when pressure is applied to the upper surface of plate 7 by pressplane 33.
As shown in FIG. 3, at the upper part of cover 21 a rod sheath 22 is provided. A cylinder rod 32 passes through this rod sheath 22, in line with driving cylinder 31 of pressboard 3. Air tight sealing is attained by O-rings 23 contacting the inner surface of rod sheath 22 and the outer surface of cylinder rod 32, which also provides the possibility of sliding contact. At the lower end of cover 22 flunge 25 is formed. When lowering cover 22, the lower surface of flunge 25 contacts the surface of main frame 10, whereby airtightness is assured by O-ring 24 , and thus, first decompression chamber 2 formed inside aforementioned cover 21 is shut tightly. When wafer 6 and carrier plate 7 are taken out and put in, the lower end of rod sheath 22 is supported by flange 34, which is used as a connection of pressboard 3 and cylinder rod 32, and when pressboard 3 is lifted up, also cover 21 goes up and the upper surface of main frame 10 is opened.
Then valve SV2 is shut, valve SV1 is opened, air enters via pipe L3, and the pressure in the second decompression chamber 49, which is ventilated from the second ventilation line L2 and connected to pipes L4 and L3, is gradually increased. By the pressure increase of the second deccmpression chamber 49 diaphragm 41 is lifted up, and wafer 6 is pressed against the lower surface of carrier plate 7 by wafer pressing plate 55 (step 107). The decompression status is continually maintained for the first decompression chamber 2 (step 106). When the pressure in the second decompression chamber 49 is increased to a value between 300 mmHg and 400 mmHg, pressure switch 13 of accumulator 11 actuates and valve SV1 shuts. Only the pressure of the second decompression chamber 49 is maintained at the aforementioned condition, and during this period a pressure on wafer 6 is maintained (step 108). Once wafer 6 is pressed against carrier plate 7, the applied wax causes it to stick to the lower surface of carrier plate.
Next, a plurality of wafers 6 above diaphragm 41 are kept in a position facing the upper surface of diaphragm 11. Carrier plate 7 is maintained at a position facing the upper surface of aforementioned plurality of wafers 6 at a fixed interval there in between.
At the beginning first decompression chamber 2 and second decompression chamber 49 are simultaneously decompressed. When first decompression chamber 2 is deaerated, also the air in the cavity of wafer 6 and carrier plate 7 is sucked out. Thereafter, while the decompressed status of decompressed chamber 2, second decompression chamber 49 is overpressured relative to first decompression chamber 2 by causing the pipe system to leak through the second decompression chamber 49. When dong this, the pressure difference between first decompression chamber 2 and second decompression chamber 49 causes the elastic diaphragm 41 to shift for a fixed interval in upward direction of carrier plate 7 of the first decompression chamber 2. Wafer 6 is pressed via wafer pressing plate 55 of wafer carrier 5, which is put in the upper surface of diaphragm 41, against the lower surface of carrier plate 7. Wax is put on the backside of the wafer (upper surface inside the equipment), and by this wax wafer 6 is carried by the lower surface of carrier plate 7. Thereafter, first decompression chamber 2 and second decompression chamber 42 are equalized, diaphragm 41 is put into its starting position; and when first decompression chamber 2 and second decompression chamber 49 are opened to the atmosphere, wafer 6 ,carried by the lower surface of carrier plate 7, is uniformly covered with wax by applying hydrostatic pressure: since no air reaches this binding plane, dimple impurities due to occurrence of air bubbles are prevented.
Another advantage of the present invention lies in the wafer binding used in the aforementioned wafer binding unit. In other words, the upper surface of the wafer and the carrier plate binding it are arranged at a position of fixed interval, facing each other and are allowed to be treated under reduced pressure. A plurality of wafers is simultaneously lifted from its lower surface and bound to the carrier plate. Thereafter, a pressure increase is carried out.
Binding is carried out by this binding part, and the LTV smoothness is lower than 0.5 μm in an area of 20 mm×20 mm on polished wafer which has a diameter of 200 mm. When polishing was performed under the same polishing conditions in prior art binding parts, LTV smoothness was ±1.0 μm, and thus the improvement is obvious.
Following the arrangement sequenced of aforementioned binding part 128 and reversing pedestals 130, 132, carrier plate transporte 134 is provided thereafter. By this carrier plate transporter 134, the transportation of carrier plates 7 between these machines is attained.
4. he cleaning-pipe 276 rotates and is placed on the top of turntable 252; after supporting the cleaning process of the surface of carrier-plate 7, the cleaning-pipe 276 is returned to its initial position.
5. After lowering cover 264 to a position where there is only a short distance to the surface of carrier-plate 7, turntable 252 rotates for a fixed interval: drops of water on the surface of carrier-plate 7 are removed by centrifugal force. Moreover, along with the rotation of turntable 252, air is blown down onto the surface of carrier plate 7. Furthermore the rotation time of turntable 252 can be arbitrarily fixed by means of the timer (not shown in the figures) provided in the electric power supply circuitry of motor 254. Moreover, along with the rotation of turntable 252, the surface of carrier plate 7 is dried by air. Due to this drying air, the adherence of water drops, scattered around the periphery due to the centrifugation, to the carrier plate 7 is prevented. In addition, the expelled drying air is set up to the equal or higher temperature than that of the liquid used in the washing process (80° C.). In order to prevent the temperature fall of carrier plate 7 due to spin-drying.
The heating units 120 through 124 , which comprise heating apparatus 118, are mutually installed in the space 13. Due to the electric heating by heating units 120 through 124 of the disk upon which carrier-plate 7 rests, the temperature of carrier-plate 7 gradually increases from room temperature to a temperature appropriate for bonding. Furthermore an axle 280 is provided in the center of respective heating units 120 through 124 as shown in FIG. 24. The tip of this axle 280 is inserted in the center of carrier-plate 7 which rests on top of heating units 120 through 124. The above mentioned axle 280 is moved up and down, as shown in FIG. 21, driven by means of pneumatic cylinders 282 through 286 which respond to the heating units 120 through 124. Due to the rising of axle 280, carrier-plate 7, supported by axle 280, is then lifted up above the surface of heating units 120 through 124. Axle 280 descends and carrier-plate 7 comes into contact with heating units 120 through 124.
For transportation frame 290 two pairs of bearings 294 are set up, which exert an influence on the support of a pair of axles 296. At the tip of each axle 296, crank arms 298 are installed respectively. At the tip of these crank arms 298, the above mentioned transportation members 292 are connected in a way that rotation is possible with axle 300 as the center. Furthermore crank arm 302 is arranged on one basic side of axle 296. Crank arm 302 is connected to pneumatic cylinder 304 . The contraction and expansion of pneumatic cylinder 304 allows axle 296 to rotate. Due to this contraction and expansion, the aforementioned pair of transportation frames 290 approach to a position where they can pile up with carrier-plate 7 or where they can detach from it. Moreover, due to the contraction and expansion of rod 308 of power-cylinder 306, the movement to the left and right ranging to space 13 is made possible.
Working beam 360 has a plurality of support plates 362, as shown in FIG. 29. In the intervals between the support plates 362, arrangement spaces 14 and equivalent spaces 14 for centering apparatus 140, washing apparatus 142, wax coater 144, hot baking apparatus 146, and OF position alignment apparatus 148 are provided. The connecting units of the wafers 6 on top of these apparatuses are designed so that that they can be lifted from the lower base parts. The aforementioned working beam 360 is supported by a vertical movement frame 364 through which upward and downward motion is possible, and is driven upward and downward by means of an pneumatic cylinder 366. Additionally, the aforementioned vertical movement frame 364 is supported such that movement in both the left and right directions in FIG. 8 is possible. As well, this vertical movement frame 364 is moved right and left by means of a feed screw 370 driven by a motor 368.
In this cleaning apparatus, first and second nozzles 408, 410 each rotate together with the turn table 400: during rotation, these nozzles jet out washing liquid onto the wafer 6 which lies o top of the turn table. The washing liquid is jetted out from the first nozzle 408 at a flow rate of 0.5-2.0 liters/ minute under a pressure of 100-300 kg/cm2. The high pressure of the washing liquid mainly removes materials which are loosely attached to the surface of the wafer. If the pressure of the washing liquid propelled out of first nozzle 408 is below a minimum fixed value, the washing is insufficient, however if a maximum fixed value is exceeded, then damage is inflicted to the surface of the wafer. The washing liquid furnished with 500-1000 KHz wave oscillations is jetted out of second nozzle 410 at a flow rate of 0.5-3.0 liters/minute. Additionally, it is enough that the pressure of the washing liquid jetted out of second nozzle 410 is sufficiently less than that of the first nozzle 408. This washing liquid furnished with the high frequency oscillation energy removes fine particles on the surface of the wafer. The washing liquid supplied from second nozzle 410, through the employment of high frequency oscillation energy, has a high washing ability, thus the pressure of the washing liquid jetted out of first nozzle 408 may be comparatively small such that there is very little chance of damage to the wafer surface by this pressure. A fear of damaging the wafer surface exists if the period of the wave oscillations added to the aforementioned washing liquid is lower than a minimum fixed value; however, when a maximum fixed value is exceeded, the oscillations are reduced, and detergency is lost.
Between the aforementioned washing apparatus 142 and the wax coater 144, a space that is two times the normal space 2×14 is provided. Consequently, in the washing apparatus once the washed wafer 6 has been placed into the space between the washing apparatus 142 and the wax coater 144, the wax coater is ushered in.
The aforementioned hot baking apparatus 146 supports the wafer 6 which lies on top of the vertically mobile table: through the heating of this above mentioned table, the organic solvents inside of the wax are removed.
In the carrier means 158 a rotating body 472 is provided which rotates by means of a motor 470. On top of this rotating body 472, an arm 474 is provided which is capable of moving radially. This arm 474 can also extend in the direction of the above mentioned turn table 460. Therefore, when the aforementioned turn table 460 is in the upraised position (the arm 474 may be relatively lowered), the arm 474 is extended and then by lowering the turn table 460 (the arm 474 is relatively raised), the wafer 6 is placed on top of the arm 474. With the wafer 6 placed on top, the arm 474 is then rotated 180 degrees and swung towards the wafer setting unit 156. In this wafer unit, a turn table 480 is provided upon which a wafer carrier 5 is placed. According to the driving of this turn table 480 by a motor 482, the wafer storage cavity of the wafer carrier 5 is brought to a position on line with the above mentioned rotating body 472.
US3562965 * Dec 26, 1967 Feb 16, 1971 Siemens Ag Method and apparatus for preparing a plurality of disc-shaped semiconductor crystals for simultaneous working by a tool
JPS63245366A * Title not available
JPS63251165A * Title not available
1 * Patent Abstracts of Japan, vol 13, No. 36 (M 790) 26 Jan. 1989 & JP A 63 245366, Aug. 1987, English Abstract.
2 Patent Abstracts of Japan, vol 13, No. 36 (M-790) 26 Jan. 1989 & JP-A-63 245366, Aug. 1987, English Abstract.
US6460424 * Mar 27, 2001 Oct 8, 2002 Florida State University Research Foundation Combined vertical and rotational motion indexing mechanism
US7594977 * Nov 26, 2004 Sep 29, 2009 Tsubaki Seiko, Inc Tape bonder, tape bonding method, and process for manufacturing electronic component
US8336595 * Oct 27, 2009 Dec 25, 2012 Tsubaki Seiko Inc. Tape adhering apparatus and tape adhering method
US9514972 * May 28, 2009 Dec 6, 2016 Air Products And Chemicals, Inc. Fixture drying apparatus and method
US20040089397 * Oct 24, 2003 May 13, 2004 Tung-Sheng Cheng FPD encapsulation apparatus and method for encapsulating the same
US20050050760 * Jun 16, 2004 Mar 10, 2005 Masamitsu Itoh Substrate drying method, substrate drying apparatus, and semiconductor device manufacturing method
US20070187868 * Jul 14, 2004 Aug 16, 2007 Tsuyoshi Aruga Pasting method and pasting apparatus
US20100071847 * Aug 28, 2009 Mar 25, 2010 Samsung Electronics Co., Ltd. Wafer bonding apparatus
US20100084096 * Oct 27, 2009 Apr 8, 2010 Kimikazu Saito Tape adhering apparatus and tape adhering method
US20100252191 * Nov 28, 2008 Oct 7, 2010 Lintec Corporation Sheet sticking apparatus and sheet sticking method
US20100258149 * May 28, 2009 Oct 14, 2010 Poly-Flow Engineering, Llc Fixture Drying Apparatus and Method
CN100440474C Nov 26, 2004 Dec 3, 2008 有限会社都波岐精工 Tape bonding apparatus and tape bonding method and electronic device production method
CN101335196B Nov 26, 2004 Apr 13, 2011 有限会社都波岐精工 Tape bonder
U.S. Classification 156/538, 451/460, 156/382, 156/286, 134/66, 156/556, 156/154
International Classification B24B37/30, B24B37/34, H01L21/683, B23Q3/08, H01L21/304, H01L21/673, H01L21/00
Cooperative Classification Y10T156/1744, H01L21/68771, H01L21/67092, Y10T156/17, H01L21/67313, H01L21/67173, H01L21/67326, B24B37/345, H01L21/67028
European Classification B24B37/34F, H01L21/67S2Z2L, H01L21/673D, H01L21/67S2F, H01L21/687S16, H01L21/67S2D4, H01L21/673B
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:TSUTSUMI, YUKIO;MATSUMOTO, TATSUMI;TAKAHASHI, KEISUKE;AND OTHERS;REEL/FRAME:005944/0337

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10.1" WIFI/4G-LTE HD PC Tablet Android 8.0 Bluetooth 8+128G SIM GPS Dual Camera | eBay
10.1" Android 9.0 WIFI/4G-LTE HD PC Tablet bluetooth 8+128G SIM GPS Dual Camera
10.1" GPS+WiFi 4G-LTE HD IPS PC 8+128G Tablet Android 8.0 Dual SIM Camera
10.1" HD WIFI/4G-LTE IPS Tablet Android 8.0 bluetooth 8+128G Dual SIM Camera
hangtuby (2307 )
Details about 10.1" WIFI/4G-LTE HD PC Tablet Android 8.0 Bluetooth 8+128G SIM GPS Dual Camera
-Select- Black US plug White US plug Golden US plug
3 available / 308 sold / See feedback
273997591844
Last updated on Nov 20, 2019 17:03:20 EST View all revisions
Storage Capacity: 128G Type: Tablet
Brand: Unbranded ROM: 128G
Resolution: 1280 x 800 Features: Bluetooth,Built-In Front Camera,LCD Display,Touch Screen
Hardware Connectivity: Bluetooth,Micro-USB RAM: 8G
Manufacturer Color: Black/White/Gold Color: Black/White/Gold
Excludes: Alaska/Hawaii, Africa, Central America and Caribbean, South America, American Samoa, Cook Islands, Fiji, French Polynesia, Guam, Kiribati, Marshall Islands, Micronesia, Nauru, New Caledonia, Niue, Palau, Papua New Guinea, Solomon Islands, Tonga, Tuvalu, Vanuatu, Wallis and Futuna, Western Samoa, Hong Kong, Macau, Taiwan, China
work great A+++++++++++++++++
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This is fake tablet use only 1gb ram and slow cant even handel youtube well.
It can't run games on emulators, and doesn't get all apps
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wrong description !! it is only 5 core !!

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Ston Easton: 2,168 properties found
3 Reasons to Visit: relaxation, tranquility & food
Surrounded by 36 acres of classical parkland southwest of Bath, Ston Easton exudes elegance, warmth and comfort. Enjoy glorious rooms, fine cuisine and large, beautiful grounds. Booked 2 times in the last 48 hours
This unique 15th-century inn is less than a mile from the center of Shepton Mallet. It offers an extensive menu and cozy log fires just a 15 minute drive from Glastonbury. Booked twice today
A small Victorian Gothic mansion in a beautiful part of Somerset, Beryl is just 1-mile from Wells Cathedral. A warm and friendly welcome awaits every guest in this family-run home. Booked twice today
The Redan Inn offers accommodations in Midsomer Norton. Guests can enjoy the on-site restaurant. Free WiFi is available throughout the property and free private parking is available on site. Booked 3 times in the last 48 hours
Located in historic Shepton Mallet, Longbridge House is close to the Somerset and Mendip Hills and just 2 minutes' walk from the High Street. Last booked: 10 hours ago
Featuring free WiFi throughout the property, The Old Stables Bed & Breakfast offers pet-friendly accommodations in Shepton Mallet. Free private parking is available on site. Latest Booking: July 25
Situated 8 miles from the historic city of Bath, the Carpenters Arms is in the tranquil and picturesque hamlet of Stanton Wick, overlooking the Chew Valley. Last booked: 48 minutes ago
A 25-minute drive from Bristol, Bath and Wells, Mezze at the Warwick Arms is a 19th-century inn offering Mediterranean-style food, a bar, free Wi-Fi and an outdoor children’s playground. Booked 3 times today
The Oakhill Inn is a traditional country pub with five elegant rooms based on the outskirts of Bath, allowing easy access to the historic city and surrounding attractions such as Cheddar Gorge and...
Set in a 15th century building in Croscombe, between Shepton Mallet and Wells, B&B The Cross at Croscombe offers bed and breakfast accommodation and a beautiful courtyard garden. Booked 2 times in the last 48 hours
A 15-minute walk from Shepton Mallet town centre and a 20-minute drive from Glastonbury, Bowlish House is a Grade II Georgian house with free Wi-Fi, a bar and a restaurant. Booked 3 times today
(5.8 miles from Ston Easton)
The Vobster Inn is surrounded by Somerset countryside, 5 miles from Frome and Radstock. The rooms with private bathrooms have flat-screen TVs and modern decor. Free Wi-Fi is available. Latest Booking: July 25
(4.9 miles from Ston Easton)
Featuring free WiFi, The Apple Shed offers accommodations in Farmborough. Free private parking is available on site. The rooms have a flat-screen TV. Latest Booking: July 20
2168 hotels found in or near Ston Easton.
140603,145180,141027,144783,143900,141613,132130,145104,142232,143209,144853,144783|5,144223,130895,143358|1,141432,144384,144783|7,140496,144167,140126,81283,144885,140623,143659,139619,141613|2,144045,144084,81283|2,140450,144972,130239,143073,145283,137962,145291,125468|1,145234,140525,142044|4,145161,144147,144450,145115,81283|3,142370,144506,131981,145414,143400,125468,137146,144584,145230,145207,144553,142735|4,144123,142683,135467,144636,144783|8,142683|3,144866,143398,142972,138421,143874,145476,143358,143065,144783|1,140867,143087,135780,142050|4

value: This website is a Dutch online travel agency for lodging reservations & other travel products, and a subsidiary of Booking Holdings. It is headquartered in Amsterdam.The website has over 28 million listings.


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Safavieh Handmade Museum Burgundy/ Multi N. Z. Wool Rug (8' x 11') - Overstock Shopping - Great Deals on Safavieh 7x9 - 10x14 Rugs
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The generous, hand-tufted pile of this handmade, wool rug is made from 100-percent wool. Soft and durable, its bold and spectacular design features deep jewel tones to accentuate any decor. Sturdy cotton canvas backing makes for years of use.
Museum rug makes a stylish and durable addition to any room Rug hand-tufted from 100-percent wool for comfort and softness Rug displays contemporary design in stunning gem tones of burgundy, rust, gold, green, and black Cotton canvas backing adds to the durability of your rug Professional cleaning recommended Measures 0.625 inch thickTip: We recommend the use of a non-skid pad to keep the rug in place on smooth surfaces. All rug sizes are approximate. Due to the difference of monitor colors, some rug colors may vary slightly. O.co tries to represent all rug colors accurately. Please refer to the text above for a description of the colors shown in the photo. Imported
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07 MAY 2007, HEALTH Coeliac disease
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text: Brett Connolly#14 RW6' 2", 193 lbsTampa Bay LightningBornMay 2, 1992 in Campbell River, British ColumbiaAge22Drafted2010: 1st Rnd, 6th by TBExperience3 years2014-15 SeasonGAPTS202Career81119Complete Stats »Go toBrett ConnollyPlayer ProfileStatsSplitsGame LogVideosPhotosShop Brett Connolly PicturesRALEIGH, NC - APRIL 04: Golkeeper Dan Ellis #31 of the Carolina Hurricanes stops a point-blank shot by Brett Connolly #14of the Tampa Bay Lightning during the first period at PNC Arena on April 4, 2013 in Raleigh, North Carolina. (Photo by Grant Halverson/Getty Images)Brett Connolly Photos »31 of 32

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