Compositions, methods of making articles, and articles

Abstract

This invention discloses a composition comprising a compound prepared by a reaction comprising an optionally crosslinked polyethyleneimine and at least one amine-reactive hydrolyzable organosilane represented by the formula R-Z-SiY3. R represents an amine-reactive group containing 1 to 18 carbon atoms; Z represents a divalent organic group containing 1 to 8 carbon atoms; and each Y independently represents a hydrolyzable group. Methods for preparing articles using the composition and articles thus manufactured are also disclosed. A composition and a method for preparing the composition are also disclosed, the composition comprising a close mixture of crosslinked polyethyleneimine and a polymer binder material.

Description

[0001] This application is a divisional application of patent application No. 201780027663.4, filed on April 25, 2017, entitled "Composition, Method of Preparing Article and Article". Technical Field

[0002] This disclosure relates broadly to compositions, especially curable compositions, methods for preparing articles using the compositions, and articles manufactured therefrom. Background Technology

[0003] Polyethyleneimine (PEI) is commercially available in several forms, such as linear, branched, and dendritic.

[0004] PEIs are available in several forms, such as linear, branched, and dendritic. A linear PEI can be represented by the following equation I: (I) Wherein --- indicates a continuous linear polyethyleneimine-derived unit or H. Linear PEI can be obtained by post-modification of other polymers such as poly(2-oxazoline) or N-substituted polyaziridine. Linear PEI is commercially available and / or can be prepared according to known methods.

[0005] An exemplary branched PEI segment can be represented by the following equation II: (II) Wherein --- indicates continuous linear and / or branched polyethyleneimine-derived units or H. Since branching is generally more or less random, branched PEI typically contains many of these general-type compounds as a mixture. Branched PEI can be synthesized by ring-opening polymerization of aziridine. Branched PEI is commercially available and / or can be prepared according to known methods.

[0006] Dendritic PEI is a special case of branched PEI. An exemplary (generation 4) dendritic PEI is represented by the following equation III: (III) In this case, PEI contains only primary and tertiary amino groups. Dendritic PEI is commercially available and / or can be prepared according to known methods.

[0007] As used in this article, the term "polyethyleneimine" also includes the protonated form.

[0008] PEI can be covalently crosslinked (i.e., at least partially cured) by combining it with a multifunctional (e.g., bifunctional) crosslinking agent such as hexanediol diacrylate (HDDA). HDDA reacts with primary amino groups through Michael addition to each acrylate group. However, the reaction with such crosslinking agents is generally too fast for use in monopartic curable compositions.

[0009] The aim is to provide a fairly stable, single-component, curable PEI-derived composition that can be applied to a substrate and cured. Summary of the Invention

[0010] This invention provides fairly stable, single-component, curable PEI-derived compositions that can be applied to and cured onto a substrate to provide a durable amine-functional coating on the substrate. These coatings can be used, for example, in chemical monitors (e.g., for monitoring exposure to aldehyde disinfectants) and / or to alter the hydrophilicity of a substrate surface and / or to protect the surface of the substrate.

[0011] In one aspect, the present invention provides a composition comprising a compound that can be prepared by a reaction comprising a component comprising polyethyleneimine and at least one amine-reactive, hydrolyzable organosilane represented by the following formula: RZ-SiY3 in: R represents an amine reactive group containing 1 to 18 carbon atoms; Z represents a divalent organic group containing 1 to 8 carbon atoms; and Each Y independently represents a hydrolyzable group.

[0012] In another aspect, the present invention provides a composition comprising a compound that can be prepared by reacting a component comprising a cross-linked polyethyleneimine and at least one amine-reactive, hydrolyzable organosilane represented by the following formula: RZ-SiY3 in: R represents an amine reactive group containing 1 to 18 carbon atoms; Z represents a divalent organic group containing 1 to 8 carbon atoms; and Each Y independently represents a hydrolyzable group.

[0013] In another aspect, the present invention provides a method for preparing an article, the method comprising: The composition according to the invention, disposed on at least a portion of the surface of the substrate, is applied to at least a portion of the surface of the substrate; and At least some of the hydrolyzable groups Y.

[0014] In another aspect, the present invention provides an article comprising: A substrate having a surface; and The reaction product of the composition according to the invention with at least a portion of the surface of the substrate.

[0015] In another aspect, the present invention provides an article comprising: A substrate having a surface; and The crosslinking reaction product of the composition according to the invention is disposed on at least a portion of the surface.

[0016] In another aspect, the present invention provides a composition comprising a close mixture of cross-linked polyethyleneimine and a polymeric binder material.

[0017] In another aspect, the present invention provides a method for preparing a composition, the method comprising sequentially and closely mixing: An aqueous solution of polyethyleneimine; Crosslinking agent used for the polyethyleneimine; and Polymer adhesive materials.

[0018] As used herein, the term "crosslinking agent" refers to a compound that forms multiple covalent bonds with a material (e.g., PEI) resulting in crosslinking.

[0019] As used herein, the terms “polymer” and “polymeric” refer only to organic polymers.

[0020] As used herein, the term "water content" means containing at least 5% by weight of water (e.g., at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or even 100% by weight of water).

[0021] The features and advantages of this disclosure will be further understood upon consideration of the specific embodiments and the appended claims. Attached Figure Description

[0022] Figure 1 This is a schematic side view of an exemplary article 100 according to the present invention.

[0023] It should be understood that those skilled in the art can devise many other modifications and embodiments that fall within the scope and substance of the principles of this disclosure. The accompanying drawings may not be drawn to scale. Detailed Implementation

[0024] The compositions according to the invention may comprise one or more compounds that can be prepared by a reaction comprising a component comprising optionally crosslinked (e.g., using a crosslinking agent) polyethyleneimine and at least one amine-reactive hydrolyzable organosilane, and optionally prepared in this way.

[0025] Polyethyleneimine comprises a wide range of water-soluble polyamines of varying molecular weights. As discussed above, the polyethyleneimine (PEI) used in the practice of this invention can be linear, branched (e.g., randomly branched), or dendritic. Preferably, the PEI is branched and contains a combination of primary and secondary amino nitrogen atoms.

[0026] It is generally known that the polymerization of ethyleneimine (i.e., aziridine) itself does not produce polymers composed entirely of units with a linear structure, but the degree of branching in polyethyleneimine depends on the acid concentration and temperature during polymerization. The degree of branching can vary, for example, between 12% and 38%. Such branched polyethyleneimine can be represented by units A, B, or C, where A is -R 5 -N(R 4 Unit 2, B is R 4 -N(R 5 -)2 units, and C is (-R) 5 )3N- element, where R 4 It is hydrogen, R 5 It is ethylene (-CH2CH2-). In some embodiments, the ratio of A to B to C units is from about 1:0.5:0.5 to about 1:2:1, preferably from about 1:1:1 to about 1:2:1.

[0027] Polyethyleneimine is widely available from commercial sources, including, for example, BASF Corp. (Florham Park, New Jersey) under the trade name “LUPASOL” (e.g., LUPASOL FG, LUPASOL G 20, LUPASOL G 20 WF, LUPASOL G 35, and LUPASOL FT FP) and Sigma-Aldrich Corp. (St. Louis, Missouri).

[0028] The molecular weight of PEI can be customized according to specific application requirements. In some implementations, the molecular weight of PEI (M...) is... w The molecular weight (M) of PEI ranges from 500 g / mole to 1500 g / mole. In some embodiments, the molecular weight (M) of PEI is... w The molecular weight (M) of PEI ranges from 1500 g / mole to 2000 g / mole. In some embodiments, the molecular weight (M) of PEI is...w The molecular weight (M) of PEI ranges from 2000 g / mole to 5000 g / mole. In some embodiments, the molecular weight (M) of PEI is... w The molecular weight (M) of PEI ranges from 5000 g / mole to 15000 g / mole. In some embodiments, the molecular weight (M) of PEI is... w The molecular weight (M) of PEI ranges from 15,000 g / mole to 30,000 g / mole. In some embodiments, the molecular weight (M) of PEI is... w The molecular weight (M) of PEI ranges from 30,000 g / mole to 60,000 g / mole. In some embodiments, the molecular weight (M) of PEI is... w The molecular weight (M) of PEI ranges from 60,000 g / mole to 100,000 g / mole. In some embodiments, the molecular weight (M) of PEI is... w ) Greater than or equal to 100,000 g / mole.

[0029] In some embodiments, polyethyleneimine is crosslinked with a crosslinking agent before or simultaneously with the reaction with an amine-reactive hydrolyzable organosilane. Suitable crosslinking agents have multiple (e.g., 2, 3, 4, or 5) amine-reactive groups that form covalent bonds with amino groups. Preferably, the crosslinking agent has two amine-reactive groups. Typically, crosslinking is achieved by simply combining PEI and the crosslinking agent under relatively high dilution conditions (favorable for intramolecular crosslinking) to minimize gelation caused by interchain crosslinking. The determination of suitable conditions is within the capabilities of those skilled in the art.

[0030] Suitable crosslinking agents for PEI include, for example, multifunctional compounds such as: haloalcohols (e.g., epichlorohydrin); alkylene dihalides (e.g., 1,4-dibromobutane, 1,2-diiodoethane); multifunctional acrylates (e.g., 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate, glycerol triacrylate, dipentaerythritol hexaacrylate); and diepoxides (e.g., aliphatic, cycloaliphatic, and glycidyl ether diepoxides, such as vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexane carboxylate). Acrylates, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, dipentene dioxide, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, 1,4-butanediol diglycidyl ether; diesters (e.g., diethyl adipate, dimethyl fumarate, diethyl sebacate, and dimethyl maleate); divinyl sulfone; polyfunctional acrylamides (e.g., piperazine diacrylamide, diacrylamide, N,N-methylene diacrylamide, and N,N'-(ethane-1,2-diyl)diacrylamide); polyisocyanates (e.g., hexamethylene diisocyanate, methylene diisocyanate) and polyaziridinyl compounds (e.g., tri-(1-aziridinyl)phosphine oxide), carbodiimides (e.g., 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide) and N-hydroxysuccinimide.

[0031] In some implementations, a suitable crosslinking agent can be represented by the following formula. RZR Each of R and Z is independent as previously defined. Examples include diacrylates (e.g., 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, and tetraethylene glycol diacrylate), triacrylates (e.g., ethoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate, and glyceryl triacrylate), and diepoxides (e.g., aliphatic, cycloaliphatic, and glycidyl ether diepoxides, such as vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6-methylcyclohexane). 3,4-epoxy-6-methylcyclohexane carboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, dipentene dioxide, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, 1,4-butanediol diglycidyl ether), diesters (e.g., diethyl adipate, dimethyl fumarate, diethyl sebacate and dimethyl maleate), diethylene sulfone and diacrylamides (e.g., piperazine diacrylamide, diacrylamide, N,N-methylene diacrylamide and N,N'-(ethane-1,2-diyl)diacrylamide).

[0032] Other crosslinking agents are known in the art and are available to those skilled in the art.

[0033] Preferably, a certain amount of crosslinking agent is used, which causes a reaction with 1% to 10%, more preferably 3% to 8%, of available primary nitrogen atoms in PEI.

[0034] Suitable amine reactivity allows for the hydrolysis of organosilanes, which can be represented by the following formula: RZ-SiY3 in, R represents an amine reactive group containing 1 to 18 carbon atoms. Preferably, R contains 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. Exemplary amine reactive groups R include isocyanate groups (-N=C=O), ethylene oxide groups (... ), epoxypropoxy group ( ), Acryloyl group ( ), Acryloyloxy group ( ), alkoxycarbonyl groups having 2 to 5 carbon atoms (e.g., ethoxycarbonyl groups). ) or methoxycarbonyl group ( )), vinylsulfonyl group ( ), cyclic anhydride groups (e.g., ), alkyl carbamate groups (e.g., ), alkyl halogen groups (e.g., BrCH2- or ClCH2-) and acrylamide groups (i.e., ).

[0035] Z represents a divalent organic group containing 1 to 8 carbon atoms. In some embodiments, Z also contains 1 to 6 heteroatoms selected from O, N, and S. Suitable divalent organic groups Z include, for example: alkylene groups having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms; alkyleneoxyalkylene groups having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms; di(alkylene)amino groups having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms; and alkylenethioalkylene groups having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples of group Z include methylene, ethylene, 1,2- and 1,3-propylene, butylene, isobutylene, hexylene, octylene, ethylcyclohexane-4,2'-diyl, ethoxyethylene, ethylaminoethylene, ethoxypropylene, ethylthioethylene, and ethyl(methyl)aminoethylene. Ethylene and 1,3-propylene are particularly preferred.

[0036] Each Y independently represents a hydrolyzable group. As used herein, the term "hydrolyzable group" indicates a group that can be hydrolyzed, meaning it can react with water to provide a silanol group (Si-OH group), which can further react with groups (e.g., hydroxyl groups) on the surface of a substrate. Hydrolysis and condensation reactions can occur spontaneously and / or in the presence of a hydrolysis / condensation catalyst. Examples of hydrolyzable groups include halogen groups, such as chlorine, bromine, iodine, or fluorine; alkoxy groups (-OR... 1 , where R 1 The alkyl group represents an alkyl group, which preferably contains 1 to 6, more preferably 1 to 4 carbon atoms, and may optionally be substituted by one or more halogen atoms; an acyloxy group (-O-(C=O)-R 2 , where R 2 For example, regarding R 1 Definition); aryloxy group (-OR) 3 , where R 3 The aryl moiety represents an aryl group, which preferably contains 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and may optionally be substituted by one or more substituents, which are independently selected from halogens and C1-C4 alkyl groups that may optionally be substituted by one or more halogen atoms. In the above formula, R 1 R 2 and R 3 It may include branched structures. In some preferred embodiments, each Y is independently selected from methoxy, ethoxy, hydroxy, acetoxy, chlorine, and bromine, with methoxy and ethoxy being particularly preferred.

[0037] Specific examples of suitable amine-reactive hydrolyzable organosilanes include 3-isocyanopropyltriethoxysilane, 3-isocyanopropyltrimethoxysilane, 2-isocyanoethyltriethoxysilane, 2-isocyanoethyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 2-acryloyloxyethyltriethoxysilane, 2,3-epoxypropyltrimethoxysilane, 2,3-epoxypropyltriethoxysilane, 3-epoxypropoxypropyltriethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane. Combinations of amine-reactive hydrolyzable organosilanes can be used.

[0038] Suitable amine-reactive hydrolyzable organosilanes are available from commercial sources (e.g., as silane coupling agents, for example, from Gelest, Inc., Morrisville, Pennsylvania) and / or can be prepared by known methods. Preferably, the amine-reactive hydrolyzable organosilane reacts with a primary amino group, and optionally with a secondary amino and / or tertiary amino group. Preferably, the reaction of the amine-reactive hydrolyzable organosilane with the primary amino group is faster (if any) than with the secondary and tertiary amino groups.

[0039] Typically, 5% to 70% of the primary amino groups in PEI, preferably 10% to 40%, react with amine-reactive hydrolyzable silanes, but this is not mandatory. To minimize leaching, preferably, at least three (e.g., at least four, five, or even six hydrolyzable silane groups) are attached to each PEI polymer chain. This reaction is typically carried out in an organic solvent, but water may be present if desired. After the silane-functionalized PEI is coated and dried on the substrate, the hydrolyzable groups hydrolyze and form siloxane crosslinks with other silane groups. This results in the crosslinked PEI being disposed on the substrate, and depending on the specific substrate, it can be chemically bonded to the substrate (e.g., if the substrate has available hydroxyl groups on its surface; e.g., in the case of cellulose paper). Exemplary substrates may include any substrate described herein.

[0040] The composition preferably contains a liquid carrier, which may be organic and / or aqueous, but this is not essential. If present, a liquid carrier should generally be chosen to minimize its reaction with the other components of the composition. Examples of organic carriers include alcohols and ethers. Examples of aqueous liquid carriers include water and water-alcohol mixtures (e.g., water-isopropanol mixtures). If a liquid carrier is present, it is preferable to dissolve and disperse the other components therein. Any amount of liquid carrier can be used, and will generally depend on the specific composition and / or intended use.

[0041] Optionally, the composition may also contain additional polymeric binders. In embodiments where a liquid carrier is present, the additional polymeric binder is preferably dispersible or soluble in the liquid carrier. Exemplary additional polymeric binders include water-soluble polymers such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, and polymeric latexes (e.g., polyurethane latex, acrylic latex, and vinyl acetate latex). Suitable polymeric binders include film-forming polymeric binders, which may be provided, for example, as latex. In some preferred embodiments, the latex is added to the composition before the mixture is deposited on a substrate. Suitable film-forming polymers include acrylics (e.g., polybutyl acrylate and polymethyl methacrylate), ethylene-vinyl acetate copolymers (and their partially or fully hydrolyzed forms), polyvinyl alcohol, polyurethane, polyamide, polyvinyl chloride, polystyrene, polyester, polycarbonate, natural and synthetic rubbers, and combinations thereof. The film-forming polymeric binder may be self-crosslinkable.

[0042] The composition may also optionally contain various additives, such as thickeners, fillers, fragrances, antioxidants, UV stabilizers and surfactants.

[0043] The compositions according to the invention can generally be prepared by simply mixing the various components in a container, optionally under heating or cooling.

[0044] The compositions according to the invention can be used, for example, in methods for preparing articles by coating at least a portion of the surface of a substrate with the composition and then hydrolyzing at least some of the hydrolyzable groups to form covalent crosslinks (e.g., having Si-O-Si units) between the PEI chains and / or the substrate. Hydrolysis can occur spontaneously during drying or standing. In some cases, optional heating may be advantageous.

[0045] Now for reference Figure 1 The exemplary article 100 includes a crosslinked layer 110 (i.e., a crosslinked reaction product of the composition according to the invention) disposed on a surface 120 of a substrate 130. The crosslinked layer is typically hydrophilic due to the presence of amino groups; however, this is not necessary. Layer 110 can have any thickness. In some embodiments, the thickness of the crosslinked layer is less than 25.4 micrometers, preferably less than 5 micrometers.

[0046] Suitable substrates can be transparent or opaque. For example, substrates may include glass, organic polymers, metals, ceramics, fabrics, paper, and / or wood. Specific examples of suitable substrates include vehicles (e.g., buses, vans, cars, railcars, locomotives, caravans, trolleys, campervans, airplanes, bicycles, boats, and barges), mirrors, windows, lenses, goggles, bridges, exterior building panels, shower fixtures, bathtubs, trailers, signs (e.g., traffic signs, advertising signs, neon lights), substrates with a polymer-coated transparent layer, and outdoor furniture (e.g., plastic or metal tables and chairs). In another embodiment, the substrate may include a transparent film (e.g., polyethylene terephthalate, polymethyl methacrylate, or polycarbonate), a membrane (e.g., nylon or polyethersulfone film), or paper suitable for use as an indicator in an automated endoscope recirculation device.

[0047] The composition can be applied by suitable methods, including, for example, spin coating, dip coating, spray coating, brush coating, roller coating, gravure coating, curtain coating, doctor blade coating, and tank coating. In some embodiments, heating may be advantageously applied after coating (e.g., to promote crosslinking and / or remove any optional solvents).

[0048] This disclosure selects an implementation scheme. In a first embodiment, the present invention provides a composition comprising a compound prepared by a reaction comprising polyethyleneimine and at least one amine-reactive, hydrolyzable organosilane represented by the following formula: RZ-SiY3 in: R represents an amine reactive group containing 1 to 18 carbon atoms; Z represents a divalent organic group containing 1 to 8 carbon atoms; and Each Y independently represents a hydrolyzable group.

[0049] In a second embodiment, the present invention provides a composition according to the first embodiment, the composition further comprising an aqueous liquid carrier for dispersing or dissolving the compound.

[0050] In a third embodiment, the present invention provides a composition according to a first or second embodiment, wherein R has 1 to 3 carbon atoms.

[0051] In a fourth embodiment, the present invention provides a composition according to any one of the first to third embodiments, wherein R is selected from isocyanate groups, ethylene oxide groups, propylene oxide groups, acryloyloxy groups, ethoxycarbonyl groups, methoxycarbonyl groups, vinylsulfonyl groups, and acrylamide groups.

[0052] In a fifth embodiment, the present invention provides a composition according to any one of the first to fourth embodiments, wherein Z further contains 1 to 6 heteroatoms selected from O, N and S.

[0053] In a sixth embodiment, the present invention provides a composition according to any one of the first to fifth embodiments, wherein Z comprises an alkylene group containing 1 to 3 carbon atoms.

[0054] In a seventh embodiment, the present invention provides a composition according to any one of the first to sixth embodiments, wherein each Y is independently selected from methoxy, ethoxy, hydroxy, acetoxy, chlorine and bromine.

[0055] In an eighth embodiment, the present invention provides a composition according to any one of the first to seventh embodiments, wherein the at least one amine-reactive hydrolyzable organosilane is selected from 3-isocyanopropyltriethoxysilane, 3-isocyanopropyltrimethoxysilane, 2-isocyanoethyltriethoxysilane, 2-isocyanoethyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 2-acryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 2,3-epoxypropyltrimethoxysilane, 2,3-epoxypropyltriethoxysilane, 3-epoxypropoxypropyltriethoxysilane, and 3-epoxypropoxypropyltrimethoxysilane.

[0056] In a ninth embodiment, the present invention provides a composition according to any one of the first to eighth embodiments, the composition further comprising a polymeric binder material.

[0057] In a tenth embodiment, the present invention provides a composition comprising a compound that can be prepared by a reaction comprising a crosslinked polyethyleneimine and at least one amine-reactive hydrolyzable organosilane represented by the following formula: RZ-SiY3 in: R represents an amine reactive group containing 1 to 18 carbon atoms; Z represents a divalent organic group containing 1 to 8 carbon atoms; and Each Y independently represents a hydrolyzable group.

[0058] In the eleventh embodiment, the present invention provides a composition according to the tenth embodiment, the composition further comprising an aqueous liquid carrier for dispersing or dissolving the compound.

[0059] In a twelfth embodiment, the present invention provides a composition according to a tenth or eleventh embodiment, wherein the crosslinked polyethyleneimine comprises a reaction product of a polyamine and a crosslinking agent represented by the following formula. RZR Each of R and Z is independent as previously defined.

[0060] In a thirteenth embodiment, the present invention provides a composition according to any one of the tenth to twelfth embodiments, wherein R has 1 to 3 carbon atoms.

[0061] In the fourteenth embodiment, the present invention provides a composition according to any one of the tenth to thirteenth embodiments, wherein R is selected from isocyanate groups, ethylene oxide groups, propylene oxide groups, acryloyloxy groups, ethoxycarbonyl groups, methoxycarbonyl groups, vinylsulfonyl groups, and acrylamide groups.

[0062] In the fifteenth embodiment, the present invention provides a composition according to any one of the tenth to fourteenth embodiments, wherein Z further contains 1 to 6 heteroatoms selected from O, N and S.

[0063] In a sixteenth embodiment, the present invention provides a composition according to any one of the tenth to fifteenth embodiments, wherein Z comprises an alkylene group containing 1 to 3 carbon atoms.

[0064] In the seventeenth embodiment, this disclosure provides a composition according to any one of the tenth to sixteenth embodiments, wherein each Y is independently selected from methoxy, ethoxy, hydroxy, acetoxy, chlorine and bromine.

[0065] In the eighteenth embodiment, the present invention provides a composition according to any one of the tenth to seventeenth embodiments, wherein the at least one amine-reactive hydrolyzable organosilane is selected from 3-isocyanopropyltriethoxysilane, 3-isocyanopropyltrimethoxysilane, 2-isocyanoethyltriethoxysilane, 2-isocyanoethyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 2-acryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 2,3-epoxypropyltrimethoxysilane, 2,3-epoxypropyltriethoxysilane, 3-epoxypropoxypropyltriethoxysilane, and 3-epoxypropoxypropyltrimethoxysilane.

[0066] In a nineteenth embodiment, the present invention provides a composition according to any one of the tenth to eighteenth embodiments, the composition further comprising a polymeric binder material.

[0067] In a twentieth embodiment, the present invention provides a method for preparing an article, the method comprising: The composition according to any one of the first to nineteenth embodiments, disposed on at least a portion of the surface of the substrate, is applied to at least a portion of the surface of the substrate and at least some of the hydrolyzable groups Y are hydrolyzed.

[0068] In a twenty-first embodiment, the present invention provides a method according to a twenty-tenth embodiment, wherein the compound is covalently bonded to the surface of the substrate.

[0069] In a twenty-second embodiment, the present invention provides the method according to the twenty-first embodiment, wherein the compound becomes cross-linked and forms Si-O-Si units.

[0070] In the twenty-third embodiment, the present invention provides an article of articles comprising: A substrate having a surface; and The reaction product of the composition according to any one of the first to nineteenth embodiments with at least a portion of the surface of the substrate.

[0071] In the twenty-fourth embodiment, the present invention provides an article of articles comprising: A substrate, the substrate having a surface; and The crosslinking reaction product of the composition according to any one of the first to nineteenth embodiments is disposed on at least a portion of the surface.

[0072] In a twenty-fifth embodiment, the present invention provides a composition comprising a close mixture of cross-linked polyethyleneimine and a polymer binder material.

[0073] In a twenty-sixth embodiment, this disclosure provides a composition according to a twenty-fifth embodiment, wherein the crosslinked polyethyleneimine is a reaction product of polyethyleneimine and an acrylic monomer having at least two acryloyl groups.

[0074] In a twenty-seventh embodiment, this disclosure provides a composition according to a twenty-fifth or twenty-sixth embodiment, wherein the crosslinked polyethyleneimine and the polymer binder material are dispersed or dissolved in an aqueous liquid carrier.

[0075] In a twenty-eighth embodiment, the present invention provides a method for preparing a composition, the method comprising sequentially and tightly mixing: An aqueous solution of polyethyleneimine; Crosslinking agent for the polyethyleneimine; and Polymer adhesive materials.

[0076] In a twenty-ninth embodiment, this disclosure provides a method according to a twenty-eighth embodiment, wherein the crosslinking agent for the polyethyleneimine comprises an acrylic monomer having at least two acryloyl groups.

[0077] The objects and advantages of this disclosure are further illustrated by the following non-limiting embodiments, but the specific materials and quantities referenced in these embodiments, as well as other conditions and details, should not be regarded as undue limitations on this disclosure.

[0078] Example Unless otherwise stated, all parts, percentages, ratios, etc., in the embodiments and the remainder of this specification are by weight.

[0079] Reagent Table

[0080] Example 1 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 3% by weight aqueous solution, abbreviated as "bPEI") was mixed with a 3% by weight aqueous solution of 3-(acryloyloxypropyl)trimethoxysilane (abbreviated as "AS", Gelest Inc.) at a bPEI:AS weight ratio of 4:1 to form solution A. NEOCRYL A612 (abbreviated as "A612", DSM Corporation) was diluted with distilled water to prepare a 3% by weight solution (solution B). Solutions A and B were then mixed together at a solution A:solution B weight ratio of 2:3 to form the final coating formulation. Filter paper samples (Whatman 410) were impregnated with the coating formulation and then dried at 80°C for 3 minutes. The dried samples were cut into test strips (20 mm × 40 mm). The coating surface of the test strip is white.

[0081] Individual test solutions of o-phthalaldehyde (OPA) in water were prepared at concentrations of 0.10 wt% OPA and 0.35 wt% OPA. The test strips were evaluated by immersing them in an OPA test solution bath for 5 minutes, maintaining the bath temperature at 25°C. The test strips were then removed from the bath and the color change was visually inspected. Additionally, the test strips were evaluated to determine if any indicator color from the test strip had seeped into the OPA bath. For this test, new test strips were immersed in and maintained in a fresh OPA bath (0.35 wt% at 25°C) for 30 minutes. This bath contained a minimum amount of OPA to completely cover the test strip (typically 1 mL to 2 mL). The test strips were then removed from the bath, and the color change of the bath solution was visually inspected (no leaching = colorless bath, leaching = bath color changes from colorless to pale yellow or yellow). The results are reported in Table 1.

[0082] Example 2 The procedure of Example 1 was followed, except that solution A and solution B were mixed together at a weight ratio of 1:1 to form the final coating formulation. The results are reported in Table 1.

[0083] Example 3 The procedure of Example 1 was followed, except that solution A and solution B were mixed together at a weight ratio of solution A:solution B of 3:2 to form the final coating formulation. The results are reported in Table 1.

[0084] Example 4 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 3% by weight aqueous solution) was mixed with a 3% by weight aqueous solution of 3-(acryloyloxypropyl)trimethoxysilane (abbreviated as "AS", Gelest Inc.) at a bPEI:AS weight ratio of 7:3 to form solution C. A612 was diluted with distilled water to prepare a 3% by weight solution (solution D). Solution C and solution D were then mixed together at a solution C:solution D weight ratio of 1:9 to form the final coating formulation. Filter paper samples (Whatman 410) were impregnated with the coating formulation and then dried at 80°C for 3 minutes. The dried samples were cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. The color change and color leaching of the test strips were evaluated according to the procedure described in Example 1. The results are reported in Table 1.

[0085] Example 5 The procedure of Example 4 was followed, except that solutions C and D were mixed together at a weight ratio of 2:3 to form the final coating formulation. The results are reported in Table 1.

[0086] Example 6 The procedure of Example 4 was followed, except that solutions C and D were mixed together at a weight ratio of 1:1 to form the final coating formulation. The results are reported in Table 1.

[0087] Example 7 The procedure of Example 4 was followed, except that solutions C and D were mixed together at a weight ratio of 3:2 to form the final coating formulation. The results are reported in Table 1.

[0088] Example 8 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 3% by weight aqueous solution) was mixed with a 3% by weight aqueous solution of 3-(acryloyloxypropyl)trimethoxysilane at a bPEI:AS weight ratio of 3:2 to form solution E. A612 was diluted with distilled water to prepare a 3% by weight solution (solution F). Solutions E and F were then mixed together at a solution E:solution F weight ratio of 2:3 to form the final coating formulation. Filter paper samples (Whatman 410) were impregnated with the coating formulation and then dried at 80°C for 3 minutes. The dried samples were cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. The color change and color leaching of the test strips were evaluated according to the procedure described in Example 1. The results are reported in Table 1.

[0089] Example 9 The procedure of Example 8 was followed, except that solutions E and F were mixed together at a weight ratio of 1:1 to form the final coating formulation. The results are reported in Table 1.

[0090] Example 10 The procedure of Example 8 was followed, except that solutions E and F were mixed together at a weight ratio of 3:2 to form the final coating formulation. The results are reported in Table 1.

[0091] Example 11 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 3% by weight aqueous solution) was mixed with a 3% by weight aqueous solution of 3-(acryloyloxypropyl)trimethoxysilane at a bPEI:AS weight ratio of 1:1 to form solution G. A612 was diluted with distilled water to prepare a 3% by weight solution (solution H). Solution G and solution H were then mixed together at a solution G:solution H weight ratio of 1:9 to form the final coating formulation. Filter paper samples (Whatman 410) were impregnated with the coating formulation and then dried at 80°C for 3 minutes. The dried samples were cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. The color change and color leaching of the test strips were evaluated according to the procedure described in Example 1. The results are reported in Table 1.

[0092] Example 12 A coating formulation was prepared by mixing branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 3% by weight aqueous solution) with 3% by weight of an aqueous solution of SR454 polyfunctional acrylate (ethoxylated trimethylolpropane triacrylate, Sartomer Corporation, Exton, PA) at a bPEI:SR454 weight ratio of 4:1. Filter paper samples (Whatman 410) were impregnated with the coating formulation and then dried at 80°C for 3 minutes. The dried samples were cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. The color change and color leaching of the test strips were evaluated according to the procedure described in Example 1. The results are listed in Table 1 below.

[0093] Table 1

[0094] For Examples 1-3 and 5-10, colorimetric analysis of the test strips after immersion in the OPA bath was performed using an X-Rite SP64 colorimeter (X-Rite Inc.). The collected CIE... The color code values ​​(established by the International Commission on Illumination) are reported in Table 2 below.

[0095] Table 2

[0096] Example 13 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 3% wt aqueous solution) was mixed with a 3% wt aqueous solution of 3-(acryloyloxypropyl)trimethoxysilane (abbreviated as AS) at a bPEI:AS weight ratio of 7:3 to form solution I. NEOREZ R966 polyurethane dispersion (abbreviated as "R966", DSM Corp.) was diluted with distilled water to prepare a 3% wt solution (solution J). Solution I and solution J were then mixed together at a solution I:solution J weight ratio of 1:9 to form the final coating formulation. Filter paper samples (Whatman 410) were impregnated with the coating formulation and then dried at 80°C for 3 minutes. The dried samples were cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white.

[0097] The o-phthalaldehyde (OPA) test solution in water was prepared at a concentration of 0.35 wt% OPA. The test strips were evaluated by immersing them in the OPA test solution bath for 5 minutes, maintaining the bath temperature at 25°C. The test strips were then removed from the bath and the color change was visually inspected. The test strips were evaluated using the procedure described in Example 1 to determine if any indicator color from the test strip had been absorbed into the OPA bath. The results are reported in Table 3.

[0098] Example 14 The procedure of Example 13 was followed, except that solution I and solution J were mixed together at a weight ratio of solution I:solution J of 3:7 to form the final coating formulation. The results are reported in Table 3.

[0099] Example 15 The procedure of Example 13 was followed, except that solution I and solution J were mixed together at a weight ratio of 1:1 to form the final coating formulation. The results are reported in Table 3.

[0100] Example 16 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 3% by weight aqueous solution) was mixed with a 3% by weight aqueous solution of 3-(acryloyloxypropyl)trimethoxysilane at a bPEI:AS weight ratio of 1:1 to form solution K. R966 polyurethane dispersion was diluted with distilled water to prepare a 3% by weight solution (solution L). Solution K and solution L were then mixed together at a solution K:solution L weight ratio of 1:9 to form the final coating formulation. Filter paper samples (Whatman 410) were impregnated with the coating formulation and then dried at 80°C for 3 minutes. The dried samples were cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. The color change of the test strips was evaluated according to the procedure described in Example 1. The test strips were also evaluated using the procedure described in Example 1 to determine whether any indicator color from the test strips had penetrated into the OPA bath. The results are reported in Table 3.

[0101] Example 17 The procedure of Example 16 was followed, except that solution K and solution L were mixed together at a weight ratio of solution K:solution L of 3:7 to form the final coating formulation. The results are reported in Table 3.

[0102] Example 18 The procedure of Example 16 was followed, except that solution K and solution L were mixed together at a weight ratio of 1:1 to form the final coating formulation. The results are reported in Table 3 below.

[0103] Table 3

[0104] Example 19 A 2.5 wt% aqueous solution of branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to 2.5 wt%) was mixed with an aqueous solution of 3-(acryloyloxypropyl)trimethoxysilane at a bPEI:AS weight ratio of 9:1 to form the final coating formulation. Samples of nylon 6,6 membranes (single-layer reinforced nylon tri-zone membrane with a nominal pore size of 1.8 μm, #080ZN, obtained from 3M Purification Inc., Meriden, Connecticut) were dipped into the coating formulation and then dried at 80°C for 3 minutes. The dried samples were cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white.

[0105] Individual test solutions of o-phthalaldehyde (OPA) in water were prepared at concentrations of 0.10 wt% OPA and 0.35 wt% OPA. The test strips were evaluated by immersing them in an OPA test solution bath for 5 minutes, maintaining the bath temperature at 25°C. The time point at which the first color change of the test strip was observed was recorded. The test strips were also evaluated using the procedure described in Example 1 to determine if any indicator color from the test strip had been absorbed into the OPA bath. The results are reported in Table 4.

[0106] Example 20 The procedure was followed as in Example 19, except that the final coating formulation contained bPEI:AS at a ratio of 4:1. The results are reported in Table 4.

[0107] Example 21 The procedure of Example 19 was followed, except that the ratio of bPEI:AS in the final coating formulation was 7:3. The results are reported in Table 4.

[0108] Example 22 The procedure was followed as in Example 19, except that the final coating formulation contained bPEI:AS at a ratio of 3:2. The results are reported in Table 4.

[0109] Example 23 The procedure was followed as in Example 19, except that the final coating formulation contained bPEI:AS at a ratio of 1:1. The results are reported in Table 4.

[0110] Example 24 The procedure was followed as in Example 19, except that the final coating formulation contained bPEI:AS at a ratio of 2:3. The results are reported in Table 4 below.

[0111] Table 4

[0112] Example 25 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 2.0 wt% aqueous solution) was mixed with a 2.0 wt% aqueous solution of 3-(acryloyloxypropyl)trimethoxysilane (abbreviated as "AS") at a bPEI:AS weight ratio of 9:1 to form the final coating formulation. A nylon film sample (described in Example 19) was impregnated with the coating formulation and then dried at 80°C for 3 minutes. The dried sample was cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. The time to color change of the test strips was evaluated according to the procedure described in Example 19. The test strips were also evaluated using the procedure described in Example 1 to determine whether any indicator color from the test strips had penetrated the OPA bath. The results are reported in Table 5.

[0113] Example 26 The procedure of Example 25 was followed, except that the ratio of bPEI:AS in the final coating formulation was 4:1. The results are reported in Table 5.

[0114] Example 27 The procedure of Example 25 was followed, except that the ratio of bPEI:AS in the final coating formulation was 7:3. The results are reported in Table 5.

[0115] Example 28 The procedure of Example 25 was followed, except that the ratio of bPEI:AS in the final coating formulation was 3:2. The results are reported in Table 5.

[0116] Example 29 The procedure of Example 25 was followed, except that the ratio of bPEI:AS in the final coating formulation was 1:1. The results are reported in Table 5.

[0117] Example 30 The procedure of Example 25 was followed, except that the ratio of bPEI:AS in the final coating formulation was 2:3. The results are reported in Table 5 below.

[0118] Table 5

[0119] Example 31 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 2.5 wt% aqueous solution) was mixed with 2.5 wt% of an aqueous solution of SR454 polyfunctional acrylate at a bPEI:SR454 weight ratio of 4:1 to form the final coating formulation. A nylon film sample (described in Example 19) was impregnated with the coating formulation and then dried at 80°C for 3 minutes. The dried sample was cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. The time to color change of the test strips was evaluated according to the procedure described in Example 19. The test strips were also evaluated using the procedure described in Example 1 to determine whether any indicator color from the test strips had penetrated into the OPA bath. The results are reported in Table 6.

[0120] Example 32 The procedure was followed as in Example 31, except that the final coating formulation contained bPEI:SR454 in a ratio of 7:3. The results are reported in Table 6.

[0121] Example 33 The procedure was followed as in Example 31, except that the final coating formulation contained bPEI:SR454 in a ratio of 3:2. The results are reported in Table 6.

[0122] Example 34 The procedure was followed as in Example 31, except that the final coating formulation contained bPEI:SR454 in a 1:1 ratio. The results are reported in Table 6.

[0123] Example 35 The procedure was followed as in Example 31, except that the final coating formulation contained bPEI:SR454 in a ratio of 2:3. The results are reported in Table 6 below.

[0124] Table 6

[0125] Example 36 Branched polyethyleneimine (MW 800, purchased from Sigma-Aldrich Corporation (catalog number 408719), abbreviated as "bPEI800") diluted to a 2.5% by weight aqueous solution was mixed with a 2.5% by weight aqueous solution of SR454 polyfunctional acrylate at a bPEI800:SR454 weight ratio of 7:3, 1:1, or 2:3 to form three separate coating formulations. Individual samples of nylon film (described in Example 19) were impregnated with one of the coating formulations and then dried at 80°C for 3 minutes. The dried samples were cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. When the test strips were immersed in an OPA bath according to the procedure described in Example 1, color leaching was observed in all test strips (visually). The sample prepared at a bPEI800:SR454 ratio of 9:1 showed the greatest amount of color leaching. For the sample with a bPEI800:SR454 ratio of 2:3, the minimum amount of color leaching was observed.

[0126] Example 37 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 2.5% by weight aqueous solution, abbreviated as "bPEI") was mixed with a 2.5% by weight aqueous solution of SR454 polyfunctional acrylate at a bPEI:SR454 weight ratio of 9:1 to form a coating formulation. A nylon film sample (described in Example 19) was impregnated with the coating formulation and then dried at 80°C for 3 minutes. The dried sample was cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white.

[0127] The o-phthalaldehyde (OPA) test solution in water was prepared at a concentration of 0.35 wt% OPA. The test strips were evaluated by immersing them in the OPA test solution bath for 5 minutes, maintaining the bath temperature at 25°C. The test strips were then removed from the bath and the color was checked for a change from white to yellow. The procedure described in Example 1 was also used to evaluate the test strips to determine if any indicator color from the test strip had been absorbed into the OPA bath. The results are reported in Table 7.

[0128] Example 38 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 2.5% by weight aqueous solution, abbreviated as "bPEI") was mixed with a 2.5% by weight aqueous solution of SR454 polyfunctional acrylate at a bPEI:SR454 weight ratio of 9:1 to form solution M. NEOCRYLA 612 was diluted with distilled water to prepare a 2.5% by weight solution (solution N). Solution M and solution N were then mixed together at a solution M:solution N weight ratio of 1:1 to form the final coating formulation. A nylon film sample (described in Example 19) was dipped into the coating formulation and then dried at 80°C for 3 minutes. The dried sample was cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. The test strips were evaluated by immersion in an OPA bath according to the procedure described in Example 37. The results are reported in Table 7.

[0129] Example 39 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 2.5% by weight aqueous solution, abbreviated as "bPEI") was mixed with a 2.5% by weight aqueous solution of SR454 polyfunctional acrylate at a bPEI:SR454 weight ratio of 9:1 to form solution M. NEOREZ R966 polyurethane dispersion was diluted with distilled water to prepare a 2.5% by weight solution (solution O). Solution M and solution O were then mixed together at a solution M:solution O weight ratio of 1:1 to form the final coating formulation. A nylon film sample (described in Example 19) was dipped into the coating formulation and then dried at 80°C for 3 minutes. The dried sample was cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. The test strips were evaluated by immersion in an OPA bath according to the procedure described in Example 37. The results are reported in Table 7.

[0130] Example 40 The procedure was followed as in Example 37, except that the final coating formulation contained bPEI:SR454 in a ratio of 7:3. The results are reported in Table 7.

[0131] Example 41 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 2.5% by weight aqueous solution, abbreviated as "bPEI") was mixed with a 2.5% by weight aqueous solution of SR454 polyfunctional acrylate at a bPEI:SR454 weight ratio of 7:3 to form solution P. NEOCRYLA 612 was diluted with distilled water to prepare a 2.5% by weight solution (solution Q). Solutions P and Q were then mixed together at a solution P:solution Q weight ratio of 1:1 to form the final coating formulation. A nylon film sample (described in Example 19) was dipped into the coating formulation and then dried at 80°C for 3 minutes. The dried sample was cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. The test strips were evaluated by immersion in an OPA bath according to the procedure described in Example 37. The results are reported in Table 7.

[0132] Example 42 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 3% by weight aqueous solution, abbreviated as "bPEI") was mixed with 2.5% by weight of an aqueous solution of SR454 polyfunctional acrylate at a bPEI:SR454 weight ratio of 7:3 to form solution P. NEOREZ R966 polyurethane dispersion was diluted with distilled water to prepare a 2.5% by weight solution (solution R). Solution P and solution R were then mixed together at a solution P:solution R weight ratio of 1:1 to form the final coating formulation. A nylon film sample (described in Example 19) was dipped into the coating formulation and then dried at 80°C for 3 minutes. The dried sample was cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. The test strips were evaluated by immersion in an OPA bath according to the procedure described in Example 37. The results are reported in Table 7 below.

[0133] Table 7

[0134] Example 43 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 2.5 wt% aqueous solution) was mixed with 2.5 wt% of an aqueous solution of crosslinking agent 3-glycidoxypropyltrimethoxysilane (abbreviated = "GPS", purchased from Gelest Inc.) at a bPEI:crosslinking agent weight ratio of 9:1, 4:1, or 7:3 to form three separate coating formulations. A separate sample of nylon film (described in Example 19) was impregnated with one of the formulations and then dried at 80°C for 3 minutes. The dried sample was cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. The test strips were immersed in an OPA bath according to the procedure described in Example 19. The time to color change of the test strips was evaluated according to the procedure described in Example 19. The test strips were also evaluated using the procedure described in Example 1 to determine whether any indicator color from the test strips had been absorbed into the OPA bath. The results are reported in Table 8. Additionally, in separate experiments, the color of each strip was determined visually after immersion in the OPA bath for 80 seconds and 300 seconds. At the 80-second time point, the test strip was a very pale yellow. At the 300-second time point, the test strip was a bright yellow.

[0135] Table 8

[0136] Example 44 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 2.5 wt% aqueous solution, abbreviated as "bPEI") was mixed with a 2.5 wt% aqueous solution of 3-(acryloyloxypropyl)trimethoxy-silicon (abbreviated as "AS") at a bPEI:AS weight ratio of 4:1 to form the final coating formulation. A nylon film sample (described in Example 19) was impregnated with the coating formulation and then dried at 80°C for 3 minutes. The dried sample was cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white.

[0137] Individual test solutions of o-phthalaldehyde (OPA) in water were prepared at concentrations of 0.10 wt% OPA and 0.35 wt% OPA. Test strips were evaluated by immersing them in baths prepared from the test solutions and maintained at 10°C, 20°C, 25°C, or 30°C. The test strips were also immersed in this bath for different time periods (1.0 min, 1.35 min, 1.62 min, or 5 min). Before immersion in the OPA bath, some test strips were immersed in a 1% Intercept detergent (Medivators Inc.) bath for 7.5 min, followed by immersion in a fresh distilled water bath for 7.5 min, and then air-dried. Each test sample was removed from the OPA bath, and the reflectance of the test strip was measured at an emission wavelength of 450 nm using an X-Rite eXactNGH handheld spectrophotometer (X-Rite Inc.) with a 1.5 mm aperture. The average reflectance values ​​(n = 3) and the corresponding test conditions are reported in Table 9 below.

[0138] Table 9

[0139] Example 45 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 2.5% by weight aqueous solution, abbreviated as "bPEI") was mixed with a 2.5% by weight aqueous solution of NEOREZ R966 polyurethane dispersion at a 1:1 weight ratio to form a coating formulation. A nylon film sample (described in Example 19) was coated using a #24 Meyer rod (RD Specialties, Webster, New York) and then dried at 80°C for 3 minutes. The dried sample was cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white.

[0140] The o-phthalaldehyde (OPA) test solution in water was prepared at a concentration of 0.35 wt% OPA. The test strips were evaluated by immersing them in the OPA test solution bath for 1.35 minutes or 5 minutes, maintaining the bath temperature at 25°C. Each test sample was removed from the bath, and the reflectance of the test strip was determined at an emission wavelength of 440 nm using an X-Rite eXact NGH handheld spectrophotometer with a 1.5 mm aperture (X-Rite Inc.). The average reflectance values ​​(n = 3) and the corresponding test conditions are reported in Table 10.

[0141] Example 46 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 2.5% by weight aqueous solution, abbreviated as "bPEI") was mixed with a 2.5% by weight aqueous solution of 3-(acryloyloxypropyl)trimethoxysilane (abbreviated as "AS") at a weight ratio of 7:3 to form a coating formulation. A nylon film sample (described in Example 19) was coated using a #24 Meyer rod and then dried at 80°C for 3 minutes. The dried sample was cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. The test strips were evaluated by immersion in an OPA bath according to the procedure described in Example 45. The average reflectance values ​​(n = 3) and the corresponding test conditions are reported in Table 10.

[0142] Example 47 Branched polyethyleneimine (MW 25,000 g / mole, purchased from Sigma-Aldrich Corporation (catalog number 408727) and diluted to a 2.5 wt% aqueous solution, abbreviated as "bPEI") was mixed with a 2.5 wt% aqueous solution of 3-(acryloyloxypropyl)trimethoxysilane (abbreviated as AS) at a weight ratio of 7:3 to form solution S. NEOREZ R966 polyurethane dispersion was diluted with distilled water to prepare a 2.5 wt% solution (solution T). Solution S and solution T were then mixed together to form the final coating formulation with a bPEI:AS:R966 weight ratio of 7:3:7. A nylon film sample (described in Example 19) was coated using a #24 Meyer rod and then dried at 80°C for 3 minutes. The dried sample was cut into test strips (20 mm × 40 mm). The coated surface of the test strips was white. The test strips were evaluated by immersion in an OPA bath according to the procedure described in Example 45. The average reflectance values ​​(n = 3) and the corresponding test conditions are reported in Table 10 below.

[0143] Table 10

[0144] Example 48 Branched polyethyleneimine (bPEI, MW 60,000 g / mole, 50% by weight aqueous solution) was mixed with 30% by weight of a polyurethane dispersion (#CS 8057, Incorez Copolymer Ltd., United Kingdom) and distilled water to form a coating formulation with a bPEI:polyurethane dispersion weight ratio of 1:3. This coating formulation (50 μL) was applied as dots to the surface of an injection-molded chip (60 mm × 50 mm × 1 mm) from Bayblend T85 raw material white (a blend of polycarbonate (PC) and acrylonitrile butadiene styrene (ABS); purchased from Bayer Material Science, Leverkusen, Germany). The chip with the coated test points was then dried at 100 °C for 15 minutes, producing a transparent coating on the white substrate.

[0145] Individual test solutions of o-phthalaldehyde (OPA) in water were prepared at concentrations of 0.35 wt% and 0.575 wt%. The coated chips were evaluated by immersing the coated portion of the chip in a bath prepared with the test solutions and maintained at 25°C. The chips were immersed in the bath for 1.35 minutes or 5 minutes. Each chip was removed from the bath, and the color of the coated spot was visually inspected to determine if it had changed from white to yellow. The results are reported in Table 11.

[0146] Example 49 The process follows that of Example 48, except that the weight ratio of bPEI to polyurethane dispersion in the coating formulation is set to 1:1.

[0147] Example 50 The procedure of Example 48 was followed, except that the weight ratio of bPEI to polyurethane dispersion in the coating formulation was set to 3:1. The results are reported in Table 11 below.

[0148] Table 11

[0149] Example 51 The test solution of orthophthalaldehyde (OPA) in water was prepared at a concentration of 0.35 wt% OPA. The test chips prepared according to Example 51 were evaluated by immersing the coated portion of the test chip in a bath prepared with the test solution and maintaining the bath temperature at 20°C, 25°C, or 30°C. The test strips were immersed in the bath for different time periods (1.0 min, 1.35 min, 1.62 min, or 5 min). Each test chip was removed from the bath, and the reflectance of the test points was determined at an emission wavelength of 440 nm using an X-Rite eXact NGH handheld spectrophotometer (X-Rite Inc.) with a 1.5 mm aperture. The average reflectance values ​​(n = 3) and the corresponding test conditions are reported in Table 12.

[0150] Example 52 The same testing procedure was followed as reported in Example 51, except that the coated chip was first immersed in a 1% Intercept detergent (Medivators Inc.) bath for 7.5 minutes before being immersed in the OPA bath, followed by immersion in a fresh distilled water bath for 7.5 minutes, and then air-dried. The results are reported in Table 12 below.

[0151] Table 12

[0152] Examples 53 to 61 The coating formulations of Examples 53 to 61 were prepared by premixing branched polyethyleneimine (bPEI, MW 60,000 g / mole, 50 wt% aqueous solution, purchased from Thermo Fisher Scientific, diluted to 10 wt% in water) and R966 (10 wt% aqueous solution). Then, while continuing mixing, the crosslinking agent 3-glycidoxypropyltrimethoxysilane (abbreviated as "GPS" and prepared as a 10 wt% isopropanol solution) and PZ-28 (polyfunctional aziridine, purchased from PolyAziridine LLC., Medford, NJ, and prepared as a 10 wt% isopropanol solution) were added to provide the specified coating formulations. The amounts of each component in the formulations (as 10 wt% solutions) are listed in Table 13. Each coating formulation was individually coated onto separate clear PET polyester film substrates (5 mils) using a #24 Meyer bar. The coated film is dried at 85°C for 5 to 10 minutes to form a transparent coating. Test strips (approximately 25 mm × 10² mm) are prepared from the coated film. An OPA bath (0.575 wt% aqueous solution) is prepared, and each test strip is evaluated by immersing it in the bath for 300 seconds. The bath is maintained at 25°C. The color of the test strips is determined visually after immersion for 80 and 300 seconds. The integrity of the test strips is determined by visually inspecting each test strip for any signs of haze, cracks, blistering, or swelling at 300 seconds. Additionally, the test strips are evaluated to determine if any indicator color from the test strip has been absorbed into the OPA bath. For this test, new test strips are immersed in and maintained in a fresh OPA bath (0.575 wt% at 25°C) for 30 minutes. This bath contains a minimum amount of OPA to completely cover the test strip (typically 1 mL to 2 mL). The test strip was then removed from the bath, and the color change of the bath solution was visually inspected (no leaching = colorless bath, leaching = bath color changes from colorless to pale yellow or yellow). The results of color change (80 and 300 seconds), test strip integrity, and leaching are reported in Table 14.

[0153] Table 13

[0154] Table 14

[0155] Examples 62 to 68 The coating formulations of Examples 62 to 68 were prepared by premixing branched polyethyleneimine (bPEI, MW 60,000 g / mole, 50% by weight aqueous solution, purchased from Thermo Fisher Scientific, diluted to 10% by weight in water) and R966 (10% by weight aqueous solution). Crosslinking agents GPS (pure liquid) or AS (pure liquid) were then added while mixing continued to form specific coating formulations. The amounts of each component in the formulations are listed in Table 15. Each coating formulation was individually coated onto a separate clear PET polyester film substrate (5 mils) using a #24 Meyer bar. The coated films were dried at 85°C for 5 to 10 minutes to form a clear coating. Test strips (approximately 25 mm × 10² mm) were prepared from the coated films.

[0156] The color change (80 seconds and 300 seconds) and integrity of the test strips were evaluated according to the process described in Example 53. The results are reported in Table 16.

[0157] Table 15

[0158] Table 16

[0159] Example 69 Branched polyethyleneimine (bPEI, MW 60,000 g / mole, 50 wt% aqueous solution, purchased from Thermo Fisher Scientific, diluted to 10 wt% in water), crosslinking agent AS (pure liquid), and polyvinyl alcohol (POVAL 49-88, purchased from Kuraray Ltd., Singapore; abbreviation = "PVA") were mixed together to form a coating formulation (amounts listed in Table 17). The coating formulation was applied to a clear PET polyester film substrate (5 mils) using a #24 Meyer rod and then dried at 85°C for 5 to 10 minutes to form a clear coating. Test strips (approximately 25 mm × 10² mm) were prepared from the coated film.

[0160] The color change (80 seconds and 300 seconds) and integrity of the test strips were evaluated according to the process described in Example 53. The results are reported in Table 18.

[0161] Example 70 Branched polyethyleneimine (bPEI, MW 60,000 g / mole, 50 wt% aqueous solution, purchased from Thermo Fisher Scientific, diluted to 10 wt% in water), crosslinking agent AS (pure liquid), and polyvinylpyrrolidone (K90, MW = 360,000 g / mole, purchased from Sigma-Aldrich Corporation, abbreviation "PVP") were mixed together to form a coating formulation (amounts listed in Table 17). The coating formulation was applied to a clear PET polyester film substrate (5 mils) using a #24 Meyer rod and then dried at 85°C for 5 to 10 minutes to form a clear coating. Test strips (approximately 25 mm × 10² mm) were prepared from the coated film.

[0162] The color change (80 seconds and 300 seconds) and integrity of the test strips were evaluated according to the process described in Example 53. The results are reported in Table 18.

[0163] Examples 71 to 75 The coating formulations of Examples 71 to 75 were prepared by premixing branched polyethyleneimine (bPEI, MW 60,000 g / mole, 50% by weight aqueous solution, purchased from Thermo Fisher Scientific, diluted to 10% by weight in water) and R966 (10% by weight aqueous solution). While mixing continued, crosslinking agent AS (pure liquid) was added, followed by PVA (10% by weight aqueous solution). The amounts of each component in the formulations are listed in Table 17. Each coating formulation was individually coated onto a separate clear PET polyester film substrate (5 mils) using a #24 Meyer bar. The coated films were dried at 85°C for 5 to 10 minutes to form a clear coating. Test strips (approximately 25 mm × 10² mm) were prepared from the coated films.

[0164] The color change (80 seconds and 300 seconds) and integrity of the test strips were evaluated according to the process described in Example 53. The results are reported in Table 18.

[0165] Table 17

[0166] Table 18

[0167] Examples 76 to 87 The coating formulations of Examples 76 to 87 were prepared by premixing branched polyethyleneimine (bPEI, MW 60,000 g / mole, 50 wt% aqueous solution, purchased from Thermo Fisher Scientific, diluted to 10 wt% in water) and R966 (10 wt% aqueous solution). Then, while continuing mixing, crosslinking agents 3-(acryloyloxypropyl)trimethoxysilane (abbreviated as "AS" and prepared as a 10 wt% isopropanol solution) and PZ-28 (prepared as a 10 wt% isopropanol solution) were added to form the specified coating formulations. The amounts of each component in the formulations (as 10 wt% solutions) are listed in Table 19. Each coating formulation was individually coated onto a separate clear PET polyester film substrate (5 mils) using a #24 Meyer bar. The coated films were dried at 85°C for 5 to 10 minutes to form a clear coating. Test strips (approximately 25 mm × 10² mm) were prepared from the coated films. The color change (80 seconds and 300 seconds), color leaching, and test strip integrity of the test strips were evaluated according to the process described in Example 53. The results are reported in Table 20.

[0168] Table 19

[0169] Table 20

[0170] Examples 88 to 92 The coating formulations of Examples 88 to 92 were prepared by premixing branched polyethyleneimine (bPEI, MW 60,000 g / mole, 50 wt% aqueous solution, purchased from Thermo Fisher Scientific, diluted to 10 wt% in water) and R966 (10 wt% aqueous solution). Then, while continuing mixing, crosslinking agents 3-(acryloyloxypropyl)trimethoxysilane (abbreviated as "AS" and prepared as a 10 wt% isopropanol solution) and PZ-28 (prepared as a 10 wt% isopropanol solution) were added to form the specified coating formulations. The amounts of each component in the formulations (as 10 wt% solutions) are listed in Table 21. Each coating formulation was individually coated onto a separate clear PET polyester film substrate (10 mils) using a #30 Meyer bar. The coated films were dried at 110°C for 10 minutes to form a clear coating. Test strips (approximately 25 mm × 10² mm) were prepared from the coated films. The o-phthalaldehyde (OPA) test solution in water was prepared at a concentration of 0.35 wt% OPA. The test strips were evaluated by immersing them in the OPA test solution bath for 1.35 minutes or 5 minutes, maintaining the bath temperature at 25°C. After immersion, the test strips were removed from the test solution and immersed in a fresh distilled water bath for 15 minutes, followed by rinsing with isopropanol for approximately 5 seconds. The test strips were placed against a white background, and the reflectance was measured at an emission wavelength of 450 nm using an X-Rite eXact NGH handheld spectrophotometer with a 4 mm aperture. The average reflectance values ​​(n = 3) and the corresponding test conditions are reported in Table 22.

[0171] Table 21

[0172] Table 22

[0173] Examples 93 to 95 The coating formulations of Examples 93 to 95 were prepared by premixing branched polyethyleneimine (bPEI, MW 60,000 g / mole, 50 wt% aqueous solution, purchased from Thermo Fisher Scientific, diluted to 10 wt% in water) and polyacrylic dispersion A612 (10 wt% aqueous solution). Then, while continuing mixing, crosslinking agents 3-glycidoxypropyltrimethoxysilane (GPS, pure) and PZ-28 (prepared as a 10 wt% isopropanol solution) were added to form the specified coating formulations. The amounts of each component in the formulations are listed in Table 23. Each coating formulation was individually coated onto a separate clear PET polyester film substrate (5 mils) using a #24 Meyer bar. The coated films were dried at 85°C for 5 to 10 minutes to form a clear coating. Test strips (approximately 25 mm × 10² mm) were prepared from the coated films. The color change (80 seconds and 300 seconds), color leaching, and test strip integrity of the test strips were evaluated according to the process described in Example 53. The results are reported in Table 24.

[0174] Table 23

[0175] Table 24

[0176] Examples 96 to 97 Branched polyethyleneimine (bPEI, MW 60,000 g / mole, 50% by weight aqueous solution, purchased from Thermo Fisher Scientific, diluted to 5% by weight in water) and diethyl pentanoate (Sigma-Aldrich Corporation) were mixed together to form a coating formulation (quantities listed in Table 25). A separate sample of the nylon film was impregnated with one of the coating formulations (described in Example 19). The coated sample was dried at 120°C for 5 minutes to form a clear coating. Test strips (approximately 25 mm × 10² mm) were prepared from the coated sample.

[0177] The color change (80 seconds and 300 seconds) and leaching of the test strips were evaluated according to the process described in Example 53. Additionally, the time point at which the color change of the test strips was first observed is reported. The results are reported in Table 26.

[0178] Table 25

[0179] Table 26

[0180] Examples 98 to 100 The coating formulations of Examples 98 to 100 were prepared by mixing ethoxylated polyethyleneimine (MW 50,000 g / mole, 37% by weight aqueous solution, purchased from Sigma-Aldrich Corporation, diluted to 5% by weight in water) and 3-(acryloyloxypropyl)trimethoxysilane (abbreviated as "AS", Gelest Inc.) in the amounts listed in Table 27. A separate sample of a nylon film (described in Example 19) was impregnated with one of the coating formulations. The coated sample was dried at 120°C for 5 minutes to form a transparent coating. Test strips (approximately 25 mm × 10² mm) were prepared from the coated sample.

[0181] The color change (80 seconds and 300 seconds) and leaching of the test strips were evaluated according to the process described in Example 53. Additionally, the time point at which the color change of the test strips was first observed is reported. The results are reported in Table 28.

[0182] Table 27

[0183] Table 28

[0184] Example 101 The coating formulation was prepared by first mixing 7 g of branched polyethyleneimine (bPEI, MW 60,000 g / mole, 50 wt% aqueous solution, purchased from Thermo Fisher Scientific, diluted to 10 wt% in water) and 3 g of R966 (10 wt% aqueous solution). Then, while continuing mixing, the crosslinking agents diethyl pentadienoate (0.14 g, pure) and PZ-28 (0.15 g, prepared as a 10 wt% isopropanol solution) were added to form the coating formulation. The formulation was applied to a transparent PET polyester film substrate (10 mils) using a #24 Meyer rod. The coated film was dried at 120°C for 5 minutes to form a transparent coating. Test strips (approximately 25 mm × 102 mm) were prepared from the coated film. The color change (80 seconds and 300 seconds), color leaching, and test strip integrity of the test strips were evaluated according to the procedure described in Example 53. The results are reported in Table 29 below.

[0185] Table 29

[0186] Example 102 The coating formulation was prepared by first mixing 6.3 g of branched polyethyleneimine (bPEI, MW 60,000 g / mole, 50 wt% aqueous solution, purchased from Thermo Fisher Scientific, diluted to 10 wt% in water) and 2.7 g of R966 (10 wt% aqueous solution). Then, while continuing mixing, the crosslinking agents 3-(acryloyloxypropyl)trimethoxysilane (0.63 g in 10 wt% isopropanol solution) and PZ-28 (0.14 g in 10 wt% isopropanol solution) were added. Finally, 1 g of Nalco 1115 silica nanoparticle aqueous dispersion (spherical, 4 nm, 15 wt%; purchased from Nalco Company, Naperville, Illinois) was added to form the coating formulation. The formulation was coated onto a transparent PET polyester film substrate (10 mils) using a #24 Meyer rod. The coated film was dried at 120°C for 5 minutes to form a transparent coating. Test strips (approximately 25 mm × 102 mm) were prepared from the coated film. The color change (80 seconds and 300 seconds), color leaching, and test strip integrity of the test strips were evaluated according to the procedure described in Example 53. The results are reported in Table 30.

[0187] Example 103 A modified silica nanoparticle dispersion was prepared by adding 1.77 g of 3-aminopropyltriethoxysilane (Sigma-Aldrich Corporation) and 50 g of 10% by weight Nalco 1115 silica nanoparticle aqueous dispersion under mixed conditions. The resulting dispersion was heated at 80 °C for 12 hours and then allowed to cool to room temperature.

[0188] The coating formulation was prepared by first mixing 6.3 g of branched polyethyleneimine (bPEI, MW 60,000 g / mole, 50 wt% aqueous solution, purchased from Thermo Fisher Scientific, diluted to 10 wt% in water) and 2.7 g of R966 (10 wt% aqueous solution). Then, while continuing mixing, the crosslinking agents 3-(acryloyloxypropyl)trimethoxysilane (0.63 g in 10 wt% isopropanol solution) and PZ-28 (0.14 g in 10 wt% isopropanol solution) were added. Finally, 1 g of modified silica nanoparticle dispersion (as described above) was added while mixing to form the coating formulation. The formulation was coated onto a transparent PET polyester film substrate (10 mils) using a #24 Meyer rod. The coated film was dried at 120°C for 5 minutes to form a transparent coating. Test strips (approximately 25 mm × 10² mm) were prepared from the coated film. The color change (80 seconds and 300 seconds), color leaching, and test strip integrity of the test strips were evaluated according to the process described in Example 53. The results are reported in Table 30 below.

[0189] Table 30

[0190] Examples 104 to 107 The coating formulations of Examples 136 to 139 were prepared by premixing a 50% by weight aqueous solution of branched polyethyleneimine (bPEI, MW 60,000 g / mole, purchased from Thermo Fisher Scientific, diluted to 5% by weight with added ethanol) and a 5% by weight ethanol solution of SR415 polyfunctional acrylate (20 moles of ethoxylated trimethylolpropane triacrylate, Sartomer Corporation). Then, a 5% by weight ethanol solution of photoinitiator IRGACURE 184 (1-hydroxycyclohexylphenyl ketone, BASF Corporation, Florham Park, New Jersey) was added to the mixture, followed optionally by a 5% by weight ethanol solution of R966 while mixing continued. The amounts of each component in the formulations are listed in Table 31. Each of the resulting coating formulations was individually coated onto a separate clear PET polyester film substrate (5 mils) using a #24 Meyer stick. The coated film was dried at 100°C for 5 minutes, and then cured three times with a Fusion “H” lamp at a speed of 12.2 m / min in a nitrogen atmosphere using a UV curing station (model MC-6RQN, Fusion UV Curing Inc., Rockville, MD) to form a transparent coating. Test strips (approximately 25 mm × 102 mm) were prepared from the coated film. The color change (80 seconds and 300 seconds), color leaching, and test strip integrity of the test strips were evaluated according to the procedure described in Example 53. The results are reported in Table 32.

[0191] Table 31

[0192] Table 32

[0193] All references, patents, and patent applications cited in the above-mentioned patent-certified applications are incorporated herein by reference in their entirety. In the event of any inconsistency or contradiction between the incorporated references and this application, the information in the foregoing description shall prevail. The foregoing description, given to enable those skilled in the art to practice this disclosure protected by the claims, should not be construed as a limitation on the scope of this disclosure, which is defined by the claims and all their equivalents.

[0194] This application also involves the following items: 1. A composition comprising a compound prepared by a reaction comprising polyethyleneimine and at least one amine-reactive, hydrolyzable organosilane represented by the following formula: RZ-SiY3 in: R represents an amine reactive group containing 1 to 18 carbon atoms; Z represents a divalent organic group containing 1 to 8 carbon atoms; and Each Y independently represents a hydrolyzable group.

[0195] 2. The composition according to item 1, wherein the composition further comprises an aqueous liquid carrier for dispersing or dissolving the compound.

[0196] 3. The composition according to item 1, wherein R has 1 to 3 carbon atoms.

[0197] 4. The composition according to Item 1, wherein R is selected from isocyanate groups, ethylene oxide groups, epoxy propoxy groups, acryloyloxy groups, ethoxy carbonyl groups, methoxy carbonyl groups, vinyl sulfonyl groups, and acrylamide groups.

[0198] 5. The composition according to item 1, wherein Z further contains 1 to 6 heteroatoms selected from O, N and S.

[0199] 6. The composition according to item 1, wherein Z comprises an alkylene group containing 1 to 3 carbon atoms.

[0200] 7. The composition according to Item 1, wherein each Y is independently selected from methoxy, ethoxy, hydroxy, acetoxy, chlorine and bromine.

[0201] 8. The composition according to Item 1, wherein the at least one amine-reactive hydrolyzable organosilane is selected from 3-isocyanopropyltriethoxysilane, 3-isocyanopropyltrimethoxysilane, 2-isocyanoethyltriethoxysilane, 2-isocyanoethyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 2-acryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 2,3-epoxypropyltrimethoxysilane, 2,3-epoxypropyltriethoxysilane, 3-epoxypropoxypropyltriethoxysilane, and 3-epoxypropoxypropyltrimethoxysilane.

[0202] 9. The composition according to item 1, wherein the composition further comprises a polymeric binder material.

[0203] 10. A composition comprising a compound prepared by a reaction comprising a cross-linked polyethyleneimine and at least one amine-reactive, hydrolyzable organosilane represented by the following formula: RZ-SiY3 in: R represents an amine reactive group containing 1 to 18 carbon atoms; Z represents a divalent organic group containing 1 to 8 carbon atoms; and Each Y independently represents a hydrolyzable group.

[0204] 11. The composition according to item 10, wherein the composition further comprises an aqueous liquid carrier for dispersing or dissolving the compound.

[0205] 12. The composition according to item 10, wherein the crosslinked polyethyleneimine comprises a reaction product of a polyamine and a crosslinking agent represented by the following formula. RZR Each of R and Z is independent as previously defined.

[0206] 13. The composition according to item 10, wherein R has 1 to 3 carbon atoms.

[0207] 14. The composition according to item 10, wherein R is selected from isocyanate groups, ethylene oxide groups, epoxy propoxy groups, acryloyloxy groups, ethoxy carbonyl groups, methoxy carbonyl groups, vinyl sulfonyl groups, carbamate groups, haloalkyl groups, cyclic anhydride groups, and acrylamide groups.

[0208] 15. The composition according to item 10, wherein Z further contains 1 to 6 heteroatoms selected from O, N and S.

[0209] 16. The composition according to item 10, wherein Z comprises an alkylene group containing 1 to 3 carbon atoms.

[0210] 17. The composition according to item 10, wherein each Y is independently selected from methoxy, ethoxy, hydroxy, acetoxy, chlorine and bromine.

[0211] 18. The composition according to item 10, wherein the at least one amine-reactive hydrolyzable organosilane is selected from 3-isocyanopropyltriethoxysilane, 3-isocyanopropyltrimethoxysilane, 2-isocyanoethyltriethoxysilane, 2-isocyanoethyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 2-acryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 2,3-epoxypropyltrimethoxysilane, 2,3-epoxypropyltriethoxysilane, 3-epoxypropoxypropyltriethoxysilane, and 3-epoxypropoxypropyltrimethoxysilane.

[0212] 19. The composition according to item 10, wherein the composition further comprises a polymeric binder material.

[0213] 20. A method for preparing an article of articles, the method comprising: The composition according to items 1 and 10 is applied to at least a portion of the surface of the substrate and at least some of the hydrolyzable groups Y are hydrolyzed.

[0214] 21. The method of claim 20, wherein the compound is covalently bonded to the surface of the substrate.

[0215] 22. The method according to item 20, wherein the compound becomes cross-linked and forms Si-O-Si units.

[0216] 23. An article comprising: A substrate, the substrate having a surface; and The reaction product of the composition according to item 1 or 10 with at least a portion of the surface of the substrate.

[0217] 24. An article of manufacture comprising: A substrate, the substrate having a surface; and The crosslinking reaction product of the composition according to item 1 or 10 is disposed on at least a portion of the surface.

[0218] 25. A composition comprising a close mixture of crosslinked polyethyleneimine and a polymeric binder material.

[0219] 26. The composition according to item 25, wherein the crosslinked polyethyleneimine is a reaction product of polyethyleneimine and an acrylic monomer having at least two acryloyl groups.

[0220] 27. The composition according to item 25, wherein the crosslinked polyethyleneimine and the polymer binder material are dispersed or dissolved in an aqueous liquid carrier.

[0221] 28. A method for preparing a composition, the method comprising sequentially and tightly mixing: An aqueous solution of polyethyleneimine; Crosslinking agent for the polyethyleneimine; and Polymer adhesive materials.

[0222] 29. The method of claim 28, wherein the crosslinking agent for the polyethyleneimine comprises an acrylic monomer having at least two acryloyl groups.

Claims

1. A composition comprising a compound prepared by a reaction comprising polyethyleneimine and at least one amine-reactive, hydrolyzable organosilane represented by the following formula: RZ-SiY3 in: R represents an amine reactive group containing 1 to 18 carbon atoms, wherein R is selected from isocyanate group, acryloyloxy group, ethoxycarbonyl group, methoxycarbonyl group, vinylsulfonyl group and acrylamide group; Z represents a divalent organic group containing 1 to 8 carbon atoms; and each Y independently represents a hydrolyzable group; and The composition further comprises a polymer binder material.

2. The composition according to claim 1, wherein the composition comprises cross-linked polyethyleneimine, wherein the polyethyleneimine is cross-linked polyethyleneimine.

3. The composition according to claim 2, wherein the composition further comprises an aqueous liquid carrier for dispersing or dissolving the compound.

4. The composition according to claim 2, wherein R has 1 to 3 carbon atoms.

5. The composition according to claim 2, wherein Z further contains 1 to 6 heteroatoms selected from O, N and S.

6. The composition according to claim 2, wherein Z comprises an alkylene group containing 1 to 3 carbon atoms.

7. The composition according to claim 2, wherein each Y is independently selected from methoxy, ethoxy, hydroxy, acetoxy, chlorine and bromine.

8. The composition according to claim 2, wherein the at least one amine-reactive hydrolyzable organosilane is selected from 3-isocyanopropyltriethoxysilane, 3-isocyanopropyltrimethoxysilane, 2-isocyanoethyltriethoxysilane, 2-isocyanoethyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 2-acryloyloxyethyltriethoxysilane, and 2-acryloyloxyethyltrimethoxysilane.

9. The composition according to claim 2, wherein the composition further comprises a polymer binder material selected from polyvinyl alcohol, hydroxyethyl cellulose, and hydroxypropyl cellulose.

10. The composition according to claim 1, wherein R is selected from ethoxycarbonyl group, methoxycarbonyl group, vinylsulfonyl group and acrylamide group.

11. An article of manufacture comprising: A substrate, the substrate having a surface; and The crosslinking reaction product of the composition according to claim 8 is disposed on at least a portion of the surface.

12. A composition comprising a mixture of crosslinked polyethyleneimine and a polymeric binder material, wherein the crosslinked polyethyleneimine is a reaction product of polyethyleneimine and an acrylic monomer having at least two acryloyl groups, and wherein the crosslinked polyethyleneimine and the polymeric binder material are dispersed or dissolved in an aqueous liquid carrier.

13. A method for preparing the composition of claim 12, the method comprising sequentially mixing: An aqueous solution of polyethyleneimine; Crosslinking agent for the polyethyleneimine; and Polymer adhesive materials, The crosslinking agent used for the polyethyleneimine comprises an acrylic monomer having at least two acryloyl groups.

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