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    • 专利摘要:
    polymer-encapsulated opacifying pigment, process for forming polymer-encapsulated opacifying pigment, composition, and ink formulation. an opacific pigment is obtained: which includes a pigment particle having an average particle diameter of 0.005 microns to 5 microns and a refractive index of at least 1.8 such as, for example uncle ~ 2 ~ at least partially encapsulated in polymer . processes for forming the encapsulated pigment particle and compositions including the encapsulated pigment particle are also provided.
    公开号:BR112012022461B1
    申请号:R112012022461-1
    申请日:2010-11-01
    公开日:2020-03-03
    发明作者:Nathan T. Allen；Andrew G. Batzell；Karl A. Bromm；Ward T. Brown
    申请人:Rohm And Haas Company；
    IPC主号:
    专利说明:

    OPACIFICATING PIGMENT ENCAPSULATED IN POLYMER, PROCESS TO FORM AN OPACIFICATING PIGMENT ENCAPSULATED IN POLYMER, AND, COMPOSITION [1] This invention relates to an opacifying pigment particle encapsulated in polymer. More specifically, the invention relates to a polymer encapsulated opacifying pigment including a pigment particle having an average particle diameter of 0.005 microns to 5 microns and a refractive index of at least 1.8; from 0.1% to 25% by weight, based on the weight of the pigment particle, of the first water-soluble polymer functionalized with acid containing sulfur; and from 10% to 200%, by weight, based on the weight of the pigment particle, of a second polymer that at least partially encapsulates the pigment particle. The invention also relates to a process for forming the polymer encapsulated opacifying pigment and to compositions including the polymer encapsulated opacifying pigment.
    [2] Opacifying pigments provide whiteness, and opacity or "masking", to opacify coatings, such as paints, and on plastics. These pigments are present in most coatings that are designed to provide an opaque coating on and to cover by covering an underlying surface or a substrate surface on which the coating is applied. These pigments are also present in most plastics that are designed to be totally or partially opaque. In paints and plastics, an opacifying pigment is present in both white and colored paint. It is often desirable for opaque coatings, paints, and plastics to have a high opacification efficiency to allow the coating or paint to completely hide the underlying surface, even if it is of a strongly contrasting color, while using a minimum thickness of coating or paint, or plastic.
    Petition 870190125569, of 11/29/2019, p. 9/49
    2/36 [3] Coating, paint, and opacifying plastics manufacturers have long sought to formulate opaque coating, paint, and plastics having a desired opacity by maximizing the concealment level while minimizing the amount of opacifying pigment used. Without the desire to be bound by a specific theory, it is believed that the effectiveness of opacification is a function of the spacing between the particles of opacifying pigment in the coating or plastic. Maximum light scattering efficiency occurs when the opacifying pigment particles have an exact diameter and exact spacing, so that the light scattering ability of each particle does not interfere with the light scattering ability of its neighboring particles. This condition can occur in coatings and plastics containing sufficiently low levels of opacifying pigment such that the individual opacifying pigment particles are isolated from each other. Coatings and plastics containing such low levels of opacifying pigment, however, often do not provide sufficient opacity or gloss over a desirable thickness. Achieving desired levels of masking or opacity typically requires higher levels of opacifying pigment. At these higher levels, a statistical distribution of opacifying pigment particles occurs, which results in at least some of the opacifying pigment particles being in such close proximity to each other that there is a loss of light scattering efficiency due to the gathering of the opaque particles. opacifying pigment. Increased masking efficiency is achieved by reducing the clumping of the opacifying pigment particles and minimizing the formation of clusters of opacifying pigment particles. One method to achieve this is to encapsulate the opacifying pigment particles within a polymer matrix by polymerizing the polymer on the surface of the opacifying pigment particles.
    Petition 870190125569, of 11/29/2019, p. 10/49
    3/36 [4] US Patent Number 4,421,660 discloses inorganic solids encapsulated in a polymer matrix, the inorganic solids being encapsulated in a hydrophobic addition polymer by a polymerization process in which a water immiscible monomer is dispersed in an aqueous colloidal dispersion of inorganic particles and polymerized by an emulsion polymerization process. Before the emulsion polymerization process, the pigment particles are dispersed in water using dispersants or surfactants. Although this process has been described as giving pigment particles encapsulated in a polymeric material, the process developed using the disclosed dispersants and surfactants produces large amounts of gel, and is not viable.
    [5] It has been found that certain polymers functionalized with acid containing sulfur, when used as dispersants for certain particles of inorganic pigment, provide the encapsulation of the pigment particles via a viable emulsion polymerization process. The polymer-encapsulated opacifying pigment provides desirably high masking efficiency and is capable of being formed in an aqueous medium with low levels of debris.
    [6] According to a first aspect of the present invention, an opacifying polymer encapsulated pigment is obtained comprising: a pigment particle having an average particle diameter of 0.005 microns to 5 microns and a refractive index of at least 1.8; from 0.1% to 25% by weight, based on the weight of said pigment particle, of the first water-soluble polymer functionalized with acid containing sulfur; and from 10% to 200%, by weight, based on the weight of said pigment particle, of a second polymer that at least partially encapsulates said pigment particle.
    [7] According to a second aspect of the present invention, a process is provided to form an encapsulated opacifying pigment
    Petition 870190125569, of 11/29/2019, p. 11/49
    4/36 polymer comprising: (a) dispersing a pigment particle having an average particle diameter of 0.005 microns to 5 microns and a refractive index of at least 1.8 in a medium of 0.1% to 25% by weight, based on the weight of said pigment particle, of the first water-soluble polymer functionalized with sulfur-containing acid; and (b) carrying out an emulsion polymerization in the presence of said dispersed pigment particle to obtain from 10% to 200% by weight, based on the weight of said pigment particle, of a second polymer that at least partially encapsulates said pigment particle scattered.
    [8] According to a third aspect of the present invention, a composition is obtained comprising said polymer-encapsulated opacifying pigment formed by the process of the second aspect of the present invention.
    [9] According to a fourth aspect of the present invention, an ink formulation is obtained comprising an opacifying pigment encapsulated in a polymer whose pigment is present in a concentration of 5% to 25% by volume relative to the total volume of solids in the formulation .
    [10] The present invention also relates to an opacifying polymer encapsulated pigment. The opacifying pigment particle has an average particle diameter of 0.005 microns to 5 microns and a refractive index of at least 1.8. "Opacifier" here means that the particle produces opacity when subjected to light of a certain wavelength, not necessarily visible light. For example, certain nanoparticles included here provide opacity when subjected to light at wavelengths shorter than the visible range. The shape of the pigment particles is not important. Suitable shapes for the pigment particles include spherical shapes, such as a regular sphere, an oblate sphere, a prolate sphere, and an irregular sphere; shapes
    Petition 870190125569, of 11/29/2019, p. 12/49
    5/36 cubic such as a regular cube and a hole; plate-like shapes, including a flat plate, a concave plate, and a convex plate; and irregular shapes. The pigment particles having spherical shapes have average diameters within the range of 5 nm to 5 microns, preferably within the range of 150 nm to 500 nm, and more preferably, within the range of 200 nm to 350 nm. Pigment particles having non-spherical shapes preferably have average diameters, defined as their maximum dimension, from 5 nm to 5 microns, more preferably from 150 nm to 500 nm, and much more preferably from 200 nm to 350 nm. The average diameters of pigment particles are typically supplied by pigment particle suppliers.
    [11] Pigment particles are also characterized by the fact that they have a refractive index [n D (20 ° C)] that is at least 1.8, preferably at least 1.9, and more preferably at least 2.0 , up to no greater than 4.0. The refractive indices for various materials are listed in "CRC Handbook of Chemistry and Physics", 80th Edition, DR Lide, editor, CRC Press, Boca Raton, Florida, 1999, pages 4-139 to 4-146.
    [12] Suitable opacifying pigment particles include zinc oxide, antimony oxide, zirconium oxide, chromium oxide, iron oxide, lead oxide, zinc sulfide, lithoponium, and forms of titanium dioxide such as anatase and rutile . Preferably, the pigment particles are selected from titanium dioxide and lead oxide. More preferably, the pigment particles are selected from rutile titanium dioxide and anatase titanium dioxide. Most preferably, the pigment particles are rutile titanium dioxide. A coating containing two different forms of a material, such as rutile titanium dioxide and anatase, is considered to have two different pigments.
    [13] The pigment particles can have a uniform composition or a heterogeneous composition with two or more phases.
    Petition 870190125569, of 11/29/2019, p. 13/49
    6/36
    Certain heterogeneous pigment particles have an inner core and surrounding it a film structure in which one type of pigment particle forms the core and the other type of particle forms the film. The heterogeneous core and film pigment particles include core / film particles having a film completely or incompletely encapsulating the core; core / film particles having more than one core; dipolar particles; and particles having multiple domains of one phase on the surface of the other phase. Pigment particles, such as titanium dioxide, can have at least one coating of one or more of silica, alumina, zinc oxide, and zirconia. For example, in certain embodiments, titanium dioxide particles suitable for use in coatings of the present invention may have a silica coating and an alumina coating.
    [14] In the first aspect of the invention the polymer encapsulated opacifying pigment includes from 0.1% to 25%, preferably from 0.25% to 10%, more preferably from 0.5% to 5%, and much more preferably from 0.5% to 2% by weight, based on the weight of the pigment particle, of the first water-soluble polymer functionalized with sulfur-containing acid. Typically the pigment particles have been dispersed in a medium, preferably an aqueous medium, with the first water-soluble polymer functionalized with sulfur-containing acid. "Aqueous medium" here means water and from 0% to 30%, by weight based on the weight of the aqueous medium, of water-miscible compound (s). "Sulfur-containing acid-functionalized polymer" includes here any water-soluble polymer including at least three sulfur-containing acids. As used herein, the term "sulfur-containing acid-functionalized monomer" means that it includes any monomer containing at least one free radical polymerizable vinyl group, and at least one sulfur-containing acid. As used herein, the term "sulfur-containing acid" means that it includes any of the
    Petition 870190125569, of 11/29/2019, p. 14/49
    7/36 following residues: -S (O) 2 (OH), -OS (O) 2 (OH), -OS (O) (OH), -S (O) (OH). Also included in the definition of the term "sulfur-containing acid" are the salts of the above residues.
    [15] As used herein, the term "first sulfur-containing acid-functionalized water-soluble polymer" means that the first sulfur-containing acid-functionalized polymer is soluble in water at 25 ° C at a pH of less than or equal to 5 to an extent of at least 5% by weight.
    [16] The first sulfur-containing acid-functionalized polymer can be any of a polymer with at least three sulfur-containing acids located randomly in the polymer backbone, a single-block block copolymer including sulfur-containing acid and at least one block which has no sulfur-containing acids, or a comb graft polymer with a main chain that includes sulfur-containing acids and teeth that do not include sulfur-containing acids. Block copolymers can have the block including sulfur-containing acid located terminally in the polymer, or within the polymer chain. In a preferred embodiment of the present invention, the sulfur-containing acid-functionalized polymer contains both the amine and sulfur-containing acid groups. In this preferred embodiment of the present invention, it is further preferred that the polymer has at least two amine groups and three sulfur-containing acids, it is more preferred that the polymer has at least three amine groups and five sulfur-containing acids, it is much more preferred than the polymer have at least four amino groups and eight sulfur-containing acids. The number of amine and sulfur-containing acid groups can be the same or different. It is preferred that the ratio of amine groups to acids containing sulfur is between 10: 1 and 1:10, more preferred that the ratio of amine groups to acids containing sulfur is between 3: 1 and 1: 4, much more preferred than the ratio of amino groups for acids
    Petition 870190125569, of 11/29/2019, p. 15/49
    8/36 containing sulfur is between 1.5: 1 and 1: 3, on a molar basis. The sulfur-containing acid-functionalized polymer can be prepared as a polymer in solution in water or a non-aqueous solvent, or as a bulk polymer. The sulfur-containing acid-functionalized polymer can be prepared by any suitable polymerization process, such as polymerization by adding ethylenically unsaturated monomers such as acrylic, styrenic or vinyl monomers. Polymers containing both the amine and sulfur-containing acid groups can be prepared by copolymerizing at least one amine-functionalized monomer and at least one sulfur-containing acid-functional monomer, or can be prepared by including at least one monomer that is both functionalized with amine and functionalized with acid containing sulfur in the monomer mixture. As a further example, polymers that include both sulfur-containing amino and acid groups can be prepared by polymerization in addition to ethylenically unsaturated monomers, including in the mixture of functional monomers that can be converted to sulfur-containing amino or acid groups after the completion of the polymerization . Examples of monomers that can be converted to amines after completion of polymerization include isocyanate-functionalized monomers, which can be reacted with primary-tertiary diamines or secondary-tertiary diamines, epoxide-functionalized monomers that can be reacted with amines, and functionalized monomers with halo-methyl-benzyl which can be reacted with amines. Examples of monomers that can be converted to sulfur-containing acids after the completion of the polymerization include isocyanate-functionalized monomers, which can be reacted with amino sulfates. Block copolymers that include a block including sulfur-containing acid-functionalized polymer can be prepared by any known process that is capable of producing such polymers. Per
    Petition 870190125569, of 11/29/2019, p. 16/49
    For example, block copolymers include a block including sulfur-containing acid-functionalized polymer can be prepared by free radical live polymerization of ethylenically unsaturated monomers which monomer composition of one of the monomer feeds includes at least one unsaturated monomer functionalized with sulfur-containing acid. As an additional example, block copolymers include a block including sulfur-containing acid-functionalized polymer can be prepared by free radical radical polymerization of ethylenically unsaturated monomers, including in the mixture of functional monomers that can be converted to sulfur-containing acids after the completion of the polymerization . Comb graft polymers that include a main chain including sulfur-containing acid-functionalized polymer can be prepared by any known process that is capable of producing such polymers. For example, comb graft polymers that include a main chain including sulfur-containing acid-functionalized polymer can be prepared by free radical polymerization of ethylenically unsaturated monomers in which the monomer composition includes at least one unsaturated macromer and at least one unsaturated functionalized monomer with sulfur-containing acid. As a further example, comb graft polymers that include a main chain including sulfur-containing acid-functionalized polymer can be prepared by free radical radical polymerization of ethylenically unsaturated monomers, including in the mixture of functional monomers that can be converted to sulfur-containing acids after completeness of polymerization. It is preferred that the sulfur-containing acid-functionalized polymer is a linear random copolymer.
    [17] The sulfur-containing acid-functionalized polymer is typically prepared by polymerization in addition to ethylenically unsaturated monomers. Suitable monomers include styrene,
    Petition 870190125569, of 11/29/2019, p. 17/49
    10/36 butadiene, alpha-methyl-styrene, vinyl-toluene, vinyl-naphthalene, ethylene, propylene, vinyl acetate, vinyl versatate, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, (meth) acrylamide, several C1 -C40 alkyl esters of (meth) acrylic acid; for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate of n-octyl, (meth) ndecyl acrylate, (meth) n-dodecyl acrylate, (meth) n-tetradecyl acrylate, (meth) lauryl acrylate, (meth) oleyl acrylate, (meth) palmitil acrylate , and stearyl (meth) acrylate; other (meth) acrylates such as (meth) isobornyl acrylate, (meth) benzyl acrylate, (meth) phenyl acrylate, (2) bromo-ethyl acrylate, (meth) 2-phenyl ethyl acrylate, and ( meth) 1-naphthyl acrylate, alkoxy-alkyl (meth) acrylate, such as ethoxy-ethyl (meth) acrylate, mono-, di-, trialkyl esters of ethylenically unsaturated anhydrides and di- and tricarboxylic acids such as maleate ethyl, dimethyl fumarate, trimethyl itaconate, and ethyl and methyl itaconate; alcohol-containing monomers such as hydroxy-ethyl (meth) acrylate, hydroxy-propyl (meth) acrylate, hydroxy-butyl (meth) acrylate; monomers containing carboxylic acid, such as (meth) acrylic acid, itaconic acid, fumaric acid, and maleic acid. Examples of sulfur-containing acid functionalized monomers include sulfo-ethyl (meth) acrylate, sulfo-propyl (meth) acrylate, styrenesulfonic acid, vinyl-sulfonic acid, and 2- (meth) acrylamido-2-methyl-propanesulfonic acid, and its salts. Examples of suitable amine functionalized monomers include dimethyl-amino-ethyl (meth) acrylate, dimethyl-aminopropyl- (meth) acrylamide, and t-butyl-amino-ethyl (meth) acrylate. As used herein, the term "(meth) acrylate" refers to either acrylate or methacrylate and the term "(meth) acrylic" refers to either acrylic or methacrylic.
    [18] The random copolymer functionalized with sulfur-containing acid, the block including sulfur-containing acid from the block copolymer, or the main chain including sulfur-containing acid from the graft polymer
    Petition 870190125569, of 11/29/2019, p. 18/49
    Comb 11/36 can have an average molecular weight of 1,000 to 200,000, preferably 1,000 to 50,000, more preferably 2,000 to 15,000, and much more preferably 3,000 to 10,000. When the sulfur-containing acid-functionalized polymer is a block copolymer or a comb graft polymer, the block (s) or teeth not including sulfur-containing acid, respectively, may have an average molecular weight of 750 to 200,000, more preferably from 1,000 to 50,000, more preferably from 1,500 to 25,000, and much more preferably from 5,000 to 15,000. Molecular weights can be determined by GPC.
    [19] The pigment particles may be dispersed in an aqueous medium with water-soluble polymer functionalized with sulfur-containing acid. The sulfur-containing acid-functionalized polymer can be made water-soluble by including sufficient amine groups or sulfur-containing acids, as well as by including sufficient levels of copolymerized water-soluble monomers such as alcohol-functionalized monomers such as (meth) acrylate hydroxy-ethyl; amide functionalized monomers such as (meth) acrylamide; acid functionalized monomers such as (meth) acrylic acid; or their combinations. The levels of water-soluble monomers needed to make the polymer functionalized with sulfur-containing acid or polymer block or water-soluble teeth will depend on the molecular weight and nature of the comonomers included in the composition of the sulfur-containing acid functionalized polymer, blocks, or teeth , as is known in the art. When the sulfur-containing acid-functionalized polymer is a block copolymer or a comb graft polymer, it is preferred that the blocks or teeth not including acid containing sulfur, respectively, are themselves soluble in water.
    [20] The polymer encapsulated opacifying pigment of the present invention includes 10% to 200% by weight, based on the weight of the
    Petition 870190125569, of 11/29/2019, p. 19/49
    12/36 pigment, a second polymer that at least partially encapsulates the pigment particle. The second polymer is typically prepared by free radical emulsion polymerization of ethylenically unsaturated monomers in the presence of the pigment particle that has been dispersed in a medium. In some embodiments, the second polymer is made of a mixture of monomers containing at least one water-soluble monomer. Examples of suitable water-soluble monomers are acid functionalized monomers such as 2-sulfo-ethyl (meth) acrylate, sulfo-propyl (meth) acrylate, styrene-sulfonic acid, vinyl-sulfonic acid, 2 (meth) acrylamido- 2-methyl-propane-sulfonic, acrylic acid, methacrylic acid, itaconic acid and its salts. Other suitable water-soluble monomers are acrylamide, diacetone-acrylamide, 2-hydroxy-ethyl methacrylate and 2-hydroxy-ethyl acrylate.
    [21] "At least partially encapsulated" here means that the second polymer is in contact with at least part of the surface of the pigment particle. The degree of encapsulation of the pigment particle can be determined using an electron micrograph. Determination of the degree of encapsulation does not include any contribution from the first polymer, surfactant, dispersant, or the like. "X% encapsulated" here means that X% of the surface area of the pigment particle is in contact with the second polymer; preferably more than 50%, more preferably more than 75%, and much more preferably 100% of the particle's surface area is in contact with the second polymer. The thickness of the second polymer film or encapsulating layer can be up to 500 nm; for T1O2 pigment, for example, preferred thickness of the second polymer encapsulating film or layer is typically between 20 nm and 150 nm, preferably 40 to 100 nm.
    [22] In one aspect of the present invention the process for forming an opaque polymer encapsulated pigment includes: (a) dispersing a
    Petition 870190125569, of 11/29/2019, p. 20/49
    13/36 pigment particle having an average particle diameter of 0.005 microns to 5 microns and a refractive index of at least 1.8 in a medium of 0.1% to 25% by weight, based on the weight of the particle of pigment, of the first water-soluble polymer functionalized with acid containing sulfur; and (b) carrying out an emulsion polymerization in the presence of the dispersed pigment particle to obtain 10% to 200% by weight, based on the weight of said pigment particle, of a second polymer that at least partially encapsulates said dispersed pigment particle .
    [23] One step in this process of the present invention is to disperse the opacifying pigment particles in a medium, preferably an aqueous medium, with a water soluble polymer functionalized with sulfur-containing acid. The dispersion step can be carried out by any means commonly used to disperse pigments in an aqueous medium, including, for example, grinding with a high speed disperser, or grinding in media mills or ball mills. The weight of the water-soluble polymer functionalized with acid containing sulfur based on the weight of the pigment particle can vary from 0.1% to 25%, preferably from 0.25% to 10%, more preferably from 0.5% to 5% , and much more preferably from 0.5% to 2%.
    [24] In any case, the opacifying pigment dispersion must have sufficient stability during storage (substantially maintaining the same particle size, no or minimal sediment formation) and must have sufficient stability to resist flocculation during the second polymer encapsulation process . During the initial stages of the encapsulation process the stabilization mechanism will typically change from a surface stabilized by dispersant at a first pH to a polymer surface stabilized by surfactant at a lower pH. It is believed that while this change is taking place there will inevitably be an interval in which dispersant stabilization is
    Petition 870190125569, of 11/29/2019, p. 21/49
    14/36 reduced and if the stabilization is very weak then T1O2 particles flocculation will occur.
    [25] A step in the process of the present invention includes at least partially encapsulating the dispersed pigment particles with from 10% to 200% by weight, based on the weight of the pigment particle, of the second polymer by carrying out an emulsion polymerization in the presence of the dispersed pigment particle. Alternatively, it is contemplated that the dispersion of polymer particles can be dried or partially dried and dispersed again in an aqueous medium before encapsulation.
    [26] Emulsion polymerization can be carried out by methods well known in the polymer art, and includes multi-stage polymerization processes. Various synthetic adjuvants such as initiators, chain transfer agents, and surfactants are optionally used in polymerization. In general, emulsion polymerization is a seed-type emulsion polymerization, with the dispersed pigment particles acting as the seeds. In one embodiment of the present invention, the reaction vessel is charged with water, dispersed pigment, and optionally surfactants and other polymerization aids, and then the monomers for the second polymer are added to the vessel. In another embodiment of the present invention, the reaction vessel is charged with water, dispersed pigment, and optionally surfactants and other polymerization aids, and then a portion of the monomers for the polymer matrix is added to the vessel, and then a seed consisting of emulsified polymer particles, prepared separately, are added, and finally the rest of the monomer for the polymer matrix is added to the vessel. In yet another embodiment of the present invention, the reaction vessel is loaded with water, and optionally surfactants and other polymerization aids and optionally a polymer seed, so a portion of the monomers for the polymer matrix is added to the vessel, then the pigment scattered
    Petition 870190125569, of 11/29/2019, p. 22/49
    15/36 is added to the vessel, and finally the remainder of the monomer to the polymer matrix is added to the vessel. Polymerization can be carried out as a one-step process, or by using multiple steps, or by continuous monomer feed over time. The monomer can be added pure or emulsified in water with an appropriate surfactant. For the process to be considered acceptable here it must be able to be carried out at a final volume solids level of 40% by volume or higher, preferably by 45% by volume or higher, preferably by 45% by volume, with less than 1.0% by weight, based on the weight of total solids, of debris formation.
    [27] In a preferred embodiment of the present invention, the second polymer includes at least one sulfur-containing acid-functionalized monomer. Examples of sulfur-containing acid functionalized monomers include sulfo-ethyl (meth) acrylate, sulfopropyl (meth) acrylate, styrene-sulfonic acid, vinyl-sulfonic acid, and 2 (meth) acrylamido-2-methyl-propane-sulfonic acid , and its salts. Preferably the sulfur-containing acid-functionalized monomer is styrenesulfonic acid or its salt.
    [28] The sulfur-containing acid-functionalized monomer may be present at a level of 0.1% to 20% by weight of the monomers used to prepare the second polymer containing the sulfur-containing acid-functionalized monomer, preferably from 0.25% to 10%, more preferably from 0.25% to 5%, much more preferably from 0.5% to 2%. If the second polymer contains more than one polymer phase, then the sulfur-containing acid-functionalized monomer may be present in only some or all of the polymer phases. If the second polymer contains more than one polymer phase, it is preferable that the sulfur-containing acid functionalized monomer is present in the first polymer stage to be polymerized.
    Petition 870190125569, of 11/29/2019, p. 23/49
    16/36 [29] Polymerization of monomers to the second polymer is carried out by the addition of a polymerization initiator. The polymerization initiator can be added to the vessel before adding monomer, or concurrently with adding monomer, after adding monomer, or as a combination thereof. Examples of suitable polymerization initiators include polymerization initiators that thermally decompose at the polymerization temperature to generate free radicals. Examples include both water-soluble and water-insoluble species. Examples of suitable free radical generating initiators include persulfates, such as ammonium and alkali metal persulfates (potassium, sodium, and lithium); azo compounds, such as 2,2'-azo-bis (isobutyronitrile), 2,2'azo-bis (2,4-dimethyl-valeronitrile), and t-butyl-azo-cyano-cyclohexane; hydroperoxides, such as t-butyl hydro-peroxide and cumene hydro-peroxide; peroxides, such as benzoyl peroxide, caprylil peroxide, di-t-butyl peroxide, 3,3'-di- (t-butyl-peroxy) -butyrate, 3,3'-di (t-amyl- peroxy) ethyl butyrate, t-amyl peroxy-2-ethylhexanoate, and tbutyl peroxy-pivalate; peresters, such as t-butyl peracetate, t-butyl perftalate, and t-butyl perbenzoate; as well as percarbonates, such as di (1-cyano-1-methyl-ethyl) peroxydicarbonate; and phosphates.
    [30] Polymerization initiators can be used alone, and alternatively, as the oxidizing component of a redox system, which also includes a reducing component, such as an acid selected from the group consisting of: ascorbic acid, malic acid, glycolic acid, oxalic, lactic acid, and thio-glycolic acid; an alkali metal sulfite, typically a hydrosulfite, such as sodium hydrosulfite; a hyposulfite, such as potassium hyposulfite; or a metabisulfite, such as potassium metabisulfite; and sodium formaldehyde sulfoxylate.
    [31] Adequate levels of initiator and optional reducing component include proportions of 0.001% to 5% of each, based on the weight of the
    Petition 870190125569, of 11/29/2019, p. 24/49
    17/36 monomers of the monomer mixture to be polymerized. Accelerators such as cobalt, iron, nickel, and copper chloride and sulfate salts are generally used in small amounts. Examples of redox catalytic systems include t-butyl hydro-peroxide / sodium formaldehyde / sulfoxylate / Fe (II), and ammonium persulfate / sodium bisulfite / sodium hydrosulfite / Fe (II).
    [32] Chain transfer agents are optionally added to the aqueous reaction medium to control the molecular weight of the second polymer. Examples of chain transfer agents include mercaptans, polymercaptans, and polyhalogen compounds. Examples of suitable chain transfer agents include alkyl mercaptans, such as ethyl mercaptan, n-propyl mercaptan, n-butyl mercaptan, isobutyl mercaptan, t-amyl mercaptan, n-hexyl mercaptan, cyclohexyl mercaptan , n-octyl-mercaptan, n-decyl-mercaptan, n-dodecyl-mercaptan; 3mercapto-propionic acid; 2-hydroxy-ethyl-mercaptan; alcohols, such as isopropanol, isobutanol, lauryl alcohol, and t-octyl alcohol; and halogenated compounds, such as carbon tetrachloride, tetrachloro-ethylene, and trichlorobromo-ethane. Generally, 0% to 10% chain transfer agent, by weight based on the weight of the monomer, is used to prepare the second polymer. Other techniques for controlling molecular weight, known in the art, include selecting the ratio of the amount of initiator to the amount of total monomer.
    [33] Catalyst and / or chain transfer agent are optionally dissolved or dispersed separately or in the same fluid medium, and gradually added to the polymerization vessel. Monomer, pure, dissolved, or dispersed in a fluid medium, is optionally added simultaneously with the catalyst and / or the chain transfer agent.
    [34] Emulsion polymerization reaction medium typically
    Petition 870190125569, of 11/29/2019, p. 25/49
    18/36 contains surfactant to stabilize the encapsulated particles with second polymer growing during polymerization and to discourage the aggregation of the polymer encapsulated pigment particles in the resulting aqueous dispersion. One or more surfactants are commonly used, including anionic and nonionic surfactants, and mixtures thereof. Many examples of surfactants suitable for emulsion polymerization are presented in “McCutcheon’s Detergents and Emulsifiers” (MC Publishing Co. Glen Rock, NF), published annually. Other types of stabilizing agents, such as protective colloids, are optionally used. However, it is preferred that the amount and type of stabilizing surfactant or other type of stabilizing agent used during the polymerization reaction are selected so that the residual stabilizing agent in the resulting aqueous dispersion does not significantly interfere with the properties of the aqueous dispersion, the properties of compositions including the aqueous dispersion, or articles prepared from the aqueous dispersion.
    [35] Suitable anionic surfactants include, for example, alkali alcohol-fatty sulfates, such as sodium lauryl sulfate; aryl-alkylsulfonates, such as potassium isopropyl-benzene-sulfonate; alkali alkyl sulfosuccinates, such as sodium octyl-sulfo-succinate; and aryl-alkylpolyethoxy-ethanol-sulfates or alkali sulfonates, such as sodium octyl-phenoxypolyethoxy-ethyl-sulfate, having 1 to 5 units of oxy-ethylene.
    [36] Suitable non-ionic surfactants include, for example, alkyl-phenoxy-polyethoxy-ethanols having alkyl groups of 7 to 18 carbon atoms and 6 to 60 oxy-ethylene units, such as, for example, heptylphenoxy-polyethoxy- ethanols; ethylene oxide derivatives of long-chain carboxylic acids, such as lauric acid, myristic acid, palmitic acid, oleic acid, or mixtures of acids, such as those found in talol, containing from 6 to 60 units of oxy-ethylene; condensates of ethylene oxide from long-chain alcohols such as octyl-, decyl-, lauryl- or cetyl-alcohols,
    Petition 870190125569, of 11/29/2019, p. 26/49
    19/36 containing from 6 to 60 oxy-ethylene units; and block copolymers of ethylene oxide sections combined with one or more propylene oxide sections. High molecular weight polymers, such as hydroxy-ethyl-cellulose, methyl-cellulose, and poly (vinyl-alcohol), are also usable.
    [37] In a preferred embodiment of the present invention the dispersed pigment particles are further stabilized with certain surfactants prior to the introduction of any monomers used to prepare the second polymer. These surfactants include the family of sulfo-succinic acid esters of the formula R — OC (O) CH 2 CH (SO3H) C (O) OR ', in which R and R' may be alkyl, aryl, ally, vinyl, styrene , or (meth) acryl, or H, and in which R and R 'can be the same or different, except that both R and R' cannot be H. Preferably, R is C 6 to C 6 alkyl and R 'is ally. It has been found that the use of such surfactants in the described manner allows emulsion polymerization to be carried out with much lower levels of gel than results when no surfactant is used, or when other surfactants are used.
    [38] After the completion of the emulsion polymerization, the polymer encapsulated pigment particles can be obtained as an aqueous dispersion, or alternatively, they can be obtained as a solid in the form of a powder or a globule. The polymer encapsulated pigment particles can be removed from the aqueous medium of emulsion polymerization by any appropriate technique including, for example, evaporative drying, spray drying, filtration, centrifugation or coagulation. When the polymer encapsulated pigment particles are obtained as a solid, it is preferred that the Tg of the second polymer, or the Tg of the outermost phase of the second polymer in the case in which the second polymer contains multiple phases, be above the temperature at which the polymer-encapsulated pigment particles will be stored, transported, and optionally processed before final application.
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    20/36 [39] The composition of the present invention including the opacifying pigment encapsulated in the second polymer of the invention is typically a coating or a plastic. Optionally, the coating or plastic also includes one or more extender particles, secondary pigment particles, and third polymers.
    [40] The coating or plastic binder of the present invention is the continuous medium containing the polymer encapsulated pigment particles. The binder can consist only of the second polymer that encapsulates the pigment particles, or it can be a mixture of the second encapsulating polymer and one or more third polymers. Both the second polymer and the third polymer are independently, alternatively a homopolymer, a copolymer, an interpenetrating network polymer, and a mixture of two or more polymers or copolymers. Suitable third polymers include acrylic (co) polymers, vinyl acetate polymers, vinyl / acrylic copolymers, styrene / acrylic copolymers, polyurethanes, polyureas, polyepoxides, poly (vinyl chlorides), ethylene / vinyl acetate polymers, styrene polymers / butadiene, polyester polymers, polyethers, and the like, and mixtures thereof.
    [41] In one embodiment the binder can be a mixture of a polymer and a prepolymeric material. The polymer-encapsulated pigment particles are alternatively obtained in a liquid medium such as an organic solvent or water, or a mixture of organic solvents and water, or are obtained as a solid, such as a powder. The optional third polymer is alternatively obtained in a liquid medium such as a polymer in solution, an emulsion polymer, or a polymer in suspension, or is obtained as a solid, such as a polymeric powder or an extrusion polymer. Either or both of the second polymer of the polymer encapsulated pigment or the optional third polymer may contain reactive groups, which under formation of a coating film or
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    21/36 finished plastic part or later, crosslink either with themselves or with externally added crosslinking agents to give a crosslinked binder. Examples of prepolymeric materials are ethylenically unsaturated monomers and oligomers, and two-part crosslinking systems such as compositions containing isocyanate groups and alcohol groups. Conventional crosslinking agents such as, for example, polyaziridine, polyisocyanate, polycarbodiimide, polyoxide, polyaminoplast, poly (alkoxy silane), polyoxazoline, polyamine, and a polyvalent metal compound can be used as externally added crosslinking agents. Typically, from 0% to 25% by weight of crosslinker is used, based on the dry weight of the polymer.
    [42] The polymers that form the binder typically have glass transition temperatures within the range of -60 ° C to 150 ° C, as calculated by Fox's equation [Bulletin of the American Physical Society 1, 3 Page 123 (1956)] . The coating or plastic composition optionally contains coalescents or plasticizers to obtain the polymers with effective film-forming temperatures at or below the temperature at which the coating is applied or cured, or the plastic part is formed. The optional coalescent level is typically within the range of 0% to 40% by weight, based on the weight of the polymer solids.
    [43] In a preferred embodiment of the present invention, the second polymer contains at least two phases, with a second polymer phase having a Tg greater than or equal to 30 ° C, preferably greater than or equal to 45 ° C , and at least one second polymer phase has a Tg less than or equal to 12 ° C, preferably less than or equal to 0 ° C, much more preferably less than or equal to -5 ° C. In this embodiment of the present invention, the second polymer phase can be between 5% and 50%, preferably between 10% and 40%, and much more preferably between 15% and 30%, by weight based on the particle weight of
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    22/36 pigment. The total weight of the remainder of the polymer phases of the second polymer can be between 5% and 150%, preferably between 10% and 125%, much more preferably between 20% and 100%, by weight based on the weight of the pigment particle.
    [44] In a preferred embodiment of the present invention, the second polymer contains at least two phases, the first polymer phase to be polymerized containing a multifunctional monomer to crosslink that phase. Suitable multifunctional monomers include, for example, allyl (meth) acrylate, divinyl-benzene, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylol-propane tri (meth) acrylate, tri glycerol (met) acrylate, and ethylene glycol poly (di (met) acrylate). The multifunctional monomer can be present from 0.01% to 50% by weight based on the total weight of the monomers that make up the first phase of the second polymer, preferably the multifunctional monomer is 0.1% to 10%, more preferably from 0.2 % to 5%, much more preferably from 0.2% to 2% of the first monomer phase. In this embodiment of the present invention, it is preferred that all phases of the second polymer have a Tg less than or equal to 5 ° C, preferably less than or equal to -5 ° C. In this embodiment of the present invention, the first phase of the second polymer can be between 5% and 50%, preferably between 10% and 40%, and much more preferably between 15% and 30%, by weight based on the weight of the pigment particle. The total weight of the remainder of the polymer phases of the second polymer can be between 5% and 150%, preferably between 10% and 125%, much more preferably between 20% and 100%, by weight based on the weight of the pigment particle.
    [45] The coating or plastic of this invention optionally contains extender particles. The extending particles do not significantly scatter light. The extending particles have a refractive index of less than 1.8 and typically greater than or equal to 1.3. Particles
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    Suitable extenders include calcium carbonate, calcium sulfate, barium sulfate, mica, clay, calcined clay, feldspar, nepheline, syenite, wollastonite, diatomaceous earth, alumina-silicates, non-film-forming polymer particles, oxide aluminum, silica and talc. Other examples of extenders include solid bead extenders, also known in the art as solid bead pigments, such as polystyrene and poly (vinyl chloride) beads.
    [46] The coating or plastic of this invention optionally contains particles of secondary pigment. The secondary pigment particles have a lower refractive index than the polymer matrix refractive index. Secondary pigment particles include pigment particles containing air voids, such as polymer particles containing air voids. The air void is characterized by the fact that it has a refractive index close to or equal to 1. Secondary pigment particles including microspherical pigments such as polymer particles containing one or more voids and vesiculated polymer particles are disclosed in US Patent.
    4,427,835; Patent US 4,920,160; Patent US 4,594,363; Patent US 4,469,825; Patent US 4,468,498; Patent US 4,880,842; Patent US 4,985,064; Patent US 5,157,084; Patent US 5,041,464; Patent US
    5,036,109; US patent 5,409,776; and US Patent 5,510,422.
    [47] The coating or plastic of this invention contains from 1% to
    50% by volume of pigment particles in the form of polymer encapsulated pigment particles, preferably from 3% to 30% by volume, and more preferably from 5% to 20% by volume, based on the total volume of the coating or plastic. The coating or plastic contains from 10% to 99% by volume of second and third polymers, preferably from 20% to 97% by volume, and more preferably from 25% to 80% by volume, based on the total volume of the coating or plastic. The coating or plastic contains from 0% to 70% by volume of extender particles, preferably from
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    0% to 65% by volume, and more preferably 0% to 60% by volume, based on the total volume of the coating or plastic. The coating or plastic contains from 0% to 20% by volume of secondary pigment particles, preferably from 0% to 17% by volume, and more preferably from 0% to 15% by volume, based on the total volume of the coating or plastic.
    [48] The coating composition of the present invention can optionally also include other materials commonly found in coatings such as extenders, other polymers, hollow spherical pigments, solvents, coalescing agents, wetting agents, defoamers, rheology modifiers, crosslinkers, dyes, agents perolescents, adhesion promoters, dispersants, leveling agents, optical brighteners, ultraviolet stabilizers, preservatives, biocides, and antioxidants.
    [49] Examples of “coatings” here include writing inks, paper coatings; architectural coatings, such as interior and exterior paints for houses, wood coatings and metal coatings; leather coverings; coatings and saturation agents for textile and non-woven materials; stickers; powder coatings; and traffic inks such as those used to mark highways, pavements, and runways. Liquid coatings can be based on water or solvent. When the coating is a powder coating, it is preferred that the Tg of the polymer matrix, or the Tg of the outermost phase of the polymer matrix in the case in which the polymer matrix contains multiple phases, is above the temperature at which the coating it will be stored, transported, and optionally processed before final application. When the coating is a solvent based coating, it is preferred that the second polymer of the polymer encapsulated pigment particles is not substantially soluble in the solvent or in the solvent mixture used in the coating.
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    25/36
    [50] The plastic of the present invention can optionally also
    include other materials commonly found in plastics such as pigment particles that do not fall within the present invention, extenders, other polymers, hollow spherical pigments, plasticizers, flow agents, and crosslinkers. “Plastics” here include solid or flexible materials in the form of objects, films, etc.
    [51] The following examples illustrate aspects of this
    invention. The abbreviation "g" stands for "grams". The abbreviation "mm" stands for "millimeters". The abbreviation "cm" stands for "centimeters". The abbreviation “thousand” represents “1 / 1,000 of an inch (25.40 microns)”. Abbreviations:
    SDS = Sodium dodecyl-benzene sulfonate (23%) SSS = Styrene sodium sulfonate
    TREM ™ LF-40 = Sodium dodecyl-allyl-sulfo-succinate (40%)
    t-BHP = T-Butyl hydro-peroxide AIBN = Azo-isobutyronitrile SSF = Sodium formaldehyde sulfoxylate IAA = Isoascorbic acid EDTA = Sodium salt of ethylene-diamino-tetraacetic acid
    (VERSENE ™)
    nDDM = n-Dodecyl-mercaptan BMA = Butyl methacrylate BA = Butyl acrylate MM A = Methyl methacrylate
    DMAEMA = Dimethyl-amino-ethyl methacrylate
    AMPS ™ = 2-acrylamido-2-methyl-propane-sulfonic acid STY = Styrene MSi = 3-Mercapto-propyl-trimethoxy-silane MAA = Glacial methacrylic acid
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    SEM = Sulfo-ethyl methacrylate water DI = Deionized water
    EXAMPLE 1. Preparation of the first water-soluble polymer functionalized with sulfur-containing acid [52] A 250 mL flask equipped with a magnetic stirrer, N2 inlet, reflux condenser, heating mantle, and thermocouple was loaded with 20 g of SEM , 4 g DMAEMA, 10 g BA, 16 g MMA,
    1.1 g of nDDM, 0.5 g of AIBN, and 100 g of n-propanol. The flask was purged with N 2 , and heated to 60 ° C, at which point the heating mantle was turned off and the reaction mixture was allowed to perform exotherm to 80 ° C. The heating mantle was switched on again and the reaction mixture was kept at 80 ° C for 3 hours. The temperature was then raised to 93 ° C, and 0.25 g of AIBN in 2.0 g of n-propanol was added. The temperature was maintained at 93 ° C for 1 h; then the flask was cooled to room temperature. The product was poured into 100 ml of hexane, then the solid polymer was collected and dried. The dry polymer was dissolved in sufficient water and NH 3 to prepare a 21.3% solution with pH 5.0.
    EXAMPLE 2. Preparation of the first water-soluble polymer functionalized with sulfur-containing acid [53] A mixture of monomers such as 20 g AMPS ™, 4 g DMAEMA, 10 g BA, 16 g MMA, 1.1 g of nDDM, 20.66 g of ethanol, and 6.88 g of water. A 250 mL flask equipped with a magnetic stirrer, N2 inlet, reflux condenser, heating mantle, addition funnel, and thermocouple was loaded with 0.5 g of VAZO ™ 52, 27.51 g of monomer solution, 5.9 g of water, and 17.67 g of ethanol. The flask was purged with N2, and heated to 55 ° C, at which point the heating mantle was turned off and the reaction mixture was allowed to perform exotherm to 70 ° C. The heating blanket was switched on again and the rest of the monomer solution was added over 30 min while
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    The temperature was maintained at 70 ° C. After the completion of the addition of the monomer solution, the reaction mixture was maintained at 70 ° C for 0.5 hour. The temperature was then raised to 77 ° C, and 0.5 g of VAZO ™ 52 in 10 g of ethanol was added. The temperature was maintained at 77 ° C for 1 h, then the flask was cooled to room temperature and the solvent was extracted. The dry polymer was dissolved in sufficient water and NH 3 to prepare a 21.0% solution with pH 4.0
    EXAMPLE 3. Preparation of the first water-soluble polymer functionalized with sulfur-containing acid [54] In a 3-liter bottle of 1 liter containing 300 g of denatured ethanol, 40 g of BA, 90 g of MMA, and 70 g of WITHOUT. Then, 4.2 g of n-DDM was added via pipette, and 2.72 g of VAZO ™ 52 primer. The combined solution was placed under positive pressure of nitrogen and heated to 60 ° C for 4 hours. After this time 1 g of VAZO ™ 52 was added to eliminate unreacted monomer. The reaction was then cooled to room temperature. The solids were determined three times by removing volatiles in a vacuum oven, 60.1%. The product was poured into 100 ml of hexane; then the solid polymer was collected and dried. The dry polymer was dissolved in sufficient water and NH 3 to prepare a 10% solution with pH 4.0
    COMPARATIVE EXAMPLE A. Preparation of acid functionalized polymer containing sulfur [55] A 1 liter glass reactor was charged with 158.59 g of ethanol. Under a nitrogen atmosphere the reactor was heated to 75 ° C. When the reactor reached 75 ° C a monomer feed consisting of 58.83 g of ethanol, 2.05 g of VAZO ™ -52, 6.02 g of n-DDM, 127.87 g of MMA and 22.56 g SEM was fed into the reactor for a period of 2 hours and 52 minutes. A temperature of 75 ° C ± 2 ° C was maintained throughout the process. At the end of the monomer feed a solution
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    28/36 of 1.50 g of VAZO ™ -52 dissolved in 22.58 g of ethanol was fed into the reactor for a period of 28 minutes. At the end of this feeding, the temperature was maintained at 75 ° C ± 2 ° C for another 40 minutes before cooling. Final solids of the product was 39.7%. The dry dispersant was not soluble in water at or below pH 5.
    COMPARATIVE EXAMPLE B. Preparation of acid functionalized polymer containing sulfur [56] A 1 liter glass reactor was charged with 158.59 g of ethanol. Under a nitrogen atmosphere the reactor was heated to 75 ° C. When the reactor reached 75 ° C, a monomer feed consisting of 58.83 g of ethanol, 2.05 g of VAZO ™ -52, 6.02 g of n-DDM, 100.79 g of MMA, 9.03 g of SEM and 40.62 g of AA was fed into the reactor for a period of 2 hours and 52 minutes. A temperature of 75 ° C ± 2 ° C was maintained throughout the process. At the end of the monomer feed a solution of 1.50 g of VAZO ™ -52 dissolved in 22.58 g of ethanol was fed into the reactor over a period of 28 minutes. At the end of this feeding, the temperature was maintained at 75 ° C ± 2 ° C for another 40 minutes before cooling. Final solids of the product was 40.4%. The dry dispersant was not soluble in water at or below pH 5. An aqueous solution of the dry dispersant was prepared by adding sufficient NH 3 to neutralize all acidic groups of MAA and SEM; the pH was greater than 6.
    COMPARATIVE EXAMPLE C. Preparation of non-functionalized polymer with sulfur-containing acid [57] A 250 ml flask equipped with a magnetic stirrer, N2 inlet, reflux condenser, heating mantle, and thermocouple was loaded with 7.75 g of MAA , 10 g BA, 32.25 g MMA, 1.08 g nDDM, 0.5 g AIBN, and 92.5 g n-propanol. The flask was purged with N2, and heated to 65 ° C, at which point the heating blanket was disconnected and the reaction mixture was allowed to perform exotherm to 80 ° C. The heating blanket was connected
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    29/36 new and the reaction mixture was kept at 80 ° C for 3 hours. The temperature was then raised to 93 ° C, and 0.25 g of AIBN in 2.5 g of n-propanol was added. The temperature was maintained at 93 ° C for 1 h; then the flask was cooled to room temperature. The dry dispersant was not soluble in water at or below pH 5. In the dry dispersant, 90.17 grams of deionized water and 20.86 grams of ammonia (2.8%) were added. The dispersant formed a clear solution after about 15 minutes of stirring at room temperature. The theoretical solids of this dispersant solution were 7.5%. The measured pH was 9.0.
    EXAMPLE 4. Formation of opacifying pigment dispersion [58] A grinding steel container was loaded with 31.7 g of Example 1 and 95.2 g of water. 450 g of TiO 2 (TIPURE ™ R-706) was added slowly while milling at -2,000 rpm using a Premier Mill Corp disperser. Model 50 equipped with a discoid blade. After adding TiO 2 , the slurry was ground for 20 min; then an additional 11.3 g of water was added. The solids were 76.5%.
    EXAMPLE 5. Formation of opacifying pigment dispersion [59] A grinding steel container was loaded with 71.6 g of Example 2 and 235.6 g of water. 1,000 g of TiO 2 (TIPURE 1 R-706) was added slowly while milling at -2,000 rpm using a Premier Mill Corp disperser. Model 50 equipped with a discoid blade. After the addition of TiO 2 the slurry was ground for 20 min. The solids were 76.5%.
    EXAMPLE 6. Formation of opacifying pigment dispersion [60] A grinding steel container was loaded with 40.0 g of Example 3 and 41.4 g of water. 265 g of TiO 2 (TIPURE ™ R-706) was added slowly while milling at -2,000 rpm using a
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    30/36 Premier Mill Corp disperser. Model 50 equipped with a discoid blade. After the addition of TiO 2 the slurry was ground for 20min. The solids were 76.5%.
    COMPARATIVE EXAMPLE D. Formation of opacifying pigment dispersion [61] A stainless steel grinding container was loaded with 100.0 g of aqueous solution of COMPARATIVE EXAMPLE B and 61.61 g of water. At 1,000 rpm 500 g of TIPURE ™ R-706 was added in about 2 minutes. Stirring was maintained at 1,000 rpm for 1 hour. The slurry was filtered through a 325 mesh filtration bag. The measured solids content was 75.5%.
    COMPARATIVE EXAMPLE E. Formation of opacifying pigment dispersion [62] A grinding steel container was loaded with 37.5 g of COMPARATIVE EXAMPLE C and 143.7 g of water. 500 g of TiO 2 (TIPURE ™ R-706) was added slowly while milling at -2,000 rpm using a Premier Mill Corp disperser. Model 50 equipped with a discoid blade. After the addition of TiO 2 the slurry was ground for 20 min. The solids were 73.4%.
    EXAMPLE 7. Formation of pigment particles encapsulated in polymer [63] A 250 ml four-necked round-bottom flask was equipped with a paddle stirrer, thermometer, nitrogen inlet, and reflux condenser. 15 g DI water and 1.2 g SDS were added to the flask. While the contents of the flask were stirred, 94.9 g of Example 6 were added to the flask. The flask was then heated to 50 ° C under a nitrogen atmosphere. A monomer emulsion (monomer emulsion, ME) was prepared by mixing 7 g DI water, 1.5 g SDS, 20.9 g BMA, 14.4 g MMA, and 0.7 g MAA. With the water in the bottle at 50 ° C, 2 g of
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    31/36 0.15% solution in DI water of ferrous sulfate heptahydrate was added to the flask. This was followed by feeding 9.5 g of 4.2% solution in DI water of t-BHP and 3.2% solution in DI water of SSF for 65 minutes. 2 minutes later, ME was started and fed into the flask for a period of 44 minutes at 50 ° C. After the monomer feed was completed, the dispersion was maintained at 50 ° C until all feeds were finished. The polymer was cooled to 25 ° C. Then the dispersion was neutralized with 1 g of 14% aqueous ammonia and then filtered. Trace amounts of gel were filtered through a 100 mesh metal wire mesh filter.
    EXAMPLE 8. Formation of pigment particles encapsulated in polymer [64] A 500 ml four-mouthed flask equipped with paddle stirrer, N 2 inlet, reflux condenser, heating mantle, and thermocouple was loaded with 197, 3 g of Example 5 (73.0% solids) together with a solution of 2.5 g SDS mixed in 20 g DI water. The flask was purged with N 2 , and heated to 50 ° C. With the flask temperature at 50 ° C, a solution of 4.0 g of 0.1% iron sulfate and 0.4 g of 1% EDTA was added to the reactor. Two minutes later number 1 coaliment consisting of 2.0 g of t-BHP dissolved in 36 g of DI water and number 2 coaliment consisting of 1.1 g of SSF dissolved in 36 g of DI water were fed into the reactor at flow rate of 0.3 g / min. Two minutes after the start of the coalimentation solutions, a monomer emulsion (monomer emulsion, ME 1) previously prepared by mixing 5.2 g DI water, 1.25 g SDS, 16.7 g BMA, 11, 5 g of MMA, and 0.6 g of MAA was fed to the reactor at a flow rate of 2.0 g / min. When ME 1 was completed, a second monomer emulsion (ME 2) prepared by mixing 22.8 g DI water, 5.0 g SDS, 66.8 g BA,
    47.2 g MMA, and 1.2 g MAA was fed to the reactor at a flow rate of
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    2.0 g / min. With the ME 2 feeding complete, the co-feeding was continued for another 20 min until completion. The reactor contents were then cooled to room temperature and 3.0 grams of aqueous ammonia (14%) were added. The reactor contents were then filtered to remove some gel. The filtered dispersion had a solids content of 60.8% with 2.5 grams of dry gel removed.
    EXAMPLE 9. Formation of pigment particles encapsulated in polymer [65] In a 500 ml four-mouthed flask, equipped with paddle stirrer, N2 inlet, reflux condenser, heating mantle, and thermocouple was loaded with 188, 23 g of Example 5 (76.5% solids) together with a solution of 1.5 g of TREM ™ LF-40 in 29 g of DI water. The flask was purged with N2, and heated to 50 ° C. With the flask temperature at 50 ° C, a solution of 4.0 g 0.1% iron sulfate and 0.4 g EDTA1% was added to the reactor. Two minutes later number 1 coaliment consisting of 2.0 g t-BHP dissolved in 31 g DI water and number 2 coaliment consisting of 1.1 g IAA dissolved in 31 g DI water were fed into the reactor in a flow rate of 0.25 g / min. Two minutes after the start of the coalimentation solutions, a monomer emulsion (monomer emulsion, ME 1) previously prepared by mixing 5.2 g DI water, 1.25 g SDS, 16.7 g BMA, 11, 5 g of MMA, and 0.6 g of MAA was fed to the reactor at a flow rate of 2.0 g / min. When ME 1 was completed, a second monomer emulsion (ME 2) prepared by mixing 22.8 g DI water, 5.0 g SDS, 66.8 g BA,
    47.2 g of MMA, and 1.2 g of MAA was fed to the reactor at a flow rate of 2.0 g / min. With the ME 2 feeding complete, the co-feeding was continued for another 20 min until completion. The reactor contents were then cooled to room temperature and 3.0 g of aqueous ammonia (14%) were added. The reactor contents were then filtered to
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    33/36 remove some gel. The filtered dispersion had a solids content of 62.8% with 0.36 grams of dry gel removed.
    EXAMPLE 10. Formation of pigment particles encapsulated in polymer [66] A 500 ml four-necked round-bottom flask was equipped with a paddle stirrer, thermometer, nitrogen inlet, and reflux condenser. 30 g of DI water was added to the flask. While the contents of the flask were stirred, 197.3 g of Example 5 with 76.5% solids were added to the flask. The flask was then heated to 50 ° C under a nitrogen atmosphere. A number 1 monomer emulsion (ME 1) was prepared by mixing 5 g DI water, 1.3 g SDS, 16.7 g BMA, 10.2 g MMA, and 1.4 g SSS. A second monomer emulsion (ME 2) was prepared by mixing 22 g of DI water, 5 g of SDS, 66.8 g of BA, and 48.4 g of MMA. With the water in the flask at 50 ° C, 4 g of 0.15% solution in DI water of ferrous sulfate heptahydrate were added to the flask together with 0.4 g of a 1% solution in VERSENE ™ DI water. This was followed by feeding 38 g of 3.7% solution in DI water of t-BHP and
    37.1 g of 3% solution in IAA DI water for 100 minutes. 2 minutes later ME1 was started and fed into the flask for an 18 minute period at 50 ° C. After the completion of ME 1, ME 2 was started. ME 2 was fed for 75 minutes. The dispersion was maintained at 50 ° C until all feeds were finished. The sample was then cooled to 25 ° C and 4 g of a 14% solution in DI water of aqueous ammonia was added. The sample was then filtered through a 100 mesh metal wire filter. 0.015 g of gel was collected.
    EXAMPLE 11. Formation of polymer-encapsulated pigment particles [67] A 500-ml four-necked round-bottom flask was equipped with a paddle stirrer, thermometer, nitrogen inlet, and
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    34/36 reflux condenser. 25 g of DI water was added to the flask. While the contents of the flask were stirred, 194.9 g of Example 5 with 73.9% solids was added to the flask. The flask was then heated to 50 ° C under a nitrogen atmosphere. A number 1 monomer emulsion (ME 1) was prepared by mixing 10 g DI water, 1.3 g SDS, 16.7 g BMA, 11.3 g MMA, and 0.3 g SSS . A second monomer emulsion (ME 2) was prepared by mixing 22 g DI water, 5 g SDS, 66.8 g BA, 47.2 g MMA and 1.2 g SSS. With the water in the flask at 50 ° C, 4 g of 0.15% solution in DI water of ferrous sulfate heptahydrate were added to the flask along with 0.4 g of 1% solution in VERSENE ™ DI water. This was followed by feeding 38 g of 3.7% solution in DI water of t-BHP and 37.1 g of 3% solution in DI water of IAA for 100 minutes. 2 minutes later ME 1 was started and fed into the flask for an 18 minute period at 50 ° C. After the completion of ME 1, ME 2 was started. ME 2 was fed for 75 minutes. The dispersion was maintained at 50 ° C until all feeds were finished. The sample was then cooled to 25 ° C and 4 g of a 14% solution in DI water of aqueous ammonia was added. The sample was then filtered through a 100 mesh metal wire filter, 0.13 g of gel was collected.
    COMP. EXAMPLE F. Formation of polymer encapsulated pigment particles [68] A 1 liter reactor was charged with 233.0 g of DI water and 6.3 g of Triton ™ X-405 (35% solids). Under agitation 290.0 g of TiO2 slurry from EXEMPUO COMP. D were slowly added to the reactor. Under a nitrogen atmosphere the reactor was heated to 50 ° C. When the reactor reached 50 ° C a feed of 0.87 g of SSF dissolved in 26.1 g of DI water was started simultaneously with a feed of 1.58 g of t-BHP (70% active agent) dissolved in 24 , 5 g of DI water. Both feeds were adjusted to take 4 hours and 5 minutes. After 5 minutes of feeding,
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    35/36 a mixture of 4.5 g of FcSCh (0.1% solids) and 11.0 g of VERSENE ™ (1% solids) was added to the reactor and a pre-emulsified monomer feed was started consisting of 28, 8 g DI water, 4.8 g DS-4 (23%),
    43.7 g of MMA, 63.5 g of BMA and 2.2 g of MAA. The pre-emulsified monomer feed was adjusted to take 3.5 hours. After about 1 hour and 12 minutes of feeding monomers, massive amounts of sediment formed making the agitation impossible. The batch was abandoned.
    COMP. EXAMPLE G. Formation of pigment particles encapsulated in polymer [69] A 250 ml four-necked round-bottom flask equipped with paddle stirrer, N2 inlet, reflux condenser, heating mantle, and thermocouple was loaded with 98 , 09 g of EXAMPLE COMP. E (73.4% solids). A solution of 1.2 g of SDS mixed in 15 g of DI water was also added to the flask. The flask was purged with N2, and heated to 50 ° C. With the flask temperature at 50 ° C, a solution of 2.0 g of 0.1% iron sulfate was added to the reactor. Two minutes later number 1 coaliment consisting of 0.5 g of t-BHP dissolved in 9 g of DI water, and number 2 coaliment consisting of 0.28 g of SSF dissolved in 9 g of DI water were fed into the reactor. at a flow rate of 0.15 g / min. Two minutes after the start of the coalimentation solutions, a monomer emulsion (monomer emulsion, ME) previously prepared by mixing 7.0 g DI water, 1.45 g SDS, 20.9 g BMA, 14.4 g of MMA, and 0.7 g of MAA was fed to the reactor at a flow rate of 1.0 g / min. After five minutes of feeding the ME, the batch had to be aborted due to a massive amount of coagulation inside the reactor.
    EXAMPLE 11. Formation of pigment particles encapsulated in polymer [70] A 500 ml four-mouthed flask, equipped with paddle stirrer, N2 inlet, reflux condenser, heating mat, and thermocouple was
    Petition 870190125569, of 11/29/2019, p. 43/49
    36/36 loaded with 188.23 g of Example 5 (73.0% solids) along with a solution of 2.5 g of SDS mixed in 20 g of DI water. The flask was purged with N2, and heated to 50 ° C. With the flask temperature at 50 ° C, a solution of 4.0 g of 0.1% iron sulfate and 0.4 g of 1% EDTA was added to the reactor. Two minutes later number 1 coaliment consisting of 2.0 g t-BHP dissolved in 36 g DI water, and number 2 coaliment consisting of 1.1 g IAA dissolved in 36 g DI water were fed into the reactor at flow rate of 0.3 g / min. Two minutes after the start of the coalimentation solutions, a monomer emulsion (monomer emulsion, ME 1) previously prepared by mixing 5.2 g DI water, 1.25 g SDS, 16.7 g BMA, 11, 5 g of MMA, and 0.6 g of MAA was fed to the reactor at a flow rate of 2.0 g / min. When ME 1 was completed, a second monomer emulsion (ME 2) previously prepared consisting of 22.8 g DI water, 5.0 g SDS, 66.8 g BA, and 47.2 g MMA was divided half. Seventy-one g of ME 2 (designated ME 2B) were removed and reserved. In the remaining half of ME 2 1.2 g of MAA (designated ME 2A) was added. ME 2A was fed to the reactor at a flow rate of 2.0 g / min. After completion of ME 2A feeding, ME2 B was fed to the reactor at a flow rate of 2.0 g / min. Five minutes after the start of ME 2B, 3.0 g of aqueous ammonia (14%) were added to the flask. With the ME 2B feeding complete, the co-feeding was continued for another 20 min until completion. The reactor contents were then cooled to room temperature and filtered to remove some gel. The filtered dispersion had a solids content of 61.0% with 0.04 grams of dry gel removed.
    权利要求:
    Claims (16)
    [1]
    1. Opacifying polymer-encapsulated pigment, characterized by the fact that it comprises: a pigment particle having an average particle diameter of 0.005 microns to 5 microns and a refractive index of at least 1.8; from 0.1% to 25% by weight, based on the weight of said pigment particle, of the first water-soluble polymer functionalized with acid containing sulfur; and from 10% to 200% by weight, based on the weight of said pigment particle, of a second polymer that at least partially encapsulates said pigment particle, wherein said first sulfur-containing acid-functionalized polymer consists, as structural units, monomers selected from: styrene; butadiene; alpha-methyl-styrene; vinyl toluene; vinylnaphthalene; ethylene; propylene; vinyl acetate; vinyl versatate; vinyl chloride; vinylidene chloride; acrylonitrile; methacrylonitrile; (met) acrylamide; C 1 -C 4 -alkyl esters of (meth) acrylic acid; (met) isobornyl acrylate; (meth) benzyl acrylate; (met) phenyl acrylate; (meth) 2-bromoethyl acrylate; (meth) 2-phenyl ethyl acrylate; (meth) 1-naphthyl acrylate; (meth) alkoxy-alkyl acrylate; mono-; di-; trialkyl esters of ethylenically unsaturated anhydrides and di- and tricarboxylic acids; monomers containing alcohol; monomers containing carboxylic acid; (met) sulfo-ethyl acrylate; (met) sulfo-propyl acrylate; styrene-sulfonic acid; vinyl sulfonic acid; 2- (meth) acrylamido-2-methyl-propane-sulfonic acid, and its salts; (meth) dimethyl-amino-ethyl acrylate; dimethyl-amino-propyl- (meth) acrylamide; and t-butyl-amino-ethyl (meth) acrylate.
    [2]
    2. The polymer encapsulated opacifying pigment according to claim 1, characterized in that said first sulfur-containing acid-functionalized polymer comprises at least two amine groups.
    [3]
    3. Polymer encapsulated opacifying pigment according to claim 1 or 2, characterized in that said second polymer
    Petition 870190125569, of 11/29/2019, p. 45/49
    2/4 comprises, as a copolymerized unit, at least one acid functionalized monomer.
    [4]
    4. Polymer encapsulated opacifying pigment according to claim 1 or 2, characterized in that said second polymer comprises at least two phases, one polymer phase having a Tg greater than or equal to 40 ° C and one polymer phase has a Tg less than or equal to 25 ° C.
    [5]
    5. Polymer encapsulated opacifying pigment according to claim 1 or 2, characterized in that said second polymer comprises at least two phases, the first polymer phase including at least one multifunctional monomer.
    [6]
    6. Polymer encapsulated opacifying pigment according to claim 1 or 2, characterized in that said pigment particle comprises TiCK
    [7]
    7. Polymer encapsulated opacifying pigment according to claim 3, characterized in that said acid-functionalized monomer is a sulfur-containing acid-functionalized monomer.
    [8]
    8. Process for forming an opacifying polymer-encapsulated pigment as defined in claim 1, characterized by the fact that it comprises:
    (a) dispersing a pigment particle having an average particle diameter of 0.005 microns at 5 microns and a refractive index of at least 1.8 in a medium of 0.1% to 25% by weight, based on the weight of said pigment particle, of the first water-soluble polymer functionalized with sulfur-containing acid; and (b) carrying out an emulsion polymerization in the presence of said dispersed pigment particle to obtain from 10% to 200% by weight, based on the weight of said pigment particle, of a second polymer that at least partially encapsulates said pigment particle scattered,
    Petition 870190125569, of 11/29/2019, p. 46/49
    3/4 wherein said first sulfur-containing acid-functional polymer consists, as structural units, of monomers selected from: styrene; butadiene; alpha-methyl-styrene; vinyl toluene; vinylnaphthalene; ethylene; propylene; vinyl acetate; vinyl versatate; vinyl chloride; vinylidene chloride; acrylonitrile; methacrylonitrile; (met) acrylamide; C 1 -C 4 -alkyl esters of (meth) acrylic acid; (met) isobornyl acrylate; (meth) benzyl acrylate; (met) phenyl acrylate; (meth) 2-bromoethyl acrylate; (meth) 2-phenyl ethyl acrylate; (meth) 1-naphthyl acrylate; (meth) alkoxy-alkyl acrylate; mono-; di-; trialkyl esters of ethylenically unsaturated anhydrides and di- and tricarboxylic acids; monomers containing alcohol; monomers containing carboxylic acid; (met) sulfo-ethyl acrylate; (met) sulfo-propyl acrylate; styrene-sulfonic acid; vinyl sulfonic acid; 2- (meth) acrylamido-2-methyl-propane-sulfonic acid, and its salts; (meth) dimethyl-amino-ethyl acrylate; dimethyl-amino-propyl- (meth) acrylamide; and t-butyl-amino-ethyl (meth) acrylate.
    [9]
    Process according to claim 8, characterized in that said sulfur-containing acid-functionalized polymer comprises at least two amine groups.
    [10]
    Process according to claim 8, characterized in that said second polymer comprises, as a copolymerized unit, at least one acid functionalized monomer.
    [11]
    Process according to claim 8, characterized in that said second polymer comprises at least two phases, the first polymer phase having a Tg greater than or equal to 30 ° C and a polymer phase having a Tg less than or equal to 12 ° C.
    [12]
    Process according to claim 8, characterized in that said dispersed pigment particle additionally comprises at least one surfactant selected from the group consisting of sulfosuccinic acid esters of formula R — OC (O) CH 2 CH (SO3H) C (O) OR ', in which R and R' can
    Petition 870190125569, of 11/29/2019, p. 47/49
    4/4 be alkyl, aryl, ally, vinyl, styrenyl, or (meth) acryl, or H, and in which R and R 'can be the same or different, except that both R and R' cannot be H, before carrying out said emulsion polymerization to form said second polymer.
    [13]
    Process according to claim 8, characterized in that said pigment particle comprises TiCh.
    [14]
    Process according to claim 10, characterized in that said acid-functionalized monomer is a sulfur-containing acid-functionalized monomer.
    [15]
    Process according to claim 8, characterized in that said second polymer comprises at least two phases, the first polymer phase comprising at least one multifunctional monomer.
    [16]
    16. Composition, characterized by the fact that it comprises said opacifying pigment encapsulated in polymer formed by the process as defined in claim 8.
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-02-12| B06T| Formal requirements before examination|
    2019-09-03| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2019-12-31| B09A| Decision: intention to grant|
    2020-03-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 01/11/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US34007110P| true| 2010-03-12|2010-03-12|
    US61/340071|2010-03-12|
    PCT/US2010/002874|WO2011112171A1|2010-03-12|2010-11-01|Opacifying pigment particle|
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