Aspartate-functional polysiloxanes, their preparation and use

Abstract

The present invention relates to novel aspartate-functional polysiloxanes, the preparation of curable compositions with polyisocyanate crosslinkers, their use, particularly in the preparation of coating compositions, cured compositions obtained from the curable compositions, and articles comprising the cured compositions.

Description

[Technical field]

[0001] The present invention relates to the preparation of curable compositions using novel aspartic acid ester functional polysiloxanes, polyisocyanate crosslinkers, their use in particular in the preparation of coating compositions, cured compositions obtained from the curable compositions, and articles containing the cured compositions. In particular, the present invention discloses the use of the novel silicone aspartic acid ester functional polysiloxanes as release coating additives for solvent-based and water-based organic coating systems. The invention may be particularly useful in formulating durable, graffiti-resistant and easy-to-remove graffiti coating systems for outdoor applications. [Background technology]

[0002] Silicone oils and modified polysiloxanes have numerous applications in the coatings industry. For example, the use of products such as flow and leveling additives, defoamers, slip additives, antiblocking agents, wetting agents and release agents is described in "BASF Handbook of Fundamental Coating Technology" by Arthur Goldschmidt and Hans-Joachim Streitberger, Vincents Network GmbH, Primedia, Hannover, Germany, ISBN: 87870-798-3. It is known in the art that silicone-based materials can be used as additives for the formulation of anti-graffiti coating systems and coating systems with graffiti cleanability. EP1193303; EP3023467; US2020283558 describe silicone structures that can be used as functional modifiers to improve the release and stain-resistant properties of organic coatings. Conventionally, silicone materials used in such applications are polysiloxane block copolymers that contain pendant or main chain organic backbones. The incorporation of an organic polymer backbone into the polysiloxane structure improves the compatibility of the base silicone material with the organic coating matrix. Examples of such hybrid polymers include, but are not limited to, polysiloxane-polyethers, polysiloxane-polyacrylates, polysiloxane-polyepoxides, polysiloxane-polyacrylates, etc. One drawback of polysiloxane block copolymers is that the organic polymer backbone can slowly degrade with exposure to the elements, which can adversely affect the release properties of the silicone material.

[0003] Polysiloxane backbones modified with aspartic acid ester groups are known in the art. For example, US2016 / 0009971, CN104312398, and CN112250868A disclose aspartic acid polysiloxane structures prepared by reacting α,ω-bis(3-aminopropylsiloxane) containing terminal amino groups with diethyl maleate. US6,664,342B1 discloses products prepared by reacting diethyl maleate with long-chain PDMS equilibrated with aminosilane. WO2020079097 discloses aspartic acid polysiloxane structures with alkoxysilane (-OMe)x and (-OEt)x functional groups synthesized by esterifying Si-OH functional fluids with the corresponding aminosilanes. The aspartic acid ester functional polysiloxanes according to WO2020079097 have sufficient reactivity and pot life in polyisocyanate-based curable compositions, are compatible with polyurea and / or polyurethane coating compositions, and can improve bending flexibility, impact resistance, elongation, chemical resistance, and corrosion resistance for metal substrates. However, WO2020079097 does not describe the use of aspartic acid ester functional polysiloxanes as release agents and anti-graffiti additives, especially for water-based organic coating systems. Summary of the Invention

[0004] Thus, the object of the present invention is to provide a silicone modified aspartic acid ester that can provide good compatibility with organic coating matrix and at the same time provide more durable release and anti-graffiti effect. More specifically, the object of the present invention is to provide the silicone aspartic acid copolymer described below, in particular its use as a release agent and anti-graffiti coating additive for water-based or solvent-based organic coating systems. A further object of the present invention is to provide an oil-in-water emulsion of the silicone-aspartic acid copolymer described above, and how to use such an emulsion as a release agent and anti-graffiti additive for solvent-based or water-based organic coating systems, preferably water-based organic coating systems. The aspartic acid ester functional polysiloxane can also provide, for example, UV resistance, water resistance, chemical resistance, and heat resistance, as well as flexibility and adhesion to polymer compositions such as organic coating systems.

[0005] According to the invention, at least one unit of formula (A): [ka] and at least one unit of formula (B): [ka] and wherein the terminal units of said polyorganosiloxane are selected from formula (C) and formula (D): [ka] and [ka] These units (A) to (D) are linked to each other in such a way that Si-O-Si bonds are formed therebetween, Each n is an average number from about 1 to 250, preferably from 1 to 100, more preferably from 1 to 40, more preferably from 1 to 30; more preferably from 1 to 20, and most preferably from 2 to 10; or Each n is an average number from about 1 to 40, preferably 1 to 30; more preferably 1 to 20, even more preferably 2 to 10, even more preferably 3 to 9, even more preferably 3 to 8, most preferably 4 to 7, R 1 are each independently selected from an organic group, preferably selected from an aliphatic or aromatic group, more preferably selected from n-alkyl, iso-alkyl, or tertiary alkyl having up to 30 carbon atoms, alkoxyalkyl having up to 30 carbon atoms, cycloalkyl having 5 to 30 carbon atoms, aryl having 6 to 30 carbon atoms, alkylaryl having 7 to 30 carbon atoms, which groups may additionally be substituted by one or more oxygen, nitrogen, sulfur, and / or fluorine atoms, or by a poly(C2-C4)-alkylene ether having up to 500 alkyleneoxy units; R 1 The group does not contain aliphatic unsaturation, and preferably R 1 are CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, C8H 17 - and C 10 H 21 -, alicyclic radicals such as cyclohexylethyl, aryl radicals such as phenyl, tolyl, and xylyl, aralkyl radicals such as benzyl and 2-phenylethyl, CF3CH2CH2-, C4F9CH2CH2-, C6F 13 Formula C such as CH2CH2- m F 2m+1 A monovalent halohydrocarbon radical having the formula CH2CH2- and m having a value of 1 to 10, or C2F5-O (CF2-CF2-O) 1-10 CF2-, F[CF(CF3)-CF2-O] 1-5 -(CF2) 0-2R is a monovalent hydrocarbon radical, including oxygen-substituted halohydrocarbon radicals such as -, C3F7-OCF(CF3)-, and C3F7-OCF(CF3)-CF2-OCF(CF3)-, more preferably R 1 is methyl or phenyl, and most preferably R 1 is methyl, R 2 are each independently selected from the group consisting of linear alkylene groups having 1 to 10 carbon atoms, branched alkylene groups having 3 to 10 carbon atoms, cycloalkylene groups having 3 to 10 carbon atoms, arylene groups having 6 to 12 carbon atoms, aralkylene groups having 7 to 10 carbon atoms, and allenylene groups having 7 to 10 carbon atoms, preferably methylene, propylene, 2-methylbutylene and 2,2-dimethylbutylene, and more preferably branched alkylene groups having 3 to 10 carbon atoms, such as 2,2-dimethylbutylene, in particular bonded to Si and N atoms, as shown diagrammatically below: [ka] R 3 and R 4 are each independently selected from the group consisting of straight chain alkyl groups having 1 to 10 carbon atoms, branched chain alkyl groups having 3 to 10 carbon atoms, and cycloalkyl groups having 3 to 10 carbon atoms; and R 5 is hydrogen, and [ka] wherein x is 1 to 3, preferably 3; R 1 are each independently selected from the organic groups defined above; and R 6is an alkylene group bonded to silicon and nitrogen atoms via carbon atoms, which can be replaced by oxygen (to form a carbonyl group) or one or more of the carbon atoms can be replaced by -O-, -S-, -NH-, and -NR 7 -, where R 7 represents an alkyl group.

[0006] In one embodiment of the present invention, R 5 is hydrogen. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] In the specification and claims of this application, the following terms and expressions shall be understood as set forth below.

[0008] The singular forms "a," "an," and "the" include the plural and reference to a particular value includes at least that particular value unless the context clearly indicates otherwise.

[0009] Other than in the examples, or unless otherwise noted, all numbers expressing quantities of ingredients, reaction conditions, lengths of time, quantified properties of materials, and the like described in the specification and claims are understood to be modified in all instances by the term "about."

[0010] All methods described herein may be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. Any and all examples provided herein, or the use of exemplary language (e.g., "such as"), are intended merely to more clearly illustrate the invention and do not pose limitations on the scope of the invention unless otherwise specified.

[0011] No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0012] The terms "comprising," "including," "containing," "characterized by," and their grammatical equivalents are understood to be inclusive or open-ended terms that do not exclude additional, unrecited elements or method steps, and include the more restrictive terms "consisting of" and "consisting essentially of."

[0013] Any numerical ranges recited herein are understood to include all subranges within that range, and any combination of the various endpoints of such ranges or subranges.

[0014] As used herein, integer valued stoichiometric subscripts refer to molecular species, and non-integer valued stoichiometric subscripts refer to mixtures of molecular species on a molecular weight average basis, a number average basis, or a mole fraction basis.

[0015] In the following description, unless otherwise stated, all weight percentages are based on the total weight percentage of the organic material(s), and all ranges given herein include all subranges therebetween, and any combination of ranges and / or subranges therebetween.

[0016] Furthermore, all compounds, materials or substances explicitly or implicitly disclosed and / or claimed herein as belonging to a group of structurally, compositionally and / or functionally related compounds, materials or substances are understood to include the individual members of that group and all combinations thereof.

[0017] The phrase "hydrocarbon group" or "hydrocarbon radical" means any hydrocarbon composed of hydrogen and carbon atoms from which one or more hydrogen atoms have been removed, and includes alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, aralkyl, and arenyl groups.

[0018] The group can be comprised of a hydrocarbon group containing at least one heteroatom, more specifically, a hydrocarbon group containing at least one oxygen, nitrogen or sulfur heteroatom.

[0019] The term "alkyl" refers to any monovalent, saturated, straight or branched chain hydrocarbon group; the term "alkenyl" refers to any monovalent, straight or branched chain hydrocarbon containing one or more carbon-carbon double bonds, where the bond position of the group can be the carbon-carbon double bond or elsewhere; and the term "alkynyl" refers to any monovalent, straight or branched chain hydrocarbon containing one or more carbon-carbon triple bonds and optionally one or more carbon-carbon double bonds, where the bond position of the group can be the carbon-carbon triple bond, the carbon-carbon double bond or elsewhere. Examples of alkyl include methyl, ethyl, propyl, and isobutyl. Examples of alkenyl include vinyl, propenyl, allyl, methallyl, ethylidenylnorbornane, ethylidenenorbornyl, ethylidenylnorbornene, and ethylidenenorbornenyl. Examples of alkynyl include acetylenyl, propargyl, and methylacetylenyl.

[0020] As used herein, the siloxy unit may be represented by a shorthand notation for convenience. This shorthand notation is: monofunctional unit, RSiO 1 / 2 M represents a difunctional unit RSiO 2 / 2 D represents a trifunctional unit RSiO 3 / 2 where R is R except for the polyorganosiloxanyl residue. 1 and SiO, which is a tetrafunctional (or tetrafunctional) unit. 4 / 2 This notation follows the nomenclature commonly applied to polyorganosiloxanes (see, for example, Walter Knoll, "Chemistry and Technology of Silicones," p. 3, Elsevier, 2012).

[0021] In one embodiment, the polyorganosiloxane (I) according to the present invention comprises at least one unit of formula (A): [ka] and at least one unit of formula (E): [ka] The terminal units in the polyorganosiloxane formula are represented by the formula (C) and the formula (F): [ka] and [ka] and these units (A), (C), (E) and (F) are bonded to each other in such a way that Si-O-Si bonds are formed therebetween, where n is as defined above, x is as defined above, and R 1 From R 7 are as defined above, and R 8 is R 1 group, with the proviso that R 8 At least one of R represents an epoxy functional group. 8 All of the groups represent epoxy functional groups.

[0022] Preferably R 8 is one or more, preferably one -O- (oxygen), and one or more, preferably one, of the following formula: [ka] Each asterisk in the formula represents a hydrogen or a single bond to the alkyl group, more preferably the epoxy group is of the formula [ka] where the asterisk represents a single bond to the alkyl group; and Most preferably R 8 is the formula [ka] where the asterisk represents a single bond to the silicon atom.

[0023] Other R 8 Groups include, for example, 2-(3,4-epoxycyclohexyl)ethyl or propyl: [ka] where the asterisk represents a single bond to the silicon atom, and the corresponding epoxy-functional trialkoxysilanes are commercially available as starting materials.

[0024] In an embodiment of the polyorganosiloxane (I) according to the invention, at least one unit of formula (A): [ka] and at least one unit of formula (G): [ka] The terminal units in the polyorganosiloxane formula are represented by the formula (C) and the formula (H): [ka] and [ka] and these units (A), (C), (G) and (H) are bonded to each other in such a way that Si-O-Si bonds are formed therebetween, wherein n is as defined above, x is as defined above, and R 1 From R 7 are as defined above.

[0025] In a preferred embodiment, the polyorganosiloxane (I) according to the invention comprises at least one group selected from the following formulae: [ka] and [ka] which includes the formula: [ka] and at least one group of the formula [ka] The bonds of the terminal silicon atoms in the formula are not shown, And R 1 , R 2 , R 3 , R 4 , R 5 and n are each as defined above. Preferably, in such an embodiment, R 5 is hydrogen.

[0026] In a preferred embodiment, the polyorganosiloxane (I) according to the invention comprises at least one group selected from the following formulae: [ka] and at least one group selected from the following formulas: [ka] which includes the formula: [ka] and at least one internal group of the formula: [ka] The bonds of the terminal silicon atoms in the formula are not shown, and where R 1 , R 2 , R 3 , R 4 and n are each as defined above. According to the invention, in particular, an internal aspartic acid group (T aspartic ) and [ka] Internal siloxyalkoxy group (T alkoxy ) [ka] It has been found that the simultaneous presence of is particularly beneficial and provides a unique combination of performance properties (i.e., branching or crosslinking during application) whereas linear silicone structures having only terminal aspartate groups may have poorer performance.

[0027] In a preferred embodiment, the polyorganosiloxane (I) according to the invention comprises at least one group selected from the following formulae: [ka] and [ka] which includes the formula: [ka] and at least one group of the formula [ka] where the bonds of the terminal silicon atoms in the formula are not shown, And in the formula R 1 , R 2 , R 3 , R 4 , R 5 , R 8 and n are each as defined above. In such embodiments, R 5 is preferably hydrogen.

[0028] The polyorganosiloxanes (I) of the present invention are essentially linear since no branching was observed during their preparation.

[0029] In a further embodiment, the units (A), (B), (E) and (G) in the polyorganosiloxane (I) according to the invention are randomly distributed.

[0030] In a further preferred embodiment in the polyorganosiloxane (II) according to the invention, the total average number of units (A) and (B) or units (A) and (E) or units (A) and (G) in the polyorganosiloxane (I) is from 1 to 10, preferably from 2 to 5. In a preferred embodiment, there is on average about 1 unit (A) and about 1 unit (B), or 1 unit (A) and about 1 unit (E), or 1 unit (A) and about 1 unit (G).

[0031] In a further preferred embodiment of the polyorganosiloxane (I) according to the present invention, the molar ratio of units (A) and units (B) or units (A) and units (E) or units (A) and units (G) in the polyorganosiloxane (I) is from about 1:20 to about 20:1, preferably from about 1:10 to about 10:1, preferably from about 1:5 to about 5:1, more preferably from about 1:2 to about 2:1, and most preferably about 1:1.

[0032] In a further preferred embodiment of the polyorganosiloxane (I) according to the invention, the average number of units (A) is from about 0 to about 10, preferably from about 0 to about 5, and the average number of units (B) or units (E) or units (G) is from about 0 to about 10, preferably from about 0 to about 5, preferably the average number of units (A) is from about 1 to 2, and the average number of units (B) or units (E) or units (G) is from about 1 to about 2.

[0033] In a further preferred embodiment of the polyorganosiloxane (I) according to the invention, the polyorganosiloxane (I) according to the invention comprises a mixture of more than one polyorganosiloxane (I) selected from the following combinations of end groups: (C)(C), (C)(D)(=(D)(C)), and (D)(D), or (C)(C), (C)(F)(=(F)(C)), and (F)(F), or (C)(C), (C)(H)(=(H)(C)), and (H)(H) Here, the groups (C) and (D) are as defined above.

[0034] In a particularly preferred embodiment, the molar percentages of units (A) to (H) or units (A) to (D) in the polyorganosiloxane (I) according to the invention are: About 25 to about 45% of (A): [ka] Preferably [ka] About 8 to about 28% (B): [ka] or from about 8 to about 28% (E): [ka] or from about 8 to about 28% (G): [ka] Approximately 3 to 23% (C): [ka] Preferably [ka] and about 20 to 45% (D): [ka] or (F) [ka] Or (H): [ka] In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8, x and n are each as defined above; The mole percentages for (A) through (H) or (A) through (D) are based on the sum of the mole percentages being 100 mole percent. These percentages are: 1 H-, 13 C-, and 29 It can be determined by NMR spectroscopy, including Si-NMR spectroscopy.

[0035] In a preferred embodiment of the present invention, R 1 is selected from alkyl and aryl groups, preferably from alkyl groups, more preferably from C1 to C6 alkyl groups, more preferably from methyl and ethyl groups, and most preferably R 1 is methyl.

[0036] In a preferred embodiment of the present invention, the polyorganosiloxane (I) has the average formula [ka] where n is as defined above, and preferably n is from about 4 to about 8.

[0037] The polyorganosiloxanes (I) according to the invention may comprise a mixture of two or more compounds selected from the following average formulae: [ka] [ka] [ka] [ka] [ka] where n is as defined above. In such mixtures, the average formula [ka] will generally be present and may even form the major component (i.e., at least 50 mole %, more preferably at least 60 mole %) of such mixtures.

[0038] The present invention further relates to a process for the preparation of polyorganosiloxanes (I), which comprises (i) a silane of formula (a) [ka] and a silane of formula (b) [ka] a silane of formula (c): [ka] and reacting with at least one of the formulas (A 1 ) units: [ka] and at least one unit of formula (B): [ka] and forming a polyorganosiloxane (II) comprising the terminal units of the polyorganosiloxane (II) having the formula (C 1 ) and (D) selected from: [ka] and [ka] R in the formula 1 , R 2 and n are each as defined above, and these units (A) to (D) are bonded to each other in such a way that Si-O-Si bonds are formed therebetween; (ii) reacting the polyorganosiloxane (II) obtained in step (i) with a compound of the formula [ka] (maleic ester) with a compound of formula R 3 and R 4 are as defined above, A polyorganosiloxane (I) as defined above is thus obtained.

[0039] Similarly, aspartic acid ester functional trialkoxysilanes [ka] Each of the substituents in the formula is as defined above, and R 5 is preferably hydrogen, Epoxy functional trialkoxysilane [ka] Each of the substituents in the formula is as defined above. and optionally a non-functional silane of formula (b): [ka] Substituent R in the formula 1 Each of the above is defined as, for example, an alkyltrialkoxysilane, or a mixture thereof. a silane of formula (c): [ka] It is also possible to react with

[0040] Optionally, the process according to the present invention further comprises the step of: [ka] wherein x and R are each independently an isocyanate functional alkoxysilane of the formula: 1 is as defined above, and R 9 preferably represents an alkylene group having 1 to 3 carbon atoms, and most preferably R 9 represents a -CH2-CH2-CH2- group, and R other than hydrogen 5 A group is introduced.

[0041] Step (i) of this process is typically carried out in the presence of a conventional condensation catalyst such as an amine, preferably DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). The reaction is carried out under stirring and heated to about 90° C., with the initiation of the reaction indicated by bubbling or reflux. After a steady reflux, the alcohol, particularly methanol, is collected in a receiving vessel. Once a suitable amount of alcohol (e.g., methanol) has been collected and no more alcohol (e.g., methanol) is escaping, a vacuum is applied to remove volatiles.

[0042] In step (ii) of this process, the polyorganosiloxane (II) obtained in step (i) is converted to a maleic acid ester (R 3 and R 4 Typically, polyorganosiloxane (II) is placed in a flask equipped with a heating mantle, a J-KEM (temperature controller), a mechanical stirrer, a dropping funnel, and a cold water condenser. A maleate ester, such as diethyl maleate, is then added dropwise from the dropping funnel while stirring at room temperature (RT). After addition, the reaction flask is heated to at least 50° C., such as 80° C., and the reaction is allowed to continue for at least 1 hour, preferably at least 2 hours to 5 hours, such as 3 hours.

[0043] In a further preferred embodiment, an oil-in-water emulsion is provided, which contains at least one polyorganosiloxane (I) according to the present invention as an oil component. Preferably, such an oil-in-water emulsion contains at least one surfactant. In a specific process, one or more surfactants are added in a flask equipped with a mechanical stirrer and a water bath for heating, and the surfactant is dissolved. After the surfactant is dissolved, the polyorganosiloxane (I) is added and mixed. The mixture is cooled to below 30° C. under stirring, and water is added to the mixture. After stirring, the mixture is put into an APV homogenizer, and after one or more passes at a pressure setting of, for example, 60 / 600 bar, a stable oil-in-water emulsion of polyorganosiloxane (I) according to the present invention (for example, 10 to 50% active by weight, for example, 35% active by weight) can be obtained.

[0044] In a preferred embodiment, the oil-in-water emulsion comprises 0.01 to 30% by weight, more preferably 0.01 to 20% by weight, of a surfactant and 10 to 80% by weight, preferably 10 to 50% by weight, of the polyorganosiloxane (I) according to the invention, the remainder being water and, optionally, an organic solvent.

[0045] The surfactant may include a cationic surfactant, an anionic surfactant, or a nonionic surfactant.

[0046] The cationic surfactants may be selected from primary, secondary or tertiary amine compounds and their salts having up to 50 carbon atoms, amidoamine compounds and their salts having up to 50 carbon atoms, such as behenamidopropyldimethylamine and quaternary ammonium compounds having up to 50 carbon atoms, and preferably tetraalkylammonium compounds having up to 20 carbon atoms in the alkyl group, such as hexadecyltrimethylammonium salts, dimethyldioctadecylammonium salts, distearyldimethylammonium salts, cetrimonium salts, cetylpyridinium salts, alkylbenzyldimethylammonium salts, such as benzalkonium salts, benzethonium salts, esterquats having at least one quaternary ammonium group and at least one ester group.

[0047] Preferred examples of cationic surfactants are quaternary ammonium compounds or amino compounds containing linear or branched C8 to C50, preferably C8 to C40, more preferably C8 to C30 organic groups, optionally with further functional groups such as alkyl, fatty alcohol and fatty acid based surfactants such as fatty acid based ester quats containing one or two fatty acid moieties, fatty amines and ethoxylated / propoxylated fatty amines such as fatty alcohol polyoxyethylene ether ammonium sulfates.

[0048] Preferably, the cationic surfactant is a mono-long alkyl-tri-short alkyl quaternized ammonium salt or a di-long alkyl-di-short alkyl quaternized ammonium salt, where one or two alkyl substituents are independently selected from optionally substituted alkyl groups of 9 to 30 carbon atoms and the other short alkyl groups are independently selected from optionally substituted alkyl groups of about 1 to 8 carbon atoms. In these cationic surfactants, the long alkyl groups may be substituted with aromatic, alkoxy, polyoxyalkylene, alkylamide, hydroxyalkyl, or alkylaryl groups having 9 to 30 carbon atoms, or the short alkyl groups may be substituted with aromatic, alkoxy, polyoxyalkylene, alkylamide, hydroxyalkyl, or alkylaryl groups having up to about 8 carbon atoms.

[0049] The counterion of the ammonium compound (which may be a quaternized ammonium compound or a protonated amino compound) comprises an anion that forms a salt and is selected from, for example, a halogen (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate, alkyl sulfate, glutamate, and alkyl sulfonate radical.

[0050] The aliphatic groups of the cationic surfactants can contain, in addition to carbon and hydrogen atoms, other groups such as ether linkages and amino groups. The long chain aliphatic groups, e.g., those containing about 9 carbon atoms or more, can be saturated or unsaturated.

[0051] Preferably, one alkyl group is selected from alkyl groups of about 9 to about 30 carbon atoms, more preferably from about 14 to about 26 carbon atoms, and even more preferably from about 14 to 22 carbon atoms; the other alkyl group is independently selected from the group consisting of -CH3, -C2H5, -C2H4OH, -CH2C6H5, and mixtures thereof; and the counterion is Cl. - , Br - , CH3OSO3 - and mixtures thereof.

[0052] Non-limiting examples of such mono-long alkyl quaternary ammonium salt cationic surfactants include: behenyl trimethyl ammonium chloride, available for example from Clariant under the trade name Genamine KDMP, from Croda under the trade name INCROQUAT TMC-80, and from Sanyo Chemical under the trade name ECONOL TM22; stearyl trimethyl ammonium chloride, available for example from Nikko Chemical under the trade name CA-2450; cetyl trimethyl ammonium chloride, available for example from Nikko Chemical under the trade name CA-2350; behenyl trimethyl ammonium methyl sulfate, available from FeiXiang; hydrogenated tallow alkyl trimethyl ammonium chloride; stearyl dimethyl benzyl ammonium chloride; and stearoyl amidopropyl dimethyl benzyl ammonium chloride. The cationic surfactant can be an amidoamine surfactant, such as stearamidopropyl dimethylamine, behenamidopropyl dimethylamine, etc. Other preferred cationic surfactants are ester quats such as dipalmitoyl ethyl hydroxyethylmonium methosulfate (eg, Stepanquat GA90) or methyl bis[tallowate ethyl]-2-hydroxyethyl ammonium methylsulfate.

[0053] Preferred cationic surfactants are, for example, mono- and diester quats based on saturated or unsaturated fatty acids having 10 to 18 carbon atoms in the alkyl chain. Commercially available examples are Arquad PC SV-60PG and Armocare VGH70 (AkzoNobel). Other examples of ester quats are dipalmitoyl ethyl hydroxyethylmonium methosulfate (e.g., Stepanquat GA90) or methyl bis[tallow fatty acid ethyl]-2-hydroxyethyl ammonium methylsulfate.

[0054] The most preferred cationic surfactants are those having the formula: [ka] A mono-long chain alkyl quaternary ammonium salt having the formula: 71 , R 72 , R 73 , and R 74 one of R is selected from an aliphatic group of about 16 to about 30 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group of up to about 30 carbon atoms; 71 , R 72 , R 73 , and R 74 the remainder are independently selected from an aliphatic group of about 1 to about 8 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group of up to about 8 carbon atoms; and X is a salt-forming anion, such as a halogen (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate, alkyl sulfate, glutamate, and alkyl sulfonate radical, where the aliphatic group can contain, in addition to carbon and hydrogen atoms, ether linkages and other groups such as amino groups. Long chain aliphatic groups, such as aliphatic groups of about 16 or more carbons, can be saturated or unsaturated. Preferably, R 71 , R 72 , R 73 , and R 74 is selected from alkyl groups of from about 16 to about 30 carbon atoms, more preferably from about 18 to about 26 carbon atoms, and even more preferably about 22 carbon atoms; R 71 , R 72 , R 73 , and R 74 the remainder being independently selected from the group consisting of -CH3, -C2H5, -C2H4OH, -CH2C6H5, and mixtures thereof; and (X - ) is Cl - , Br - , CH3OSO3 -and mixtures thereof. Most preferred are trimethyl (C12 to C24) alkyl ammonium salts such as cetrimonium chloride, cetrimonium bromide, behentrimonium chloride.

[0055] More suitable specific cationic surfactants are disclosed, for example, in WO2009 / 035970 (in particular, page 7, line 8 to page 17, last line), the entire disclosure of which is incorporated herein by reference, and in US2013 / 259820 (in particular, paragraphs

[0074] to

[0078] ), the entire disclosure of which is incorporated herein by reference.

[0056] The anionic surfactant is preferably selected from the group consisting of organic sulfates, organic sulfonates, organic phosphates, organic phosphonates, and organic carboxylates, including, for example, ammonium lauryl sulfate, sodium lauryl sulfate, and alkyl sulfates, such as alkyl ether sulfates, including sodium laureth sulfate and sodium myreth sulfate.

[0057] Preferred examples for anionic surfactants are organic carboxylates, sulfates, sulfonates, phosphates and phosphonates, preferably containing linear or branched organic groups having C8 to C50 carbon atoms, preferably C8 to C40 carbon atoms, more preferably C8 to C24 carbon atoms, such as alkyl, and also fatty alcohol and fatty acid based surfactants, i.e. C8 to C24 fatty acid carboxylates, C8 to C24 fatty acid polyether carboxylates, C8 to C24 fatty acid polyether sulfates, C8 to C24 maleic acid addition products, C8 to C24 fatty alcohol sulfates, C8 to C24 sulfonates, C8 to C40 phosphonates containing one or more fatty acid moieties.

[0058] Preferably, the anionic surfactant suitable for use in the composition is alkyl sulfate and alkyl ether sulfate.Other suitable anionic surfactants are the water-soluble salts of organic sulfuric acid reaction products.Still other suitable anionic surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Exemplary anionic surfactants for use in the coating include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric acid monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium cocoyl isethionate, and combinations thereof. In a further embodiment of the invention, the anionic surfactant is sodium lauryl sulfate or sodium laureth sulfate.

[0059] Preferred anionic surfactants are polyether sulfates based on saturated or unsaturated fatty alcohols with 10 to 18 carbon atoms in the alkyl chain and 2 to 30 ethylene oxide (EO) units. Commercially available examples are Emulsogen EPM type (Clariant).

[0060] Further preferred anionic surfactants are polyether carboxylates based on saturated or unsaturated fatty alcohols having from 10 to 18 carbon atoms in the alkyl chain and from 2 to 30 ethylene oxide (EO) units. Commercially available examples are the Empicol types (Huntsman).

[0061] Details of the anionic surfactants are disclosed in US2015 / 011449 (page 10 of WO2015 / 002812A1), the entire contents of which are incorporated herein by reference.

[0062] Preferred examples of nonionic surfactants are ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO)-containing linear or branched C8 to C50, preferably C8 to C40, more preferably C8 to C24 fatty alcohol and fatty acid-based emulsifiers, as well as sugar-based emulsifiers, i.e., alkyl glycosides, alkoxylated fatty acid sorbitan esters, and fatty acid glucamides. Other classes of preferred nonionic surfactants include semi-polar amine oxides, phosphine oxides, and sulfoxides.

[0063] Preferred nonionic surfactants are saturated or unsaturated natural alcohol-based ethoxylates having 10 to 18 carbon atoms in the alkyl chain and 5 to 80 ethylene oxide (EO) units. Commercially available examples include Genapol C, LA, V, O, and T types (Clariant). Other commercially available examples from Aldrich include Brij C2, a cetyl alcohol-based nonionic alcohol ethoxylate, and Brij S100, a polyoxyethylene (100) stearyl ether.

[0064] Preferred nonionic surfactants are ethoxylates based on linear or branched oxoalcohols having 11 to 17 carbon atoms in the alkyl chain and 5 to 100 ethylene oxide (EO) units. Commercially available examples are Genapol UD, OA, OX, X, LCN types (Clariant).

[0065] Preferred nonionic surfactants are saturated or unsaturated alcohol-based blocked ethoxylate-propoxylates having 10 to 18 carbon atoms in the alkyl chain and 2 to 20 EO units. Commercially available examples are the Genapol EP types (Clariant).

[0066] Preferred nonionic surfactants are ethoxylate-propoxylate block copolymers having 5 to 70% by weight of EO units, commercially available examples being Genapol PF and PH types (Clariant).

[0067] Preferred nonionic surfactants are saturated or unsaturated fatty acid-based ethoxylates having 10 to 18 carbon atoms in the alkyl chain and 5 to 100 EO units. Commercially available examples are the Genapol O and S types (Clariant).

[0068] Preferred nonionic surfactants are castor oil ethoxylates based on saturated or unsaturated fatty acids having 10 to 18 carbon atoms in the alkyl chain and 5 to 80 EO units. Commercially available examples are Emulsogen HCO and EL types (Clariant).

[0069] Preferred nonionic surfactants are oligoglycerols derived from saturated or unsaturated fatty acids. Preferred examples are di-, tri- or tetraglycerols derived from fatty acids, i.e. mono- or diesters of diglycerol with 10 to 18 carbon atoms in the alkyl chain and optionally 5 to 100 EO units. Commercially available examples are Hostacerine types (Clariant).

[0070] Preferred nonionic surfactants are ethoxylates based on saturated or unsaturated fatty acid sorbitan esters having 10 to 18 carbon atoms in the alkyl chain and 5 to 50 EO units attached to the sorbitan ring. A commercially available example is Emulsogen 4156 (Clariant).

[0071] Preferred nonionic surfactants are saturated or unsaturated alcohol-based glycosides having 8 to 18 carbon atoms in the alkyl chain and 1 to 10 glycosyl units. Commercially available examples are Plantacare 818up and 1200up (BASF).

[0072] Preferred nonionic surfactants are saturated or unsaturated fatty acid-based glucamides having 8 to 18 carbon atoms in the alkyl chain, preferably fatty acid N-methyl glucamides. Commercially available examples are the MEGA-10 type (Avanti).

[0073] Preferred nonionic surfactants are saturated or unsaturated fatty acid-based alkanolamides, fatty acid-based ethanolamides having 8 to 18 carbon atoms in the alkyl chain. Commercially available examples are Aminon C type (Kao Corporation).

[0074] Preferred nonionic surfactants are amine oxides based on fatty amines or fatty amides having from 8 to 30 carbon atoms in the alkyl chain. Commercially available examples are Tomamine AO ​​types (Air Products) and Genamineox types (Clariant).

[0075] Preferably, suitable betaine surfactants include those broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical is straight or branched, one of the aliphatic substituents contains from about 8 to about 30 carbon atoms, and one contains an anionic group such as a carboxylate, sulfonate, sulfate, phosphate, or phosphonate. Exemplary amphoteric surfactants for use in the formulations of the present invention include cocoamphoacetic acid, cocoamphodiacetic acid, lauroamphoacetic acid, lauroamphodiacetic acid, and mixtures thereof.

[0076] These also include surfactants that can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic radical is straight or branched chain, one of the aliphatic substituents contains from about 8 to about 30 carbon atoms, and one contains an anionic group such as a carboxylate, sulfonate, sulfate, phosphate, or phosphonate.

[0077] Preferred carbobetaine surfactants are sarcosides based on saturated or unsaturated fatty acids having from 10 to 18 carbon atoms in the alkyl chain. A commercially available example is Medialan LD (Clariant).

[0078] Preferred carbobetaine surfactants are amidopropyl betaines based on saturated or unsaturated fatty acids having from 10 to 18 carbon atoms in the alkyl chain. A commercially available example is Genagen CAB (Clariant).

[0079] Preferred sulfobetaine surfactants are taurates based on saturated or unsaturated fatty acids having from 10 to 18 carbon atoms in the alkyl chain. A commercially available example is Hostapon CT (Clariant).

[0080] Details of betaine surfactants are disclosed in US 2015 / 011449, the entire contents of which are incorporated herein by reference.

[0081] Preferred examples of cationic silicone-based emulsifiers include ABA-type quaternary ammonium or amino group-containing emulsifiers having EO / PO moieties attached to the terminal quat or amino ends of the silicone chain (WO 2009 / 042083, the entire contents of which are incorporated herein by reference), or quat / amino emulsifiers having polyether moieties attached in a comb-like configuration to the silicone chain (US 2008 / 213208, the entire contents of which are incorporated herein by reference).

[0082] In another preferred embodiment of the present invention, a hydrophilic polyhydroxy moiety and a lipophilic fatty alkyl or fatty alkyl ester moiety are attached to the silicone chain (US2012 / 289649, the entire contents of which are incorporated herein by reference). A commercially available example of this type of W / O emulsifier is Silform EOF (Momentive).

[0083] It is also within the scope of the present invention to use multiple surfactants to optimize the stability of the formulation.

[0084] The polyorganosiloxane (I) or its oil-in-water emulsion according to the present invention can be used, for example, to manufacture paints, coatings, adhesives, foams, sealants, including polyurethane vacuum molding resins, polyurethane rapid molding resins, elastomer-cured polyurethane molding resins, electrical potting compositions, and edge molding compositions; polyurethane articles, including mattresses, shoe soles, gaskets, hoses, flooring, insulating materials, sealants, skis, car seats, stadium athletic tracks, dashboards, molding compositions, latex-free condoms, and molded flooring.

[0085] The polyorganosiloxanes (I) according to the invention or their oil-in-water emulsions can further be used, for example as additives or co-resins, in industrial / architectural / construction coatings, adhesives and sealants (water- and solvent-based acrylic, epoxy, urethane, silicone, melamine, polyester, powder coatings, etc.).

[0086] Particular preference is given to the use of the polyorganosiloxanes (I) according to the invention or their oil-in-water emulsions as additives for coating compositions, preferably as easy-to-clean coating compositions and as release agents and anti-graffiti additives for coating compositions.

[0087] Particular preference is further given to the use of the polyorganosiloxanes (I) according to the invention or their oil-in-water emulsions as additives for polyurethane resin- or acrylic resin-based coating compositions, preferably solvent- or water-based two-component anti-graffiti polyurethane topcoats.

[0088] Particular preference is further given to the use of the polyorganosiloxanes (I) according to the invention or their oil-in-water emulsions as additives for curable compositions, preferably those which contain polyisocyanates.

[0089] The polyisocyanates include a variety of polyisocyanates, including in particular aliphatic, aromatic or cycloaliphatic polyisocyanates having an NCO functionality of 2 or more, which are known to those skilled in the art.

[0090] Representative, non-limiting examples of such suitable polyisocyanates include 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, bis(4,4'-isocyanatocyclohexyl)methane, isomeric mixtures containing bis(4,4'-isocyanatocyclohexyl)methane in any desired isomer content, 1,4-cyclohexylene diisocyanate, 4-isocyanatomethyl-1,8-octane diisocyanate, 1,4-furan diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4-trimethylhexamethylene diisocyanate, bis(4,4'-isocyanatocyclohexyl)methane, isomeric mixtures containing bis(4,4'-isocyanatocyclohexyl)methane in any desired isomeric content, 1,4-cyclohexylene diisocyanate, 4-isocyanatomethyl-1,8-octane diisocyanate, 1,4-furan diisocyanate, 1,6-hexamethylene ... Examples of suitable isocyanates include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-bis(2-isocyanatoprop-2-yl)benzene, 1,4-bis(2-isocyanatoprop-2-yl)benzene, 1,3-bis(isocyanatomethyl)benzene, alkyl 2,6-diisocyanatohexanoates having C1-C8 alkyl groups (lysine diisocyanate), and mixtures thereof.

[0091] Polyisocyanates also include high molecular weight oligomeric polyisocyanates prepared therefrom using suitable modification reactions such as trimerization or biuretization. Hexamethylene diisocyanate and isophorone diisocyanate can be used as starting diisocyanates to prepare the corresponding polyisocyanates. In the present invention, such oligomeric polyisocyanates are preferred. These include polyisocyanates in which at least two generally equal diisocyanate units are bonded to each other by reacting a portion of the isocyanate groups, optionally by adding, for example, monohydric or polyhydric alcohols.

[0092] Particularly preferred oligomeric polyisocyanates are dimers, trimers or mixtures of dimers and trimers of diisocyanates. These oligomeric polyisocyanates have a higher molecular weight than the corresponding diisocyanates. Oligomeric polyisocyanates based on hexamethylene diisocyanate preferably have a molecular weight (=number average) of more than 168.20 grams / mol, calculated on the basis of the molecular base structure. Oligomeric polyisocyanates based on isophorone diisocyanate preferably have a molecular weight of more than 222.29 grams / mol, calculated on the basis of the molecular base structure. In the sense of the present invention, it is particularly preferred that the oligomeric polyisocyanates are obtained by reacting only one diisocyanate, such as only hexamethylene diisocyanate or only isophorone diisocyanate as diisocyanate units. Preferably, the oligomeric polyisocyanates have a molecular weight of less than 1500 grams / mol, calculated on the basis of the molecular base structure. Depending on the reaction conditions, different reactions of the diisocyanate units can occur to form polyisocyanates.

[0093] Polyisocyanates also include the reaction products of diisocyanates with preferably low molecular weight polyols to form polyurethanes. Such polyols preferably have a molecular weight range of 62 to 400 grams per mole, calculated on the molecular base structure.

[0094] The reaction of diisocyanates can form different functional groups, such as, for example, uretdione, isocyanurate, iminooxadiazinedione, urethane, allophanate, biuret and / or oxadiazinetrione groups. Oligomeric polyisocyanates having at least one of these functional groups may be called "derivatives" of the corresponding diisocyanate. In general, the synthesis of oligomeric polyisocyanates does not occur in the form of a defined compound, but in the form of a mixture of different oligomers with a molecular weight distribution. Oligomeric polyisocyanates may preferably include the following types of structures having formulae (IX) to (XV), as disclosed in News from Chemistry 55, 380-384 (2007): [ka] [ka]

[0095] where X is an aliphatic residue, R is an organic group, n is an integer ranging from 1 to 10, preferably 2 or 3, and m is an integer ranging from 2 to 10, preferably 2 or 3. The oligomeric polyisocyanates can contain at least one of these functional groups and may contain two or more of these different functional groups. Particularly preferred structures for X are -CH2CH2CH2CH2CH2CH2- for oligomeric polyisocyanates based on hexamethylene diisocyanate and -CH2CH2CH2CH2CH2- for oligomeric polyisocyanates based on isophorone diisocyanate. [ka] It is.

[0096] Thus, oligomeric polyisocyanates with a functionality of ≧2, selected from the uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione or oxadiazinetrione compounds of the formulae (IX)-(XV) and mixtures of these compounds, are preferred, in particular those containing aliphatic groups with a valency of 3 or more in the polyisocyanates such as biurets, allophanates, urethanes, isocyanurates, and higher oligomers of diisocyanates, in particular oligomers of hexamethylene diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and / or bis(isocyanatocyclohexyl)-methane, having the following structure: Specific examples of such polyisocyanates are, for example, biurets of hexamethylene diisocyanate and those sold under the trade name Desmodur from Covestro, which have the following structure: 登録商標 Its oligomers, which are commercially available under 100: [ka] It has the following structure and is sold by Covestro under the trade name Desmodur 登録商標 Isocyanurate trimer of hexamethylene diisocyanate commercially available under N3300: [ka] Desmodur, a product name from Covestro 登録商標 Z4470 or from Bencorex under the trade name Tolonate IDT 70B, higher oligomers such as pentamers based on hexamethylene diisocyanate having the following structure: [ka] and similar pentamers based on 4,4'-methylenebis(cyclohexylisocyanate), or asymmetric trimers based on hexamethylene diisocyanate, such as [ka] and a similar asymmetric trimer based on 4,4'-methylenebis(cyclohexyl isocyanate).

[0097] Particularly suitable polyisocyanates include isocyanates, or mixtures thereof, preferably having an average NCO functionality of 2.0 to 5.5, preferably 2.8 to 5.0, and more preferably 3.0 to 4.5. The NCO content based on the solids content of the polyisocyanate is preferably from about 2 to about 50% by weight, preferably from about 10 to about 30% by weight, and more preferably from about 11 to about 25% by weight. The content of diisocyanate monomers in the polyisocyanate is preferably less than about 10% by weight, more preferably less than about 2% by weight, and most preferably less than about 0.5% by weight.

[0098] Particularly suitable polyisocyanates include polyisocyanate adducts containing biuret, isocyanurate, iminooxadiazinedione, uretdione, allophanate, and / or urethane groups. The urethane groups are based on the reaction products of isocyanate monomers with polyfunctional alcohols such as trimethylolpropane, 1,6-hexanediol, 1,5-pentanediol, diethylene glycol, triethylene glycol, 2,2,4-trimethyl-1,3-propanediol, neopentyl glycol, and mixtures thereof. Such polyisocyanate adducts are described, for example, in "Journal of Practical Chemistry" 336, 185-200 (1994) and in "Paint Resins, Chemistry, Properties and Applications", edited by D. Stoie and W. Freytag, Hanser-Verlag GmbH, Munich and Vienna, 1996.

[0099] Polyisocyanate adducts may be prepared by oligomerizing diisocyanate monomers, for example, as described in Journal of Practical Chemistry 336, 185-200 (1994). Suitable diisocyanate monomers include 1,4-butane diisocyanate, 1,6-hexane diisocyanate, 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 2-methyl-1,5-pentane diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, bis(isocyanatomethyl)norbornane, and 4,4'-diisocyanato-cyclohexylmethane.

[0100] Particularly preferred are polyisocyanates containing isocyanurate groups (trimers) having an NCO functionality of 3.0 to 4.5 and a monomer content of less than 2 weight percent. They may be prepared by the trimerization process described in EP 330,996. Furthermore, exemplary polyisocyanates include, but are not limited to, 4,4'-diphenylmethane diisocyanate ("MDI"), polymeric MDI, carbodiimide-modified liquid MDI, 4,4'-dicyclohexylmethane diisocyanate ("H 12dimethyl-4,4'-biphenylene diisocyanate ("TODI"), isophorone diisocyanate ("IPDI"), hexamethylene diisocyanate ("HDI"), naphthalene diisocyanate ("NDI"), xylene diisocyanate ("XDI"), p-tetramethylxylene diisocyanate ("p-TMXDI"), m-tetramethylxylene diisocyanate ("m-TMXDI"), ethylene diisocyanate, propylene-1,2-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexyl diisocyanate, Isocyanates, 1,6-hexamethylene-diisocyanate ("HDI"), dodecane-1,12-diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, methylcyclohexylene diisocyanate, isocyanurates of HDI, triisocyanates of 2,4,4-trimethyl-1,6-hexane diisocyanate ("TMDI"), tetracenediisocyanate, naphthalene diisocyanate, anthracene diisocyanate, tris(4-isocyanatophenyl)methane (available from Covestro under the trade name Desmodur R), 1,3,5-tris(3-isocyanato-4-methylphenyl)-2,4,6-trioxohexahydro-1,3,5-triazine (commercially available from Covestro under the trade name Desmodur IL), N-isocyanatohexyl-aminocarbonyl N,N'-bis(isocyanatohexyl)urea (commercially available from Covestro under the trade name Desmodur N), 2,4,6-trioxo-1,3,5-tris(6-isocyanatohexyl)hexahydro-1,3,5-triazine (commercially available from Covestro under the trade name Desmodur N3390), 2,4,6-trioxo-1,3,5-tris(5-isocyanato-1,3,3-trimethylcyclohexylmethyl)hexahydro-1,3,These include 5-triazine (available from Covestro under the trade name Desmodur N4370), 4,4'-dimethyldiphenylmethane-2,2',5,5-tetraisocyanate, 4-methyldiphenylmethane-3,5,2',4',6'-pentaisocyanate, and others.

[0101] For better handling, the polyisocyanate (mixture) can be diluted with up to about 50% by weight of conventional solvents. Suitable solvents are those which are not reactive towards NCO groups, such as butyl acetate, ethyl acetate, 1-methoxy-2-propyl acetate, toluene, 2-butanone, xylene, 1,4-dioxane, N-methylpyrrolidone, diethylacetamide, dimethylformamide, and dimethylsulfoxide.

[0102] In a further preferred embodiment, the present invention relates to a curable coating composition comprising at least one polyorganosiloxane (I) according to the invention.

[0103] Preferably, the curable coating composition of the present invention comprises: A) at least one polyorganosiloxane (I) according to the invention as defined above; B) at least one polyisocyanate; and C) contains one or more isocyanate-reactive compounds (different from A).

[0104] The isocyanate-reactive compound is not particularly limited, but preferably includes a compound having two or more active hydrogen atoms in the molecule that are reactive with an isocyanate group. Representative non-limiting examples of the compound having two or more active hydrogen atoms in the molecule include polyols, polyamines, and polythiols. Among these, polyols and polyamines are preferred. Polyamines are particularly preferred. Specific non-limiting examples of polyols include polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, and fluorine-containing polyols, preferably acrylic polyols and / or polyester polyols. These compounds having two or more active hydrogen atoms in the molecule may be used alone or in combination of two or more. Preferred are polyols, particularly hydroxy-functional acrylic resins.

[0105] The curable composition using the compound of the present invention can be a solvent-based or water-based composition.When preparing a solvent-based or water-based curable composition, additives such as other isocyanate-reactive compounds, catalysts, pigments, leveling agents, antioxidants, UV absorbers, light stabilizers, plasticizers, surfactants, and other ingredients typically used in coatings can be added.Organic solvents or water can be added to adjust the viscosity of the mixture if necessary.The isocyanate-reactive compound can also be added as an aqueous dispersion or dissolved in water.

[0106] The polyester polyols can be obtained, for example, but not limited to, by condensation reaction between a single acid or a mixture of dibasic acids, such as carboxylic acids, such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid, and a single polyhydric alcohol or a mixture of polyhydric alcohols, such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, pentaerythritol, 2-methylolpropanediol, and ethoxylated trimethylolpropane. Furthermore, polycaprolactones, obtained by ring-opening polymerization of lactones, such as ε-caprolactone, with polyhydric alcohols, can also be used as polyester polyols.

[0107] Representative, non-limiting examples of polyether polyols include polyether polyols obtained by random or block addition of a single alkylene oxide or a mixture of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, cyclohexane oxide, and styrene oxide, to a polyhydric hydroxy compound by using hydroxides, such as lithium hydroxide, sodium hydroxide, or potassium hydroxide, strong basic catalysts, such as alcoholates or alkylamines, and composite metal cyanide complexes, such as metal porphyrins or zinc hexacyanocobaltate complexes; polyether polyols obtained by reacting alkylene oxides with polyamine compounds, such as ethylenediamine; and so-called polymer polyols obtained by polymerizing acrylamide, etc., using these polyether polyols as a medium.

[0108] Representative, non-limiting examples of polyhydroxy compounds include polyols such as diglycerol, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; sugar alcohol compounds such as erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, and rhamnitol; and sugars such as oligosaccharides.

[0109] Acrylic polyols can be obtained, for example, by copolymerizing a polymerizable monomer having one or more active hydrogen atoms in one molecule with another monomer that is copolymerizable with the polymerizable monomer. Examples of acrylic acid esters containing active hydrogen include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate, and examples of methacrylic acid esters include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate; polyvalent active hydrogen-containing (meth)acrylic acid esters include the monoesters of (meth)acrylic acid with triols such as glycerin and trimethylolpropane. Copolymerizable monomers include (meth)acrylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, and glycidyl methacrylate, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid, unsaturated amides such as acrylamide, N-methylolacrylamide, and diacetoneacrylamide, or hydrolyzable silyl group-containing vinyl monomers such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and γ-(meth)acryloxypropyltrimethoxysilane, and other polymerizable monomers such as styrene, vinyltoluene, vinyl acetate, acrylonitrile, and dibutyl fumarate.

[0110] Representative, non-limiting examples of polyolefin polyols include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene having two or more hydroxyl groups, polyisoprene having two or more hydroxyl groups, and hydrogenated polyisoprene having two or more hydroxyl groups.

[0111] In a preferred embodiment, the curable composition comprises at least one aliphatic polyamine. As used herein, "polyamine" refers to a compound having at least two amino groups, each of which contains at least one active hydrogen (NH group) selected from primary amino groups and secondary amino groups. Exemplary aliphatic polyamines include aliphatic primary polyamines, aliphatic secondary polyamines, and combinations thereof. Non-limiting examples of aliphatic primary polyamines include poly(oxypropylene) diamines, such as Huntsman's JEFFAMINE D-230 and JEFFAMINE D-400, poly(oxypropylene) triamines, preferably having a molecular weight in the range of 400 to 5000 grams / mole, 1,4-diaminobutane, 1,2-ethylenediamine, 1,2-diaminopropane, and 1,3-diaminopropane. Non-limiting examples of secondary amines include cyclic aliphatic secondary diamines, non-cyclic aliphatic secondary diamines. Further non-limiting exemplary secondary amines include aspartic acid ester polyamines. Useful cycloaliphatic secondary diamines include two hexyl groups linked by an optionally substituted bridging group, where each of the hexyl rings includes a secondary amine substituent, for example, as described in WO2013 / 188176. Commercially available cycloaliphatic secondary diamines with this structure include those available from Dorffketal as CLEARLINK 1000 and CLEARLINK 3000. In another embodiment, useful cycloaliphatic secondary diamines include a single hexyl ring. Commercially available cycloaliphatic secondary diamines with this structure are available from Huntsman as JEFFLINK 754, for example.

[0112] Useful aliphatic cyclic secondary diamines can be prepared by the reaction of isophorone diamine with a compound having a Michael acceptor group that reduces the nucleophilicity of the resulting secondary amine group. Representative Michael acceptors include acrylonitrile and α,β-unsaturated carbonyl compounds, with acrylonitrile typically being preferred. In some embodiments, the terminal -CN group and the alkylene group of the amine group have at least two carbon atoms. Commercially available aliphatic cyclic secondary diamines having this structure include, for example, HXA CE 425 from Hanson Group and BAXXODUR PC-136 from BASF.

[0113] Exemplary acyclic aliphatic secondary diamines include N,N'-bis(3',3'-dimethylbutan-2-yl)-1,6-diaminohexane, available commercially from Albemarle Corporation under the trade name ETHACURE 90.

[0114] Particularly preferred polyamines are aspartate polyamines. These aspartate polyamines are polyamines with secondary amino groups and can be prepared, for example, by the addition of primary aliphatic diamines to maleic or fumaric acid dialkyl esters, or by the addition of primary aliphatic amines to unsaturated oligoesters or polyesters. Useful aspartate polyamines include, for example, aspartate polyamines having the general formula: [ka] wherein R 7 is a divalent organic group having up to 40 carbon atoms, and R 8 Each independently represents a lower alkyl group having 1 to 4 carbon atoms. For example, R 8 may be methyl, ethyl, propyl, or butyl. Preferably, R 7 R preferably represents a divalent aliphatic group having from 1 to 20 carbon atoms and which can be, for example, branched, unbranched, or cyclic. More preferably, R 7is selected from the divalent hydrocarbon radicals butylene, hexylene, 2,2,4-trimethylhexylene, or obtained by removing an amino group from 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 4,4'-diamino-dicyclohexylmethane, or 3,3-dimethyl-4,4'-diamino-dicyclohexylmethane. 7 is a branched C4 to C12 alkylene group.

[0115] Suitable aspartate amine resins are commercially available from Covestro under the trade names DESMOPHEN NH1420, DESMOPHEN NH1520, and DESMOPHEN NH1220. DESMOPHEN NH1420 resin consists essentially of the following compounds: [ka] DESMOPHEN NH1520 resin consists essentially of the following compounds: [ka] DESMOPHEN NH1220 consists essentially of the following compounds: [ka]

[0116] The aliphatic polyamine(s) may be combined with one or more aromatic polyamines. Suitable solid aromatic polyamines include alkylanilines such as 4,4'-methylenebis(2-isopropyl-6-methylaniline), available from Lonza under the trade name LONZACURE M-MIP A, 4,4'-methylenebis(2,6-diisopropylaniline), available from Lonza under the trade name LONZACURE M-DIPA, 4,4''methylenebis(2-ethyl-6-methylaniline), and 4,4'-methylenebis(3-chloro-2,6-diethylaniline), available from Lonza under the trade name LONZACURE MCDEA.

[0117] One or more isocyanate-reactive compounds, polyisocyanate composition can be used as it is or mixed with organic solvent. Organic solvent is not particularly limited, but organic solvent preferably does not have functional groups that react with hydroxyl group and isocyanate group, and is also preferably fully compatible with polyisocyanate composition. Examples of such organic solvent include, but are not limited to, the following compounds that are commonly used as solvents for coating materials, such as ester compounds, ether compounds, ketone compounds, aromatic compounds, ethylene glycol dialkyl ether compounds, polyethylene glycol dicarboxylate compounds, hydrocarbon solvents, and aromatic solvents.

[0118] The curable coating compositions of the present invention may contain various conventional additives such as catalysts, pigments, leveling agents, antioxidants, UV absorbers, light stabilizers, plasticizers, and surfactants.

[0119] Representative, non-limiting examples of catalysts for promoting polymerization include metal salts such as dibutyltin dilaurate, tin 2-ethylhexanoate, zinc 2-ethylhexanoate, and cobalt salts; and tertiary amines such as triethylamine, pyridine, methylpyridine, benzyldimethylamine, N,N-dimethylcyclohexylamine, N-methylpiperidine, pentamethyldiethylenetriamine, N,N'-endoethylenepiperazine, and N,N'-dimethylpiperazine.

[0120] The curable coating composition of the present invention can be used as a coating material for, but not limited to, roll coating, curtain flow coating, spray coating, bell coating, and electrostatic coating. For example, the curable coating composition of the present embodiment is also useful as a coating material for primer coatings or top and middle coatings for materials such as metals, including steel sheets and surface-treated steel sheets, plastics, wood, films, and inorganic materials. The curable coating composition of the present embodiment is also useful as a coating material for imparting, for example, aesthetics, weather resistance, acid resistance, rust prevention, and chipping resistance to pre-coated metals, including, for example, anti-corrosive steel sheets and automotive coatings. Furthermore, the curable coating composition of the present embodiment is also useful as a urethane starting material for adhesives, pressure-sensitive adhesives, elastomers, foams, and surface treatment agents.

[0121] The present invention further relates to a cured composition obtainable by curing the curable composition according to the present invention.

[0122] The curable compositions according to the present invention can be used in a variety of applications such as the manufacture of polyurethane articles such as paints, coatings, adhesives, foams, and sealants, such as polyurethane vacuum molding resins, polyurethane quick molding resins, elastomer cured polyurethane molding resins, electrical potting compositions, and edge molding compositions; mattresses, shoe soles, gaskets, hoses, flooring, insulation materials, paints, adhesives, sealants, skis, automobile seats, stadium athletic tracks, dashboards, molding compositions, latex-free condoms, and molded flooring.

[0123] The present invention further relates to an article comprising a cured composition according to the present invention.

[0124] The present invention further relates to a coating obtained by curing the curable composition according to the invention, and to the resulting composite article, which comprises at least one substrate, which has on at least a portion of its surface a cured composition comprising at least one polyorganosiloxane (I) according to the invention. Preferred substrates to which the coating composition of the invention can be applied are, for example, selected from the group consisting of metals, plastics, concrete and wood. Particularly preferred are metals, which include all types of metals, including metals that have been pretreated, for example by galvanization.

[0125] While the above description contains many specifics, these specifics should not be construed as limitations on the scope of the invention, but merely as exemplifications of preferred embodiments thereof. Those skilled in the art may envision many other possible variations that are within the scope and spirit of the invention as defined in the claims and its preferred embodiments.

[0126] Embodiments of the present invention include, among others: 1. At least one unit of formula (A): [ka] and at least one unit of formula (B): [ka] and wherein the terminal units of said polyorganosiloxane are selected from formula (C) and formula (D): [ka] and [ka] These units (A) to (D) are linked to each other in such a way that Si-O-Si bonds are formed therebetween, Each n is an average number from about 1 to 250, preferably from 1 to 100, more preferably from 1 to 40, more preferably from 1 to 30; more preferably from 1 to 20, and most preferably from 2 to 10; R 1 are each independently selected from an organic group, preferably selected from an aliphatic or aromatic group, more preferably selected from n-alkyl, iso-alkyl, or tertiary alkyl having up to 30 carbon atoms, alkoxyalkyl having up to 30 carbon atoms, cycloalkyl having 5 to 30 carbon atoms, aryl having 6 to 30 carbon atoms, alkylaryl having 7 to 30 carbon atoms, which groups may additionally contain one or more oxygen, nitrogen, sulfur, and / or fluorine atoms, and R 1 optionally having substituents such as functional groups such as epoxy groups, alkenyl groups such as vinyl groups, acrylate groups, mercapto groups, or poly(C2-C4)-alkylene ethers having up to 500 alkyleneoxy units; R 1 The group preferably contains no aliphatic unsaturation, and R 1 is R3SiO 1 / 2 , R2SiO 2 / 2 , RSiO 3 / 2 and SiO 4 / 2wherein R can be an organic group, preferably R is a methyl group or a phenyl group, and preferably R 1 are CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, C8H 17 - and C 10 H 21 -, alicyclic radicals such as cyclohexylethyl, aryl radicals such as phenyl, tolyl, and xylyl, aralkyl radicals such as benzyl and 2-phenylethyl, CF3CH2CH2-, C4F9CH2CH2-, C6F 13 Formula C such as CH2CH2- m F 2m+1 A monovalent halohydrocarbon radical having the formula CH2CH2- and m having a value of 1 to 10, or C2F5-O (CF2-CF2-O) 1-10 CF2-, F[CF(CF3)-CF2-O] 1-5 -(CF2) 0-2 R is a monovalent hydrocarbon radical, including oxygen-substituted halohydrocarbon radicals such as -, C3F7-OCF(CF3)-, and C3F7-OCF(CF3)-CF2-OCF(CF3)-, more preferably R 1 is methyl or phenyl, and most preferably R 1 is methyl, R 2 are each independently selected from the group consisting of linear alkylene groups having 1 to 10 carbon atoms, branched alkylene groups having 3 to 10 carbon atoms, cycloalkylene groups having 3 to 10 carbon atoms, arylene groups having 6 to 12 carbon atoms, aralkylene groups having 7 to 10 carbon atoms, and allenylene groups having 7 to 10 carbon atoms, preferably methylene, propylene, 2-methylbutylene and 2,2-dimethylbutylene, and more preferably branched alkylene groups having 3 to 10 carbon atoms, such as 2,2-dimethylbutylene, in particular bonded to Si and N atoms, as shown diagrammatically below: [ka] R 3 and R 4 each is independently selected from the group consisting of straight chain alkyl groups having from 1 to 10 carbon atoms, branched chain alkyl groups having from 3 to 10 carbon atoms, and cycloalkyl groups having from 3 to 10 carbon atoms.

[0127] 2. Polyorganosiloxane (I) according to embodiment 1 above, having the formula: [ka] and [ka] which includes the formula: [ka] and at least one group of the formula [ka] The bonds of the terminal silicon atoms in the formula are not shown, And R 1 , R 2 , R 3 , R 4 and n are each as defined above.

[0128] 3. Polyorganosiloxane (I) according to any of the above embodiments 1 and 2, wherein units (A) and (B) are randomly dispersed.

[0129] 4. The polyorganosiloxane (I) according to any of the preceding embodiments 1 to 3, wherein the total average number of units (A) and (B) in the polyorganosiloxane (I) is 1 to 10.

[0130] 5. A polyorganosiloxane (I) according to any one of the preceding embodiments 1 to 4, wherein the molar ratio of units (A) to (B) in the polyorganosiloxane (I) is from about 1:20 to about 20:1, preferably from about 1:10 to about 10:1, more preferably from about 1:5 to about 5:1, more preferably from about 1:2 to about 2:1, and most preferably about 1:1.

[0131] 6. Polyorganosiloxane (I) according to any of the preceding embodiments 1 to 5, wherein the average number of units (A) is from about 0 to about 10, preferably from about 0 to about 5, and the average number of units (B) is from about 0 to about 10, preferably from about 0 to about 5, and preferably the average number of units (A) is from about 1 to 2, and the average number of units (B) is from about 1 to about 2.

[0132] 7. The polyorganosiloxane (I) according to any of the previous embodiments 1 to 6, comprising a mixture of polyorganosiloxanes (I) having the following combinations of end groups: (C)(C), (C)(D)(=(D)(C)), and (D)(D).

[0133] 8. The polyorganosiloxane (I) according to any of the previous embodiments 1 to 7, wherein the mole percentages of units (A) to (D) in the polyorganosiloxane (I) are: About 25 to about 45% of (A): [ka] About 8 to about 28% (B): [ka] Approximately 3 to 23% (C): [ka] and Approximately 20 to 45% (D): [ka] where R 1 , R 2 , R 3 , R 4 and n is as defined above, Based on the sum of the mole percentages for (A) through (D) equaling 100 mole percent.

[0134] 9. The polyorganosiloxane (I) according to any one of the preceding embodiments 1 to 8, wherein R 1 is methyl.

[0135] 10. A polyorganosiloxane (I) according to any one of the preceding embodiments 1 to 9, having the average formula: [ka] where n is as defined above.

[0136] 11. A polyorganosiloxane (I) according to any of the previous embodiments 1 to 10, comprising at least two compounds selected from the following average formulas: [ka] [ka] [ka] [ka] [ka] where n is as defined above.

[0137] 12. A process for producing a polyorganosiloxane (I) according to any one of the preceding embodiments 1 to 11, (i) a silane of formula (a) [ka] and a silane of formula (b) [ka] with a silane of formula (c): [ka] Formula (A 1 ) at least one unit: [ka] and at least one unit of formula (B): [ka] wherein the terminal units of the polyorganosiloxane (II) are represented by the formula (C 1 ) and (D) selected from: [ka] and [ka] R in the formula 1 , R 2 and n are each as defined above, and these units (A) to (D) are bonded to each other in such a way that Si-O-Si bonds are formed therebetween; (ii) reacting the polyorganosiloxane (II) obtained in step (i) with a compound of formula: [ka] R in the formula 3 and R 4 are as defined above, The polyorganosiloxane (I) defined above is obtained.

[0138] 13. An oil-in-water emulsion comprising as an oil component at least one polyorganosiloxane (I) according to any of the preceding embodiments 1 to 11.

[0139] 14. Use of polyorganosiloxane (I) according to any of the preceding embodiments 1 to 11 in the manufacture of polyurethane articles including polyurethane vacuum molding resins, polyurethane rapid molding resins, elastomer cured polyurethane molding resins, electrical potting compositions, edge molding compositions, paints, coatings, adhesives, foams, and sealants; mattresses, shoe soles, gaskets, hoses, flooring, insulating materials, paints, adhesives, sealants, skis, car seats, stadium athletic tracks, dashboards, molding compositions, latex-free condoms, and molded flooring.

[0140] 15. Use of a polyorganosiloxane (I) according to any of the previous embodiments 1 to 11 as an additive for a coating composition, preferably an easy-to-clean coating composition, and as a release agent and anti-graffiti additive for a coating composition.

[0141] 16. Use of a polyorganosiloxane (I) according to any of the previous embodiments 1 to 11 as an additive for a coating composition based on polyurethane resin or acrylic resin.

[0142] 17. Use of a polyorganosiloxane (I) according to any of the previous embodiments 1 to 11 as an additive for a curable composition, preferably a curable composition comprising a polyisocyanate.

[0143] 18. A coating composition comprising at least one polyorganosiloxane (I) as defined in any of the previous embodiments 1 to 11.

[0144] 19. A cured composition obtained by curing a curable composition comprising a polyorganosiloxane (I) as defined in any of the previous embodiments 1 to 11.

[0145] 20. An article comprising the cured composition of embodiment 19 on a substrate. The present invention will now be described in more detail by the following examples. EXAMPLES

[0146] Example 1: Synthesis of aspartic acid ester-functional polysiloxane AEAFP-1 (Example 2 of WO2020 / 079097, comparative product) 3-Aminopropyltriethoxysilane (221 grams, 1 mole, available from Momentive under the trade name Silquest TMA-1100 silane (available under the name Silane A-1100) was charged into a 1000 ml 4-neck flask equipped with stirrer, condenser, thermometer, and dropping funnel. From the dropping funnel, 260 grams of hydroxyl-terminated polydimethylsiloxane with -OH content of 4.4 mmol / g or 1.15 moles of -OH were added to the aminosilane over 30 minutes starting from room temperature. During the addition feed, the temperature rose to 31°C. After the addition feed, the mixture was heated to 70°C and held at 70°C for 2 hours. The ethanol formed was then removed at 150°C and 20 mbar. Yield: 450 grams of low viscosity amino-functional polysiloxane (AFP-1) with an amine content of 2.5 mmol N / g as determined by titration with 1 molar hydrochloric acid. In the next step, the amino-functional polysiloxane AFP-1 (610 grams, 2 moles of amino groups) was charged into a 2000 ml 4-neck flask equipped with a stirrer, condenser, thermometer, and dropping funnel. Diethyl maleate (340 grams, 2 moles) was added dropwise from the dropping funnel to the amino-functional polysiloxane AFP-1 during a period of 4 hours while maintaining the reaction temperature at 20-30°C. Then, the temperature of the flask was raised to 80°C and the reaction mixture was maintained at this temperature for 4 hours. Finally, the reaction mixture was cooled and used in subsequent experiments without further purification. The following general structure of the product (AEAFP-1) is shown: 1 H and 29 This was confirmed by Si NMR analysis. [ka] wherein n1 is from about 4 to about 8.

[0147] Example 2: Synthesis of aspartic acid ester functional polysiloxane AEAFP-2 (present invention) Into a 2-liter flask equipped with a J-KEM temperature controller, stir bar, and cold finger reflux distillation unit was added 950 g of silanol terminated polydimethylsiloxane (2.0 moles, Momentive, containing 7.15% -OH groups), 163.6 g of methyltrimethoxysilane (1.2 moles, Momentive A-1630), 215.2 g of γ-aminopropyltrimethoxysilane (1.2 moles, Momentive A-1110), and 0.1 g of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene, Aldrich). With stirring, the flask was heated to approximately 90° C. to initiate the reaction, as evidenced by bubbling or reflux. After constant reflux, methanol began to collect in the receiver. Once a reasonable amount of methanol was collected and no more methanol was coming out, a vacuum was applied to capture more volatiles in a collection bottle, gradually maximizing the vacuum until no more volatiles were coming out. The product in the reaction flask was collected as AFP-2 intermediate. In the next step, 990 g of AFP-2 sample (amine equivalent is 990 grams per mole of NH2 group) was charged to a 2-liter flask equipped with a heating mantle, J-KEM temperature controller, mechanical stirrer, dropping funnel, and cold water condenser. Then, 189 g of diethyl maleate (Aldrich, 97% purity) was added dropwise to the flask from the dropping funnel under stirring at room temperature. After the addition, the reaction flask was heated to 80° C. and the reaction was continued for at least 3 hours. Then, the heating was stopped, the flask was allowed to cool to room temperature, and the reaction product was collected as AEAFP-2 resin and used as such in the following step. The following average general structure of the product (AEAFP-2) is shown: 1 H and 29 This was confirmed by Si NMR analysis. [ka] where n is an average value of from about 4 to about 7.

[0148] Example 3: Preparation of aspartic acid ester functional polysiloxane emulsion em1-AEAFP-2 (present invention) In a flask equipped with a mechanical stirrer and a heated water bath, 40 g of the solvent Texanol (Aldrich) was charged, along with 8.4 g of Brij C2 (Aldrich) and 5.6 g of Brij S100 (Aldrich), the latter two products being nonionic surfactants. The water bath was heated to melt or dissolve the two surfactants. After the surfactants were completely melted, 140 g of AEAFP-2 sample (from Example 2) was mixed in. The mixture was cooled to below 30° C. under efficient stirring and 206 g of deionized (DI) water was charged. The mixture was stirred for an additional 30 minutes. Mixing was stopped and the mixture was poured into an APV homogenizer. After three passes at a pressure setting of 60 / 600 bar, ∼400 g of stable em1-AEAFP-2 emulsion (35 wt% active) was obtained.

[0149] Example 4: Preparation of aspartic acid ester functional polysiloxane emulsion em2-AEAFP-2 (present invention) In a flask equipped with a mechanical stirrer and heated water bath, 146 g DI water, 20.7 g Stepanol WA-EXTRA (29%, Stepan), and 23.3 g Stenol CS-230 (26%, Stepan) were added. The mixture was stirred for 10 minutes at 35-40°C, then 200 g AEAFP-2 sample (from Example 2) was mixed and the mixture was stirred for an additional 30 minutes. Mixing was stopped and the mixture was poured into an APV homogenizer. After 3 passes at a pressure setting of 50 / 500, ~400 g of stable em2-AEAFP-2 emulsion (50% activity) was obtained.

[0150] Example 5: Formulation and Application of Solvent-Based (SB) Anti-Graffiti Two-Component (2K) Polyurethane Topcoat 2K solvent-based polyurethane anti-graffiti coatings were prepared by cold blending a commercial white topcoat material with various anti-graffiti additives listed in Table 1. The anti-graffiti additives were used at a concentration of 5 wt% based on the total amount of ready-to-use formulation (paint with activator). After mixing for 1 hour, the white topcoat was activated with a commercial aliphatic polyisocyanate crosslinker (2:1 paint:activator ratio). After mixing the paint for 5 minutes at 150-300 rpm, the resulting paint system was transferred to a conventional pneumatic gravity-fed manual spray gun equipped with a 1.6 mm spray nozzle. The spray pressure was adjusted to 2.0-2.5 bar. The as-applied film thickness of the coating system was adjusted with a laboratory paint thickness gauge. The topcoat system was applied to cold-rolled steel substrate panels (Gardobond The coatings were sprayed on a 100% acrylic (OC) substrate. Prior to spraying, the substrate panels were cleaned with a paper cloth soaked in xylene and then with a paper cloth soaked in isopropyl alcohol. After spraying, the liquid coating films were cured at room temperature (50% relative humidity (RH)) for 14 days. The dry film thickness of the coating system was set to 80-85 micrometers.

[0151] [Table 1]

[0152] Example 6: Formulation and Application of Water-Based (WB) Anti-Graffiti 2K Polyurethane Topcoat The formulation of a white 2K polyurethane topcoat system was carried out according to the general recipe outlined in Table 2. For this, the components in positions 1-8 were charged into a double jacketed mixing vessel equipped with a Coles Blade Dispersion Mixer and stirred at 300 rpm. After charging the pigment, the mixture was dispersed at 1000 rpm for 30 minutes. During this mixing and dispersing process, the mixing vessel was cooled to 35-55°C. Then, 1 kilogram of zirconia beads (1.2-1.4 mm diameter) was charged into the resulting premix and milled at 1000 rpm for 45 minutes. During this mixing and milling process, the mixing vessel was cooled to 35-55°C. After the process was completed, the liquid phase of the resulting mixture was separated from the zirconia beads and the components in positions 9-14 were charged into the resulting titanium dioxide dispersion. After charging, the mixture was stirred at 300-500 rpm for 30 minutes. The resulting white topcoat (component A) was carefully collected and stored in a dry and dark place until use. Separate from the white topcoat, the ingredients in positions 15-17 were mixed under nitrogen by stirring in a 3-neck glass flask equipped with a mechanical stirrer and nitrogen inlet. The resulting polyisocyanate crosslinker (component B) was stored in a dry, dark place under nitrogen until use.

[0153] [Table 2]

[0154] 2K water-based polyurethane anti-graffiti coatings were prepared by cold blending the white topcoat material (Table 2, component A) with various anti-graffiti additives listed in Table 3. The anti-graffiti additives were used at a concentration of 2 wt% (calculated as 100% solids of the anti-graffiti additive) based on the total amount of ready-to-use formulation (paint with activator). After mixing for 1-72 hours, the white topcoat was activated with an aliphatic polyisocyanate crosslinker (Table 2, component B). After mixing the paint with the activator for 5 minutes at 150-300 rpm, the resulting paint system was transferred to a conventional pneumatic gravity-fed manual spray gun equipped with a 1.6 mm spray nozzle. The spray pressure was adjusted to 2.0-2.5 bar. The as-applied film thickness of the coating system was adjusted with a laboratory film thickness gauge. The topcoat system was applied to cold-rolled steel substrate panels (Gardobond The coatings were sprayed onto a 100% acrylic resin (HDG7 OE). Prior to spraying, the substrate panels were cleaned with a paper cloth soaked in xylene and then with a paper cloth soaked in isopropyl alcohol. After spraying, the liquid coating films were cured at room temperature (50% relative humidity (RH)) for 14 days. The dry film thickness of the coating system was set to 75-80 micrometers.

[0155] [Table 3]

[0156] Example 7: Test Method The mechanical, chemical and physical properties of the tested coating systems were evaluated using the following test methods and procedures: (i) cross-hatch adhesion according to EN ISO 2409; wet cross-hatch adhesion according to DIN EN ISO 6270-2, measured after conditioning of the test specimens in a condensate humidity chamber; (ii) cylindrical mandrel bending test according to DIN EN ISO 6860; (iii) impact resistance test of the front and back side according to DIN EN ISO 6272; (iv) chemical resistance test using a 0.5 M solution of sulfuric acid. In this test, the tested coatings were exposed to etching with a sulfuric acid solution (one drop) at 50° C. for 30, 60 and 90 minutes. After exposure, the drop was removed and the test surfaces were washed with demineralized water and inspected for defects. The test was assigned a score as follows: R10 - no visible etch marks; R9 - slight marks but no fingertip palpable irregularities; R8 - marks and palpable irregularities; R6 - marks and matte white shiny spots (cloudiness); R4 - onset of deterioration, white spots of obvious damage to the coating; R2 - blistering; R0 - coating peeling. The final score was calculated as the sum Σ of the Rs at 30, 60 and 90 minutes; (v) contact angle measurements were made with a Cruz contact angle meter using water and methylene iodide; (vi) gloss was measured according to DIN EN ISO 2813; (vii) QUV-B accelerated weathering test was according to ASTM G-154; (viii) Erichsen cupping test was according to DIN 50101. (ix) To study the anti-graffiti performance, the test specimens were painted with graffiti nitrocellulose paint from a spray can (four colors were used: blue, red, green, and black). The sprayed graffiti paint was then dried at room temperature. The peeling property was tested by rubbing an adhesive tape (Tesa 4651) onto the surface of the test panel and then slowly peeling the adhesive tape off. The tests were performed 1 hour, 24 hours, and 240 hours after the graffiti paint was applied. The anti-graffiti property was evaluated based on how much graffiti paint was removed from the test surface.The following scores were used to rank the anti-graffiti performance: 3 - complete removal of paint; 2 - partial (≧50%) removal of paint; 1 - slight (≦50%) removal of paint; 0 - no removal of paint. The appearance of the coating systems was evaluated visually. (x) Characterization of the coating thickness was performed according to the general principles of the DIN EN ISO2808:2019-12 standard.

[0157] Example 8: Investigation of a solvent-based (SB) polyurethane anti-graffiti coating The results of the testing studies of two-component (2K) solvent-based (SB) polyurethane (PUR) white topcoats modified with various anti-graffiti additives are summarized in Table 4.

[0158] [Table 4]

[0159] The experimental evaluation results show that the silicone aspartate structure AEAFP-2 from Example 2 has significantly improved anti-graffiti performance compared to the polysiloxane aspartate structure from Example 1. In particular, the modification of solvent-based polyurethane paints with the AEAFP-2 additive results in a more efficient, durable, anti-strip, anti-graffiti coating system.

[0160] Example 9: Study of Water-Based (WB) Polyurethane (PUR) Anti-Graffiti Coatings The results of testing studies of 2K water-based polyurethane white topcoats modified with various anti-graffiti additives are summarized in Table 5.

[0161] [Table 5]

[0162] The experimental evaluation results show that the silicone aspartic acid structure em1-AEAFP-2 in emulsion form according to Example 3 has significantly improved compatibility with water-reducible polymers compared to the polysiloxane aspartic acid structure of Example 2. In particular, the modification of water-based polyurethane paint with the em1-AEAFP-2 additive results in a coating system with good flowability and smoothness, and a coating system without unevenness or orange peel.

[0163] Example 10 Process 1 In a 500 ml flask equipped with a heating mantle, J-KEM temperature controller, mechanical stirrer, addition funnel, and cold water condenser, 179.3 g of gamma-aminopropyltrimethoxysilane (Momentive A-1110) was added. Then, with stirring at room temperature, 189.2 g of diethyl maleate (97%, Aldrich) was added dropwise from the addition funnel to the flask. After addition was complete, the reaction was heated to 80° C. and allowed to continue for 5 hours. The reaction was allowed to cool to room temperature, resulting in an aspartate functionalized silane.

[0164] Process 2 In the next step, a 1-liter flask equipped with a J-KEM temperature controller, stir bar, and cold finger reflux distillation unit was charged with 475 g of silanol terminated polydimethylsiloxane (Momentive, 1.0 mole, containing 7.15% -OH groups), 142 g of γ-glycidoxypropyltrimethoxysilane (Momentive A-187), 221 g of the silane from step 1, and 0.5 g of DBU (Aldrich 1,8-diazabicyclo-[5.4.0]-undec-7-ene). With stirring, the flask was heated to approximately 90° C. to initiate the reaction, which was evidenced by bubbling or reflux. After constant reflux, methanol was collected in a receiver. Once no more methanol was distilling, a vacuum was applied to remove additional volatiles, gradually maximizing the vacuum until no more material was collected. The product epoxy and aspartate functional polysiloxane remained in the reaction flask. A stable emulsion of epoxy and aspartate functional polysiloxane was also prepared in the same manner as described in Example 4.

[0165] Example 11 500 g of AEAFP-2 (sample prepared in Example 2 of the present invention) was added to a 1 liter flask equipped with a heating mantle, J-KEM temperature controller, mechanical stirrer, dropping funnel, and cold water condenser. 88.7 g of γ-isocyanatopropyltrimethoxysilane (Momentive A-Link35) was then added dropwise from the dropping funnel with stirring at room temperature. After the addition was complete, the reaction was stirred at room temperature for an additional 2 hours to yield the product of Example 11.

Claims

1. At least one unit of formula (A): 【Chemical 104】 and at least one unit of formula (B): 【Chemistry 105】 wherein the terminal units of said polyorganosiloxane are selected from formula (C) and formula (D): 【Chemistry 106】 and 【Chemistry 107】 These units (A) to (D) are interconnected in such a way that Si—O—Si bonds are formed therebetween, and Each n is an average number from about 1 to 250, preferably 1 to 100, more preferably 1 to 40, more preferably 1 to 30; more preferably 1 to 20, and most preferably 2 to 10; R １ are each independently selected from an organic group, preferably selected from an aliphatic or aromatic group, more preferably selected from n-alkyl, iso-alkyl, or tertiary alkyl having up to 30 carbon atoms, alkoxyalkyl having up to 30 carbon atoms, cycloalkyl having 5 to 30 carbon atoms, aryl having 6 to 30 carbon atoms, alkylaryl having 7 to 30 carbon atoms, which groups may additionally contain one or more oxygen, nitrogen, sulfur, and / or fluorine atoms, and R １ is optionally an epoxy group, an alkenyl group such as a vinyl group, an acrylate group, a mercapto group, or a poly(C ２ -C ４ )-having a substituent such as a functional group such as an alkylene ether, R １ The group preferably contains no aliphatic unsaturation, and R １ is R ３ SiO １／２ , R ２ SiO ２／２ , RSiO ３／２ and SiO ４／２ wherein R can be an organic group, preferably R is a methyl group or a phenyl group, and preferably R １ is CH ３ -, CH ３ CH ２ -, CH ３ CH ２ CH ２ -, (CH ３ ) ２ CH-, C ８ H １７ - and C １０ H ２１ -, alicyclic radicals such as cyclohexylethyl, aryl radicals such as phenyl, tolyl, xylyl, aralkyl radicals such as benzyl and 2-phenylethyl, CF ３ CH ２ CH ２ -, C ４ F ９ CH ２ CH ２ -, C ６ F １３ CH ２ CH ２ Formula C such as - ｍ F ２ｍ＋１ CH ２ CH ２ - and m has a value of 1 to 10, or C ２ F ５ -O(CF ２ -CF ２ -O) １－１０ CF ２ -, F[CF(CF ３ )-CF ２ -O] １－５ -(CF ２ ) ０－２ -, C ３ F ７ -OCF (CF ３ )- and C ３ F ７ -OCF (CF ３ )-CF ２ -OCF (CF ３ )-, and more preferably R １ is methyl or phenyl, and most preferably R １ is methyl, R ２ are each independently selected from the group consisting of straight chain alkylene groups having 1 to 10 carbon atoms, branched chain alkylene groups having 3 to 10 carbon atoms, cycloalkylene groups having 3 to 10 carbon atoms, arylene groups having 6 to 12 carbon atoms, aralkylene groups having 7 to 10 carbon atoms, and allenylene groups having 7 to 10 carbon atoms, preferably methylene, propylene, 2-methylbutylene, and 2,2-dimethylbutylene, and more preferably branched chain alkylene groups having 3 to 10 carbon atoms, such as 2,2-dimethylbutylene, particularly bonded to Si and N atoms, as shown schematically below: 【Chemistry 108】 R ３ and R ４ are each independently selected from the group consisting of straight chain alkyl groups of 1 to 10 carbon atoms, branched chain alkyl groups having 3 to 10 carbon atoms, and cycloalkyl groups having 3 to 10 carbon atoms; and R ５ is hydrogen, and the formula: 【Chemistry 109】 Preferably R 5 is hydrogen, wherein x is 1 to 3, preferably 3; R １ are each independently selected from the organic groups defined above, and R ６ is an alkylene group bonded to the silicon and nitrogen atoms via a carbon atom, which can be substituted by oxygen (to form a carbonyl group) or one or more of the carbon atoms can be substituted by —O—, —S—, —NH—, and —NR ７ -, where R ７ represents an alkyl group.

2. At least one unit of formula (A): 【Chemical 110】 and at least one unit of formula (E): 【Chemistry 111】 wherein the terminal units of the polyorganosiloxane are selected from formula (C) and formula (F): 【Chemistry 112】 and 【Chemistry 113】 These units (A), (C), (E) and (F) are interconnected in such a way that Si—O—Si bonds are formed therebetween, wherein: n is as defined in claim 1; x is as defined in claim 1; R １ From R ７ are each as defined in claim 1, and R ８ is R １ group, with the proviso that R ８ 2. The polyorganosiloxane (I) according to claim 1, wherein at least one of the groups represents an epoxy functional group.

3. At least one unit of formula (A): 【Chemistry 114】 and at least one unit of formula (G): 【Chemical 115】 wherein the terminal units of the polyorganosiloxane are selected from formula (C) and formula (H): 【Chemistry 116】 and 【Chemistry 117】 These units (A), (C), (G) and (H) are interconnected in such a way that Si—O—Si bonds are formed therebetween, wherein: n is as defined in claim 1; x is as defined in claim 1, and R １ From R ７ and each are as defined in claim 1.

4. At least one group of the following formula: 【Chemistry 118】 and 【Chemical 119】 which includes: 【Chemical 120】 and at least one group of the formula: 【Chemistry 121】 The bond of the terminal silicon atom in the formula is not shown, And R １ , R ２ , R ３ , R ４ and n are each as defined in claim 1.

5. At least one group of the following formula: 【Chemistry 122】 and [[Chemical 123]] which includes: 【Chemistry 124】 and at least one group of the formula: 【Chemistry 125】 The bond of the terminal silicon atom in the formula is not shown, And R １ , R ２ , R ３ , R ４ , R ５ 2. A polyorganosiloxane (I) according to claim 1, wherein n and n are each as defined in claim 1, and R 8 is selected from R 1 groups, with the proviso that at least one of R 8 represents an epoxy functional group.

6. the total average number of units (A) and (B), or units (A) and (E), or units (A) and (G) in polyorganosiloxane (I) is 1 to 10; or The molar ratio of units (A) and (B) or units (A) and (E) or units (A) and (G) in polyorganosiloxane (I) is from about 1:20 to about 20:1, preferably from about 1:10 to about 10:1, more preferably from about 1:5 to about 5:1, more preferably from about 1:2 to about 2:1, and most preferably about 1:1; or The polyorganosiloxane (I) according to claim 1, wherein the average number of units (A) is from about 0 to about 10, preferably from about 0 to about 5, and the average number of units (B) or (E) or (G) is from about 0 to about 10, preferably from about 0 to about 5, and preferably the average number of units (A) is from about 1 to 2, and the average number of units (B) or (E) or (G) is from about 1 to about 2.

7. The polyorganosiloxane (I) according to claim 1, comprising a mixture of polyorganosiloxanes (I) having the following combination of end groups: (C) (C), (C)(D) (=(D)(C)), and (D) (D), or (C) (C), (C)(F) (=(F)(C)), and (F) (F), or (C) (C), (C)(H) (=(H)(C)), and (H) (H).

8. The mole percentages of units (A) through (H), or units (A) through (D) in polyorganosiloxane (I) are: About 25 to about 45% of (A): 【Chemistry 126】 Preferably 【Chemistry 127】 About 8 to about 28% of (B): 【Chemistry 128】 or about 8 to about 28% of (E): 【Chemistry 129】 or about 8 to about 28% (G): 【Chemistry 130】 About 3 to 23% of (C): 【Chemistry 131】 Preferably 【Chemistry 132】 and about 20 to 45% (D): 【Chemistry 133】 or about 20 to 45% (F): 【Chemistry 134】 or about 20 to 45% (H): 【Chemistry 135】 where R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , x and n are each as defined in claim 1, and R 8 is selected from R 1 groups, with the proviso that at least one R 8 represents an epoxy functional group; 2. The polyorganosiloxane (I) according to claim 1, based on the sum of the mole percents for (A) through (H) or (A) through (D) adding up to 100 mole percent.

9. Average formula: 【Chemistry 139】 2. The polyorganosiloxane (I) according to claim 1, having the formula:

10. It comprises at least two compounds selected from the following average formula: [Chemical 140] 【Chemistry 141】 【Chemistry 142】 【Chemistry 143】 【Chemistry 144】 2. Polyorganosiloxane (I) according to claim 1, wherein n is as defined in claim 1.

11. A process for producing a polyorganosiloxane (I) according to any one of claims 1 to 10, comprising: (i) a silane of formula (a) 【Chemistry 145】 and a silane of formula (b) 【Chemistry 146】 with a silane of formula (c): 【Chemistry 147】 Formula (A １ ) at least one unit of: 【Chemistry 148】 and at least one unit of formula (B): 【Chemistry 149】 wherein the terminal units of the polyorganosiloxane (II) are represented by the formula (C １ ) and (D): [Chemical 150] and 【Chemistry 151】 In the formula R １ , R ２ and n are each as defined in claim 1, and these units (A) to (D) are bonded to each other in such a way that Si—O—Si bonds are formed therebetween; (ii) reacting the polyorganosiloxane (II) obtained in step (i) with a compound of the formula: 【Chemistry 152】 In the formula R ３ and R ４ are each as defined in claim 1, and optionally an isocyanate-functional alkoxysilane, preferably of the formula 【Chemistry 153】 wherein x and R 1 are as defined in claim 1, R 9 preferably represents an alkylene group having 1 to 3 carbon atoms, and most preferably R 9 represents a —CH 2 —CH 2 —CH 2 — group, introducing an R 5 group different from hydrogen, A process for obtaining polyorganosiloxane (I).

12. in the manufacture of paints, coatings, adhesives, foams, sealants, including polyurethane vacuum forming resins, polyurethane rapid molding resins, elastomer-cured polyurethane molding resins, electrical potting compositions, edge molding compositions; in the manufacture of polyurethane articles, including mattresses, shoe soles, gaskets, hoses, flooring, insulating materials, paints, adhesives, sealants, skis, automobile seats, stadium tracks, dashboards, molding compositions, latex-free condoms, and molded flooring; or as additives for coating compositions, preferably easy-to-clean coating compositions, and as release and anti-graffiti additives for coating compositions, or as an additive for polyurethane or acrylic resin based coating compositions, or 11. Use of a polyorganosiloxane (I) according to any one of claims 1 to 10 as an additive for a curable composition, preferably a curable composition comprising a polyisocyanate.

13. A coating composition comprising at least one polyorganosiloxane (I) according to any one of claims 1 to 10.

14. A cured composition obtainable by curing a curable composition comprising a polysiloxane (I) according to any one of claims 1 to 10.

15. 15. An article comprising the cured composition of claim 14 on a substrate.

Images