JP2012525479A - Photocatalyst introduction composition and photocatalyst introduction method - Google Patents

Abstract

  The present invention includes an active substance having a functional group capable of covalently bonding to a substrate in the presence of an acid or a base, a photocatalyst capable of generating an acid or a base upon exposure to light, and an excipient. Including a composition. Also included herein are methods for treating substrates with these compositions. The method includes applying at least one active substance having a functional group to a substrate, applying a photocatalyst to the substrate, and exposing the photocatalyst and the at least one active substance to light to provide a functional group on the substrate. Forming a covalent bond between the group and the component group. The compositions and methods described herein are useful for consumer care and personal care product applications.

Description

  Silicone polymers, copolymers and mixtures thereof, active materials having functional groups that can be covalently bound to a substrate in the presence of acids or bases, photocatalysts capable of generating acids or bases upon exposure to light, and shaping Compositions and methods for covalent modification of the surface properties of a substrate, including agents.

  The material can be characterized in terms of bulk properties and surface properties. The overall properties of the material are controlled in large part by the surface and bulk properties of the material. The surface properties of a material are largely controlled by the surface chemistry and surface structure of the material. The bulk properties of a material are largely controlled by the bulk chemistry and bulk structure of the material. It may be desirable to modify the surface chemistry and / or surface structure of the material to produce certain surface properties. In addition, it may be desirable to modify the bulk chemistry and / or bulk structure of the material to produce certain bulk properties.

  Substrates including hair and skin are of interest for surface and / or bulk modification. The substrate is subject to repeated mechanical cleaning, chemical treatment and environmental conditions where there are many factors that can cause loss of properties desired for the substrate, such as naturally occurring and synthetically generated shine, gloss and feel. Be exposed. In addition, environmental factors can add to these effects and cause the substrate to become substantially dry or damaged. Acute damage to the substrate surface, including hair and skin, can accumulate over time and lead to chronic damage.

  Accordingly, there is a need for compositions and methods that provide durable conditioning and protective effects to compensate for such events as loss of F and stratum corneum from hair fibers and skin, respectively. Covalent modification of the surface properties of damaged substrates and materials is an example of such an approach. There is also a need to protect, repair and / or strengthen these materials. Modification of a material surface by reacting one or more active ingredients to form a covalent bond between the one or more active ingredients to form an active material locally on the material surface, and the like Modifying the bulk of the material by forming the active material in the bulk of the material in this way is a promising approach.

  An active agent having one or more functional groups that can be covalently linked to one or more complementary functional groups in the presence of an acid or base; a photocatalyst capable of generating an acid or base upon exposure to light; and A composition for dispersing or dissolving an active substance and a photocatalyst for application of the composition to a substrate, wherein the active substance is selected from the group consisting of silicone polymers, copolymers, and mixtures thereof And a composition comprising at least one organic functional group.

  A method for treating a substrate comprising applying the composition described above to the substrate and exposing the substrate treated with the composition to ambient light. Alternatively, the method can be carried out in a plurality of steps, the method comprising applying at least one active substance to a substrate, the active substance having one or more functional groups, Applying an active agent having one or more complementary functional groups, applying to the substrate at least one photocatalyst capable of generating an acid or base upon exposure to light, and the photocatalyst and at least one Exposing the active substance to light. Regardless of which method is used, exposure to light results in the formation of a covalent bond between one or more functional groups of at least one active agent and the substrate.

Various embodiments described herein may be understood by reference to the following description, taken in conjunction with the accompanying drawings, in which:
Schematic showing damage to FCSM of fibers containing covalent bonds to 18-MEA by thioester bonds. 1 is a schematic diagram illustrating one non-limiting embodiment of the compositions and methods described herein for treating a substrate comprising fibers with an active ingredient and a photocatalyst. 1 is a schematic diagram illustrating one non-limiting embodiment of the compositions and methods described herein for treating biological substrates such as fibers with active ingredients and photocatalysts. FIG. 1 is a schematic diagram illustrating one non-limiting embodiment of the compositions and methods described herein for treating biological substrates such as fibers with active ingredients and photocatalysts. FIG. 1 is a schematic representation of one non-limiting embodiment of the mechanism of action of the compositions and methods described herein, wherein the substrate surface is modified by covalent bonding. 1 is a schematic representation of a non-limiting embodiment of the mechanism of action of the compositions and methods described herein, wherein the substrate surface is modified by covalent bonding. 1 is a schematic representation of a non-limiting embodiment of the mechanism of action of the compositions and methods described herein, wherein the porous substrate material is treated with an active material capable of forming a secondary active material. .

  The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”.

  As used herein, the term “functional group” means an atom or group of associated atoms that at least partially defines the structure and determines the properties of a particular group of compounds. A functional group can be a region on or in a molecule or substance that is a specific chemically reactive site compared to other regions of the molecule or substance. Functional groups generally have unique properties and to some extent can control the overall molecular reactivity. Examples of functional groups include, but are not limited to, hydroxyl groups, thiol groups, carbonyl groups, carboxyl groups, sulfonate groups, sulfide groups, ether groups, halogen atoms, amino groups, cyano groups, nitro groups, and the like. Examples of the compound roughly classified (structurally and / or functionally) by functional group include, for example, alkane, alkene, alkyne, aromatic compound, halide, alcohol, ether, ester, amine, imine, imide, carboxylic acid, Amides, acid halides, acid anhydrides, nitriles, ketones, aldehydes, carbonates, peroxides, hydroperoxides, carbohydrates, acetals, epoxides, sulfonic acids, sulfonate esters, sulfides, sulfoxides, thioethers, thiocyanates, disulfides, phosphones Acids, phosphate esters, phosphines, azides, azo compounds, nitro compounds, nitrates, nitriles, nitrites, nitroso compounds, thiols, cyanates, and isocyanates are included, but are not limited to these.

  The terms “active substance”, “active ingredient”, “active compound” and combinations and variations of these terms as used herein refer to a substrate to modify the surface and / or bulk properties of the substrate material. It means the substance applied to. These terms may be used interchangeably. Examples of substrate surface properties include surface hydrophobicity / hydrophilicity, oleophilicity / lipophilicity, color, optical properties, absorptivity, adsorptivity, binding ability, brightness, matteness, friction resistance, stain resistance, surface Mention may be made of texture, odor, wash resistance, wettability, elasticity, plasticity and stiffness. Substrate bulk properties can include, for example, tensile strength, stiffness, absorptance, elasticity, plasticity, and biological activity.

  The active agent may comprise a compound having one or more functional groups that can be covalently bonded to one or more complementary functional groups present in the surface or bulk of the substrate in the presence of an acid or base. The active substance may further comprise a compound capable of forming a covalent bond between the molecules in the presence of an acid or base, for example an acid or base catalyzed and / or copolymerizable monomer. “Beauty active substance” is an active substance suitable for use in personal care products without excessive toxicity, incompatibility, instability, allergic reaction, and the like.

  The term “monomer” as used herein means a compound that can be covalently bonded to another monomer (which may have the same or different chemical structure) to form a polymer and / or copolymer. To do. The terms “polymer” and “copolymer” as used herein mean a compound comprising a plurality of monomers. Thus, as used herein, the terms “polymer” and / or “copolymer” include dimers, trimers, oligomers, and the like.

  As used herein, the terms “modify”, “modify”, “functionalize” or “functionalize” in the context of a substrate (1) share the active ingredient on the substrate surface. Between, (2) covalently binding the active ingredient to the substrate within the bulk of the substrate material, and (3) between two or more active ingredients (which can be the same or different chemical moieties) Forming a covalent bond (where the resulting secondary active substance is localized on the substrate surface) and / or (4) two or more active ingredients (which may be the same or different chemical moieties) Forming a covalent bond between the active ingredients where the active ingredient is present in the bulk of the substrate.

  The term “consumer care product” as used herein includes, for example, soft surface cleaners, hard surface cleaners, glass cleaners, ceramic tile cleaners, toilet cleaners, wood cleaners, multi-surface cleaners, surface disinfectants, dishwashing Means products such as cosmetic compositions, laundry detergents, fabric dyes, surface protectants, surface disinfectants, automotive surface treatment agents, and similar consumer products. Consumer care products include forms such as liquids, gels, suspensions, powders and the like. The consumer care product may also be for home or home care applications in addition to professional, professional and / or industrial applications.

  Consumer care products include, for example, lipstick, mascara, rouge, foundation, teak, eyeliner, lip liner, lip gloss, nail enamel, nail conditioner, and other cosmetics; personal care products such as facial powder and body powder; mousse, Hair spray, styling gel, shampoo, hair conditioner (leave in or rinse out), cream rinse, hair dye, hair coloring product, hair shine product, hair beauty product, hair curling prevention product, hair Hair treatment products such as split hair restoration products, perm solutions, anti-dandruff formulations; skin care products including bath gels, shower gels, body wash, facial cleaners, sunscreens and sunscreen lotions, lip balms, skin conditioners Conditioner, cold cream, moisturizer, body spray, soap, body scrub, release agent, astringent, scrub lotion, hair remover, antiperspirant composition, deodorant, shaving product, pre-shaving product, post-shaving product , "Personal care products" such as toothpastes, mouthwashes, or oral care strips.

  As used herein, the term “cleaner” includes compositions for cleaning substrates including but not limited to hair or skin, including but not limited to the scalp, face, and body. Thus, the term “shampoo” includes, but is not limited to, a hair shampoo, body soap, face wash, or other surface cleaning composition in the usual sense. In addition, the term “shampoo” includes compositions for use in humans and / or animals.

  The term “conditioner” as used herein protects a substrate from mechanical, chemical and / or environmental factors that cause damage and / or drying and / or reduces such damage characteristics. For the purpose of a composition for treating substrates comprising fibrous materials such as fabrics, hair and skin (including scalp, face and body). In this context, the term “conditioner” includes, but is not limited to, fabrics and hair conditioners (leave on and / or rinse out), skin lotions, or facial humectants in the normal sense. It is done.

  One purpose of the compositions and methods described herein is to modify the surface and / or bulk properties of a substrate by covalently binding an active agent to the substrate surface. Another object of the compositions and methods described herein is that an active compound can form a secondary active agent by reacting with each other to form a covalent bond between two or more molecules of the active compound. By modifying the material, the surface properties and / or bulk properties of the substrate are modified. Yet another object of the compositions and methods described herein is to functionalize the surface of a substrate by covalently attaching an active agent to the substrate surface. For effective processing, an active substance containing a plurality of similar functional groups in its molecule is first bound onto the substrate and then reacted with the first bound active substance / It may be desirable to continue with another process of binding the benefit agent. This is particularly useful when the substrate contains functional groups at a very limited density that can react with the active / beneficial agent to form chemical bonds. For example, when malic acid (2-hydroxy-1,4-dibutanoic acid) is first bound onto the substrate, the reactivity of the substrate is doubled and the active substance is subsequently bound. Yet another object of the compositions and methods described herein is a method that easily conforms to health and safety regulations and that can be easily introduced into the personal care product and / or consumer care product space. Providing such modification / functionalization.

  Embodiments generally relate to compositions and methods for treating a substrate. As used herein, the term “substrate” means any material that is useful for treating its surface and / or bulk with the compositions and methods described herein. The terms “substrate” and “substance” may be used interchangeably in the context of objects modified by the compositions and methods described herein. In addition, biological materials such as, but not limited to, hair, skin, nails, gingiva, and teeth are also included. Substrates include, for example, fabric, paper, wood, plastic, glass, tiles, stones, concrete, bricks, other ceramics, coated or painted metal surfaces, coated glass, polymer films, and composite materials Or non-biological material such as a combination thereof may also be meant. The substrate may further include a pre-modified surface, such as a coated surface (eg, varnished or painted) or a laminated surface. The terms “substrate” and “substance” may be used interchangeably in the context of objects modified by the compositions and methods described herein. In embodiments, the compositions described herein comprise an active ingredient capable of modifying a substrate in the presence of an acid or base, a photocatalyst capable of generating an acid or base upon exposure to light. And suitable excipients (which may be physiologically acceptable excipients if desired). In embodiments, the compositions described herein include surfactants, emulsifiers, oxidizing agents, reducing agents, pH adjusting agents, emollients, wetting agents, proteins, peptides, amino acids, added polymers or copolymers, Polishing agents, essential oils and / or fatty acids, lubricants, sequestering / chelating agents, antistatic agents, rheology modifiers, feel agents, fillers, preservatives, perfumes, other functional ingredients, Alternatively, one or more optional ingredients may be included, including combinations thereof.

  In embodiments, the methods described herein include treating a substrate by forming one or more covalent bonds between the active agent and / or the substrate, wherein the covalent bond Is formed in the presence of an acid or base produced by a photocatalyst upon exposure to light. In embodiments, the methods described herein include treating a substrate by forming one or more covalent bonds between two or more active ingredient molecules, wherein the covalent The bond is formed in the presence of an acid or base that is generated by the photocatalyst upon exposure to light, and the active agent is localized on the surface and / or bulk of the substrate. As used herein, the term “molecule” means a sufficiently stable group of at least two atoms in a fixed configuration that are united by chemical bonds. Thus, the term “molecule” includes, but is not limited to, neutral molecular compounds, polyatomic ions, radical species, biomolecules, monomers, dimers, trimers, oligomers, polymers or copolymers, and And similar. In embodiments, the methods described herein include providing a substrate, providing one or more reagents, providing a photocatalyst, and in the presence of the substrate and one or more reagents. By exposing the photocatalyst to light, by preparing the active substance and covalently bonding it to the substrate, or by forming a covalent bond in situ between the active substances on the substrate surface or in the substrate bulk, Treating the substrate, wherein the photocatalyst generates an acid or base that reacts between the one or more reagents and / or the one or more reagents and the substrate. Reaction (s) between and the reaction (s) form a covalent bond. In embodiments, the methods described herein can generate an acid or base in response to exposure to light, and an active agent capable of modifying the substrate in the presence of the substrate, acid or base. Providing a system comprising a photocatalyst, and exposing the system to light.

  In general, it has proven difficult in many cases to covalently attach active substances onto substrates such as hair and skin. This is especially true when water is present, which can quickly degrade the reactive moiety before substrate functionalization occurs. Further, aqueous media are known to chemically promote hydrolysis and oxidation reactions that can compete with the covalent binding of the active agent to the substrate. This can pose particular problems, for example, in consumer care products where water is often used as a physiologically acceptable excipient. Consumer care products also often use water at various volumes, most notably as a solvent.

  In addition, substrates such as hair, skin, fabric, glass and ceramic, for example, may not contain particularly reactive chemical functional groups on the surface that readily react with the active ingredient to form covalent bonds. . This relatively low substrate surface reactivity results in a reaction system that falls outside the practical period of application and rinsing environments (eg, hair washing and conditioning, skin washing, fabric washing, or hard surface washing). Can be done. Furthermore, stringent legal requirements regarding product safety and environmental protection include compositions and methods for treating substrates such as hair, skin, fabric, glass or ceramic by covalent bonding of active ingredients. Raise hurdles to provide.

  However, embodiments of the compositions and methods described herein use light to, for example, covalently bond an active ingredient to a substrate or between two or more active ingredients. It is about photocatalytic technology that promotes reactions such as in situ formation of covalent bonds on the surface or in bulk. For example, to replenish and / or strengthen these substrates that are normally hydrophobic, various embodiments are used to covalently attach long chain alkyl groups to damaged hydrophilic hair and / or skin. May be promoted. In addition, various embodiments can be used, for example, to promote the covalent attachment of active agents to fabrics or hard surfaces. In addition, various embodiments are used to locally polymerize or copolymerize monomers on and / or in the surface of a substrate material, for example, to modify the surface and / or bulk properties of the material. can do.

  In embodiments, covalent bonds can produce a variety of substantial benefits. For example, fibers such as hair or fabrics, in particular, have improved feel, low friction, ease of handling such as wave formation and braiding / brushing, reduced drying, improved smoothness, reduced curling, radiant Conditioning effects may be experienced, including improvements, reduction of static electricity, and improved protection against damage by other mechanical, chemical and environmental factors. Conditioning effects for biological substrates such as skin can include, among other things, reduced dryness, reduced redness, reduced dermatitis, reduced exfoliation, and improved texture and smoothness. At least some of these benefits can be conferred by increasing or targeting the attachment of the active agent resulting from surface modification via covalent bonds. For non-biological substrates that are hard surfaces such as glass or ceramic tiles, there are effects such as reduced water stain, increased brightness or gloss, and easier subsequent cleaning. The benefits conferred by the compositions and methods described herein are non-labile covalent bonds that have been used in previous conditioners to deposit or apply active ingredients onto the hair and / or skin. Absorption, adsorption, hydrogen bonding, ionic bonding, other electrostatic interactions, and / or other temporary non-covalent associations are generally used) Because it is potentially more durable. This can greatly reduce the frequency of application and reapplication encountered with previous conditioners.

  Embodiments of the compositions and methods described herein provide for the covalent attachment of the active agent to a substrate, which may be, for example, to repair and / or strengthen the hair F layer or skin stratum corneum. May be described as an approach. In relation to fibers, including hair, it is not bound by theory or limited by theory, but is mediated by various mechanical, chemical, and / or environmental factors as shown in FIG. By the processed process, the F layer of virgin hair may be stripped from the hair fibers. These processes can include, for example, oxidation and hydrolysis reactions commonly encountered during permanent hair dyeing and permanent perm treatment.

  FIG. 1 shows a hair fiber comprising a keratin outer epidermal portion covalently bound to 18-MEA by a thioester bond between a carboxyl group on 18-MEA and a thiol group on a cysteine residue in a keratin protein in the outer epidermis. It is the schematic which shows FCSM. Hydrolysis and / or oxidation processes (eg, due to the combination of hydrogen peroxide, ammonia and high pH commonly encountered during permanent hair dyeing and permanent permanent treatment) are other mechanical, chemical, and environmental Similar to the factor, at least a portion of the F layer may be removed by cleaving the cysteine-lipid thioester bond, leaving an exposed outer epidermis containing a sulfonate group on the cysteine residue.

  The anionic sulfonate group on the cysteine residue on the surface of the outer epidermis renders the surface of any damaged hair fiber hydrophilic, which can lead to undesirable properties of the damaged hair. In addition, if the hair fibers are more hydrophilic (and therefore more damaged), conventional hydrophobic conditioning actives (eg, dimethylsiloxane, aliphatic alcohols and acids) due to non-covalent interactions and associations. , As well as quaternary amines) was observed to be reduced. Thus, the compositions and methods described herein provide an attractive approach for treating such damaged substrates.

  FIG. 2 schematically illustrates one non-limiting embodiment of the compositions and methods for substrate processing described herein. In the presence of a substrate comprising a surface sulfonate and a carboxyl group, a composition is provided comprising an active ingredient having a hydroxyl group (R-OH) and a photocatalyst capable of generating an acid or base upon exposure to light. The photocatalyst is exposed to light, thereby causing the photocatalyst to form an acid or base. The acid or base catalyzes the formation of a covalent ester bond between the hydroxyl group on the active substance and the carboxyl group on the substrate.

  FIGS. 3 and 3A schematically illustrate one non-limiting embodiment of the compositions and methods for substrate processing described herein when viewed together. A part of hair fiber including a lipid layer (F layer) and a protein layer (outer epidermis) is shown. The protein layer includes, for example, a structural protein such as keratin having a disulfide bond between cysteine residues. Hair may be treated with a reducing agent to break disulfide bonds and form the corresponding thiol group. The hair is further treated with an active ingredient comprising one or more compounds capable of reacting to form a covalent bond between one or more active ingredient compounds and / or between one or more active ingredient compounds and a thiol group. It's okay. The hair fibers are further treated with a photocatalyst. One or more active ingredients and the photocatalyst penetrate the surface of the hair fiber substrate. The hair fiber substrate treated with one or more active ingredients and the photocatalyst is exposed to light of a suitable wavelength to activate the photocatalyst, and the one or more active ingredients and thiol groups in the hair fiber base Catalyze the reaction between.

  In embodiments, the active agent may be one or more monomers that are polymerizable or copolymerizable in the presence of an acid or base. The fiber is treated with a composition comprising a photocatalyst and an active agent monomer that at least partially penetrates the fiber. In response to exposure to light, the photocatalyst is activated, thereby producing an acid or base and catalyzing the active agent monomer to polymerize or copolymerize the monomer, thereby optionally thiol groups and the polymer or copolymer. An active agent polymer or copolymer is formed in situ that can bind to the fibers in a manner in which covalent bonds are formed between them.

  In other embodiments (not shown), these active agent polymers or copolymers do not covalently bond to the fibers. For example, the polymer or copolymer formed in situ may be physically immobilized on the surface of the hair fiber or within the pores of the hair fiber. The polymer or copolymer formed in situ also has a surface and / or bulk of the substrate, such as adsorption, absorption, electrostatic interaction, frictional interaction, steric interaction, and / or size exclusion effects, etc. It may associate with the hair fibers by physical and / or chemical interactions.

  In embodiments, the active agent monomer may be styrene or may be a styrene derivative such as, for example, α-methylstyrene. A monomer is a mixture of different monomers such that in situ polymerization or copolymerization (on the surface of the substrate and / or in the bulk of the substrate) produces a polymer or copolymer. May be included.

  FIG. 4 schematically illustrates one non-limiting embodiment of the compositions and methods for substrate processing described herein. Compositions are provided comprising an active agent having a carboxyl group in the presence of a substrate containing surface hydroxyl groups and a photocatalyst capable of generating an acid or base upon exposure to light. The photocatalyst is exposed to light, thereby causing the photocatalyst to form an acid or base. The acid or base catalyzes the formation of a covalent ester bond between the hydroxyl group on the substrate and the carboxyl group on the active substance.

  Thus, the photocatalytic activity of the reaction that forms an ester and / or thioester covalent bond between the active ingredient and the substrate in embodiments of the compositions and methods described herein is, for example, in hair and skin. It provides an efficient, controllable, stable and physiologically acceptable approach to substrate processing such as F-layer and stratum corneum repair and / or reinforcement, respectively.

  FIG. 5 is a schematic illustration of one non-limiting embodiment of the mechanism of use of the compositions and methods described herein in the context of a photoacid catalyst. In the first step, a reagent solution comprising a reagent that can be an active ingredient and a photoacid catalyst is provided. Reagent solutions may include shampoos, conditioners, other personal care products or consumer care products. In the second step, the reagent solution is applied to a substrate that can be, for example, skin, hair, fabric, or a hard surface. The components of the reagent solution are deposited on the substrate surface. In the third step, the system comprising the reagent solution and the substrate is exposed to light. Light causes deprotonation of the photocatalyst. In the fourth step, a photoacid-catalyzed esterification reaction occurs between the reagent and the substrate surface. In the fifth step, unreacted catalyst, reagents, and protons diffuse from the substrate surface and are removed from the system. In the sixth step, the modified / functionalized substrate is dried. In the seventh step, the modified / functionalized substrate is washed and rinsed. The modified / functionalized substrate substantially retains the covalently bound reagent after washing and rinsing.

  FIG. 6 is a schematic representation of one non-limiting embodiment of the compositions and methods described herein. A porous substrate material 10 is provided. The substrate material 10 includes a bulk portion 20 having a substrate surface 15 and pores 25. The substrate material 10 is treated with a composition comprising the active material 30 and the photocatalyst 35. The active substance 30 may include molecules capable of reacting together in the presence of an acid or base to form a secondary compound. For example, the active agent 30 may include one or more types of monomers that can react in the presence of an acid or base to form a polymer or copolymer. The active substance 30 and the photocatalyst 35 penetrate at least partially into the surface 15 of the substrate 10 through the pores 25 into the bulk portion 20. Substrate 10 is exposed to light of a suitable wavelength and activates photocatalyst 35 that generates an acid or base to catalyze the reaction of active substance 30 on surface 15 and / or in bulk portion 20. When the active substance is catalyzed and binds to the substrate, other active substances, secondary active substances are formed from two or more components of the composition that are catalyzed in situ. This secondary active material 40 binds on the surface 15 of the substrate material 10 and / or in the bulk portion 20. Secondary active material 40 may comprise, for example, a polymer, copolymer, or a combination thereof. The secondary active material 40 may form a polymer network 45 that may modify the surface and / or bulk properties of the substrate material 10.

  Secondary active materials formed according to the photocatalyzed acid or base mechanism described herein can be localized to the surface and / or bulk of the substrate material. In embodiments, the localization may be the result of the secondary active agent being covalently bound to the substrate material. In other embodiments, the localization may be the result of a non-covalent chemical or physical interaction between the secondary active material and the surface and / or bulk of the substrate material. For example, FIG. 6 includes a polymer network that is immobilized on the surface of a substrate material and partially in its bulk by the physical formation of the polymer in pores located within the material. Indicates a secondary active substance. In other embodiments (not shown in FIG. 6), the secondary active material formed according to the photocatalyzed acid or base mechanism described herein is capable of adsorption, absorption, electrostatic interaction, friction. Interactions such as interactions, steric interactions, and / or size exclusion effects may localize on the substrate surface and / or in the bulk of the substrate. Thereby, for example, various material properties such as the porosity of the treated substrate can be manipulated.

  In embodiments, secondary active materials formed according to the photocatalyzed acid or base mechanism described herein are such that these materials have properties when covalent bonds are formed between the molecules. By varying, it can be localized on the substrate surface and / or within the bulk of the substrate. For example, if the active agent comprises a monomer / polymer system, the active agent may be polymerized and / or crosslinked on the substrate surface. Polymerization and / or cross-linking can change the solubility of the active substance in the reaction medium, which can promote the attachment of the secondary active substance on the substrate surface. In this way, a surface layer of a secondary active material is formed on the substrate surface, thereby modifying the surface properties. Thereby, the fiber which is a component can be enclosed in fibrous base materials, such as hair and a fabric, for example. In embodiments (not shown in FIG. 6), the photocatalytic acid or base forms the active material to covalently bond to the substrate (surface and / or bulk) as described herein.

  The compositions and methods described herein promote in situ and local modification of material properties in a controlled manner. The active ingredient is covalently modified within the photoacid or photobase reaction system (eg, by forming a covalent bond between active substances and / or active to form a secondary active substance) By forming a covalent bond between the material and the substrate material).

  The substrate to be modified is treated by spraying, dipping, spreading, coating, rinsing, or any other suitable means of introducing the composition onto the substrate surface or into the bulk of the substrate material. Good. In embodiments, it is important to ensure that the entire substrate surface is wetted by the reagent solution in order to reliably and sufficiently modify the substrate surface and / or bulk. If the active substance is at least partially insoluble in the excipient, contact between the active substance and the substrate, for example by minimizing the droplet size or particle size of the active substance in the excipient It is important to maximize In embodiments, it may be desirable to introduce the reagent solution to only a single portion or multiple portions of the substrate surface. In other embodiments, it may be desirable to irradiate only a single portion or multiple portions of the substrate surface with light of a wavelength suitable to activate the photocatalyst. Covalent modification only occurs on substrate surface (and underlying bulk) regions that have been irradiated with light of a wavelength suitable for activating the photocatalyst in contact with the reagent solution. This allows the location and extent of surface and / or bulk modification to be controlled.

  The acid or base photocatalytic covalent modification / functionalization mechanism described herein may be reversible. For example, a substrate surface that has been covalently modified or functionalized by an esterification and / or thioesterification reaction may be contacted with an aqueous acidic surfactant solution. Alternatively, an alkaline surfactant solution may be used. These solutions can facilitate the hydrolytic cleavage of the ester and / or thioester bond that binds the active ingredient to the substrate, thereby removing the active ingredient.

  This removability is limited to active ingredient-substrate bonds that are reversible under appropriate conditions. For example, in the case of photoacid catalyzed esterification, ester bonds are formed when reagents and catalysts are present in the vicinity of the substrate and exposed to the appropriate light. An ester bond that is maintained as it is is formed by high-concentration protons at the time of irradiation because the generated protons diffuse quickly into the bulk of the medium. A low content of photoacid provides a stable and near neutral pH bulk aqueous solution. Under these conditions, ester bonds are hydrolyzed at a very slow rate. However, when treated with an aqueous solution at a very low (or very high) pH, the ester bonds are broken more quickly and the original unmodified substrate surface is obtained.

  Removal of the covalently bound active agent can also be achieved by treating the modified or functionalized substrate with a composition comprising a photocatalyst (photoacid or photobase). Thereby, control of the removal timing of the active ingredient from a base material is improved. This can be achieved when the photocatalyst is selected such that it can generate acid or base species under the specific wavelength of light provided by a suitable device without being affected by ambient light.

  Each of the various components of the composition and the attendant methods described herein, as well as preferred and optional components, are described in detail.

Active Substances Active substances of the present invention include branched, cyclic, cross-linked and combinations thereof, silicone polymers, copolymers, and polymer combinations, at least 150 grams / mole, alternatively 1000 grams / mole, 3000 grams / mole to A molecular weight of 10 million grams / mole, 10,000 grams / mole to 7 million grams / mole, or 50,000 grams / mole to 4 million grams / mole, and at least one organic functional group (and a plurality in one embodiment) Organic functional groups) include, but are not limited to, hydroxy, amino, carboxysulfonate, thiol, epoxide, ester groups and / or any combination thereof, and iii) the degree of substitution of the silicone polymer or copolymer and Properties, as well as molecular weight, depending on the desired substrate It can be selected appropriately according to the modification and application conditions. For example, if increased hydrophobicity is desired, less than 2% of the silicon atoms in the silicone polymer, copolymer, and polymer and copolymer combination can be replaced with organic groups. The silicone copolymer or copolymer may be derived from a monomer containing an organic alcohol group (primary or secondary) that has the following structure:
R1- [Si (CH2) (R3-CH2OH) -O] n- [Si (CH2) 2-O] m-R2
In which R 1 and R 2 are methyl; R 3 is —CH 2 CH 2 CH 2 — (OCH 2 CH 2 O) q—H, where q ≧ 1.

  For example, hair modification can be obtained by treating damaged hair with a silicone polymer and / or copolymer active. Treatment with such actives in an emulsion, dispersion, and / or solution state using a photoacid generator such as 8-hydroxyquinoline is resistant to damaged hair (eg, multiple shampoos). Such as lasting after the wash cycle). Examples of durable benefits include hair softening (wet and dry hair softening), compatibility, anti-curling, hairstyle and hair color retention, moisturizing, and gloss.

  The surface modification method involves the formation of a covalent bond between the silicone polymer or copolymer and the substrate. The bond is formed by an acid-catalyzed reaction of a primary or secondary alcohol of the polymer or copolymer with a compatible functional group of the hair substrate (eg, carboxylic acid groups contribute to the condensation).

  Suitable silicone polymers and copolymers include those having alkoxyalkanol groups. In one embodiment, the silicone polymer and / or copolymer is bis-hydroxyethoxypropyl dimethicone having the following structure:

  Suitable bis-hydroxyethoxypropyl dimethicones include, but are not limited to, materials available from Dow Corning as 5562 Carbinol Fluid and from Momentive as Baysilone OF OH 702 E.

Photocatalyst The photocatalyst can be any acid, base (or complex thereof) having a pKa (or pKb) value that decreases (or increases) in response to exposure to light. The light can be any suitable wavelength of light to obtain a decrease or increase in pKa or pKb, respectively. For example, the light source can be ambient light, sunlight, white light, fluorescence, LED light, laser light, and the like. The compositions of the present invention utilize light in the electromagnetic spectrum ranging from infrared light to visible to ultraviolet light having a wavelength of about 1200 nm to about 200 nm.

  The use of ultraviolet light and visible light (VIS) is not exclusive to many photoactive materials with a broad absorption spectrum covering both. Independently, some examples have shown that chemical reactions activated by ultraviolet light can be accelerated to the extent measurable by VIS. In practice, the action spectrum of the entire reaction needs to be considered in order to clarify which wavelengths contribute significant contributions to the results. One skilled in the art will readily appreciate that the appropriate light wavelength is determined depending on the characteristics of the one or more photocatalysts employed.

  In addition, suitable light may be provided from any source capable of illuminating the substrate surface. For example, ambient sunlight, white light, fluorescence, etc. can provide light of a suitable wavelength. Thus, light may be provided by conventional sources such as lamps and portable or battery-powered light. In addition, certain devices may be developed or adapted for use in the compositions and methods described herein. For example, the surface of the fiber may be covalently modified using a hairbrush configured to incorporate LEDs that provide light of a suitable wavelength. In embodiments, a laser may be used to provide accurate targeting of, for example, covalent modification of the substrate surface.

  In embodiments, the photocatalyst is, for example, an aromatic hydroxy compound, a sulfonated pyrene compound, an onium salt, a diazomethane derivative, a bissulfone derivative, a disulfuno derivative, a nitrobenzyl sulfonate derivative, a sulfonate ester derivative, an N-hydroxyimide Photoacids such as sulfonate esters or combinations thereof.

  Examples of the photoacid catalyst include 8-hydroxyquinoline, 8-hydroxyquinoline sulfate, 8-quinolinol-1-oxide, 5-hydroxyquinoline, 6-hydroxyquinoline, 7-hydroxyquinoline, 5-iodo-7-sulfo- 8-hydroxyquinoline, 5-fluoro-8-hydroxyquinoline, 5-fluoro-7-chloro-8-hydroxyquinoline, 5-fluoro-7-bromo-8-hydroxyquinoline, 5-fluoro-7-iodo-8- Hydroxyquinoline, 7-fluoro-8-hydroxyquinoline, 5-chloro-8-hydroxyquinoline, 5,7-dichloro-8-hydroxyquinoline, 5-chloro-7-bromo-8-hydroxyquinoline, 5- Chloro-7-iodo-8-hydroxyquinoline, 7-chloro-8-hydride Xylquinoline, 5-bromo-8-hydroxyquinoline, 5-bromo-7-chloro-8-hydroxyquinoline, 5,7-dibromo-8-hydroxyquinoline, 5-bromo-7-iodo-8-hydroxyquinoline, 7- Bromo-8-hydroxyquinoline, 5-iodo-8-hydroxyquinoline, 5-iodo-7-chloro-8-hydroxyquinoline, 5,7-diiodo-8-hydroxyquinoline, 7-iodo-8-hydroxyquinoline, 5 -Sulfonic acid-8-hydroxyquinoline, 7-sulfonic acid-8-hydroxyquinoline, 5-sulfonic acid-7-iodo-8-hydroxyquinoline, 5-thiocyano-8-hydroxyquinoline, 5-chloro-8-hydroxyquinoline 5-bromo-8-hydroxyquinoline, 5,7-dibromo-8-hydroxyquino Phosphorus, 5-iodo-8-hydroxyquinoline, 5,7-diiodo-8-hydroxyquinoline, 7-azaindole, 7-cyano-2-naphthol, 8-cyano-2-naphthol, 5-cyano-2-naphthol And hydroxy-substituted aromatics such as 1-hydroxy-3,6,8-pyrenetrisulfonic acid, trans-3-hydroxystilbene, 2-hydroxymethylphenol, or pelargonidin.

  Examples of the photoacid catalyst include bis (4-tert-butylphenyl) iodonium perfluoro-1-butanesulfonate, diphenyliodonium perfluoro-1-butanesulfonate, diphenyliodonium-9,10-dimethoxyanthracene-2-sulfonate, and diphenyliodonium. Hexafluorophosphate, diphenyliodonium nitrate, diphenyliodonium p-toluenesulfonate, diphenyliodonium triflate, (4-methylphenyl) diphenylsulfonium triflate, (4-methylthiophenyl) methylphenylsulfonium triflate, 2-naphthyldiphenylsulfonium triflate Rate, (4-phenoxyphenyl) diphenylsulfonium triflate, (4-phenylthio Phenyl) diphenylsulfonium triflate, thiobis (triphenylsulfonium hexafluorophosphate), triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate salt, triphenylsulfonium perfluoro-1-butanesulfonate, triphenylsulfonium triflate, tris (4-tert-butylphenyl) sulfonium perfluoro-1-butanesulfonate, tris (4-tert-butylphenyl) sulfonium triflate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate, bis (4-tert- Butylphenyl) iodonium triflate, (4-bromophenyl) diphenylsulfonium triflate, tert-butoxycarbonylmethoxynaphthyl) diphenylsulfonium triflate, (tert-butoxycarbonylmethoxyphenyl) diphenylsulfonium triflate, (4-tert-butylphenyl) diphenylsulfonium triflate, (4-chlorophenyl) diphenylsulfonium triflate, (4 -Fluorophenyl) diphenylsulfonium triflate, [4-[(2-hydroxytetradecyl) oxy] phenyl] phenyliodonium hexafluoroantimonate, (4-iodophenyl) diphenylsulfonium triflate, (4-methoxyphenyl) diphenylsulfonium Triflate, diphenyliodohexafluorophosphate, diphenyliodohexafluoroarsenate, diphenyl Phenyliodohexafluoroantimonate, diphenyl p-methoxyphenyl triflate, diphenyl p-toluenyl triflate, diphenyl p-isobutylphenyl triflate, diphenyl p-t-butylphenyl triflate, triphenylsulfonium hexafluorophosphate, triphenyl Sulfonium hexafluoroarsenate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium triflate, dibutylnaphthylsulfonium triflate, diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) phenyliodonium trifluoromethanesulfonate, diphenyliodonium p- Toluenesulfonate, (p-tert-butoxy Phenyl) phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert) -Butoxyphenyl) -sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl) diphenylsulfonium p-toluenesulfonate, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (P-tert-butoxyphenyl) sulfonium p-toluenesulfone Triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) -sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxo (Cyclohexyl) sulfonium p-toluenesulfonate, dimethylphenyl-sulfonium trifluoromethanesulfonate, dimethylphenyl-sulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium triflate Fluoromethane-sulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, (2-norbornyl) methyl (2-oxocyclo-hexyl) sulfonium trifluoromethanesulfonate, ethylenebis- [methyl (2-oxocyclopentyl) sulfonium trifluoromethane- Sulfonate] or onium salts such as 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate may be mentioned.

  Examples of the photoacid catalyst include bis (benzenesulfonyl) -diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) -diazomethane, bis (cyclopentylsulfonyl) diazomethane, and bis (n -Butylsulfonyl) diazomethane, bis (isobutylsulfonyl) -diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) -diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (N-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) -diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-a Rusulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, or 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) ) Diazomethane derivatives such as diazomethane may be mentioned.

  Examples of the photoacid catalyst include bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (p-toluenesulfonyl) -α-diphenylglyoxime, and bis-o- (p-toluene). Sulfonyl) -α-dicyclohexyl-glyoxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedione-glyoxime, bis-o- (p-toluenesulfonyl) -2-methyl-3,4-pentane- Dione glyoxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α -Dicyclohexylglyoxime, bis-o- (n-butane-sulfonyl) -2,3-pentanedione glyoxime, bis- -(N-butane-sulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoro-methanesulfonyl) -α -Dimethylglyoxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-o- ( Perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-o- (cyclohexane-sulfonyl) -α-dimethylglyoxime, bis-o- (benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluoro) Benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-tert-butylbenzene) Ruhoniru)-.alpha.-dimethylglyoxime, bis-o-(xylene sulfonyl)-.alpha.-dimethyl - glyoxime, or bis-o-(may include the glyoxime derivatives such as camphor-sulfonyl)-.alpha.-dimethylglyoxime.

  Examples of the photoacid catalyst include bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonyl. Bissulfone derivatives such as methane, 2-cyclohexyl-carbonyl-2- (p-toluenesulfonyl) propane (β-ketosulfone derivative), 2-isopropyl-carbonyl-2- (p-toluenesulfonyl) propane (β-ketosulfone derivative) You may mention.

  Examples of the photoacid catalyst may include disulfono derivatives such as diphenyldisulfone or dicyclohexyldisulfone.

  Examples of the photoacid catalyst may include nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate or 2,4-dinitrobenzyl p-toluenesulfonate.

  Examples of the photoacid catalyst include 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoro-methanesulfonyloxy) benzene, or 1,2,3-tris (p- Mention may also be made of sulfonic acid ester derivatives such as toluenesulfonyloxy) benzene.

  Examples of the photoacid catalyst include N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide ethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N- Hydroxysuccinimide 1-pentanesulfonate, N-hydroxysuccinimide 1-octanesulfonate, N-hydroxysuccinimide p-toluenesulfonate, N-hydroxysuccinimide p-methoxybenzenesulfonate, N-hydroxysuccinimide 2-chloroethanesulfonate, N-hydroxysuccinimide benzenesulfonate N-hydroxysuccinimide 2,4,6-tri Cyl-benzenesulfonate, N-hydroxysuccinimide 1-naphthalenesulfonate, N-hydroxysuccinimide 2-naphthalenesulfonate, N-hydroxy-2-phenylsuccinimide methanesulfonate, N-hydroxymaleimide methanesulfonate, N-hydroxymaleimide ethane-sulfonate, N -Hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate, N-hydroxyglutarimide benzenesulfonate, N-hydroxyphthalimide methanesulfonate, N-hydroxyphthalimide benzenesulfonate, N-hydroxyphthalimide trifluoromethanesulfonate, N- Hydroxyphthalimide p-toluenesulfonate, N-hydroxy Naphthalimidomethanesulfonate, N-hydroxynaphthalimidebenzenesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide p-toluenesulfonate, N-hydroxynaphthalimide triflate, N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate, etc. The sulfonic acid ester of N-hydroxyimide may be mentioned.

  In certain embodiments, the photocatalyst is 8-hydroxyquinoline, which can act as a photoacid catalyst in a low pH solution or as a photobase catalyst in a high pH solution. In certain other embodiments, the photocatalyst is 8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt (D & C Green 8). In embodiments, the photocatalyst is a photobase. Examples of the photobase catalyst include trityl alcohol derivatives such as malachite green. Examples of the photobase catalyst include acridine derivatives such as 9-hydroxy-10-methyl-9-phenyl-9,10-dihydroacridine. Photobase catalysts can also include photoactive carbamate-containing compounds.

  The photocatalyst may be present in the compositions and methods described herein in an amount of 0.00050 wt% to 30 wt%, based on the total weight of the composition. There is usually a preferred concentration of photocatalyst. The preferred concentration of photocatalyst depends to some extent on various factors including, for example, the chemical structure of the catalyst, the reaction medium, the reaction type, and the substrate.

Excipients The compositions described herein generally comprise an excipient suitable for dispersing or dissolving the active agent, a photocatalyst, and an active agent on the substrate surface or in the bulk portion of the substrate. Contains any other ingredients that facilitate application. The excipient may include one or more of solvents, emulsifiers, surfactants, or other dispersants. The properties of suitable excipients will depend, at least in part, on the other components of the composition and the properties of the substrate being modified. For example, when used in a composition intended to be applied to living tissue, the excipients used in the composition do not compromise the stability of the composition, and the targeted living tissue and target It is selected to avoid the occurrence of problems such as inflammation or injury of surrounding tissues that are not.

  Suitable excipients act to disperse or dissolve the active substance, photocatalyst, and any other ingredients, and to facilitate application of the active substance to the substrate surface. Suitable excipients facilitate sufficient contact between the active agent and the substrate. In one embodiment, the physiologically acceptable excipient may be any carrier, solvent, or solvent-containing composition suitable for application to living tissue such as human hair and human skin. .

  As mentioned above, a suitable excipient can be a solvent. For example, water is generally considered to be a useful solvent for consumer care products, including personal care products. In various consumer care products, including the consumer care product of the present invention, water can be used at a concentration of 1% to 98% by weight of the composition. Water is particularly useful in personal care products because it does not harm living tissue. Additional solvents or solvent-containing excipients include, but are not limited to, liquids containing hydroxy groups (eg, alcohols), silicones, oils, hydrocarbons, glycols, ammonium lauryl sulfate, sodium lauryl sulfate, and combinations thereof Is mentioned. In certain embodiments, other solvents, dispersants, or emulsifiers, for example, as an acceptable excipient, alone or in combination with each other and / or water, if the active substance is at least partially insoluble in water. May be used.

  Accordingly, suitable excipients are generally used to dilute and / or emulsify the components to form the compositions described herein. Suitable excipients may dissolve the ingredients (true solution or micelle solution) or the ingredients may be dispersed throughout the excipient (suspension, dispersion or emulsion). Suspension, dispersion or emulsion excipients are typically these continuous phases. That is, other components of the suspension, dispersion or emulsion are distributed throughout the excipients at the molecular level or as separate or spurious particles. The preparation of such emulsions or dispersions of the active substance can be very important in such cases. Small particles contribute to intimate contact between the active material, the substrate and the photoacid catalyst, increasing the reaction rate. For example, in the case of fiber surface modification using aliphatic alcohol and 8-hydroxyquinoline in an aqueous medium, in providing a durable hydrophobic surface, very small particles (eg, less than 500 nanometers, more preferably Emulsions containing less than 200 nanometers) may be clearly more effective than emulsions containing larger particles.

  Those skilled in the art will recognize that the appropriate excipient (s) are specific active agent (s), photocatalyst (s) used in the compositions described herein. , And other optional components (single or multiple) will be readily apparent.

Optional Components The compositions and methods described herein may include various components as desired. For example, in embodiments, the compositions and methods described herein include surfactants, emulsifiers, oxidizing agents, reducing agents, pH adjusting agents, emollients, wetting agents, proteins, peptides, amino acids, additions Polymers or copolymers, polishes, oils and / or fatty acids, lubricants, sequestering / chelating agents, antistatic agents, rheology modifiers, feel agents, fillers, dyes, pigments, preservatives, Perfumes, other functional ingredients, or combinations thereof may further be included. Certain optional ingredients can be found in the CTFA International Cosmetic Indication Dictionary, Tenth Edition, 2004; and McCutcheon, Detergents and Emulsifiers, North American Edition (1986). It will be readily apparent to those skilled in the art that the particular optional ingredients utilized will depend, at least in part, on the particular application of the composition and method.

  In embodiments, the compositions and methods described herein include an oxidant (oxidant). An oxidant may be added, for example, to make the substrate surface more susceptible to photocatalytic covalent modification / functionalization according to various embodiments described herein. The oxidizing agent may be present in an amount of 0.00050% to 25%, 0.1% to 10%, 0.5% to 5% by weight relative to the total weight of the composition. Suitable oxidizing agents include, for example, hydrogen peroxide, urea peroxide, melamine peroxide, percarbonate, peracid, alkali metal bromate, perborate, bromate, hypochlorite. , Chlorite, perchlorate, iodate, periodate, permanganate and persulfate. In certain embodiments, the oxidant is hydrogen peroxide.

  The identity of the reaction system, the amount and concentration of reagents used, and the reaction conditions are all at least in part, the substrate to be modified, the active material used, and the manner in which the active material is associated with the substrate Depends on. These considerations can be readily determined by one skilled in the art in the practice of the compositions and methods described herein.

  The following examples are intended to more clearly illustrate aspects of the compositions and methods described herein, but are not intended to be limited to these ranges.

Example 1A
Preparation of Prototype Silicone Emulsion 1A 200 mL of tetrahydrofuran is added to a 500 mL beaker. Then 6.0 grams of silicone polymer or copolymer (Dow Corning® 5562 Carbinol Fluid) is added. Dissolve the solution with gentle mixing. Using a Silverson® L4RT homogenizer at 6000 rpm, drop 200 mL of water over 15 minutes under high shear. The resulting emulsion is continuously mixed under high shear for over 2 hours. Add 0.030 grams of 8-hydroxyquinoline and stir for 10 minutes.

(Example 1B)
Preparation of Prototype Silicone Emulsion 1B Dow Corning® 5562 Fluid is replaced with Momentive® silicone polymer, Baysilone OF OH 702E, and the procedure of Example 1A is repeated.

(Example 2A)
Hair treatment by soaking in prototype silicone emulsion 1A A 20 cm long (4.0 gram) hair piece is bleached, washed and air dried. In a dark room, the hair piece is immersed in a beaker containing 100.0 g of the emulsion of Example 1A. After 15 minutes, the hairpiece is removed from the beaker and exposed to bright light (Aquarium 20W fluorescent light AquaRays® model number F20WT12-AR-FS) for 15 minutes. The hair piece is rinsed 3 times with 100 mL of methyl isobutyl ketone / toluene (1: 1) and then immersed in 250 mL of a fresh solution of this mixed solvent for 30 minutes. Hang the hair piece and let it air dry. After drying, the hairpiece is washed with a cleansing shampoo (Pantene Pro-V® Clarifying Shampoo), rinsed firmly with tap water for 3.0 minutes and allowed to air dry for at least 5 hours. Repeat the wash / rinse cycle three times. In addition, the procedure is performed with two equivalent hair pieces (hair pieces from the same lot or source).

(Example 2B)
Hair Treatment by Soaking in Prototype Silicone Emulsion 1B Prototype silicone emulsion 1A is replaced with prototype silicone emulsion 1B, and the procedure of Example 2A is repeated.

(Example 3)
Fabric Treatment by Dipping in Prototype Silicone Emulsion 1A A 20 cm long (4.0 gram) piece of cotton fabric is washed and air dried. In a dark room, the fabric switch is immersed in a beaker containing 100.0 g of the emulsion of Example 1A. After 15 minutes, the fabric is removed from the beaker and exposed to bright light (Aquarium 20W fluorescent light AquaRays® model number F20WT12-AR-FS) for 15 minutes. The fabric is rinsed 3 times with 100 mL of methyl isobutyl ketone / toluene (1: 1) and then immersed in 250 mL of a fresh solution of this mixed solvent for 30 minutes. The fabric is hand dried and air dried and washed with Tide® liquid detergent at the dilution concentration indicated on the product label. The fabric is rinsed firmly and allowed to air dry for at least 5 hours. Repeat the wash / rinse cycle three times. Repeat the procedure with two more equivalent fabrics (fabrics from the same lot).

Example 4
Fabric Treatment by Spraying Prototype Silicone Emulsion 1A A 20 cm long (4.0 gram) piece of cotton fabric is washed and air dried. In the dark room, spray 10.0 g of the emulsion of Example 1A onto the fabric switch. The fabric is exposed to bright light (Aquarium 20W fluorescent light AquaRays® model number F20WT12-AR-FS) for 15 minutes. The fabric is rinsed 3 times with 100 mL of methyl isobutyl ketone / toluene (1: 1) and then immersed in 250 mL of a fresh solution of this mixed solvent for 30 minutes. Hang to air dry, dry completely, and then wash with Tide® liquid detergent at the dilution concentration indicated on the product label. The fabric is rinsed firmly and allowed to air dry for at least 5 hours. Repeat the wash and rinse cycle three times. Repeat the procedure with two more equivalent fabrics (fabrics from the same lot).

(Example 5)
Fabric Treatment by Adding Prototype Silicone Emulsion 1A to Laundry Detergent Five 10 cm × 10 cm pieces of cotton cloth are washed and air dried. In the dark room, the fabric is added to 10 L of the diluted concentration of Tide® liquid detergent cleaning solution as described on the product label and 100.0 g of the emulsion of Example 1A. Wash the fabric with stirring for 15 minutes. The fabric is removed from the wash solution and exposed to bright light (Aquarium 20W fluorescent light AquaRays® model number F20WT12-AR-FS) for 15 minutes. The fabric is rinsed 3 times with 100 mL of methyl isobutyl ketone / toluene (1: 1) and then immersed in 250 mL of a fresh solution of this mixed solvent for 30 minutes. Hang the fabric to air dry. After drying, the fabric is washed with Tide® liquid detergent at the dilution concentration indicated on the product label, rinsed thoroughly, and allowed to air dry for at least 5 hours. Repeat wash / rinse 3 times.

(Example 6)
Fabric Treatment by Adding Prototype Silicone Emulsion 1B to Laundry Detergent Five 10 cm × 10 cm pieces of cotton cloth are washed and air dried. In the dark room, the fabric is added to 10 L of the diluted concentration of Tide® liquid detergent as described on the product label and 100.0 g of the emulsion of Example 1B. The fabric is washed with stirring for 15 minutes, removed and exposed to bright light (Aquarium 20W fluorescent light AquaRays® model number F20WT12-AR-FS) for 15 minutes. The fabric is rinsed 3 times with 100 mL of methyl isobutyl ketone / toluene (1: 1) and then immersed in 250 mL of a fresh solution of this mixed solvent for 30 minutes. The fabric is hung and air dried, and after drying, it is washed with Tide® liquid detergent at the concentration indicated on the product label and rinsed firmly. Allow to air dry for at least 5 hours. Repeat the wash / rinse cycle three times.

(Example 7)
Hard surface treatment by spraying prototype silicone emulsion 1A A 10 cm × 10 cm long white ceramic tile is cleaned and air dried. In the dark room, 10.0 g of the emulsion of Example 1A is sprayed onto the tile. The tiles are exposed to bright light (Aquarium 20W fluorescent light AquaRays® model number F20WT12-AR-FS) for 15 minutes. The tile is rinsed 3 times with 100 mL of methyl isobutyl ketone / toluene (1: 1) and then immersed in 250 mL of a fresh solution of this mixed solvent for 30 minutes. Hanging to air dry, after drying, the tiles are washed with Mr Clean® cleaner, rinsed thoroughly, and air dried for at least 5 hours. Repeat the wash and rinse cycle three times. This procedure is repeated for 10 cm × 10 cm pieces of glass and 10 cm × 10 cm of painted metal (car panel).

(Example 8)
Fabric Treatment by Spraying Prototype Silicone Emulsion 1C A 20 cm long (4.0 gram) piece of cotton fabric is washed and air dried. In the dark room, spray 10.0 g of the emulsion of Example 1C onto the fabric switch. The fabric is exposed to bright light (Aquarium 20W fluorescent light AquaRays® model number F20WT12-AR-FS) for 15 minutes. The fabric is rinsed 3 times with 100 mL methyl isobutyl ketone / toluene (1: 1), then immersed in 250 mL fresh solution of mixed solvent for 30 minutes and then air dried. After drying, wash with Tide® liquid detergent at the dilution concentration indicated on the product label, rinse thoroughly, and air dry for at least 5 hours. Repeat the wash / rinse cycle three times. Repeat the procedure with two more equivalent fabrics (fabrics from the same lot).

Example 9
Fabric Treatment by Dipping in Prototype Silicone Emulsion 1D A 20 cm long (4.0 gram) piece of cotton cloth is washed and air dried. In a dark room, the fabric switch is immersed in a beaker containing 100.0 g of the emulsion of Example 1D. After 15 minutes, the fabric is removed from the beaker and exposed to bright light (Aquarium 20W fluorescent light AquaRays® model number F20WT12-AR-FS) for 15 minutes. The fabric is rinsed three times with 100 mL of a 1: 1 volume ratio of methyl isobutyl ketone and toluene mixed solvent, then immersed in 250 mL of a fresh solution of this mixed solvent for 30 minutes and then suspended for air drying. After drying, wash with Tide® liquid detergent at the dilution concentration indicated on the product label, rinse thoroughly, and air dry for at least 5 hours. Repeat the wash / rinse cycle three times. Repeat the procedure with two more equivalent fabrics (fabrics from the same lot).

(Example 10)
Fabric treatment by soaking in prototype silicone emulsion 1F A 20 cm long (4.0 gram) piece of cotton fabric is washed and air dried. In a dark room, the fabric switch is immersed in a beaker containing 100.0 g of the emulsion of Example 1F. After 15 minutes, the fabric is removed from the beaker and exposed to bright light (Aquarium 20W fluorescent light AquaRays® model number F20WT12-AR-FS) for 15 minutes. The fabric is rinsed 3 times with 100 mL of 1: 1 volume ratio of methyl isobutyl ketone / toluene, then immersed in 250 mL of a fresh solution of this mixed solvent for 30 minutes and then suspended to air dry. After drying, wash with Tide® liquid detergent at the concentration indicated on the product label and rinse thoroughly. Allow to air dry for at least 5 hours. Repeat the wash / rinse cycle three times. Repeat the procedure with two more equivalent fabrics (fabrics from the same lot).

(Example 11)
Hard Surface Treatment by Spraying Prototype Silicone Emulsion 1E A 10 cm × 10 cm long white ceramic tile is cleaned and air dried. In the dark room, spray 10.0 g of the emulsion of Example 1E onto the tile. The tiles are exposed to bright light (Aquarium 20W fluorescent light AquaRays® model number F20WT12-AR-FS) for 15 minutes. The tile is washed 3 times with 100 mL of 1: 1 volume ratio of methyl isobutyl ketone / toluene, then immersed in 250 mL of a fresh solution of this mixed solvent for 30 minutes and then air dried. After drying, the tiles are washed with a Mr Clean® cleaner, rinsed thoroughly and allowed to air dry for at least 5 hours. Repeat the wash / rinse cycle three times. This procedure is repeated for 10 cm × 10 cm pieces of glass and 10 cm × 10 cm pieces of painted metal (such as an automobile side panel).

(Example 12)
Hard Surface Treatment by Spraying Prototype Silicone Emulsion 1D 10 cm × 10 cm long white ceramic tile is cleaned and air dried. In the dark room, 10.0 g of the emulsion of Example 1D is sprayed onto the tile. The tiles are exposed to bright light (Aquarium 20W fluorescent light AquaRays® model number F20WT12-AR-FS) for 15 minutes. Rinse the tile 3 times with 100 mL of 1: 1 volumetric methyl isobutyl ketone / toluene. The tile is immersed in 250 mL of a fresh solution of this mixed solvent for 30 minutes and allowed to air dry. After drying, the tiles are washed with a Mr Clean® cleaner, rinsed thoroughly and allowed to air dry for at least 5 hours. Repeat the wash / rinse cycle three times. This procedure is repeated for 10 cm × 10 cm pieces of glass and 10 cm × 10 cm pieces of painted metal (such as an automobile side panel).

(Example 13)
Fabric Treatment by Adding Prototype Silicone Emulsion 1D to Laundry Detergent Five 10 cm x 10 cm pieces of cotton fabric are washed and air dried. In the dark room, the fabric is added to 10 L of the diluted concentration of Tide® liquid detergent cleaning solution described on the product label and 100.0 g of the emulsion of Example 1D. Wash the fabric for 15 minutes with stirring. The fabric is removed from the wash solution and exposed to bright light (Aquarium 20W fluorescent light AquaRays® model number F20WT12-AR-FS) for 15 minutes. The fabric is rinsed 3 times with 100 mL of 1: 1 volume ratio of methyl isobutyl ketone / toluene and then immersed in 250 mL of a fresh solution of this mixed solvent for 30 minutes. Hang and dry. After drying, the fabric is washed with the diluted concentration of Tide® liquid detergent as described on the product label, rinsed thoroughly and allowed to air dry for at least 5 hours. Repeat the wash / rinse cycle three times.

(Example 14)
Hard Surface Treatment by Spraying Prototype Silicone Emulsion 1C A 10 cm × 10 cm long white ceramic tile is cleaned and air dried. In a dark room, 10.0 g of the emulsion of Example 1C is sprayed onto the tile. The tiles are exposed to bright light (Aquarium 20W fluorescent light AquaRays® model number F20WT12-AR-FS) for 15 minutes. The tile is rinsed 3 times with 100 mL of 1: 1 methyl isobutyl ketone / toluene and then immersed in 250 mL of a fresh solution of this mixed solvent for 30 minutes. Allow to air dry. After drying, the tiles are washed with a Mr Clean® cleaner, rinsed thoroughly and allowed to air dry for at least 5 hours. Repeat the wash / rinse cycle three times. This procedure is repeated for 10 cm × 10 cm pieces of glass and 10 cm × 10 cm pieces of painted metal (such as an automobile side panel).

  Various embodiments of the compositions and methods described herein are discussed primarily with respect to hair, skin and fabric substrates. Nevertheless, it is recognized that the present invention as defined in the following claims is not limited to application to any particular substrate. The invention as defined in the following claims relates to any substrate for which surface treatment with the compositions and methods described herein is useful, as will be appreciated by those skilled in the art. May be used. Non-limiting examples of such substrates include, for example, fabric, paper, wood, plastic, glass, tile, stone, concrete, brick, other ceramics, and composite materials.

  All references cited herein, including any patents or application documents that are cross-referenced or related, are hereby incorporated by reference in their entirety, unless expressly excluded or limited. Citation of any document is such prior art as to any invention disclosed and claimed herein, or whether such reference alone or in any combination with any other reference. No teaching, suggestion, or disclosure is permitted. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the definition or meaning given to that term in this document applies. Shall be.

  While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, all such changes and modifications that fall within the scope of the invention are intended to be covered by the appended claims.

Claims (12)

(A) an active substance having one or more functional groups that form a covalent bond with a complementary functional group of a non-biological substrate in the presence of an acid or base;
(B) a photocatalyst capable of generating an acid or base in response to exposure to light, and (c) a delivery agent excipient for 1 (a) and 1 (b), or the active substance dissolved and dispersed A delivery agent excipient that is a solvent capable of delivery, or a delivery excipient selected from the group consisting of water, silicone, oil, hydrocarbons, lauryl sulfate, and combinations thereof, A composition for treating a substrate comprising:
A composition in which the substrate does not contain a biological substance.   The active substance is selected from the group of hydrophilic active substances, hydrophobic active substances, and mixtures thereof; or is a hydrophobic substance; or fatty acid, aliphatic alcohol, aliphatic amine, aminosilicone, polyvinyl alcohol, polyvinyl Group consisting of alcohol-polyvinylpyrrolidone copolymer, polycaprolactone, optical brightener, humectant, silanol, dimethyl silicone functionalized with one or more primary, secondary carboxyl or hydroxyl functional groups, and combinations thereof The composition according to claim 1, which is a hydrophobic active substance selected from.   The composition according to claim 1 or 2, wherein the photocatalyst absorbs light in the infrared to visible and infrared to ultraviolet electromagnetic spectrum of 1200 nm to 200 nm.   The photocatalyst is an aromatic hydroxyl compound, pyrenesulfonic acid compound, onium salt, diazomethane derivative, bissulfone derivative, disulfuno derivative, nitrobenzyl sulfonate derivative, sulfonate ester derivative, sulfonate ester of N-hydroxyimide. And a photoacid selected from the group consisting of combinations thereof; or a photoacid that is an aromatic hydroxyl compound.   A surfactant, an emulsifier, and an auxiliary component selected from the group consisting of an oxidizing agent, a pH adjusting component, a feel improving agent, a rheology modifier, a filler, a fragrance, and combinations thereof. The composition as described in any one of these.   The substrate is fabric, paper, wood, plastic, glass, tile, stone, concrete, brick, other ceramics, glass, metal, polymer film, composite material, laminate, painted or varnished as listed above The composition according to any one of claims 1 to 5, which is selected from the group consisting of: a coated surface, and all of these combinations.   The composition is a soft surface cleaner, hard surface cleaner, glass cleaner, ceramic tile cleaner, toilet bowl cleaner, wood cleaner, multi-surface cleaner, surface disinfectant, dishwashing composition, laundry detergent, fabric conditioner, fabric dye, automotive surface The composition as described in any one of Claims 1-6 which is a consumer care composition selected from the group which consists of a processing agent, a surface protection agent, and a surface disinfectant.   The composition according to any one of claims 1 to 7, wherein the photocatalyst is present in an amount of 0.00050% to 10% by weight relative to the total weight of the composition.   9. A composition according to any one of the preceding claims, wherein water is present in an amount of 1% to 98% by weight relative to the total weight of the composition.   The oxidant present in an amount of 0.00050% to 25% by weight relative to the total weight of the composition, or the oxidant is hydrogen peroxide. A composition according to 1. A method for treating a substrate with the composition according to any one of claims 1 to 10, wherein the method comprises the following steps:
a) applying at least one photocatalyst to the substrate; and b) one or more functionalities bound to the active material and the substrate by exposing the photocatalyst and the at least one active material to light. Forming a covalent bond between groups;
A method wherein the substrate does not contain biological material. A method for treating a substrate with the composition according to any one of claims 1 to 10, wherein the method comprises the following steps:
a) applying at least one active substance to the substrate, wherein the active substance has one or more functional groups that are complementary to the functional groups of the substrate And a process of
b) applying at least one photocatalyst to the substrate that generates an acid or base in response to exposure to light; and c) exposing the photocatalyst and the active agent to light.
A method wherein the substrate does not contain biomaterial.

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