Triggered response compositions

专利摘要:
The present invention relates to a triggered reaction composition in the form of a barrier material and delivery device comprising one or more polymer electrolytes in contact with an aqueous system that are stable and insoluble in a liquid medium and exhibit one or more chemical / physical reactions in a liquid medium. Wherein the chemical / physical reaction of the composition is triggered upon a change in the ionic strength of the liquid medium.
公开号:KR20040012487A
申请号:KR1020030050292
申请日:2003-07-22
公开日:2004-02-11
发明作者:창칭-젠；그레이리차드；구오하일란；웨인스테인바리
申请人:롬 앤드 하스 캄파니；
IPC主号:

专利说明:

Triggered Response Compositions
[4] The present invention is directed to chemical or physical reactions that are triggered when the composition is exposed to a fluid and liquid medium, each having one or more or a series of triggering events, including the characteristics of the chemical / physical process or medium. It relates to a composition that can be represented. In particular, it relates to controlling the stability of a polymer electrolyte composition in aqueous and non-aqueous systems by one or more triggering actions in an aqueous system in which the polymer electrolyte composition is dissolved, degraded, deformed, expanded or dispersed at a particular time, In this case, the triggering action is caused by not only the display change in ionic strength and the ionic strength: other chemical and / or physical changes in the system. The present invention further relates to a device comprising a triggered reaction composition useful for delivering an active ingredient and a beeficial agent in a fluid medium to a use environment.
[5] There is a need to provide compositions and devices that deliver or provide controlled release of one or more active ingredients / solvents to the environment of use.
[6] International Publication No. WO 00/17311 discloses a coated detergent activity encapsulated with a coating material which allows for a delayed release of detergent activity in the wash solution, the coating material being insoluble in a wash solution having a pH of 10 or higher at 25 ° C., but at 25 ° C. It is soluble if the pH is below 9 Coating materials disclosed above include amines, waxes, Schiff base compounds, and mixtures thereof. US patent application Ser. No. 2001/0031714 A1 discloses a portion of a laundry detergent having two or more detergent components, at least two of which are released into the wash solution at different times, and at least one temperature or pH switch. The switch materials disclosed above include waxes, aminoalkyls, methacrylate copolymers and polymers having pyridine groups.
[7] However, there are many limitations to the encapsulated active ingredient having a pH sensitive coating material for delaying the active release. The use of pH reactants to trigger triggered release of detergent activity in a rinse cycle is undesirable due to premature leakage of active or useful agents into the liquid use environment. As a result, all or most of the active ingredients are dispersed too quickly or subsequently removed before they are used in the intended environment, thus preventing controlled release of the desired activity in a single or multi-step process or preventing controlled release. The result is that the desired active ingredient is released in an amount that is ineffective to achieve a beneficial active action. In addition, it includes a variety of soil-containing loads used by users around the world, different components, different water purity, changes in hydraulic hardness, changes in washing conditions, changes in detergent concentrations, wider washing machine design, cycle length, washing and rinsing temperatures. It is difficult to precisely control the release of the active ingredient in complex systems such as fabric washing systems. Important issues in controlling the delivery of active ingredients and / or useful agents associated with current controlled release substances include: incompatibility of ingredients, inability to release at or within a specified time period for a particular active ingredient; Early release and stability control and trigger inability to the materials used.
[8] The use of substances that only respond to changes in pH such that the actives are site specific delivery is typically difficult due to the rapid release of 10-30% of the active ingredients due to degradation of the substances at high pH. Thus, it is desirable to provide compositions in which the stability can be altered by chemical and / or physical triggering action, where such a reaction can affect the controlled release of a wide range of active ingredients and useful agents. The inventors have found a composition comprising one or more polyelectrolytes whose stability can be changed by changing the ionic strength, and compositions having one or more trigger means as well as ionic strength can be used for fiber protection. It has significant utility in trigger response blocking substances, encapsulating agents and devices of active ingredients, personal protective active ingredients, pharmaceutical useful agents and other related useful agents.
[9] One effective solution to the problem of controlled release of one or more active ingredients / beneficial agents in aqueous or non-aqueous systems is that the polymer properties such as the stability and solubility of the triggered reaction polymer electrolyte composition are dispersed in the polymer electrolyte. It is to use a triggered reaction polyelectrolyte composition that acts to change one or more chemical and / or physical properties of an aqueous or non-aqueous system. Destabilizing, dissolving, disintegrating, deforming, expanding, and / or aqueous in an aqueous system by adjusting one or more chemical and / or physical properties such as ionic strength in the aqueous system. The polymer electrolyte is triggered in response to dispersion in the system. Ion intensity triggering actions include one or more changes in the ionic strength of an aqueous system. One type of trigger reaction composition remains stable and insoluble under relatively high ionic strength conditions, but reacts with destabilization, dissolution, decomposition, expansion, and / or dispersion in aqueous systems at relatively low ionic strength conditions. In addition, other trigger reaction compositions can be destabilized, dissolved, decomposed, deformed, expanded, or dispersed in an aqueous system at relatively high ionic strength conditions, but changed or maintained in a separate aqueous system under relatively low ionic strength conditions. To maintain a stable and insoluble condition.
[10] Active ingredients and useful agents contained within or encapsulated in trigger reaction blockers and devices made from such polymer electrolyte compositions are not limited thereto, but may be used in combination with skin using textile laundry cycles, personal protective delivery devices and / or pharmaceutical delivery devices. Retained to protect these active ingredients and agents in aqueous systems comprising the same aqueous system-substrate interface, It is then triggered to release the desired activity through dissolution, degradation, collapse, expansion and / or dispersion of the polymer electrolyte during subsequent processing such as fabric wash rinse cycles, skin washes or sweating on the skin, or The chemical and / or physical polymer reaction may be manipulated by one or more or more chemical and / or physical property changes of one or more aqueous systems, including ionic strength, as well as: hydro hardness, acid Strength and concentration, base strength and concentration, surfactant concentration, pH, buffer strength and buffer capacity, temperature, hydrogen bonding, solvent, hydrogen bonding solvent, organic solvent, osmotic pressure, polymer expansion, charge density, Neutralization of acid and base functional groups, degree of quaternization of basic functional groups, dilution, viscosity, electrochemical potential, conductivity, ion mobility, And mobility, diffusion, surface area, mechanical force, pressure, shear force, radiation, and combinations thereof.
[11] The present inventors have found a polymer electrolytes usefully used in the present invention. As the polymer electrolyte, the type and amount of acid or basic monomer, the degree of neutralization of acid or basic monomer, type and amount of amphoteric monomer, type and amount of non-ionic vinyl surfactant, type and amount of radioactive functional group, residual Types and amounts of unsaturated functional groups, types and amounts of chemically reactive functional groups, types and amounts of electronically reactive functional groups, types and amounts of electrochemically active functional groups, types of radiation reactive (ultraviolet, visible, infrared, X-ray) functional groups, and Contacting (eg, dispersing) the polymer electrolyte with one or more parameters, including the amount, the ionic strength of the system, the ion concentration of the system, the pH of the system, the temperature of the system, and the surfactant concentration of the system. Specify that the chemical and / or physical reactions of the polymer trigger as one or more properties of both the fluid or the liquid medium change. These include the monomer composition, and specifically designed polymer structure.
[12] Suitable polyelectrolytes include, for example, alkali soluble / expandable emulsion (ASE) polymers, hydrophobically modified alkali soluble / expandable emulsion (HASE) polymers, acid soluble / expandable emulsion polymers, hydrophobically modified acid soluble / expandable emulsion polymers, acidic Homopolymers, copolymers and salts thereof; Basic homopolymers, copolymers and salts thereof; Poly (quaternized amine) homopolymers, copolymers and salts thereof; Amphoteric polymers; Anionic, cationic and amphoteric polysaccharide homopolymers, copolymers and salts thereof; Anionic, cationic and amphoteric polysaccharide derivatives; Anionic, cationic and amphoteric polypeptide homopolymers, copolymers and salts thereof; Anionic, cationic and amphoteric polypeptide derivatives; Chemically modified polypeptide homopolymers, copolymers and salts thereof; Nucleic acid homopolymers, copolymers and salts thereof; Chemically modified nucleic acids, natural nucleic acids, enzymes, synthetic and natural proteins, gelatin, lignosulfonic acid homopolymers, copolymers and salts thereof; Ionene homopolymers, copolymers and salts thereof; Anionic, cationic and amphoteric polyester homopolymers, copolymers and salts thereof; Anionic, cationic and amphoteric polyurethane homopolymers, copolymers and salts thereof; Copolymer blends of the foregoing homopolymers, copolymers and salts thereof; Ionic and nonionic micelles; Stoichiometric and non-stoichiometric interpolymer blends of the foregoing homopolymers, copolymers and salts thereof; Polymer matrices of the foregoing homopolymers and copolymers and salts thereof; Physical mixtures of the foregoing homopolymers, copolymers and salts thereof; Homopolymers, copolymers and salts described above having grafted cationic, anionic and amphoteric components and combinations thereof.
[13] The inventors further note that such polymer electrolytes are effective for blocking, enclosing, depositing, enclosing, encapsulating and / or forming a matrix having one or more active ingredients in an aqueous system. The stability of the barrier material is not only in terms of ionic strength but also, for example, ion concentration, surfactant concentration, acid strength and concentration, base strength and concentration, pH, buffer strength and capacity, temperature, hydrogen bonding, Solvents, hydrogen bonding solvents, organic solvents, osmotic pressure, polymer swelling, charge density, neutralization, dilution, viscosity, electrochemical potential, conductivity, ion mobility, charge mobility, diffusion, surface area, mechanical force, radiation and these It has been found that it can be usefully manipulated to respond to changes in one or more chemical / physical properties of an aqueous system comprising a combination of.
[14] In one embodiment, the polymer electrolyte composition of the present invention is sufficiently stable and effective to contain, encapsulate and / or form a matrix with one or more active ingredients / solvents in aqueous systems with relatively high ionic strength conditions. Form a block. Exposure of the composition to an aqueous system at relatively low ionic strength conditions triggers destabilization of the composition such that the active ingredient is rapidly dispersed in the aqueous system. The triggered reaction compositions of the present invention overcome the limitations of the prior art and provide new compositions, devices and methods that allow controlled release of one or more active ingredients / solvents in the environment of use.
[1] 1 is a graph showing the cubic expansion rate of PEL free-standing film in aqueous NaCl solution of pH 12,
[2] 2 is a graph showing the expansion rate of the PEL (composition D) film in 0.1M salt and a base solution,
[3] Figure 3 is a graph showing the expansion rate of PEL (composition D) film in 0.001M salt and base solution.
[15] According to the present invention there is provided a triggered reaction composition comprising one or more polyelectrolytes in contact with a fluid or liquid medium that is stable in a liquid medium exhibiting one or more chemical / physical reactions, The physical reaction is triggered upon one or more ionic strength changes to the liquid medium. The polyelectrolyte may comprise: (a) one or more acidic, basic or amphoteric monomers; (b) one or more non-ionic vinyl monomers; Optionally (c) one or more non-ionic vinyl surfactant monomers; And optionally (d) one or more polyethylene-unsaturated monomers or crosslinkers, wherein the chemical / physical reaction of the composition is not only a change in ionic strength, but also the chemical / physical reaction of the composition may include: Amount, (ii) type and amount of basic monomers, (iii) degree of neutralization of acidic and basic monomers including degree of quaternization of basic monomers, (iii) type and amount of non-ionic monomers, (Iii) a kind and amount of a nonionic vinyl surfactant monomer, (iii) a kind and amount of a polyunsaturated polyunsaturated monomer, and (iii) a kind and amount of a crosslinking agent. Depends on more parameters.
[16] In a preferred embodiment, the polyelectrolyte comprises (a) 15-70% by weight of one or more acidic monomers; (b) 15-80% by weight of one or more non-ionic vinyl monomers; (c) 0-30% by weight of one or more non-ionic vinyl surfactant monomers; And optionally (d) 0.001-5% by weight of one or more polyethylene-based unsaturated monomers. Moreover, the polyelectrolyte composition is stable and insoluble in relatively high ionic strength aqueous systems, and the composition is aqueous in relatively low ionic strength aqueous systems or when the ionic strength of the aqueous system is lowered in contact with the composition. Disperses, dissolves, deforms, expands or disintegrates in the system. The aqueous system optionally comprises a hydrogen bonding solvent and / or an organic solvent, wherein the chemical / physical reaction of the composition is not only in ionic strength, but also in ion concentration, surfactant concentration, acid strength and concentration, base strength and concentration, pH , Strength and capacity of buffer, temperature, hydrogen bonding, solvent, hydrogen bonding solvent, organic solvent, osmotic pressure, polymer swelling, charge density, neutralization, dilution, viscosity, electrochemical potential, conductivity, ion mobility, charge Triggered by one or more parameters selected from mobility, polymer entanglement and combinations thereof. Preferably, the HASE polymer comprises (a) 20-50% by weight of one or more acidic monomers; (b) 20-70% by weight of one or more non-ionic vinyl monomers; (c) 2-20% by weight of one or more non-ionic vinyl surfactant monomers; And optionally (d) 0.05-0.5% by weight of one or more polyethylene unsaturated monomers.
[17] In another embodiment, the polyelectrolyte may comprise (a) 15-70% by weight of one or more acidic monomers; (b) 15-80% by weight of one or more non-ionic vinyl monomers; And optionally (c) one or more alkali soluble / expandable emulsion polymers comprising 0.001-5% by weight of one or more metal crosslinkers.
[18] In another embodiment, the polyelectrolyte comprises (a) one or more basic monomers; (b) one or more non-ionic vinyl monomers; (c) one or more non-ionic vinyl surfactant monomers and optionally (d) one or more polyethylene unsaturated monomers or crosslinkers, wherein the basic monomers are quaternized before or after polymerization. One or more acid soluble / expandable emulsion polymers.
[19] Furthermore, in another embodiment, the polyelectrolyte may comprise (a) one or more acidic and basic monomers; (b) one or more non-ionic vinyl monomers; one or more amphoteric emulsion polymers comprising (c) one or more non-ionic vinyl surfactant monomers and optionally (d) one or more polyethylene unsaturated monomers, metals and / or other crosslinkers.
[20] In another embodiment, the polyelectrolyte comprises (a) 15 to 70 wt% of one or more acidic monomers; (b) 15-80 weight percent of one or more non-ionic vinyl monomers; And optionally (c) 0.001-5% by weight of one or more polyethylene unsaturated monomers, metals and / or other crosslinkers.
[21] In another embodiment, the polyelectrolyte may comprise (a) 15-70% by weight of one or more acidic monomers; (b) 15-80 weight percent of one or more non-ionic vinyl monomers; (c) 0.5-30% by weight of one or more polyethylene unsaturated or functionalized vinyl monomers; and optionally (d) 0.001-5% by weight of one or more polyethylene unsaturated monomers, metals and / or other crosslinkers. Is one or more polymers.
[22] In another embodiment, the polyelectrolyte may comprise (a) 15-70% by weight of one or more basic monomers; (b) 15-80 weight percent of one or more non-ionic vinyl monomers; (c) 0.5-30% by weight of one or more polyethylene-based unsaturated or functionalized vinyl monomers; And optionally (d) 0.001-5% by weight of one or more polyethylene-unsaturated monomers, metals and / or other crosslinkers, wherein the basic monomers may be quaternized before or after polymerization. to be.
[23] Next, a triggered reaction barrier composition is provided comprising one or more polymer electrolytes in contact with a liquid medium, wherein the barrier composition surrounds, encapsulates, or encapsulates a matrix having one or more active ingredients. Or form; The barrier is one or more selected from dispersion, decomposition, collapse, dissolution, destabilization, deformation, expansion, softening, melting, electrical current conduction, spreading, absorption, adsorption, flow, and combinations thereof. The above chemical / physical reactions; The chemical / physical reaction of the composition is triggered by one or more chemical / physical changes to the liquid medium; The barrier composition may release the active ingredient into the liquid medium as a result of the triggered reaction. One or more triggering actions in the form of chemical / physical changes to the polymer or to the system containing the polymer or the polymer itself are usefully employed in the present invention.
[24] In one preferred embodiment, the chemical / physical change for the liquid medium is one or more changes in ionic strength. In another embodiment, the chemical / physical change for the liquid medium is a change in ion concentration. In another embodiment, the chemical / physical change for the liquid medium is a change in ionic strength and pH. In another embodiment, the chemical / physical change for the liquid medium is a change in ionic strength and temperature. In another embodiment, the chemical / physical change for the liquid medium is a change in ionic strength, pH and temperature. In another embodiment, the chemical / physical change for the liquid medium is a change in ionic strength and mechanical shear force (eg, agitation, convection). In another embodiment, the chemical / physical change for the polymer dispersed in or in contact with the aqueous medium is a change in the amount and intensity of ultraviolet / visible light. In the present invention, the chemical / physical change for the polymer dispersed in or in contact with the aqueous medium is a number of chemical / physical changes triggered in the aqueous medium.
[25] According to the present invention,
[26] (a) one or more active ingredients;
[27] (b) one or more additives; And
[28] (c) a device for triggered release of one or more active ingredients in an environment of use comprising a blocking composition comprising one or more ionic strength reactive polymer electrolytes,
[29] Wherein said blocking composition surrounds, encapsulates or forms a matrix having one or more active ingredients; The barrier composition is stable in a liquid medium; The barrier exhibits one or more chemical / physical reactions in the liquid medium; Chemical / physical reactions of the composition are triggered upon one or more ionic strength changes in the liquid medium; The device may release the active ingredient into the environment of use as a result of the triggered reaction of the barrier composition.
[30] In addition, according to the present invention,
[31] (a) When in contact with a liquid medium, one or more of the active ingredients may be prepared with an ionic strength reaction blocking composition that is substantially impermeable to the release of the active ingredient and is not triggered for reaction. Surrounding, encapsulating or forming the matrix having; And
[32] (b) modifying the chemical / physical properties of the liquid medium
[33] Including;
[34] At this time, the barrier composition is dispersed, destabilized, disintegrated, disintegrated, dissolved, deformed or expanded and is substantially permeable, thus releasing one or more active ingredients into the environment of use, which triggers the release of active ingredients into the environment of use. A method of triggering is provided.
[35] As used herein, the term "polyelectrolyte" includes a plurality of ionized and / or ionizable groups in a polymer as a result of the polymerization of one or more monomers having ionized and / or ionizable groups, with a liquid medium and It refers to a polymer or macromolecular compound that is contacted. Preferably, the polyelectrolyte is contacted with an aqueous system capable of dissolving a plurality of ions including the polymer electrolyte or a non-aqueous system comprising a solvent. Suitable aqueous systems include, for example, water, water incorporating hydrogen bonding solvents, polar solvents and organic solvents. Typical polar compounds include, for example, both organic and inorganic acids, bases and buffers. Typical organic solvents include, but are not limited to, alcohols, polyalkylene glycols, poly (alcohols), ethers, poly (ethers), amines, poly (amines), carboxylic acids, oligomeric carboxylic acids, organophosphorus compounds, And combinations thereof. Fluids and liquid media refer to aqueous systems, non-aqueous systems, or free flowing solids systems. Suitable liquid media include, for example, aqueous dispersions, aqueous solutions, aqueous dispersions comprising one or more solvents, and dispersions free of flow of polymer solids. For example, non-aqueous systems comprising solvents capable of dissolving ions and charged groups of the polyelectrolyte are also usefully used in the present invention.
[36] The polymer electrolyte usefully used in the present invention includes, for example, only an cationic group, an anionic group or an amphoteric group containing a mixture of a cation and an anionic group. Individual ionized or ionizable components of the polymer electrolyte include, for example, weak or strong acid groups such as carboxy, sulfone, phosphone and phosphine groups, respectively; Strong or weak bases such as primary amine, secondary amine, tertiary amine and phosphine, respectively; And alternating acidic and basic groups of amphoteric groups and copolymers such as amino acids. Suitable examples of polymer electrolytes usefully employed in the present invention include, for example, alkali soluble / expandable emulsion (ASE) polymers, hydrophobically modified alkali soluble / expandable emulsion (HASE) polymers, acid soluble / expandable emulsion polymers, hydrophobically modified Acidic homopolymers such as acid-soluble / expandable emulsion polymers, polycarboxylic acids, Morez polymers, polycarboxylates, poly (acrylic acid), poly (methacrylic acid) and polyacrylates, copolymers and salts thereof; Basic homopolymers, copolymers and salts thereof such as polyamines, poly (amideamino) acrylates and poly (amino) acrylamides; Poly (quaternized amine) homopolymers such as quaternized poly (amino) acrylates, copolymers and salts thereof, amphoteric emulsion polymers such as poly (amino acid) and poly (amino acid) acrylate emulsion polymers; Anionic, cationic and amphoteric polysaccharide homopolymers, copolymers and salts thereof; Anionic, cationic and amphoteric polysaccharide derivatives; Anionic, cationic and amphoteric polypeptide homopolymers, copolymers and salts thereof; Anionic, cationic and amphoteric polypeptide derivatives; Chemically modified polypeptide homopolymers, copolymers and salts thereof; Nucleic acid homopolymers, copolymers and salts thereof; Chemically modified nucleic acids, natural nucleic acids, enzymes, synthetic and natural proteins, gelatin, lignosulfonic acid homopolymers, copolymers and salts thereof; Ionene homopolymers, copolymers and salts thereof; Anionic, cationic and amphoteric polyester homopolymers copolymers and salts thereof; Anionic, cationic and amphoteric polyurethane homopolymers, copolymers and salts thereof; Copolymer blends of the foregoing homopolymers, copolymers and salts thereof; Physical mixtures of the foregoing homopolymers, copolymers and salts thereof; Homopolymers, copolymers and salts described above having grafted cationic, anionic and amphoteric components and combinations thereof. Suitable polyelectrolytes (PELs) of the present invention include both synthetic, natural and chemically modified polyelectrolytes. Preferred polymer electrolytes include alkali and acid soluble / expandable emulsion polymers, amphoteric emulsion polymers, poly (amino acid) polymers and Morez® polymers.
[37] Synthesis of synthetic PELs comprising acid and alkali soluble emulsion polymers is well known in polymer chemistry, including, for example, free-radical polymerization, ion polymerization, condensation polymerization, addition polymerization, and polymer modification in homogeneous and heterogeneous phases. It is performed by a normal method. Separation of the preformed PEL from natural sources and / or products is done by conventional separation methods, including, for example, conventional methods involving chemical modification of isolated nonionic polymer biopolymers, and combinations of the two methods. The chemical structure and useful properties of PELs within the scope of the present invention are further modified and modified by the synthesis of copolymers comprising different amounts of ionic and non-ionic monomer units and nonionic vinyl surfactant monomer units. This acts to impart very different properties to aqueous systems and very different intermolecular and intermolecular interactions and very different interactions at the solid surface and interface with aqueous systems and combinations thereof. Hydrophobic co-monomers, as well as hydrophilic co-monomers.
[38] Synthetic PELs are free radicals using ethylenically unsaturated monomers having unstrained and strained ring systems by ionic processes, step growth processes and modification of preformed polymers. It is prepared by a method including a chain growth process such as polymerization. Included in free radical polymerization are, for example, PEL homopolymers, copolymers, random copolymers, alternating copolymers, block copolymers, graft copolymers, mixtures of one or more homopolymers, copolymers Mixtures thereof and combinations thereof. The PEL chemical structure and the PEL macromolecular structure can be adjusted or modified in various ways and with the properties of the monomer unit, including polymerization conditions such as initiators and other variables. Step-growth condensation polymerization is useful for the synthesis of polypeptides and polynucleotides with native PEL.
[39] PELs usefully used in the present invention include, for example, (i) the type and amount of acidic monomers, (ii) the type and amount of basic monomers, and (i) the degree of quaternization of the basic monomers. Degree of neutralization, (iii) types and amounts of non-ionic monomers, (iii) types and amounts of non-ionic vinyl surfactant monomers, (iii) types and amounts of polyethylene-based unsaturated monomers, Type and quantity, (iii) PEL macromolecular structures such as linear and branched structures, (iii) PEL electrochemical properties such as ion mobility and ionic conductivity, (iii) PEL macromolecular polydispersities such as Mn and Mw, and related One or more properties / parameters, including properties, and (iii) combinations thereof.
[40] The term “triggered reaction” in connection with the present invention controls and manipulates one or more chemical / physical properties of a polymer composition in contact with a liquid medium that is triggered by or changes the chemical / physical properties of the liquid medium. Or to change.
[41] Typical chemical / physical properties of liquid media as well as ionic strength are, for example, surfactant concentrations, acid strengths and concentrations, base strengths and concentrations, pH, buffer strength and buffer capacity, temperature, hydrogen bonding, hydrogen Binding solvent, organic solvent, osmotic pressure, dilution, viscosity, electrochemical potential, conductivity, ion mobility, charge mobility, polymer entanglement, diffusion, surface area, emulsion particle size, mechanical force, radiation and their Combinations. The inventors have found that the solubility, expandability, and stability of liquid soluble / expandable triggered reactive polymer compositions, barrier materials, and devices in liquid media is triggered by altering or changing the ionic strength and / or one or more additional variables of the liquid medium. It has been found that the liquid medium is preferably an aqueous or non-aqueous system.
[42] Alkali soluble / swellable emulsion (ASE) polymers are polymer electrolytes based on acid-containing emulsion polymers disclosed in US Pat. Nos. 3,035,004 and 4,384,096 (HASE polymers) and UK Pat. By controlling the type and level of acidic monomers and comonomers in ASE and HASE polymers that are related to the degree of neutralization, the inventors have found that it is optimal to provide stable polymers with low degree of expansion and insolubility in aqueous systems of relatively high ionic strength. It has been found that charge density can be achieved. The polymer may be characterized by incorporating an ionic strength trigger or may be called an ionic strength reactive polymer. As the ionic strength of the aqueous system changes to a lower level, the polymer quickly disperses, dissolves or expands to a significant extent in the aqueous system.
[43] Thus, in a preferred embodiment, one in contact with an aqueous system that is stable and exhibits one or more chemical / physical reactions selected from dispersion, decomposition, dissolution, destabilization, collapse, deformation, expansion, softening, melting, spreading and flow. Or a trigger reaction composition comprising more than one polyelectrolyte; The chemical / physical reaction of the composition is triggered upon one or more ionic strength changes in the aqueous system. The polyelectrolyte may comprise (a) 15-70% by weight of one or more acidic, basic or amphoteric monomers, (b) 15-80% by weight of one or more non-ionic vinyl monomers, and (c) one or more One or more alkali soluble emulsion polymers comprising 0-30% by weight of non-ionic vinyl surfactant monomers, and 0-5% by weight of any (d) one or more polyethylene-based unsaturated monomers.
[44] The ASE and HASE polymers of the present invention are typically prepared using standard emulsion polymerization techniques under acidic conditions, and the carboxylic acid groups are in a protonated form to insolubilize the polymer and provide a liquid emulsion. This class of PEL is also called anionic PEL. When added as a liquid colloidal dispersion, the finely divided ASE polymer particles dissolve almost immediately upon pH adjustment. The degree of neutralization, the type and amount of both the acidic monomers and non-ionic surfactant groups of the HASE polymer are precise to provide the stability, dispersibility, expandability and solubility of the ionic strength reactive polymer depending on the ionic strength of the aqueous system. Can be controlled. The polymer composition usefully used in the present invention comprises one or more triggering means, for example ionic strength triggering conditions. Due to the ease of handling, metering, and dispersing of ASE and HASE polymers, charge density for fast dissolving and neutralized acidic functionalities controlled by pH control, and highly desirable film formability and barrier properties, ASE and HASE polymers Controlled release of personal care actives, household actives and pharmaceutical utility agents, capsule compositions, media and devices, sensory and detection devices, imaging and diagnostic agents, isolation, to enable controlled release of useful agents and active ingredients It is the most effective and efficient barrier composition for a wide range of applications, including solvents and devices, molecular recognition, tracing and biological molecular conjugation assays.
[45] The HASE polymer of the present invention comprises three components as disclosed in US Pat. No. 4,384,096: (a) 15-70% by weight of one or more acidic monomers, (b) 15-80% by weight of one or more non-ionic vinyl monomers. %, (c) 0-30% by weight of one or more non-ionic vinyl surfactant monomers, and 0.01-5% by weight of any (d) one or more polyethylene-based unsaturated monomers. The efficiency of ASEs and HASEs as ionic strength and pH reactive compositions for triggered release is determined by the following components: (i) the type and amount of acidic monomers, (ii) the degree of neutralization of the acidic monomers, and (i) the type of nonionic vinyl surfactant monomers. And amount, (iii) type and amount of non-ionic vinyl surfactant monomer, (iii) type and amount of polyunsaturated polyunsaturated monomer, (iii) pH of the aqueous system, and (iii) a combination thereof. Was found.
[46] Acid monomers that provide the required ionic strength and pH reactivity and the degree of neutralization of the acid monomers are important for the optimization of the acid group charge density. The non-ionic vinyl monomers provide an expanded polymer backbone structure and added hydrophobic balance. The non-ionic vinyl surfactant monomers provide a bound surfactant. All four components contribute to the preparation of ionic strength reactive polymers and barrier compositions and their stability, swellability and solubility depend on the ionic strength of the aqueous system. Within this limit, the proportion of the individual monomers can be varied so that optimal properties for a particular triggered release application are achieved.
[47] The ASE and HASE polymers include acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, aconic acid, vinyl sulfonic acid and vinylphosphonic acid, acrylicoxypropionic acid, methacrylicoxypropionic acid, monomethyl maleate, mono One or more acidic monomers selected from the group consisting of C ₃ -C ₈ α, β-ethylenically unsaturated carboxylic acid monomers such as methyl fumarate, monomethylitaconate, and the like and mixtures thereof, based on the total monomer content 15-70% by weight is required. Acrylic acid (AA) or methacrylic acid (MAA) or mixtures thereof are preferred. In particular, when small amounts of acrylic acid or methacrylic acid are mixed together, a mixture of itaconic acid or fumaric acid and AA or MAA is suitable, a mixture of crotonic acid and aconitic acid and their semiesters and C ₁ -C Other polycarboxylic acids such as maleic acid with ₄ alkanols are also suitable. In the present invention, it is preferred that the acidic monomer is at least about 15% by weight, most preferably about 20-50% by weight. However, polycarboxylic acid monomers and half esters may be replaced with about 1-15% by weight based on the content of acrylic or methacrylic acid moieties, for example total monomers.
[48] C ₂ -C ₁₈ α, β-ethylenically unsaturated monomers, ethylacrylates, ethyl methacrylates, methyl methacrylates to provide stable aqueous dispersions and desirable hydrophobic: hydrophilic balances required for the ASE and HASE polymers of the present invention C ₁ -C ₈ alkyl of acrylic and methacrylic acid, including acrylate, 2-ethylhexyl acrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate and C ₂ -C ₈ hydroxy alkyl esters; Styrene, vinyltoluene, t-butylstyrene, isopropylstyrene, and p-chlorostyrene; Vinyl acetate, vinyl butyrate, vinyl caprolate; About 15-80% by weight of one or more co-polymerizable non-ionic monomers selected from the group consisting of acrylonitrile, methacrylonitrile, butadiene, isoprene, vinyl chloride, vinylidene chloride, and the like are required. In practice, monovinyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate are preferred.
[49] Of course, these monomers must be co-polymerizable with acidic monomers and vinyl surfactant monomers. Generally, about 15-80% by weight, preferably about 20-70% by weight, of nonionic vinyl monomers, based on the total weight of the monomers, is used to prepare the ASE polymer.
[50] The third monomer component is about 0.1-30% by weight, preferably at least two oxyalkylene units, preferably at least 6-70 oxyalkyl, based on the total monomer content of one or more non-ionic vinyl surfactant monomers. From about 0.1 to 30% by weight of one or more non-ionic vinyl surfactant monomers selected from the group consisting of acrylic or methacrylic acid esters of C ₁₂ -C ₂₄ alkyl monoethers of polyalkylene glycols with ethylene units . Alkyl phenoxy poly (ethyleneoxy) ethyl acrylate and methacrylate; More preferred are acrylate and methacrylate surfactant esters selected from the group consisting of alkoxy poly (ethyleneoxy) ethyl acrylate and methacrylate; The ethyleneoxy unit is then about 6-70. Preferred monomers may be defined by the general scheme H ₂ C═C (R) —C (O) —O (CH ₂ CH ₂ O) _n R ′ _wherein R is H or CH ₃ , the latter being preferred n is at least 2 and preferably has an average value of at least 6, at most 40-60 and even at most 70-100, R 'is a hydrophobic group, having, for example, 12-24 carbon atoms or an average of 12-24 or more It is an alkyl group or alkylphenyl group which has a carbon atom.
[51] Typical vinyl surfactant monomers are acrylic or methacrylic esters of certain nonionic surfactant alcohols. Such surfactant esters are known in the art. For example, US Pat. No. 3,652,497 to Junas et al. Discloses the use of alkylphenoxy poly (ethyleneoxy) ethyl acrylates for the production of several other polymeric surfactant thickeners. Dickstein's US Pat. No. 4,075,411 discloses commercially available BBs such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or aconic acid and alkylphenoxy poly (ethyleneoxy) ethyl alcohol and block-polymerized glycols. Several methods of preparing such vinyl surfactant esters are disclosed, including acid catalyzed condensation of warm polyoxyalkylene surfactant alcohols. Alternate esterification methods are also disclosed, including alcohol degradation and transesterification. Other suitable vinyl surfactant esters may be prepared from monoethers of mixed or heteropolymerized ethyleneoxypropyleneoxy-butyleneoxy polyglycols such as those disclosed in Patton's US Pat. No. 2,786,080. Additional surfactant alcohols that may be esterified for use herein are disclosed in "McCutcheon's Detergents and Emulsifiers" 1973, North American Edition, (Allured Publishing Corp., Ridgewood, N.J. 07450).
[52] Certain vinyl surfactant monomer esters, ie those defined by the formula, are useful in the preparation of the HASE polymers disclosed herein. It is essential that the surfactant be incorporated into the liquid emulsion product by copolymerization. Advantageously required surfactant esters are prepared by direct acid catalyzed esterification of a suitable surfactant alcohol with the excess carboxylic acid monomer used as component A. The resulting mixture with excess acid can be used directly in the copolymerization such that at least 30% and preferably 50-70% or more of the surfactant alcohols in the mixture are esterified. The vinyl surfactant esters can also be recovered and purified in a conventional manner using suitable inhibitors such as hydroquinone or p-tert-butylcatechol to prevent unwanted single polymerization and then used to prepare the HASE polymer. have.
[53] The balance of acidic monomers with non-ionic monomers has been found to be an important factor in the triggered release response and performance of the resulting ASE and HASE polymers used in barrier or encapsulated compositions.
[54] Optionally, the ASE and HASE polymers comprise a small amount of at least one polyethylene unsaturated monomer to provide a polymer having a network structure. One or more polyethylene unsaturated monomers may be combined with the monomers during the polymerization process or may be added after the polymerization of the monomers. Suitable examples include alkyl methacrylate (ALMA), ethylene glycol dimethacrylate (EGDMA), butylene glycol dimethacrylate (BGDMA), diallyl phthalate (DAP), methylenebisacrylamide, pentaerythritol di- , Tri- and tetra-acrylates, divinylbenzene, polyethylene glycol diacrylates, bisphenol A diacrylates, and combinations thereof. Low levels of polyethylene-unsaturated monomers are preferred, with levels above about 5% by weight tending to overcrosslink the polymer or by providing a polymer of network structure, the efficiency is significantly reduced in the present invention. Preferred amounts of polyethylene-based unsaturated monomers are from 0.01 to 5% by weight, more preferably from 0.05 to 0.5% by weight, based on the total weight of the polymer.
[55] Optionally, the ASE and HASE polymers also include a small amount of at least one metal and / or alkaline earth crosslinker to provide a polymer with a tighter structure and better mechanical properties. One or more metal and / or alkaline earth crosslinkers may be combined with the monomers during the polymerization process or may be added after the monomer polymerization. Suitable metal and / or alkaline earth crosslinkers include, for example, alkaline earth ions of calcium, magnesium and barium and transition metal ions of iron, copper and zinc. Other suitable examples such as aluminum ions are disclosed in US Pat. No. 5,319,018. The preferred amount of metal and / or alkaline earth crosslinker is from 0.01 to 5% by weight, more preferably from 0.05 to 0.5% by weight, based on the total weight of the polymer.
[56] Alkali soluble / expandable emulsion (ASE) polymers are polyelectrolytes based on acid-containing emulsion polymers disclosed in US Pat. No. 3,035,004 and UK 870,994. Alkali soluble resins (ASR) are polyelectrolytes based on acid-containing polymers and conventional methods used for their preparation are disclosed in US Pat. No. 5,830,957. ASR includes a polymer called Morez polymer. By controlling the type and level of acid monomers and co-monomers in the ASE and ASR polymers associated with the degree of neutralization, the inventors have found that they are optimal to provide stable, less expanded, and insoluble polymers in aqueous systems of relatively high ionic strength. It was found that charge density was achieved. The polymer can be characterized by incorporating an ionic strength trigger, or referred to as ionic strength, base strength or dilution reaction polymer. By changing the ionic strength, base strength or dilution of the aqueous system to a lower level, the polymer disperses, dissolves or expands rapidly to the aqueous system to a significant extent.
[57] Alkali expandable / soluble polymers of the present invention are typically prepared using standard emulsion polymerization methods under acidic conditions such that carboxylic acid groups are protonated to render the polymer insoluble and provide a liquid emulsion. When provided as a liquid colloidal dispersion, the finely divided polymer particles dissolve almost immediately upon pH adjustment. Alkali expandable / soluble resins are typically prepared in heated pressurized reactors (also referred to as continuous tube reactors or Morez® reactors), and conventional methods used for their preparation are disclosed in US Pat. No. 5,830,957. ASR includes a polymer called Morez polymer. The degree of neutralization, the type and amount of acidic monomeric and non-ionic surfactant groups of the polymers of both ASE polymers and ASR are precisely controlled to provide ionic strength, base strength or dilution sensitive / reactive polymers, and their stability, expansion properties And solubility depends on the ionic strength, base strength or dilution of the aqueous system. The polymer composition also applies to the incorporation of ionic strength, base strength and dilution triggering conditions. The ease of handling, measuring and dispersing polymers, rapid solubilization by controlled pH control and optimization of charge density for neutralized acid functionalities, and highly desirable film formation and barrier properties, make alkali soluble / expandable emulsion polymers and alkali soluble / expandable resins. To be the most effective and effective barrier composition for a wide range of applications, including floor protection and controlled release devices for household actives. Both ASE polymers and ASR are usefully used in the present invention to prepare, process, and / or manufacture and encapsulate compositions comprising at least one active ingredient / solvent; Accordingly, chemical / physical triggers contained within the encapsulated composition and activated upon contact with chemical / physical changes in the environment of use (eg, aqueous systems) allow controlled release of the useful agent and active ingredient into the environment of use.
[58] The ASE polymer and ASR of the present invention comprise (a) 5 to 70% by weight of one or more acidic monomers and (b) 30 to 95% by weight of one or more non-ionic vinyl monomers. Optionally, the ASE polymer may comprise 0.01 to 5% by weight of a third component of one or more metal cross-linkers or one or more polyethylene-based unsaturated monomers. The effectiveness of an ionic strength, base strength or dilution reaction composition on the triggered release of a polymer can be determined by (i) the type and amount of acidic monomers, (ii) the degree of neutralization of the acidic monomers, and (i) the type and amount of non-ionic vinyl monomers. And (iii) the kind and amount of polyethylene-based unsaturated monomers or the kind and amount of metals and other cross-linkers, (i) the pH of the aqueous system, and (iii) combinations thereof.
[59] Alkali expandable / soluble resins are typically made in heated pressurized reactors (also called continuous tube reactors or Morez® reactors), and the conventional methods used for their preparation are described in US Pat. No. 5,830,957. The physical properties of the final ASR depend on the monomer content, initiator type and amount, reaction time and reaction temperature. ASR includes a polymer called Morez® polymer. ASR has a weight average molecular weight in the range of 1,000 to 20,000. The acid number of the polymer may also vary depending on the desired degree of water solubility and dispersibility. The acid value of the resin is in the range of 50 to 300. Aqueous solutions or dispersions of ASR can be prepared by simply mixing the resin with a solution of water and at least one base. The monomer feed to this reactor contains from 5 to 15 weight percent solvent to control the process viscosity. Typical solvents include, but are not limited to, alkylene glycols including dipropylene glycol monomethyl ether (DPM) and diethylene glycol monomethyl ether (DE). Some solvents are esterified in the ASR product and most of the residual solvent (50% by weight) is removed by stripping. The level of solvent incorporated affects the performance of the dispersant when used as an aqueous emulsion or as a stabilizer in emulsion polymerization. ARS is typically supplied as an aqueous ammonia neutralized solution, which can also be prepared as a sodium hydroxide neutralizing solution. The resulting ASR dispersion may be formulated into a dispersion or emulsion that does not contain volatile organic compounds (VOCs). Both hydrophilic and hydrophobic ASR can be prepared. Hydrophobic monomers used to prepare hydrophobic or oil soluble ASR are disclosed in US Pat. Nos. 5,521,266 and 5,830,957. Hydrophobic monomers used to prepare hydrophobic or oil soluble ASR are disclosed in US Pat. No. 4,880,842.
[60] Multistage ASR is also usefully used in the present invention, in which the partially or fully neutralized ASR emulsion is prepared in the first stage (core stage) and from partially cross-linked to fully cross-linked ASR and / or substantially An ASR with a different Tg (typically but not only higher than the core stage) is used in the second stage (shell stage). "Multistage" polymer or resin refers to polymer particles having at least one inner phase or "core" phase and at least one outer phase or "shell" phase. The phases of the polymer are incompatible. Immiscibility means that internal and external phases can be distinguished using analytical characterization techniques known to those skilled in the art. Typically, such techniques include, but are not limited to, electron microscopy and staining methods that differentiate or differentiate phases. Morphological configurations of the polymer or dendritic phase are for example core / shell; A core / shell in which the shell particles partially encapsulate the core; Core / shell particles having a plurality of cores; Cores / shells with significantly cross-linked shells; Cores / shells having partially or highly residual unsaturated or chemical reactive groups; Or infiltrating reticulated particles. The preparation of multistage polymers is described in US Pat. No. 3,827,996; 4,325,856; 4,654,397; 4,814,373; 4,916,171; 4,921,898; 5,521,266 and European Patent EP 0 576 128 A1.
[61] Acid monomers provide the necessary ionic and base strength reactivity, and the degree of neutralization of acidic monomers is important for optimizing the charge density of acidic groups in both ASE polymers and ASR. Non-ionic vinyl monomers provide elongated polymer backbone structure and added hydrophobic balance. Non-ionic vinyl surfactant monomers provide a bound surfactant. All components contribute to the preparation of ionic and base strength sensitive polymers and barrier compositions whose stability, swelling properties and solubility depend on the ionic strength of the aqueous system. Within the above ranges, the proportion of each monomer can be varied to achieve optimal properties for the particular triggered release application.
[62] ASE polymers and ASR are acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, aconic acid vinyl sulfonic acid and vinylphosphonic acid, acrylicoxypropionic acid, methacrylicoxypropionic acid, monomethyl maleate, monomethyl puma C ₃ -C ₈ α, β-ethylenically unsaturated carboxylic acid monomers such as latex, monomethyl itaconate, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid (oleic acid), ricinoleic acid, linoleic acid, linoleic acid, linolenic acid, eleostearic acid, laconic acid, gadoleic acid, arachidonic acid One or more acidic monomers selected from the group consisting of fatty acids such as erucic acid, clupanodonic acid and nisinic acid, and mixtures thereof, based on the total monomer content. It is required to 5-70% by weight. Acrylic acid (AA), methacrylic acid (MAA) or mixtures thereof and oleic acid are preferred. Mixtures of itaconic acid or fumaric acid with AA or MAA are suitable, in particular when mixtures with acrylic acid or methacrylic acid are used in small amounts, mixtures of crotonic acid and aconitic acid and their half esters and C ₁ -C Other polycarboxylic acids such as maleic acid with ₄ alkanols are also suitable. In the present invention, it is preferred that the acidic monomer is at least about 15% by weight, most preferably about 5-50% by weight. However, the polycarboxylic acid monomers and the half esters can be replaced with parts of acrylic or methacrylic acid, such as about 1-15% by weight, based on the total monomer content.
[63] C ₂ -C ₁₈ α, β-ethylenically unsaturated monomer, ethylacrylate, ethyl methacrylate, methyl methacrylate to provide the stable aqueous dispersion and desirable hydrophobic: hydrophilic balance required for the ASE polymers and ASR of the present invention C ₁ -C ₈ alkyl of acrylic and methacrylic acid, including latex, 2-ethylhexyl acrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate and C ₂ -C ₈ hydroxy alkyl esters; Styrene, alpha-methylstyrene, vinyltoluene, t-butylstyrene, isopropylstyrene, and p-chlorostyrene; Vinyl acetate, vinyl butyrate, vinyl caprolate; About 30 to 95 weight percent of one or more co-polymerizable non-ionic monomers selected from the group consisting of acrylonitrile, methacrylonitrile, butadiene, isoprene, vinyl chloride, vinylidene chloride, and the like are required. In practice, monovinyl esters such as methyl acrylate, MMA, ethyl acrylate, butyl acrylate are preferred. For ASR implementations, mixtures of styrene and mono vinyl esters as well as mixtures of mono vinyl esters are preferred.
[64] Of course these monomers must be co-polymerizable with acidic monomers. Generally, based on the total weight of the monomers, about 30 to 95 weight percent, preferably about 45 to 95 weight percent of the nonionic vinyl monomer is used to prepare the polymer.
[65] The balance of acidic monomers with non-ionic monomers is an important factor in the triggered release reaction and performance of the resulting polymer used in the blocking agent or composition. The polymers of the invention have the property of encapsulating as well as their use as barrier compositions.
[66] Optionally, the polymer comprises a small amount of at least one polyethylene unsaturated monomer to provide a polymer having a network structure. One or more polyethylene unsaturated monomers may be combined with the monomers during the polymerization process or may be added after the polymerization of the monomers. Suitable examples include allyl methacrylate (ALMA), ethylene glycol dimethacrylate (EGDMA), butylene glycol dimethacrylate (BGDMA), diallyl pentaerythritol (DAP), methylenebisacrylamide, pentaerythritol Di-, tri- and tetra-acrylates, divinylbenzene, polyethylene glycol diacrylates, bisphenol A diacrylates and mixtures thereof. Preference is given to using polyethylene unsaturated monomers at low levels, with levels above about 5% by weight tending to overcrosslink the polymer or providing a polymer of network structure, thereby significantly reducing the efficiency in the present invention. The preferred amount of polyethylene unsaturated monomer is from 0.001 to 5% by weight, more preferably from 0.05 to 1.0% by weight, based on the total weight of the polymer.
[67] Small amounts of at least one metal and / or alkaline earth cross-linker are included with other optional monomer components to provide polymers with tighter structures and better mechanical properties. One or more metal and / or alkaline earth cross-linkers may be combined with the monomers during the polymerization or may be added after the polymerization of the monomers. Suitable metal and / or alkaline earth crosslinkers include, for example, alkaline earth ions of calcium, magnesium and barium, transition metal ions of iron, copper and zinc. Other suitable examples such as aluminum ions are disclosed in US Pat. No. 5,319,018. The preferred amount of metal and / or alkaline earth crosslinker is from 0.01 to 5% by weight, more preferably from 0.05 to 5% by weight, based on the total weight of the polymer.
[68] In other embodiments, one or more selected from stable, insoluble, disperse, decompose, dissolve, destabilize, deform, expand, soften, melt, spread, flow, and combinations thereof in a relatively high ionic strength aqueous system. A trigger reaction composition is provided comprising one or more polyelectrolytes in contact with an aqueous system exhibiting the above chemical / physical reaction, wherein the chemical / physical reaction of the composition is one or more of the ionic strength changes, dilution or Trigger on one or more changes in base concentration. Preferred polymers are ASE emulsion polymers, which comprise (a) 15-70% by weight of one or more acidic monomers; (b) 15-80 weight percent of one or more non-ionic vinyl monomers; And optionally (c) one or more alkali soluble / expandable emulsion polymers comprising 0-5% by weight of one or more metal crosslinkers.
[69] In another embodiment, one that is stable and insoluble in a relatively high ionic strength aqueous system and is selected from dispersion, decomposition, dissolution, destabilization, deformation, expansion, softening, melting, spreading, flow, and combinations thereof, or A trigger reaction composition is provided comprising one or more polyelectrolytes in contact with an aqueous system exhibiting more chemical / physical reactions, wherein the chemical / physical reaction of the composition is one or more ionic strength changes, dilution of the aqueous system. Or trigger on one or more changes in base concentration. The polymer electrolyte may be (a) 15 to 70% by weight of one or more acidic monomers; (b) 15-80 weight percent of one or more non-ionic vinyl monomers; And optionally (c) 0-5% by weight of one or more polyethylene-unsaturated monomers or crosslinkers. Suitable Morez® polymers and conventional methods used for their preparation are described in US Pat. No. 5,830,957.
[70] In another related embodiment using an ASE emulsion polymer, the composition comprises 52.5% methyl methacrylate (MMA), 29.5% butyl acrylate (BA), 18% methacrylic acid (MAA) and 3-mercaptopropionic acid ( 3-MPA) 1.5% by weight of a polymer electrolyte. The polymer electrolyte is stable in NaOH aqueous solution of 2.5M or more, and is triggered to expand / dissolve / disperse by lowering the concentration of NaOH to 1.0M or less.
[71] In another related embodiment using an ASE emulsion polymer, the composition comprises 33% styrene (Sty), 355% butyl acrylate (BA), 18% methyl methacrylate (MMA) and 25% methacrylic acid (MAA) It is a polymer electrolyte in%. The polymer electrolyte is stable in an aqueous NaOH solution of 1.0 M or more, and is triggered to expand / dissolve / disperse by lowering the concentration of NaOH to 1.0 M or less.
[72] The ASE and HASE polymers are commonly prepared from the monomers disclosed above via conventional emulsion polymerization at acidic pH lower than about 5.0 using free-radical production initiators generally in amounts of 0.01-3% by weight of monomer. . Typically, free-radical production initiators include peroxygen compounds, in particular inorganic persulfate compounds such as ammonium persulfate, potassium persulfate, sodium persulfate; Peroxides such as hydrogen peroxide; Organic hydroperoxides such as cumene hydroperoxide, t-butyl hydroperoxide; Organic peroxides such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, peracetic acid, and perbenzoic acid (sometimes activated with water-soluble reducing agents such as iron compounds or sodium bisulfate); As well as other free-radical products such as 2,2'-azobisisobutyronitrile.
[73] The ASE polymer preparation process of the present invention comprises a free radical thermal initiator or redox initiator system under emulsion polymerization conditions. Suitable monomers for the new process include hydrophobic and hydrophilic monoethylenically unsaturated monomers to which free radical polymerization in a straight forward manner can be applied. "Hydrophilic" refers to monoethylenically unsaturated monomers having high solubility in water under emulsion polymerization conditions, as disclosed in US Pat. No. 4,880,842. "Hydrophobic" refers to monoethylenically unsaturated monomers having low solubility in water under emulsion polymerization conditions, as disclosed in US Pat. No. 5,521,266.
[74] ASE polymers are commonly prepared from the monomers described above by conventional emulsion polymerization at acidic pH lower than about 5.0 using free-radical production initiators generally in amounts of 0.01 to 3% by weight of monomer. Alkali expandable / soluble resins are typically prepared in reactors (eg, continuous flow tube reactors or Morez® reactors) heated and pressurized at temperatures below 300 ° C. and typically below 200 psi (1379 kPa). Conventional methods used are described in US Pat. No. 5,830,957. The physical properties of the final ASR depend on the monomer content, initiator type and amount, reaction time and reaction temperature.
[75] Free-radical production initiators, including thermal initiators, are commonly used in the preparation of HASEs, ASE polymers, and ASR. Suitable thermal initiators include, for example, hydrogen peroxide, peroxy acid salts, peroxodisulfuric acid and salts thereof, peroxyester salts, ammonium and alkali metal peroxide salts, perborates, and peroxides. Sulfate, dibenzoyl peroxide, t-butyl peroxide, lauryl peroxide, 2,2'-azobis (isobutyronitrile) (AIBN), tert-butyl hydroperoxide, tert-amyl hydroperoxide, pinene Alkyl hydroperoxides such as hydroperoxide and cumyl hydroperoxide, t-butyl peroxyneodecanoate, t-butyl peroxypivalate and mixtures thereof.
[76] Suitable oxidizing agents of the redox initiator system include, for example, hydrogen peroxide, peroxide salts, disperoxide and salts thereof, peroxide ester salts, ammonium and alkali metal peroxide salts, perborates and persulfates, for example. It includes. Also suitable oxidants of the redox initiator system are, for example, dibenzoyl peroxide, t-butyl peroxide, lauryl peroxide, 2,2'-azobis (isobutyronitrile) (AIBN), tert Water-insoluble, such as -butyl hydroperoxide, tert-amyl hydroperoxide, alkyl hydroperoxides such as pinene hydroperoxide and cumyl hydroperoxide, t-butyl peroxyneodecanoate and t-butyl peroxypivalate Contains oxidizing compounds. Oxygen is released while forming free radicals and transition metal oxide compounds such as peroxides such as alkali metal chlorate and perchlorate, potassium permanganate, manganese dioxide and lead oxide, and non-organic compounds such as iodobenzene are considered as oxidants. It can be usefully used in the invention. The term "water-insoluble" oxidizing agent means an oxidizing compound having a water solubility of less than 20% by weight in water at 25 ° C. Peroxides, hydroperoxides and mixtures thereof are preferred, with tert-butyl hydroperoxide being most preferred. Typical levels of oxidant are 0.01 to 3.0%, preferably 0.02 to 1.0%, and more preferably 0.05 to 0.5% by weight, based on the weight of the monomers used.
[77] Suitable reducing agents of the redox initiator system include, for example, ketone additives of bisulfite, such as sulfite, hydrogen sulfite, alkali metal bisulfite, acetone bisulfite, alkali metal disulfite, metabisulfite and salts thereof, Low-oxidation sulfur compounds such as thiosulfate, formaldehyde sulfoxylate and salts thereof, reducing nitrogen compounds such as hydroxyl amine, hydroxylamine hydrosulfate and hydroxylammonium salts, polyamines and sorbose, fructose, Reducing sugars such as glucose, lactose and derivatives thereof, endoils such as ascorbic acid and isoascorbic acid, hydroxy alkylsulfinic acids such as sulfinic acid, hydroxy methylsulfinic acid and 2-hydroxy-2-sulfinacetic acid and salts thereof, Alkyl sulfin, such as formadine sulfinic acid and salts thereof, propyl sulfinic acid and isopropyl sulfinic acid Acids, reducing compounds such as aryl sulfinic acids such as phenylsulfinic acid. The term "salt" includes, for example, sodium, potassium, ammonium and zinc ions. Sodium formaldehyde sulfoxylate, also known as SSF, is preferred. Typical reducing agent levels are 0.01 to 3.0% by weight, preferably 0.01 to 0.5% by weight and more preferably 0.025 to 0.25% by weight, based on the weight of the monomers used.
[78] Metal promoter complexes of the redox initiator system include water-soluble catalytic metal compounds and chelating ligands in salt form. Suitable metal compounds include, for example, iron (II, III) salts such as iron sulfate, iron nitrate, iron acetate and iron chloride, cobalt (II) salts, copper (I, II) salts, chromium (II) salts, Metal salts such as hepatitis, nickel (II) salts, vanadium (III) chloride, vanadium sulfate (IV) and vanadium salts such as vanadium (V) chloride, molybdenum salt, rhodium salt and cerium (IV) salt. The metal compound is preferably in the form of a hydrated metal salt. Typical catalyst metal salt levels used in the present invention are 0.01-25 ppm. In addition, a mixture of two or more catalytic metal salts may be usefully used in the present invention.
[79] The metal complexes that promote the redox cycle in the redox initiator system must be soluble as well as have a suitable oxidation and reduction potential. In general, the oxidant must be capable of oxidizing (eg, Fe (II)-> Fe (III)) metal promoter complexes in a low oxidation state, while the reducing agent reduces the metal promoter catalyst in a high oxidation state (eg, For example, Fe (III)-> Fe (II)) should be possible. The choice of specific oxidizing and reducing agents usefully used in redox initiator systems for preparing aqueous emulsion polymers from two or more ethylenically unsaturated monomers is determined by the redox potential of the metal salt. In addition, the ratio of oxidant to reducing agent is 0.1: 1.0 to 1.0: 0.1, depending on the redox potential of the metal salt used. For effective reduction of monomer levels in aqueous polymer dispersions made from one or more ethylenically unsaturated monomers, the chelating ligands used in conjunction with soluble metal salts contain less than six groups of multidentate aminocarbatable coordinating metal salts. It is preferred that it is a carboxylate ligand.
[80] The oxidizing agent and the reducing agent are typically added to the reaction mixture in separate streams or in a single shot, preferably together with the monomer mixture. The reaction temperature is maintained at a temperature lower than 100 ° C throughout the reaction path. Reaction temperature is 30-85 degreeC, Preferably it is less than 60 degreeC. The monomer mixture can be added without watering or as an emulsion in water. The monomer mixture can be added one or more or continuously, linearly or nonlinearly, or a combination thereof over the reaction cycle. The type and amount of redox initiator system may be the same or different at different stages of the emulsion polymerization.
[81] Optionally, chain transfer agents and additional emulsifiers can be used. Representative chain transfer agents include carbon tetrachloride, bromoform, bromotrichloromethane, n-dodecyl mercaptan, t-dodecyl mercaptan, octyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, butylthioglycolate, Long chain alkyl mercaptans and thioesters such as isooctyl thioglycolate and dodecyl thioglycolate. The chain transfer agent is used in amounts of up to about 10 parts per 100 parts of polymerizable monomer.
[82] At least one anionic emulsifier is often included in the polymerization charge, and one or more known nonionic emulsifiers may also be present. Examples of anionic emulsifiers are alkali metal alkyl aryl sulfonates, alkali metal alkyl sulfates and sulfonated alkyl esters. Specific examples of well-known emulsifiers are sodium dodecylbenzene sulfonate, sodium discontinuous-butylnaphthalene sulfonate, sodium lauryl sulfate, disodium dodecyldiphenyl ether disulfonate, disodium n-octadecylsulfosuccinamate And sodium dioctylsulfosuccinate.
[83] Optionally, other components that are well known in emulsion polymerization techniques may include such chelating agents, buffering agents, inorganic salts, and pH adjusting agents.
[84] Polymerization at an acidic pH lower than about 5.0 allows for the direct preparation of aqueous colloidal dispersions with relatively high solids content without problems of excessive viscosity and flocculation. The polymerization is carried out in batch-wise, sequential or continuous batch and / or continuous addition of monomers in conventional manner.
[85] The required monomers can be co-polymerized in this proportion and the resulting emulsion polymer can be physically mixed to form a product with the desired balance of properties for a particular application. As such, by varying the monomers and their proportions, an emulsion polymer with optimal properties for a particular triggered reaction application can be designed.
[86] In practice, generally about 15-60 weight percent, preferably about 20-40 weight percent, one or more non-ionic vinyl monomers, based on the weight of the total monomers, about 15-80 weight percent It is preferred to co-polymerize% by weight, preferably about 40-70% by weight, and about 1-30% by weight of one or more non-ionic vinyl surfactant ester monomers, preferably about 2-20% by weight. Do. In particular, effective liquid emulsion polymer polyelectrolytes include about 20-50% by weight total acrylic acid and methacrylic acid, about 40-70% by weight ethyl acrylate, and methacrylic acid of C ₁₂ -C ₂₄ alkoxypoly (ethyleneoxy) ethyl alcohol Obtained by copolymerization of about 2-12% by weight ester.
[87] Synthesis of hydrophobically modified PELs is usefully used in the present invention. Water soluble / dispersible / expandable polymers incorporating hydrophobic groups can be aggregated and self-organized due to various hydrophobic interactions, such as non-ionic vinyl surfactant monomer units. When left in an isotropically soluble state, such PELs are not phase-separated from homogeneously dissolved PELs, including, for example, monolayers and vesicles, but significantly between self-organized systems. Has an intermediate of. PELs having a plurality of nonionic vinyl surfactant moieties bound by a polymeric backbone are micelle-forming macromolecules and are used in the present invention as triggered reaction compositions, barriers and devices. Such "micelle" PELs or "polysoaps" are described in detail by P. Anton, P. Koeberle and A. Laschewsky in "Makromolekular Chemie" (194, pp 1ff, 1993). Synthesis of hydrophobically modified PELs can be accomplished, for example, by reacting a hydrophilic polymer with one or more hydrophobic compounds or non-ionic vinyl monomer units or starting with a hydrophobic polymer to introduce a hydrophilic moiety, Copolymerization of hydrophobic ethylenically unsaturated monomer units and polymerization of non-ionic surfactants having non-ethylenically unsaturated groups (non-ionic vinyl surfactant monomer units) may proceed to synthetic routes comprising modifying the macromolecules preformed. This gives the PEL with the chemically best characterized structure. Suitable hydrophilic and hydrophobic polymers are described in US Pat. No. 5,521,266. The combination of the polymer and surfactant structure forms some modifiable structural configuration. This is, for example, the length and branching of the polymer side chain, the nature of the ionic "head" group, the nature of the hydrophobic "tail" group, the chemical structure and macromolecular structure of the PEL backbone and the PEO unit Incorporation of flexible spacer groups.
[88] Compositions useful in the present invention related to alkali soluble / expandable polymers include poly (acid) homopolymers, copolymers and salts thereof. Examples include polycarboxylic acids and salts thereof, polyacrylate salts, HASE, ASE, ASR, Morez® polymers and salts thereof. Suitable examples include Morez® polymers and salts thereof and combinations thereof. Suitable examples of such polymers are described in US Pat. No. 4,095,035; 4,175,975; 4,189,383; 4,267,091; 4,331,572; And 5,830,597. Suitable examples of other polycarboxylic acid polymers are also poly (oxalic acid), poly ((meth) acrylic acid), poly (vinyl sulfonic acid), poly (sulfonic acid), poly (sulfuric acid), poly (phosphoric acid), poly (phosphonic acid), Poly (vinyl phosphonic acid), poly (maleic acid), poly (beta-malic acid), poly (glutaric acid), poly (fumaric acid), poly (lactic acid), poly (itaconic acid), poly (crotonic acid) and Poly (D, L-glutamic acid). This kind of PEL is also called anionic PEL.
[89] Anionic, cationic, amphoteric PEL compositions and their physical mixtures and combinations thereof are barrier materials that encapsulate, and / or surround and / or form a matrix having a trigger reaction composition, one or more useful agents / active ingredients. And devices for delivering one or more oil-soluble / active ingredients to the environment of use. Environments of use include, for example, liquid media, aqueous systems, non-aqueous systems, free flowing solids systems, textile laundry systems, cleaning systems, human and animal skins, and plant materials. PEL synthesis can be optimized to enhance triggering properties, to enhance the activity of the polymer in trigger specificity and other triggered reaction applications and implementations. Typical examples include alkali expandable / soluble polymers, poly (D, L-aspartic acid), poly (amino acid) polymers, and natural and chemically modified PELs, which are enhanced ecological and environmental aspects of both PEL and PEL processes. Miscibility / biodegradability. We provide triggered reaction PELs that include well characterized chemical / physical triggers and well characterized macromolecular structures.
[90] Hydrophobically modified acid-soluble / expandable polymers including acid soluble / expandable polymers including emulsion polymers, emulsion polymers, poly (acidic) homopolymers, copolymers and salts thereof; Poly (basic) homopolymers, copolymers and salts thereof; Amphoteric homopolymers, copolymers and salts thereof, including emulsion polymers, poly (amino) acid homopolymers, copolymers and salts thereof; Anionic, cationic and amphoteric polysaccharide homopolymers, copolymers and salts thereof; Chemically modified anionic, cationic and amphoteric polysaccharide derivatives; Anionic, cationic and amphoteric polypeptide homopolymers, copolymers and salts thereof; Chemically modified anionic, cationic and amphoteric polypeptide derivatives, chemically modified natural polypeptides, chemically modified nucleic acids, synthetic nucleic acids, chemically modified enzymes, chemically modified proteins, gelatin and chemically modified Gelatin, lignosulfonic acid homopolymers, copolymers and salts thereof; Ionene homopolymers, copolymers and salts thereof; Anionic, cationic and amphoteric polyester homopolymers, copolymers and salts thereof; Chemically modified synthetic and natural polyester derivatives; Anionic, cationic and amphoteric polyurethane homopolymers and copolymers and salts thereof; Chemically modified synthetic and natural polyurethane derivatives; Synthetic methods for preparing acid soluble / expandable polymers comprising copolymer blends of the above-described PELs, physical mixtures of the above-described PEL polymers, grafted cations, anions and amphoteric components are described in H. Dautzenberg, W. Jaeger, J. Koetz, B. Phillip, Ch. "Polyelectrolytes" by Seidel and D. Stscherbina et al. (Chapters 1-3, Hanser: Munich, 1994); R.Y. Lochhead, J. A. Davidson and G.M. Thomas "Poly (acrylic acid) Thickeners"; "Polymer in Aqueous Media" (J.E. Glass Ed., ACS: Washington, Chapter 7, 1989); And G.D. Shay's "Alkali-Swellable and Alkali-Soluble Thickener Technology", "Polymers in Aqueous Media" (J.E. Glass Ed., ACS: Washington, Chapter 25, 1989).
[91] Related PELs are cationic polymers and hydrophobically modified cationic polymers. Cationic PELs include, for example, acid soluble / expandable homopolymers, including copolymers of emulsions, copolymers and salts thereof; Hydrophobically modified acid-soluble / expandable homopolymers including emulsion polymers, copolymers thereof and salts thereof. Also included are non-neutralized, partially neutralized and fully neutralized PELs as well as non-quaternized, partially quaternized and fully quaternized PELs. Suitable examples of cationic PELs are amine homopolymers, copolymers and salts thereof, quaternized amine polymers, copolymers and salts thereof, poly (amino) acrylates and salts thereof, poly (amido) amines and salts thereof , Quaternized poly (amido) amines, poly (acrylate) amines and salts thereof, poly (amino) acrylate esters and salts thereof, polyacrylamides, poly (amino) acrylamides and salts thereof, quaternization Poly (amino) acrylamide, poly (amino) urethane and salts thereof, quaternized poly (amino) urethane, poly (amino) ester, quaternized poly (amino) ester, poly (acrylate) phosphonate, phosphono Terminated polyacrylates, poly (phosphono) acrylates, poly (sulfonate) acrylates and salts thereof, polymeric ammonium salts, poly (sulfonium) salts, poly (phosphonium) salts, quaternized poly (amino ) Alkyl acrylates, Copolymers of acid soluble and cationic PELs, physical mixtures of these PELs and their cationic PEL salts. Acid soluble and cationic PELs are prepared by conventional solution, suspension and emulsion polymerization. Basic groups such as amino groups and cationic portions such as quaternary ammonium and phosphonium groups can be prepared by graft polymerization. Mixtures of acid soluble / expandable and / or cationic PEL homopolymers and copolymers may also be usefully used. Block, alternating and random acid soluble / expandable and / or cationic PEL copolymers are also usefully used in the present invention. Polymerization conditions such as the type, type of initiator, temperature, ionic monomers and non-ionic monomers described above for ASE and HASE polymers are usefully employed.
[92] Polymer quaternary ammonium containing PELs comprising ionized and ionizable nitrogen atoms in the polymer backbone are useful in the present invention. These are called ionenes in the art and provide acid soluble and cationic PEL.
[93] Cationic PELs can also be used, for example, in the base catalyst Mannich reaction of formaldehyde and alkylamines with polyacrylamides, primary and tertiary, which lead to amino-substituted PELs having polyacrylamides and pendant tertiary amine groups. Prepared by chemical modification of polyacrylamide by reaction including reaction of amines with secondary functional groups and Hofmann reaction of polyacrylamide with basic hypochlorite, for example to form polyvinyl amino PEL . The former forms a stable PEL by subsequent quaternization of the amine functional group. Polyacrylonitrile is chemically usefully modified in a similar manner.
[94] Acid soluble and cationic PELs are based on the total monomer content: N-alkyl (amino) acrylate, N-alkyl (amino) methacrylic acid, N, N-dialkyl (amino) acrylate and methacrylate, (Amino) acrylamide and methacrylamide, N-alkyl acrylamide, (vinyl) amino sulfonate and vinyl phosphonate, N-substituted (ammonium) acrylate and (ammonium) alkyl acrylate, (phosphonium) acrylic 15 to 70% by weight of one or more basic and cationic monomers selected from the group consisting of C ₃ -C ₈ α, β-ethylenically unsaturated amino monomers, such as the rate, terminally substituted phosphonium acrylates and combinations thereof Need. Other suitable acid soluble and cationic monomers include, for example, diallyldimethylammonium halide (e.g. chloride is referred to as DADMC), dimethylaminoethylacrylate and methacrylate, dimethylaminopropylmethacrylate, Dimethylaminomethacrylateamide, Acryoxyethyltrimethylammonium halide, methacrylamidopropyltrimethyl ammonium halide, 3-methacryloxy (2-hydroxy) propyltrimethylammonium halide and (3-acrylamido-3-methyl ) Butyltrimethylammonium halide and combinations thereof. Also suitable are those containing maleic acid and other esters of polyethylene-unsaturated amines and polyvinyl amines with C ₁ -C ₄ alkanols. It is preferred to have at least about 15% by weight, and most preferably about 20-50% by weight of basic and cationic monomers. Acid soluble / expandable emulsion polymers, hydrophobically modified acid soluble / expandable emulsion polymers can be converted to cationic and hydrophobically modified PELs by conventional acid and alkylation reactions. Cationic quaternary ammonium monomers derived from AA and AAA, as well as homopolymers thereof, as well as copolymers with acrylamide are useful due to their usefulness for their various applications. Monomer N-substituted acrylamides are more expensive than N-alkylaminoacrylates, but some advantages include higher reactivity of monomer units and relatively increased hydrolytic stability of both monomers and PEL. Serves the purpose. Cationic monomers such as DADMAC and one or more ethylenically unsaturated monomers including, for example, acrylonitrile, methylstearyldiallylammonium chloride, vinyl acetate, styrene, alkyl acrylates, AA, MAA, and maleic anhydride Copolymers of are usefully used in the present invention. Suitable poly (amines), including poly (D, L-lysine) and poly (amideamine), are also useful in the present invention. Copolymers of acrylamide and DADMAC are also useful.
[95] Copolymerization of cationic vinyl monomers with non-ionic co-monomers advantageously provides PELs with variable charge densities, charge intensities and neutralization degrees. The charge density can be confirmed by different co-monomer reactions of different amounts in the initial co-monomer mixture or in the feed. PELs with different charge strengths can be obtained using quaternary ammonium derivatives of alkyl (amino) and AA and MAA as described above. Polymeric cation PELs having pendant aromatic nuclei are useful in the present invention and include, for example, alkylamino styrenes, (p-vinyl (benzyl) trialkylammonium halides), vinylpyrines, vinylpyridinium halides, pyrrolies Obtained by the polymerization of vinyl monomers comprising don and vinylpyrrolidinium halides. Polymerization in aqueous solution requires a low pH to ensure polymer and emulsion stability, where the properties of the charge in the cationic PEL are controlled. It is markedly changed due to partial ionization. Basic, vinyl heterocyclic monomers including, for example, vinyl imidazole, vinyl imidazolinium, vinyl piperidine and vinyl piperidinium halides may also be usefully used.
[96] Useful compositions related to acid soluble / expandable polymers and their use in the present invention are basic homopolymers, copolymers and salts thereof. Suitable examples include ammonium and quaternary ammonium salts of polyamines and poly (amino) acrylates, alkyl ammonium salts of polyamines and poly (amino) acrylates, phosphonium salts of polyamines and poly (amino) acrylates, polyamines and poly (amino) acrylates Sulfonium salts of salts and combinations thereof.
[97] Amphoteric PELs are usefully prepared by free radical polymerization. The presence of both anionic and cationic charges has a pronounced effect on the solution and solid state properties of these PELs. The hydrodynamic volume of the amphoteric PEL is influenced by aqueous system parameters including, for example, pH, charge density, salt concentration, ionic strength, type and concentration of salt added, and combinations thereof. In the absence of low molecular weight PEL, large amounts of PEL do not dissolve in the aqueous medium, but exist as hydrogels. The extent of this effect can be modified by incorporating one or more nonionic monomers to increase the PEL polymer chain. We have found that the polymerization process is affected by such parameters in aqueous systems. Synthesis of amphoteric PEL by free radical polymerization includes, for example, copolymerization of acidic and basic ethylenically unsaturated monomer units such as acidic and basic monomer units comprising AA and alkyl (amino) acrylates. Changes in ionic strength and pH, for example, change the reactivity of the ionizable monomer units with unionized AA and carboxylate ions. Typical two-component copolymers are not applicable in this case. Polymerization of amphoteric ion-pair comonomers in solution, suspension or emulsion is also useful in the present invention. Such amphoteric monomers include, for example, vinyl anionic monomers that are gegenions (counter-ions) of vinyl cationic monomer units. Non-polymerizable ions are absent. The pairs are separated and characterized: The polymerization of such ion pairs is described in "Polymeric Amines and Ammonium Salts" by JCSalmone, CC Tsai, AC Watterson and AP Olson (E. Goethals, Pergamon Press: New York, pp. 105 ff, The homopolymerization of monomers incorporating two separate polymerizable ethylenically unsaturated groups is described in 1980. The resulting PEL bulk contains the same molar amount of cation and anion charges pendant along the polymer chain. In addition, the charged comonomers are not alternating and, moreover, all individual polymer chains do not have to contain the same amount of cationic and anionic monomer units. The foam is random, optionally wherein the terpolymer of the ion-pair comonomer and one or more non-ionic monomer units has an amphoteric PEL ionomer (rigidity) with improved rigidity by the presence of an ionic interaction. polydispersity and molecular weight depend on any solvent affecting the degree of intermolecular cohesion Also useful for the synthesis of amphoteric PEL is the polymerization of sulfobetaine and carbobetaine monomer units. Have well-characterized ion charge arrangements: In these PELs, zwitterions maintain their di-ionic form over a wide range of ionic strengths and pH. Contains both anionic and cationic sites in the same pendant group and is readily polymerizable in aqueous systems. There is a tendency showing a cross (intermolecualr) and intramolecular dihydro represented by (intramolecular) ion interaction gel (hydrogel) characteristics. The addition of simple salts promotes the water solubility / dispersibility of the PEL. Unlike other PEL properties, the viscosity of the polymeric zwitterionic aqueous system increases with increasing salt concentration.
[98] Amphoteric PEL is usefully used in the present invention. Suitable examples include poly (amino) acids such as poly (D, L-aspartic acid), poly (glycine) and (D, L-phenylalanine).
[99] Useful methods for the preparation of such poly (amino) acids are, for example, by altering the copolymer of maleic anhydride and excess diamine to give a regular polyamphoteric PEL containing amines and carboxyl groups. Aminolysis, hydrolysis of cyclic polymers having amide bonds in the ring, which can be readily prepared by cyclopolypolymerization, to form poly-amphoteric PEL, and a single copolymer of AA and vinylamine into random copolymers Curtius-, Rossen on preformed polymers that induce amphoteric PEL of regular, alternating sequences, exemplified by Hofmanndegradation of polyacrylonitrile providing the route )-, Is a chemical modification of homopolymers and copolymers that involves the interaction of neighboring functional groups during Hofmann-type rearrangements.
[100] Moreover, for example, the reaction of hydroxyamines, as well as polyacrylonitrile and dicyandiamide, gives amphoteric PEL, which is soluble / dispersible only in acidic or basic media and in high or low ionic strength media. . Between pH 3-9, they are insoluble in aqueous systems and form precipitates. Such PELs are used, for example, in encapsulating and antifreeze agents of flocculants, active ingredient promoters, oil soluble agents.
[101] Useful acidic, basic, cationic and anionic monomers usefully employed in the present invention for preparing amphoteric PELs are as described above. Moreover, suitable monomer units used in the preparation of such PEL copolymers include, for example, allyl and diallylamino monomers having MA and maleamic acids. Such PELs have regular alternating structures. The pH of this monomer reaction mixture has a value corresponding to the isoelectric points of each of the resulting PELs.
[102] Both synthetic and natural PELs are usefully used in the present invention. Natural polymers suitable for the production of such PELs include, for example, polysaccharides, polysaccharide derivatives, proteins, nucleic acids and lignin. Depending on the starting natural polymer and the intended PEL macromolecular structure, the PEL can, for example, separate the soluble, expandable / dispersible PEL of the preformed PEL from the natural product moiety (monomer unit motif) by conventional extraction and precipitation techniques. Separation by a combination of extraction and chemical modification to liberate preformed ionogenic groups and / or to degrade natural products to obtain and separated nonionics into anionic, cationic or amphoteric PELs Synthetic methods involving derivatization of polymers are obtained from biological polymers ("biopolymers").
[103] Suitable examples of amphoteric natural PELs include, for example, an integral type of polyester consisting of phosphoric acid and deoxyribose units, each having a heterocyclic weak base attached to a carbohydrate unit, also called a nucleic acid. In aqueous systems, these nucleic acids generally act as anionic PELs with Na + ions acting as counter-ions to phosphoric acid units with relatively strong acid action. The variability of the nucleic acid PEL macromolecular structure may include, for example, the selection and sequence of the weak N-base adenine, guanine, thymine, cytosine, cysteine and uracil attached to the sugar moiety of the biopolymer backbone, the sugar unit Selection, namely bio-stabilized by hydrogen bonds (H-bonds) resulting from ribose in the case of ribonucleic acid (RNA) and deoxyribose in the case of deoxyribonucleic acid (DNA), and heterocyclic bases attached to the sugar moiety. Polymer chain forms.
[104] Related to the nucleic acid are the included teicosic acids. Teicoic acid is a linear polyester consisting of a phosphoric acid unit and glycerol, each ribitol unit acting as a diol and carrying various sugars and amino acids as side groups. The anionic nature of these water soluble / expandable / dispersible PELs is due to the free acid action of phosphoric acid units that are not involved in ester bonds, similar to nucleic acids. Teicoic acid is found in a variety of microorganisms, including Lactobacillus cerabiosus , and can be separated therefrom by conventional techniques.
[105] Additional suitable natural PELs usefully employed in the present invention are polypeptide and protein based PEL homopolymers, copolymers and salts thereof, and chemically modified derivatives of natural polypeptides and proteins. The monomeric unit of such a biopolymer is α-amino carboxylic acid of the formula RCHNH ₂ · COOH which is bound by peptide bonds, ie, amide bonds between amino and adjacent carboxyl groups. In particular, when the monomer has additional acidic and basic functional groups, anionic, cationic and amphoteric polymer electrolyte peptides and proteins are obtained. Suitable examples of amphoteric PELs useful for the present invention are poly (aminocarboxylic acids), such as poly (D, L-aspartic acid), poly (glycine), poly (D, L-phenylalanine), type-A- Gelatin, type-B-gelatin and collagen. Synthesis of polyaspartic acid is described in US Pat. No. 5,057,597; 5,328,631; 5,319,145; 5,491,212; 5,380,817; 5,484,878; 5,371,170; 5,410,017; 5,459,234; 5,457,176; 5,552,514; 5,556,938; 5,554,721; 5,658,464; 5,531,934 and EP 0 700 987; EP 0 705,794; EP 0 644 257; And EP 0 625 531 are described in detail.
[106] Additional suitable natural PELs usefully employed in the present invention are polysaccharide-based homopolymers, copolymers and salts thereof, and chemically modified derivatives. Most natural polymer based PELs have polysaccharide backbones with PELs that represent ionic groups and pendant types that are chemically attached to side groups. Suitable polysaccharide-based PELs include, for example, cyclodextrins, glucose, pentose, hexose, glucoside derivatives (half acetal), celluloses, chemically modified celluloses, cellulose derivatives, microcrystalline celluloses, galactose, starch, mannose, Gel-forming anionic galactans, agarose, chemically modified agarose, agar such as D-galactose and agaropeptin, poly-D, such as lactose, fructose, sucrose, carrageenan, carrageenan fractions Gels with sulfate half-ester groups such as those derived from pectin, seaweeds, furcellans, porphyrans, phyllophyran and ascophyllan, such as galacturonic acid and esters thereof Anionic galactan, algin, alginic acid, mannuronic acids, guluronic acid, alginate salts, traganth, arabinose, galactose, fucose and Traganth gum with xylose units, gum arabic, hylauronic acid such as D-glucuronic acid, pectins or preformed ionic sites such as chitosan and heparin PEL obtained from the natural polymer product by glass of.
[107] Polysaccharide-based PELs are mostly anionic in their properties, and their respective macromolecular structures are linear, branched, block copolymers and mixtures of polysaccharides and other polymers. Anionic PELs are due to carboxylate and sulfate half-ester groups attached to the side chain or polymer backbone. They can also be obtained from plant tissues, animal tissues, plant extracts, animal extracts, microbial products and chitin, bone, cartilage and cytoplasmic extracts. Cellulose-based PEL is a subclass of PEL used in the present invention. Such PELs are for example esterified of cellulose providing anionic polyelectrolyte esters such as, for example, a two-phase system with cellulose in at least initially a solid phase, cellulose xanthogenate and cellulose phosphate esters. , Esterification of cellulose which provides PEL such as carboxymethyl cellulose (CMC), carboxymethyl cellulose, dicarboxymethyl cellulose and sulfoethyl cellulose, epoxidation of cellulose, aminoalkylation of cellulose, 6-carboxycellulose, anhydroglucose and It is usually prepared by a synthetic method involving the oxidation of cellulose giving the same PEL. Xylan-based PEL is a subclass of PEL used in the present invention. Starch-based PEL is a subclass of PEL used in the present invention. Suitable examples include anionic starch esters such as starch phosphate, anionic ethers and cationic starch. Dextran-based PEL is a subclass of PEL used in the present invention. Lignin-based PELs derived from wood and wood articles are celluloses related to the cross-linked PEL family used in the present invention.
[108] PEL cannot be understood as a simple duplication of electrolyte and polymer properties. Excluded volume effects are the only important interactions in non-ionic polymers, and Coulomb interactions at long distances in PEL result in a wide range of triggers in aqueous systems. Unlike simple electrolytes, one type of charge bundles together along the polymer chain, resulting in a strong field around the polymer chain even in highly diluted aqueous systems. This unique property of PEL is useful for controlling the ionic strength of aqueous media to induce various ion triggers and is believed to result in PEL exhibiting rod-like properties in aqueous systems without infinite dilution and addition of salts. . Useful electrochemical properties of PEL include, for example, potentiometer triggers in the presence or absence of added salts, dissociation due to the action of ionic strength (equilibrium), structural triggers based on potentiometric changes, and added polyanions ( polyanions) and buffer effects, triggers based on conductivity changes, ionic strength and salt concentrations that depend on conductivity triggers, electrophoretic triggers based on ion mobility changes in both macroscopic and microscopic domains, adsorption triggers, radiation responses, and PEL's monomer units. Trigger means useful in aqueous systems based on variables including ultraviolet and visible light triggers, luminescence triggers, UV and visible light triggers and fluorescence triggers based on changes in specific chromophores incorporated And dissociat content of ionized and / or ionizable groups of ionic macromolecules that provide ion) state.
[109] In general, the obtained ASE and HASE copolymer dispersions have a solids content of 20-50% by weight, and the copolymers are gel permeation chromatography when no polyethylene-based unsaturated monomer or metal cross-linker is incorporated into the polymer. It has a weight average molecular weight of about 200,000 to 10,000,000 measured by (GPA). Chain transfer agents can be used to have a weight average molecular weight of less than 30,000.
[110] HASE copolymer products prepared by emulsion polymerization at acidic pH are in the form of generally stable aqueous colloidal dispersions with a typical milky latex appearance. Such liquid emulsions include copolymers dispersed into distinct particles having an average particle diameter of about 500 to 300,000 mm 3 measured by light scattering.
[111] In the form of an aqueous colloidal dispersion, which is stable at an acidic pH of about 2.5 to 5.0, the ASE and HASE copolymers are particularly useful and have desirable film forming properties. Such aqueous dispersions may contain about 10-50% by weight of polymer solids and have a relatively low viscosity. Thus, it is easily measurable and mixed with an aqueous product system. However, the dispersion is ionic strength and / or pH responsive. If the ionic strength and / or pH of the polymer dispersion is controlled by addition of a base such as ammonia, amines or non-volatile inorganic bases such as sodium hydroxide, potassium carbonate and the like, when the polymer is at least partially dissolved in the aqueous phase, The aqueous mixture becomes translucent or transparent at the same time as the viscosity is increased. The neutralization can occur in situ when the liquid emulsion polymer is mixed with an aqueous solution comprising a suitable base. Alternatively, if required for a given application, pH adjustment by partial or complete neutralization can be made before or after mixing the liquid emulsion polymer and the aqueous product.
[112] The resulting ASE copolymer dispersion had a solids content of 20-50% by weight, and the ASE copolymer was measured by gel permeation chromatography (GPA) when no polyethylene-based unsaturated monomer or metal cross-linker was incorporated into the polymer. It has a weight average molecular weight of about 200,000 to 10,000,000. The chain transfer agent may be used to have a weight average molecular weight of 30,000 or less. The resulting ASR aqueous dispersion has a solids content of 10 to 50% by weight, and ASR is 1,000 to 20,000 as measured by gel permeation chromatography (GPA) when no polyethylene unsaturated monomer or metal cross-linker is incorporated into the polymer. It has a weight average molecular weight of Typical pH of ASR aqueous ammonia dispersion is 7.0-9.0. At acidic pH the ASR dispersion is in the form of a stable colloidal dispersion with a typical opaque appearance. Typical viscosities of ASR range from 300 to 2500 cps, with non-volatile 25 to 35 weight percent. Morez The polymer is typically prepared in the form of a resin or as an aqueous solution of neutralized ammonia. Such liquid dispersions include copolymers dispersed into distinct particles having an average particle diameter of about 5-3000 mm 3 measured by light scattering methods. The particle size may range from 0.5 nm to 3000 μm, depending on the polymerization conditions and the process used.
[113] ASE copolymer products prepared by emulsion polymerization at acidic pH are generally in the form of stable aqueous colloidal dispersions with a typical milky latex appearance. Such liquid emulsions include copolymers dispersed into distinct particles having an average particle diameter of about 500-3000 mm 3 measured by light scattering. The particle size may range from 0.5 nm to 3000 μm, depending on the polymerization conditions and the process used.
[114] In the form of an aqueous colloidal dispersion, stable at an acid pH of about 2.5-5.0, both the ASE copolymer and ASR are particularly useful for preparing barrier materials and have desirable film forming properties. Such aqueous dispersions contain about 10-50% by weight of polymer solids and the viscosity is still relatively low. Thus, it is easily measurable and mixed with an aqueous product system. However, the dispersion responds to changes in base strength, pH, ionic strength and / or dilution of the aqueous system. If the ionic strength and / or pH of the polymer dispersion is controlled by addition of a base such as ammonia, amines or non-volatile inorganic bases such as sodium hydroxide, potassium carbonate and the like, when the polymer is at least partially dissolved in the aqueous phase, The aqueous mixture becomes translucent or transparent at the same time as the viscosity is increased. The neutralization can occur in situ when the liquid emulsion polymer is mixed with an aqueous solution comprising a suitable base. Alternatively, if required for a given application, the pH adjustment or non-pH adjustment by partial or complete neutralization can be done before or after mixing the liquid emulsion polymer and the aqueous product.
[115] The glass transition temperature ("Tg") of the ASE and HASE polymers is typically -60 to 150 ° C, preferably -20 to 50 ° C, and the amount of monomers and monomers selected to achieve the desired polymer Tg range is It is well known in the art. Tg as used herein is calculated by the Fox equation (T.G. Fox, Bull. Am. Physics Soc., Volume 1, Issue No. 3, page 123 (1956)). In other words, the Tg of the copolymer of monomers M1 and M2 is calculated as follows.
[116] 1 / Tg (calc.) = W (M1) / Tg (M1) + w (M2) / Tg (M2),
[117] Where
[118] Tg (calc.) Is the calculated glass transition temperature of the copolymer,
[119] w (M1) is the weight fraction of monomer M1 in the copolymer,
[120] w (M2) is the weight fraction of monomer M2 in the copolymer,
[121] Tg (M1) is the glass transition temperature of M1 homopolymer,
[122] Tg (M2) is the glass transition temperature of the M2 homopolymer.
[123] All temperatures are ° K. Glass transition temperatures of homopolymers can be found, for example, in J. Brandrup and E.H Immergut's "Polymer Handbook" (Interscience Publisher).
[124] The term "liquid emulsion polymer" as applied to the above ASE and HASE polymers refers to polymers prepared by emulsion polymerization that at room temperature (usually) the polymer itself is a solid, but in the form of a liquid solution or dispersion, becoming a "liquid" emulsion polymer. it means.
[125] In a preferred embodiment of the invention, the ASE and HASE polymers comprise one or more active ingredients / solvents It is advantageously used as a barrier composition to enclose or encapsulate. Two or more ASE and / or HASE polymers may be used as needed. Of course, the HASE polymers are preferably film-formed at temperatures below about 25 ° C., either inherently or using a plasticizer. Both ASE and HASE polymers form effective barrier materials that enclose and / or encapsulate one or more active ingredients immersed in an aqueous system, and the stability of the barrier material is dependent on the ionic strength, pH, temperature, mechanical strength of the aqueous system and their It was found that by changing the combination of. In aqueous systems, the material is stable and forms an effective barrier to contain or encapsulate one or more active ingredients. Exposing the material to the subsequent aqueous system triggers the instability of the material, so that the active material disperses quickly in the aqueous system.
[126] In a preferred embodiment, the barrier composition made from one or more ASE and / or HASE polymers inhibits release of the useful agent and provides sufficient structural support before the barrier of the device is ionic strength triggered dissolution. It forms an impermeable membrane that surrounds or encapsulates one or more active ingredients. An aqueous system refers to any fluid or solution containing water as the main liquid component (eg a solution of organic or inorganic material, in particular a mixture of substances in electrolytes, water and physiological fluids). Typically, the blocking composition completely surrounds, encapsulates and / or forms the matrix with the oil soluble / active ingredient. One or more additives may be combined with ASE and HASE polymers to produce composite blockers that completely enclose, encapsulate and / or form a matrix with a useful agent as needed. The barriers and composite barriers combine thickness and mechanical force, thus they are cleaved by the triggered reaction of ASE and HASE polymers (triggered reaction compositions), thereby releasing the useful agent. Preferably the thickness of the barrier film is 0.1㎛ ~ 1mm. Preferably the thickness of the barrier film for personal care and laundry applications is 10㎛ ~ 300㎛. The barrier layer may be a thin film, a high density film, a composite barrier, a container, a capsule and / or matrix beads.
[127] Inorganic materials such as suitably treated ceramics, metals or glass may be used, but typically, the barrier composite consists of a triggered reactive polymer and polymer blend, biopolymers and any other natural and synthetic materials. The following is a list of preferred components and additives that may be incorporated into the barrier materials and devices of the present invention.
[128] Cellulose acetate, cellulose acetate acetoacetate, cellulose acetate benzoate, cellulose acetate butylsulfonate, cellulose acetate butyrate, cellulose acetate butyrate sulfate, cellulose acetate butyrate valerate, cellulose acetate caprate, cellulose acetate caproate, cellulose acetate cap Phthalate, cellulose acetate carboxymethoxypropionate, cellulose acetate chloroacetate, cellulose acetate dimethaminoacetate, cellulose acetate dimethylaminoacetate, cellulose acetate dimethylsulfate, cellulose acetate dipalmitate, cellulose acetate dipropylsulfate, cellulose Acetate on Cyacetate, cellulose acetate ethyl carbamate, cellulose acetate ethylcarbonate, cellulose acetate ethyl oxalate, cellulose acetate furoate, cellulose acetate heptanoate, cellulose acetate heptylate, cellulose acetate isobutyrate, cellulose acetate laurate, cellulose acetate methacrylate Latex, cellulose acetate methoxyacetate, cellulose acetate methylcarbamate, cellulose acetate methylsulfonate, cellulose acetate myristate, cellulose acetate octanoate, cellulose acetate palmitate, cellulose acetate phthalate, cellulose acetate propionate, cellulose acetate propionate Nate sulfate, cellulose Acetate propionate valerate, cellulose acetate p-toluene sulfonate, cellulose acetate succinate, cellulose acetate sulfate, cellulose acetate trimellitate, cellulose acetate tripropionate, cellulose acetate valerate, cellulose benzoate, cellulose butyrate Naphthylate, cellulose butyrate, cellulose chlorobenzoate, cellulose cyanoacetate, cellulose dicaprylate, cellulose dioctanoate, cellulose dipentanate, cellulose dipentaneate, cellulose formate, cellulose methacrylate, cellulose methoxy Benzoate, cellulose nitrate, cellulose nitrobenzoate, cellulose phosphate (sodium salt), cellulose phosphine , Cellulose phosphite, cellulose phosphonate, cellulose propionate, cellulose propionate crotonate, cellulose propionate isobutyrate, cellulose propionate succinate, cellulose stearate, cellulose sulfate (sodium salt), Cellulose triacetate, cellulose tricaprylate, cellulose triformate, cellulose triheptanoate, cellulose triheptylate, cellulose trilaurate, cellulose trimyristate, cellulose trinitrate, cellulose trioctanoate, cellulose tripalmi Cellulose esters such as tate, cellulose tripropionate, cellulose trisuccinate, cellulose trivalateate, cellulose valerate palmitate and mixtures thereof . 2-hydroxybutyl methyl cellulose, 2-hydroxyethyl cellulose, 2-hydroxyethyl ethyl cellulose, 2-hydroxyethyl methyl cellulose, 2-hydroxypropyl cellulose, 2-hydroxypropyl methyl cellulose, dimethoxyethyl cellulose Acetate, ethyl 2-hydroxyethyl cellulose, ethyl cellulose, ethyl cellulose sulfate, ethyl cellulose dimethyl sulfamate, methyl cellulose, methyl cellulose acetate, methylcyanoethyl cellulose, sodium carboxymethyl 2-hydroxyethyl cellulose, sodium carboxymethyl Cellulose ethers such as cellulose. Polycarbonate. Polyurethane. Polyvinyl acetate. Polyvinyl alcohol. Polyester. Polysiloxanes such as poly (dimethylsiloxane) and polyamino acids such as polyaspartic acid. Polyacrylates, polymethyl methacrylates, alkyl esters higher than poly (acrylic acid), poly (ethylmethacrylate), poly (hexadecylmethacrylate-co-methylmethacrylate), poly (methylacrylate-co Styrene), poly (n-butyl methacrylate), poly (n-butyl-acrylate), poly (cyclododecyl acrylate), poly (benzyl acrylate), poly (butyl acrylate), poly (sec Butyl acrylate), poly (hexyl acrylate), poly (octyl acrylate), poly (decyl acrylate), poly (dodecyl acrylate), poly (2-methyl butyl acrylate), poly (adamantyl meta Acrylates), poly (benzyl methacrylate), poly (butyl methacrylate), poly (2-ethylhexyl methacrylate), poly (octyl methacrylate), polyacrylic acid derivatives such as acrylic resins. Poly (octyloxyethylene), poly (oxyphenylethylene), poly (oxypropylene), poly (pentyloxyethylene), poly (phenoxy styrene), poly (secbutoxyethylene), poly (tert-butoxyethylene) , Polyethers such as copolymers thereof and polymer mixtures thereof.
[129] Natural materials include: insect and animal waxes such as chinese insect wax, beeswax, spermaceti, fat and wool wax; Bamboo Leaf Wax, Candelilla Wax, Carnauba Wax, Japanese Wax, Wooicury Wax, Jojoba Wax, Bayberry Wax, Douglas-Fir Wax, Cotton Wax, Cranberry Wax , Cape berry wax, rice-bran wax, castor wax, Indian corn wax, hydrogenated vegetable oils (eg castor, palm, cottonseed, soybean), sorghum grain wax, spanish moss wax, sugar cane wax Vegetable waxes such as caranda wax, bleach wax, Espparto wax, flax wax, Madagascar wax, orange peel wax, shellac wax, sisal wax, and rice wax; Mineral waxes such as montan wax, peat wax, petroleum wax, petroleum ceresin, wax wax, microcrystalline wax and paraffin; And synthetic waxes such as chemically modified hydrocarbon waxes including polyethylene wax, Fisher-Tropsch wax, polyethyleneglycolated wax and cetyl ester wax.
[130] In a preferred embodiment, the ionic strength trigger is an ionic strength reactive blocking composition surrounding the component, wherein the blocking material is substantially impermeable to the release of the active ingredient into an aqueous system and has a relatively high ionic strength (e.g. For example, it is insoluble in an aqueous system of sodium carbonate (0.01 M equivalent or more) and the barrier is soluble in an aqueous system of relatively low ionic strength (e.g., less than 0.01 M equivalent of sodium carbonate), and the activity Allow the ingredient to release quickly.
[131] The barrier material or the triggered reaction composition in the device is usefully used in the form of, for example, polymer particles, films, coatings, tablets, capsules, pellets, sachets, matrix beads, and capsule polymer granules in the present invention. Or is supported on a substrate. Suitable substrates include, for example, films, nonwovens, fabrics, solids, papers, fabrics, and skin. The ionic strength reactivity trigger means may be formed into a capsule or tablet, for example by bonding a portion of the blocking material to a bonding, encasing, friction fitting, eg blocking material. The barrier material is either partially encapsulated as an adhesive or as an external coating or formed into capsules or tablets by forming encapsulated and co-granulated particles together. Ion intensity responsive trigger means in the aqueous system allow one or more of the useful agent / active ingredient to be released after bursting of the device.
[132] Optionally, the ionic strength reactive blocking material is a trigger reaction polymer mixture or they are mixed with an inert non-soluble material. Inactive refers to a material that is substantially unaffected by ionic strength and / or pH change in the triggering range. By varying the ratio of ionic strength and / or pH reactive material to one or more inert non-soluble materials, one can control the time delay after triggering and before release. The inert non-soluble material is added to provide additional mechanical strength and stability to the barrier material or device during use (eg after expansion of the polymer and barrier) or storage. Typical inert non-soluble materials usefully employed in the present invention are those described as additives to the barrier material or device. Preferably, the inert material is selected from the list of additives described above.
[133] The term beneficial agent refers to a substance that is desirable and / or beneficial for triggered delivery to the environment of use. Useful agents include reagents in gas, solid or liquid form.
[134] The term useful agent refers to a substance that is desirable and / or beneficial for controlling delivery to the environment of use. Examples of such materials are, for example: fabric softeners, fabric softener formulations, cationic and anionic surfactants, scale regulators, foam inhibitors, buffers, amphoteric additives, enhancers, bleaches, organic additives, inorganic additives, Bleaches, dyes, stain removers, water hardness agents, reducing agents, oxidizing agents, optical brighteners, UV protectors, anti-wrinkle agents, gray-inhibitors, soil-water repellents, oil-absorbers Polymers, waterproofing polymers, active-retaining polymers, reprecipitation agents, reprecipitation inhibitors, polymers that prevent the formation of soil and oily substances, detergent addition formulations, biocidal compositions and combinations, antimicrobial compositions and formulations, activators, stabilizers, Polymers with specific detergent properties such as co-enhancers and anti-reprecipitants, pH adjusting agents, enzymes, enzyme inhibitors, fungicides, personal care agents, water repellents, absorbents, flavors, Fragrance, and a personal care active, and a pharmaceutically active agent. Suitable examples of pharmaceutical effect agents / solvents are disclosed in US Pat. No. 5,358,502.
[135] Any mixture of the aforementioned components can be used to deliver sufficient useful agent, typically the ionic strength-trigger means is between 0.01 and 50% by weight of the device, and a barrier comprising ionic strength trigger means is typically one of the devices. It is -30 weight%. Preferably the ion intensity-trigger means is 0.1-20% of the device and the membrane comprising ion intensity-trigger means is 1-20% of the device. The amount of the useful agent is an amount sufficient to achieve the desired effect (eg, washing effect, softening effect, personal care effect, and combinations thereof). The remaining weight may consist of any desired compounding ingredients (disclosed above) and other additives.
[136] Preferably, the device of the present invention comprises a solid beneficial core or a liquid venetary core. Optionally, the device of the invention can also be administered in a capsule comprising a water-soluble wall. For example, the device may be manufactured to be of a size suitable for inclusion in a single or multiple in gelatin capsules, so that when the capsule is dissolved, the device is released into the environment of use. The devices included in the capsule may be of various shapes, with the preferred shape of such devices being spherical or substantially spherical. The exact number and size of such devices can and will be determined in accordance with changes in well-known factors. For example, the environment of use, the useful agent or agents, the amount and release rate of the useful agent are all factors that must be considered to determine the size, shape and number of such capsules as well as the devices in which the composition of the capsule is included.
[137] The device of the present invention having the desirable properties disclosed above can be manufactured using the materials disclosed above in the following processes and in other conventional methods.
[138] Capsule formulations can be prepared by forming caps and bodies of the above described polymers. In a conventional manner, the triggered reaction polymer may be molded into the desired shape and sintered or dip-coated (cured gelatin capsules are prepared in a similar manner). Preferably they are prepared by conventional coating techniques including, for example, spray coating, Wurster coating and pan coating. In addition, the cured gelatin capsules may be coated with a barrier coating. These capsule bodies and caps are then filled with gases, liquids or solids, and other excipients (eg, osmagent, useful components in the form of expanded components) using standard capsule filling techniques. The capsule is then sealed and assembled with the desired ionic strength-reactive material, which can be done using conventional capsule-sealing devices.
[139] Tablets can be prepared using conventional processes and conventional tableting and tablet-coating apparatus. The tablet cores may be prepared by direct compression of useful agents and other preferred excipients (eg osmagents, expansion components) or by other common tableting methods. In order to minimize immiscibility or to provide a substrate suitable for barrier coating, the tablets may first be coated with a water-soluble pre-coat. The pre-coat may be made of sugar, salts, soluble cellulose derivatives or other water-soluble materials.
[140] The tablet core is coated with one of the dense triggered reaction barriers or composites using conventional coating techniques. Such films can be applied using conventional devices such as fluid-layer coaters, pan-coaters, Wurster coaters, spray-dryers or in dip-coats.
[141] In a preferred embodiment, the barrier composition is stable and insoluble in aqueous systems of relatively high ionic strength; Wherein the barrier exhibits one or more chemical / physical reactions selected from dispersible, disintegratable, soluble, instability, deformable, expandable, softenable, flowable, and combinations thereof; Wherein the chemical / physical reaction of the composition is triggered by one or more ionic strength changes of the aqueous system; The device may release the active ingredient into the aqueous system as a result of the triggered reaction of the blocking composition; The device is manufactured using a coating technique selected from the group consisting of fluid layer spray coating, Wurster coating, Pan coating and co-extrusion, coacervation, spray drying and spray chilling; Optionally said one or more useful liquid ingredients are co-granulated with one or more solid active ingredients in the form of solid granules, pellets, tablets, capsule granules, sachets, matrix beads and capsules.
[142] One or more layers or coatings of ionic strength reactants are applied on the tablet core. The coating can be applied using a standard coating method similar to that disclosed above to apply the barrier coating.
[143] Beads, granules or multiple particles can be prepared in a similar manner to the method used to prepare tablets.
[144] Blocking compositions made from one or more ASE and HASE polymers surround or encapsulate a matrix with one or more active ingredients that provide sufficient structural support while inhibiting release of the useful agent prior to triggered dissolution or dispersion of the device barrier. And / or forming impermeable barriers. Aqueous systems refer to, but are not limited to, solutions containing water as the main liquid component (eg, organic or inorganic solutions, in particular electrolyte and surfactant mixtures in water). Typically the blocking composition completely surrounds, encapsulates or forms the matrix with the oil-soluble / active ingredient or forms an impermeable matrix of the blocking composition and the oil-soluble / active ingredient. The impermeable barrier material is a combination of thickness and mechanical force, which is not limited thereto, but will be sufficiently stable in a predetermined system, including heavy duty liquid (HDL) formulations or fabric washing cycles, once desired trigger If a release environment is created, it will rupture quickly and release useful components. Preferably, the impermeable barrier film has a thickness of 5 μm to 300 μm for home and personal care applications such as fabric care laundry applications. The impermeable barrier layer may be a dense film, a composite membrane, an asymmetric structure, or the like. The preferred particle size of the impermeable matrix beads of the barrier composition and the oil-soluble / active ingredient is 20-5000 μm. Typically, the device comprising the barrier composition and useful components consists of an emulsion polymer and personal care and home care actives including, but not limited to, fabric care actives, fragrances and pharmaceutical useful agents.
[145] In a preferred embodiment, in any structural form, the selected group of ASE and HASE polymers comprises ion intensity trigger means; Or pH, surfactant concentration level, temperature, mechanical force, and combinations thereof, as well as ionic strength triggering means, wherein the trigger means maintains the integrity of the device until triggered with a solution of desired conditions. it means. The trigger device may be, for example, an impermeable dense coating or an impermeable matrix. Preferably, the trigger device is sufficient to provide sufficient structural support and is impermeable to water, which prevents the core from contacting the aqueous system and releases the useful agent until triggered. Typically the trigger device is selected from the group of ASE, ASR and HASE blocking compositions surrounding the component, the blocker being substantially impermeable to the release of the active ingredient into the aqueous system and insoluble in the aqueous system of the predetermined conditions. The barrier is used in an aqueous system when the ionic strength changes, as well as the ionic strength change, as well as the pH, temperature, surfactant concentration level, mechanical force, and combinations thereof that cause the active ingredient to be released quickly. Soluble or dispersible or degraded.
[146] Typically the barrier material is an insoluble solid in an aqueous system. In the case of textile care, the barrier material is not limited to this, but insoluble solids in an aqueous system comprising a textile laundry cycle, but then the ionic strength changes; And ionic strength changes, as well as changes in pH, surfactant concentration levels, mechanical forces, and combinations thereof in the system (or disintegrate, swell, and disperse).
[147] Devices of the present invention having the desirable properties disclosed above can be made using the materials disclosed above using the following processes and other conventional techniques and methods. Conventional and typical pharmaceutical active ingredients used in the manufacture of medicaments and / or personal care delivery devices include those disclosed in US Pat. No. 5,358,502.
[148] In one preferred embodiment of the present invention, one or more of the useful components is not limited thereto, but may be one or more through conventional coating techniques including, but not limited to, fluid layer spray coating, Wurster coating, Pan coating, and the like. Encapsulated with an impermeable membrane of the blocking composition. In the liquid state the useful ingredient may be co-granulated with the other active form of the active ingredient to form solid granules or tablets prior to the coating process or it may be used alone or in capsules made of water-soluble polymers such as, for example, gelatin. It may be incorporated with other active ingredients. Gelatin capsules filled with useful ingredients of this kind are then provided with a coating comprising the blocking composition. The coating will be thick enough to be sufficiently stable in the wash cycle, and useful ingredients will be released and quickly dispersed in the rinse cycle.
[149] In order to ensure that the coating of the barrier composition does not dissolve at the beginning of the washing or cleaning process, eg at the start of the main washing cycle in the case of machine washing, the stability of the barrier composition membrane can be controlled by controlling the degree of neutralization of the barrier composition, Thus, it is insoluble at the beginning of the wash cycle when the detergent does not dissolve, and then upon neutralization by the aqueous system after dissolution of the detergent, the barrier membrane remains stable in the wash cycle and dissolves quickly in the rinse cycle. Or will be distributed.
[150] In another preferred embodiment of the invention, one or more of the useful components is an impermeable membrane or one or more useful components and one or more of the one or more barrier compositions via emulsion polymerization, suspension polymerization, and micro-suspension polymerization. It is encapsulated in an impermeable matrix of the above blocking composition. Depending on the polymerization process used, the particle size of the final encapsulated particles or matrix particles is between 0.01 and 1000 μm.
[151] In another preferred embodiment of the invention, one or more useful components are encapsulated in one or more barrier compositions to form polymeric matrix beads. The matrix beads have the same activity in the core as described above and are surrounded by solid polymer protective cells formed during solidification by spray drying or spray cold treatment or precipitation with inorganic salt solutions such as CaCl ₂ or Na ₂ SO ₄ . All. Beads and the like are preferably about 10 to 5000 mu m in size. The matrix beads prepared from the polymer barrier composition and the useful component comprise 5 to 80% of the polymer barrier composition, 5 to 75% of the useful component, and 0 to 10% of an adjuvant comprising a surfactant. Preferably, the matrix beads comprise 5-50% ASE blocking polymer, 20-75% useful ingredient and 0-10% adjuvant comprising a surfactant.
[152] The shape and dimensions of the device may vary depending on the particular application (eg, tablets, beads or capsules). The shape and size may also vary depending on the application, for example, tablets are suitably determined by the amount and rate of release of the useful agent that varies with the application. Preferably, the tablet has a diameter of 0.5 ~ 20mm, the beads are 5㎛ ~ 5mm in diameter. However, typical device dimensions in personal care and household applications are about 1 to 2.5 cm in length and about 0.3 to 1 cm in diameter. In other applications, such as flavors, fragrances and other active ingredients used in home and personal care, the shape and size will depend on the method of use and may differ from those listed above.
[153] The triggered reaction composition of the present invention is a controlled release device for personal care products, controlled release of active ingredients and agents, sensors, imaging agents and diagnostic agents, separations, molecular recognition , Tracking devices and molecular biological conjugate assays.
[154] It is to be understood that the invention is not to be limited to the specific implementations of this specification, and that various modifications and modifications fall within the scope of the invention. Accordingly, the foregoing is merely illustrative of the present invention, which does not limit the present invention.
[155] Example 1
[156] Triggered reaction of thin film of HASE polymer:
[157] Thin Film Cast Preparation on Glass Slides: First pre-neutralize the polymer emulsion to a desired pH with 0.1 M aqueous NaOH solution, then cast the emulsion on a glass slide and dry at 60-70 ° C. for 20-30 minutes on a hotplate to obtain a thickness A polymer thin film having a thickness of about 50 μm was prepared.
[158] Preparation of free standing film: A free standing polymer film was prepared by casting 1 gram of a pre-neutralized emulsion on an aluminum weighing pan and drying in a 70 ° C. oven for 120 minutes. After drying the film, a freestanding film having a thickness of 100-200 μm was peeled off the aluminum substrate.
[159] Beaker test: 0.6% Tide It was immersed in powder detergent solution and tap water (adjusted with NaOH) at pH 8.5. No mechanical agitation was applied to the beaker test.
[160] The reaction results of films of different compositions are summarized in the table below:
[161] TABLE 1 PEL compositions suitable for laundry applications
[162] SamplePolymer Composition pHStability in Washing ConditionsStability in Rinsing Conditions Beaker testTerg testBeaker testTerg test Composition A10 Sipomer BEM (ai) / 60 MA / 20 AA / 10 MAA4.92stabilityPartial meltingPartial meltingPartial melting Composition B10VSM-1 / 60 MA / 20 AA / 10 MAA5.04stabilityPartial meltingDissolutionDissolution Composition C10 VSM-1 / 60 EA / 20 AA / 10 MAA5.2stabilitystabilityDissolutionDissolution Composition D10 VSM-1 / 60 EA / 20 AA / 10 MAA // 0.2 DAP5.2Very stablestabilityDissolutionDissolution Composition E10 VSM-1 / 70 EA / 20 AA5.5stabilitystabilityInsolublePartial melting
[163] Sipomer BEM is supplied by Rhodia and its active ingredient is behenyl (EO) ₂₅ methacrylate. VSM-1 is a Rohm and Hass surfactant monomer, cetyl-stearyl (EO) ₂₀ methacrylate. MA is methacrylate, AA is acrylic acid, MAA is methacrylic acid, EA is ethyl acrylate, and DAP is diallyl phthalate. The term “dissolution” indicates that no polymer particles larger than 100 mesh (@ 150 μm) were collected after the wash cycle.
[164] By varying the choice of monomer, polymer charge density and degree of neutralization, the properties of the polymer film can be adjusted to be sufficiently stable in the fabric laundry wash cycle and are dissolved or dispersed under fabric laundry rinse cycle conditions.
[165] Example 2:
[166] Free-standing PEL Film Curing Flat Rate at Different Salt Concentrations
[167] Experiment:
[168] A free-standing film with a thickness of 50 μm was cast from the composition (60BA / 10Sty / 12MMA / 18MAA / 0.5LOFA) at room temperature. The film (dimension 1 × 1 cm) was placed in an aqueous NaCl solution of pH 12, and after reaching equilibrium, the cubic expansion rate of each film was evaluated. The results are shown in FIG.
[169] PEL films are stable in high ionic strength aqueous media and expand upon low ionic strength or dilution with water.
[170] Example 3:
[171] Triggered reaction of free-standing PEL film with different degrees of neutralization (Composition D)
[172] Composition D emulsions were pre-neutralized with 0.2M aqueous NaOH solution with different neutralization, and the triggered reaction of their corresponding free standing films was Terg-O for 20 minutes at 40 ° C. for the wash cycle and 5 minutes at room temperature for the rinse cycle. The test was performed under the following conditions in a -ometer.
[173] Terg-O-Tometer Test: Freestanding film was tested on a Terg-O-Tometer.
[174] The test conditions are as follows:
[175] A: Laundry conditions:
[176] Detergent concentration: 0.6% Tide powder detergent;
[177] Temperature: 25 ° C .;
[178] Stirring: 90 RPM;
[179] Hardness of wash water: 300ppm
[180] Added fabric: 5 grams of black cotton fabric
[181] 0.2 grams of the conjugated polymer film was placed in a Terg pot and washed at 25 ° C. After the wash cycle, the wash water was collected using a screen with pore size smaller than 200 mesh.
[182] B: Rinsing Condition:
[183] Temperature: room temperature;
[184] Stirring: 90 RPM;
[185] Fabric added: 5 grams;
[186] Time: 5 minutes.
[187] The results are summarized in Table 2 below:
[188] TABLE 2 Triggered Reactions of PEL Composition D with Different Neutralization
[189] Neutralization (%)Emulsion pHFilm thickness (㎛)Laundry stabilityRinsing stability 02.3100Partial meltingDissolve in 5 minutes 2.53.850Partial meltingDissolve in 5 minutes 54.550InsolubleDissolve in 5 minutes 7.54.850InsolubleDissolve in 5 minutes 155.270-90InsolubleDissolve in 5 minutes
[190] BGDMA is butyleneglycol dimethacrylate.
[191] The triggered response of the barrier film is affected by both neutralization and film forming properties. When the degree of neutralization of the emulsion is at least 5%, the corresponding emulsion has better film forming properties. Thus, the resulting membranes exhibit better stability in the system.
[192] Example 4
[193] Expansion rate of thin film PEL cast on glass slides at different salt concentrations and ionic strengths of aqueous solutions (Composition D)
[194] Experiment: Samples were prepared under the conditions of Example 1. The expansion rate of the film was evaluated at ambient temperature and at 40 ° C. in 0.1 M and 0.001 M NaOH, NaCl and Na ₂ CO ₃ aqueous solutions. The results are summarized in FIGS. 2 and 3.
[195] The effect of temperature alone on the expansion rate of the polymer film in NaCl and Na ₂ CO ₃ solutions is small. At room temperature and 40 ° C., the swelling ratio of the films with these two solutions shows minimal change. The temperature has a greater influence on the expansion rate of the film in 0.1M NaOH solution. At 40 ° C., it is impossible to accurately measure the weight of the polymer film since the film is already partially dissolved in the solution after the film has been expanded in NaOH solution for 15 minutes. The film with composition D expands five times faster in 0.1 M NaOH solution compared to NaCl and Na ₂ CO ₃ solutions at the same concentration.
[196] 0.001M NaOH, and NaCl (composition D) in the PEL Na ₂ CO ₃ aqueous solution expansion coefficient of the film is different from the expansion coefficient of the same film in 0.1M NaOH, NaCl and Na ₂ CO ₃ solution. The film expands rapidly in the first 5 minutes in NaOH solution and then slowly dissolves as indicated by weight loss in FIG. 3. The expansion rate of the film in NaCl and Na ₂ CO ₃ solutions increases markedly in the first low ionic strength environment and then slowly dissolves.
[197] The swelling rate that is reduced after soaking the film in the solution for 5 minutes indicates that the film partially dissolves or falls off the slide.
[198] Example 5
[199] Controlled release of encapsulated direction
[200] Experiment: A PEL (Composition D) emulsion was mixed with the aromatic blend using a homogenizer to obtain a stable emulsion system. The resulting freestanding film was cast from a polymer emulsion and an aromatic blend mixture. The film was then placed in the next solution and the fragrance release was tested.
[201] a) DI number:
[202] b) 1 M NaCl solution
[203] c) 5M NaCl solution
[204] When the films are placed in the salt solution, the rate of release of aromatics from their polymer matrix is significantly reduced. After one month, the oriented freestanding film loses most of its direction when it is placed in DI water, and the film itself expands and breaks into pieces. The film placed in the NaCl solution remains intact and maintains orientation.
[205] Example 6-14
[206] Preparation of Additional PEL Compositions
[207] The polymer emulsion of interest was diluted to 20 weight percent polymer solids and completely neutralized by raising the pH of the aqueous emulsion to 10 with aqueous sodium hydroxide solution (2%). To the emulsion is added 100 ppm FC-120 wetting aid and if necessary 10-20% of the binder to the polymer solids. The binder used is typically Dowanol DE (diethylene glycol monomethyl ether). A portion of the emulsion was cast on a glass plate and allowed to dry. The dried film was cut into test strips. In order to measure the cubic expansion rate during the test, the strip was cut to 2 cm in length.
[208] Film strips were tested for triggered responses to ionic and base strength (concentration) changes of 1.2% Bold detergent solution and 0.6% Tide detergent solution in vials maintained at 60 ° C. for at least 30 minutes. If the film was still intact after this time, 95% of the detergent solution in the vial was removed and replaced with tap water to evaluate the reaction of the film to water of neutral pH and relatively low ionic strength. The cubic expansion rate was measured after the test, which is equal to the cubic ratio [final length / original length] ³ of the length of the film exposed to the ions and bases versus the original film length cast.
[209] Example 6
[210] The composition consists of 52.5% methyl methacrylate (MMA), 29.5% butyl acrylate (BA), 18% methacrylic acid (MAA) and 1.5% by weight 3-mercaptopropionic acid (3-MPA). to be. The polyelectrolyte is stable in an aqueous NaOH solution of 2.5M or more and is triggered to expand / dissolve / disperse as the NaOH concentration is lowered to 1.0 or less.
[211] Example 7
[212] The composition is a polyelectrolyte consisting of 33% styrene (Sty), 35% butyl acrylate (BA), 18% methyl methacrylate (MMA) and 25% methacrylic acid (MAA). The polymer electrolyte is stabilized in an aqueous NaOH solution of 1.0 M or more and is triggered to expand / dissolve / disperse as the NaOH concentration is lowered to 0.1 or less.
[213] Example 8
[214] Composition 60 BA / 21 MMA / 10 2-ethyl hexyl acrylate (HEMA) / 9 MAA (1% backbone crosslink with zinc ions) was adjusted to pH 10.5 using a 2% NaOH aqueous solution. The film was separated apart in 4 minutes at 60 ° C., 1.2% Bold and disintegrated in 8 minutes. The film nearly degraded after 30 minutes at 60 ° C., 0.6% Tide. Dropped at 20: 1 dilution (volume / volume), but has not yet dissolved or disintegrated. The film dropped within 60 minutes at 60 ° C., 0.6% Bold and collapsed within 30 minutes.
[215] Example 9
[216] An aqueous solution of the composition 60 BA / 21 MMA / 10 HEMA / 9 MAA (1% backbone crosslink with calcium ions) was adjusted to pH 11.0 using an aqueous 2% NaOH solution. After 20 minutes at 60 ° C., 1.2% Bold, the film became brittle / soft (broken) and collapsed within 30 minutes. The film became brittle / soft (broken) after 35 minutes at 60 ° C., 0.6% Tide. Dropped at 20: 1 dilution (volume / volume), but not yet dissolved or collapsed.
[217] Example 10
[218] An aqueous solution of the composition 60 BA / 21 MMA / 10 HEMA / 9 MAA (1% backbone crosslink with magnesium ions) was adjusted to pH 10.5 using an aqueous 2% NaOH solution. The film disintegrated after 30 minutes at 60 ° C., 1.2% Bold. The film expanded after 35 minutes at 60 ° C., 0.6% Tide, but still remained. Drop at 20: 1 dilution (volume / volume).
[219] Example 11
[220] An aqueous solution of a composition comprising 65% by weight of 60 BA / 21 MMA / 10 HEMA / 9 MAA and 35% by weight of 80 Sty / 10MMA / 10AA (1% backbone crosslinked with zinc ions) was prepared using 2% aqueous NaOH solution. Adjusted to 10.5. After 20 minutes at 60 ° C., 1.2% Bold, the film fell and collapsed within 35 minutes. The film expanded after 35 minutes at 60 ° C., 0.6% Tide, but remained intact. The film was broken into 20 pieces with gentle stirring at 20: 1 dilution (volume / volume). It did not dissolve or collapse.
[221] Example 12
[222] An aqueous solution of a composition comprising 60% by weight of BA / 21 MMA / 10 HEMA / 9 MAA and 35% by weight of 80 Sty / 10MMA / 10AA (1% backbone crosslinking with calcium ions) was prepared using 2% aqueous NaOH solution. Adjusted to 11.0. The film expanded upon 20: 1 dilution (volume / volume) but maintained integrity. Cubic expansion rate (CSR) and CSR = 4.91 for 0.6% Tide wash. CSR = 6.86 in Tide rinse water. CSR = 3.38 at 1.2% Bold number. CSR = 5.36 in Bold rinse water.
[223] Example 13
[224] An aqueous solution of a composition comprising 65% by weight of 60 BA / 21 MMA / 10 HEMA / 9 MAA and 35% by weight of 80 Sty / 10MMA / 10AA (1% backbone crosslink with magnesium ions) was prepared using 2% aqueous NaOH solution. Adjusted to 10.5. The film expanded upon 20: 1 dilution (volume / volume) but maintained integrity. Cubic expansion rate (CSR) and CSR = 6.86 for 0.6% Tide wash. CSR = 27.0 in Tide rinse water. CSR = 4.33 at 1.2% Bold number. CSR = 9.94 in Bold rinse water.
[225] Example 14
[226] An aqueous solution of a composition comprising 50% by weight of 35 BA / 33Sty / 7MMA / 25 MAA and 50% by weight of 60BA / 21MMA / 10HEMA / 10AA (1% backbone crosslinking with zinc ions) was added at pH 10.5 using a 2% aqueous NaOH solution. Adjusted to. An aqueous solution of composition JLE-1983 (1% backbone crosslink with calcium ions) was adjusted to pH 11.0 using an aqueous 2% NaOH solution. An aqueous solution of composition JLE-1980 (1% backbone crosslink with magnesium ions) was adjusted to pH 10.5 using an aqueous 2% NaOH solution. The zinc cross-linked film disintegrated within 60 minutes at 60 ° C., 1.2% Bold. The magnesium cross-linked film collapsed after 35 minutes at 60 ° C., 1.2% Bold. The calcium cross-linked film collapsed after 35 minutes at 60 ° C., 1.2% Bold. All films had good integrity and remained intact after 35 minutes at 60 ° C., 0.6% Tide. All four non-destructive films expanded more in rinse water diluted to 20: 1 (volume: volume) but remained intact.
[227] The cubic expansion rates for selected ionic strengths and base reactive polymer electrolyte compositions are shown in Table 3 below.
[228] Table 3 Cubic Expansion Rate for Ionic Strength and Base Reactive Polymer Electrolyte Compositions
[229] Polymer electrolyte weight% monomerExpansion solutionCSR 40Sty / 35BA / 9MMA / 16MAA (Zn ²⁺ and NH ₃ Glass)2.5M NaOH1.0M NaOH0.25M NaOH0.1M NaOH1.461.642.893.9111.0 40Sty / 35BA / 9MMA / 16MAA (1% n-DDM)2.5M NaOH1.0 M NaOH0.1M NaOH1.521.738 (film collapse) 40Sty / 35BA / 9MMA / 16MAA (1.5% n-DDM)1.0 M NaOH 0.1 M NaOH1.73 Film Melting 20Sty / 35BA / 29MMA / 16MAA (1.5% n-DDM)2.5M NaOH0.1M NaOH4.1 Film Melting 20Sty / 35BA / 29MMA / 16MAA2.5M NaOH1.0M NaOH0.1M NaOH1.623.216.33> 30 40Sty / 35BA / 7MMA / 18MAA2.5M NaOH1.0M NaOH0.1M NaOH1.331.424.111.02 41Sty / 34BA / 9MMA / 16MAA2.5M NaOH1.0M NaOH0.1M NaOH1.331.623.559.6 33Sty / 35BA / 7MMA / 16MAA (1% LOFA)2.5M NaOH1.0M NaOH0.1M NaOH1.392.467.59> 100 32Sty / 35BA / 12MMA / 21MAA (0.5% LOFA)2.5M NaOH1.0M NaOH0.1M NaOH1.522.158.62 (melting) 33Sty / 35BA / 7MMA / 25MAA (0.5% LOFA)2.5M NaOH1.0M NaOH0.1M NaOHQuick dissolution JLE-193737 wt% gelatin2.5M NaOH 1.0M NaOH 0.1M NaOH, film pre-neutralization 0.1M NaOH, film non-neutralized water1.161.624.14.117.6
[230] n-DDM is n-dodecylmercaptan and LOFA is linseed oil fatty acid.
[231] Rhoplex® B-1604 is a product of Rohm and Haas Company.
[232] Triggered reaction compositions in the form of barrier materials and delivery devices comprising one or more polymer electrolytes in contact with an aqueous system that are stable and insoluble in the liquid medium of the present invention and exhibit one or more chemical / physical reactions in the liquid medium. The chemical / physical reaction upon changing the ionic strength of the silver liquid medium triggers the liquid medium.

权利要求:
Claims (8)
[1" claim-type="Currently amended] One or more polyelectrolytes in contact with a liquid medium that is stable and exhibits one or more chemical / physical reactions; The chemical / physical reaction is triggered upon one or more ionic strength changes to the aqueous medium; The polyelectrolyte may comprise one or more acidic homopolymers, copolymers thereof, polymer mixtures and salts; One or more basic homopolymers, copolymers thereof, polymer mixtures and salts; And one or more amphoteric homopolymers, copolymers, polymer mixtures, and salts thereof.
[2" claim-type="Currently amended] The method of claim 1, wherein the polymer electrolyte is (a) 15-70% by weight of one or more acidic monomers; (b) 15-80% by weight of one or more non-ionic vinyl monomers; (c) 0-30% by weight of one or more non-ionic vinyl surfactant monomers; And optionally (d) 0-5% by weight of one or more polyethylene unsaturated monomers;
As a function of the ionic strength change, the chemical / physical reaction of the polymer may include (i) the type and amount of the acidic monomers, (ii) the degree of neutralization of the acidic monomers, (i) the type and amount of the non-ionic vinyl surfactant monomers, One or more selected from the group consisting of (iii) types and amounts of non-ionic vinyl monomers, (iii) types and amounts of polyethylene-unsaturated monomers, (iii) pH of aqueous systems, and (iii) combinations thereof Depends on the above parameters;
The chemical / physical reaction of the composition is selected from dispersion, disintegration, dissolution, destabilization, deformation, expansion, softening, flow, and combinations thereof;
Wherein the liquid medium is an aqueous system.
[3" claim-type="Currently amended] One or more polyelectrolytes in contact with the liquid medium,
The blocking composition surrounds, encapsulates or forms a matrix having one or more active ingredients;
The blocking composition is stable in the liquid medium;
Barriers represent one or more chemical / physical reactions triggered upon one or more ionic strength changes to the liquid medium;
The blocking composition can release the active ingredient into the liquid medium as a result of the triggered reaction;
The polyelectrolyte may comprise one or more acidic homopolymers, copolymers thereof, polymer mixtures and salts; One or more basic homopolymers, copolymers thereof, polymer mixtures and salts; A triggered reaction block composition characterized by one or more amphoteric homopolymers, copolymers, polymer mixtures and salts thereof.
[4" claim-type="Currently amended] 4. The barrier composition of claim 3, wherein the barrier composition is in film form, the liquid medium is an aqueous system, and the chemical / physical reaction of the composition is dispersed, collapsed, dissolved, destabilized, deformed, expanded, softened, flowed, and combinations thereof. Triggered reaction block composition, characterized in that selected from.
[5" claim-type="Currently amended] 5. The barrier composition of claim 4, wherein the barrier composition is stable and insoluble in relatively high ionic strength aqueous systems, and the composition disperses, dissolves, expands or disintegrates in relatively low ionic strength aqueous systems. Physical reactions include ionic strength, ion concentration, surfactant concentration, acid strength and concentration, base strength and concentration, pH, buffer strength and buffer capacity, temperature, hydrogen bonding, hydrogen bonding solvent, organic solvent, Acts on changes in one or more parameters selected from the group consisting of osmotic pressure, dilution, viscosity, electrochemical potential, conductivity, ion mobility, charge mobility, diffusion, surface area, mechanical force, radiation and combinations thereof Triggered reaction block composition, characterized in that.
[6" claim-type="Currently amended] (d) one or more active ingredients;
(e) one or more additives;
(f) a blocking composition comprising one or more ionic strength reactive polyelectrolytes,
The blocking composition surrounds, encapsulates or forms a matrix having one or more active ingredients; The barrier composition is stable in a liquid medium;
The polyelectrolyte may comprise one or more acidic homopolymers, copolymers thereof, polymer mixtures and salts; One or more basic homopolymers, copolymers thereof, polymer mixtures and salts; And one or more amphoteric homopolymers, copolymers thereof, polymer mixtures and salts; The barrier represents one or more chemical / physical reactions selected from dispersion, collapse, dissolution, destabilization, expansion, softening, flow, and combinations thereof; Chemical / physical reactions of the composition are triggered upon one or more ionic strength changes to the aqueous system; The device releases the active ingredient into the aqueous system as a result of the triggered reaction of the blocking composition.
A device for triggered release of one or more active ingredients in a liquid medium.
[7" claim-type="Currently amended] (c) surrounds, encapsulates, or encapsulates, a matrix having one or more active ingredients with an ionic strength reactive barrier composition that is substantially impermeable to release of the active ingredient into the liquid medium and remains insoluble in the liquid medium; Forming; And
(d) changing the ionic strength of the liquid medium;
Including;
The polyelectrolyte may comprise one or more acidic homopolymers, copolymers thereof, polymer mixtures and salts; One or more basic homopolymers, copolymers thereof, polymer mixtures and salts; And one or more amphoteric homopolymers, copolymers thereof, polymer mixtures and salts; The barrier composition is dispersed, disintegrated, dissolved or expanded and is substantially impermeable, thus triggering the release of the active ingredient into the liquid medium,
A method of triggering the release of one or more active ingredients into a liquid medium.
[8" claim-type="Currently amended] 8. A device according to claim 7, wherein a device for the triggered release of one or more active ingredients into an aqueous system is prepared,
The device may comprise (a) one or more active ingredients; (b) one or more additives; And (c) a blocking composition comprising one or more ionic strength reactive polyelectrolytes;
The blocking composition surrounds, encapsulates or forms a matrix having one or more active ingredients; The barrier composition is stable and insoluble in aqueous systems of relatively high ionic strength; The barrier represents one or more chemical / physical reactions selected from dispersion, collapse, dissolution, destabilization, expansion, softening, flow, and combinations thereof; Chemical / physical reactions of the composition are triggered upon one or more ionic strength changes to the aqueous system; The device may release the active ingredient into the aqueous system as a result of the triggered reaction of the blocking composition; The apparatus is from a group consisting of fluid bed spray coating, Wurster coating, Pan coating and co-extrusion, coacervation, spray drying and spray chilling. Prepared using selected coating techniques; Optionally, the one or more useful liquid ingredients may be formulated as one or more solid active ingredients in the form of solid granules, pellets, tablets, encapsulated granules, sachets, matrix beads and capsules in an altered or separate aqueous system. Granulated.

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同族专利:

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公开号 | 公开日

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BR0302410A|2004-09-08|

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EP1386959A1|2004-02-04|

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MXPA03006643A|2005-08-16|

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CA2435735C|2008-10-14|

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JP2004131708A|2004-04-30|

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US20040030034A1|2004-02-12|

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CN1477173A|2004-02-25|

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AU2003231315A1|2004-02-19|

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CA2435735A1|2004-01-31|

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CN1320077C|2007-06-06|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2002-07-31|Priority to US39990402P

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2002-07-31|Priority to US60/399,904

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2003-07-22|Application filed by 롬 앤드 하스 캄파니

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2004-02-11|Publication of KR20040012487A

优先权:

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申请号 | 申请日 | 专利标题

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US39990402P| true| 2002-07-31|2002-07-31|

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US60/399,904|2002-07-31|