Polymers, compositions, and their uses

Abstract

The present invention relates to polymers obtained by polymerization between at least (A) or a combination of (A) and (B); and at least two selected from (C), (D), (E), optionally (F) and combinations thereof. Furthermore, an object of the present invention is compositions comprising such polymers, and the use of such polymers or compositions as water-repellent and / or oil-repellent and / or anti-fouling and / or anti-graffiti agents for substrates.

Description

Technical Field

[0001] The present invention belongs to the fields of water and / or oil repellents, antifouling agents and / or anti-writing agents.

Background Art

[0002] Fluorinated materials have become mainstream in the antifouling applications of construction materials, textiles, leather and paper due to their excellent hydrophobicity and oleophobicity.

[0003] To date, most of the most excellent performance antifouling solutions still rely on fluorine chemistry. Highly water- and oil-repellent coating films are widely used worldwide in daily life as well as in industrial and research fields such as self-cleaning performance, anti-freezing performance and anti-biofouling performance.

[0004] The environmental persistence, degradation and changes caused by fluorinated compounds have raised concerns about the medium- and long-term effects on human health and wildlife. For these reasons, efforts to reduce the impact of such compounds are increasing.

[0005] Fluorine-containing substances and fluoropolymers in various applications may release substances such as perfluoroalkyl carboxylates and perfluoroalkyl sulfonates into the environment. Therefore, the ECHA (European Chemicals Agency) has established many strict regulations regarding fluorine-containing substances.

[0006] Currently regulated fluorine compounds are perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorocarboxylic acids (C9 - C14 PFCAs) having a chain consisting of 9 to 14 carbon atoms, their salts and related substances. ​​The use of other fluorinated compounds—undecafluorohexanoic acid (PFHxA), perfluorohexanesulfonic acid (PFHxS), perfluorinated compounds—CF2 (PFAS), and their salts and compounds derived therefrom—is expected to be restricted or banned in the near future. Such substances can actually persist in the environment and ecosystems and are suspected of being highly toxic.

[0008] WO2016 / 163435A1, EP2794725B1, and WO2009 / 065004A2 are prior art. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] International Publication No. 2016 / 163435A1 [Patent Document 2] European Patent No. 2794725 [Patent Document 3] International Publication No. 2009 / 065004A2 [Overview of the project] [Problems that the invention aims to solve]

[0010] Following a long period of intensive research and development activities, the applicant has developed polymers and compositions that can adequately address existing limitations, shortcomings, and problems. In particular, the applicant has developed novel non-fluorinated polymers ("fluorine-free") that can reduce or avoid environmental and health problems associated with fluorine chemistry without sacrificing hydrophobic and / or oleophobic properties. [Means for solving the problem]

[0011] Therefore, the object of the present invention is a polymer having the features of the appended claims.

[0012] Furthermore, an object of the present invention is a composition comprising the polymer having the features of the appended claims.

[0013] Furthermore, an object of the present invention is the use of the polymer or the composition having the features of the appended claims.

[0014] An object of the present invention is, at least, (A) or a combination of (A) and (B); and at least one selected from (C), (D), (E), optionally (F), and combinations thereof; and a polymer obtained by polymerization between Here, (A) is a compound of general formula (A.I) or (A.II), or a mixture of (A.I) and (A.II):

Chemical formula

[0015] In this specification, the terms "(meth)acrylic" and "(meth)acrylate," or similar terms, mean "acrylic or methacrylic" and "acrylate or methacrylate," respectively. Furthermore, the compounds listed herein include relative isomers, even if not explicitly indicated.

[0016] Preferably, the polymer is obtained by polymerization between at least the following: (A) or a combination of (A) and (B); and (C), (D), (E), (F) (optionally), and at least two, at least three, or at least four selected from combinations thereof.

[0017] More preferably, the polymer is obtained by polymerization of at least the following: (A) and (C), or a combination of (A), (B), and (C); and (D), (E), (F) (optionally), and at least one, at least two, or at least three selected from combinations thereof.

[0018] (A) or (A) and (B) have structural features suitable for exhibiting high levels of surface activity comparable to those generated by short-chain perfluorinated groups, while avoiding the drawbacks associated with fluorine chemistry.

[0019] (C) comprises one or more crosslinkable groups.

[0020] A crosslinkable group is a functional group that can react with a substrate and / or an added polyfunctional compound. Such crosslinkable groups may be carboxylic acid groups, ethylenically unsaturated groups, hydroxyl groups, amino groups, N-alkylolamide groups, isocyanates, or protected isocyanate groups.

[0021] Preferably, (C) is selected from the group consisting of glycidyl (meth)acrylate, (meth)acrylic acid, itaconic acid, vinyl (meth)acrylate, allyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, poly(ethylene glycol) mono(meth)acrylate, N-hydroxymethyl (meth)acrylamide, N-methoxymethylacrylamide, N-isopropoxymethylacrylamide, 2-carboxyethyl acrylate, and mixtures thereof.

[0022] (D) must have the function of improving water repellency, while also possessing properties such as not significantly impairing oil repellency.

[0023] (D) is preferably selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, eptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isobornyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, tridecyl (meth)acrylate, behenyl (meth)acrylate, (meth)acrylate with a longer chain than C18, and mixtures thereof.

[0024] More preferably, (D) is selected from the group consisting of decyl (meth)acrylate, isobornyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, tridecyl (meth)acrylate, behenyl (meth)acrylate, and mixtures thereof.

[0025] (E), when properly formulated, can be used to adjust water-repellent and oil-repellent properties. In aqueous compositions, the monomer can be added as a salt to dissolve the product in the aqueous solution (compatibilization function).

[0026] Preferably, (E) is selected from the group consisting of 2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, and mixtures thereof.

[0027] Possible functions of (F) include, for example, a fixative used particularly in the textile sector. Nevertheless, among monomers (F), N-vinylpyrrolidinone may have different or additional functions compared to acting as a fixative, such as improving water repellency.

[0028] Preferably, (F) is selected from N-vinylpyrrolidinone, vinyl chloride, vinylidene chloride, and mixtures thereof.

[0029] According to a preferred embodiment: (A) is a compound of general formula (AI), where R3 is preferably methyl; (B) is a compound of general formula (BI), where R1 is preferably methyl; (C) is selected from 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, glycidyl methacrylate, acrylic acid, methacrylic acid, 2-carboxyethyl acrylate and mixtures thereof; (D) is at least one selected from the group consisting of decyl (meth)acrylate, isobornyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, tridecyl (meth)acrylate, behenyl (meth)acrylate, (meth)acrylates longer than C18, and mixtures thereof; more preferably, (D) is stearyl (meth)acrylate, tridecyl methacrylate, or a mixture thereof, or behenyl (meth)acrylate, and even more preferably, (D) is stearyl (meth)acrylate or behenyl (meth)acrylate; In the compound of general formula (EI), Rp is an alkylene radical having 2 to 5 carbon atoms, R5 and R6 are independently hydrogen or a linear or branched alkyl radical having 1 to 5 carbon atoms, and more preferably (E) is selected from 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl acrylate, 2-diethylaminoethyl methacrylate, and mixtures thereof.

[0030] In this specification, the term "behenyl (meth)acrylate" means the following mixture: 40% to 44% by weight of octadecyl acrylate (CAS No. 4813-57-4) and / or octadecyl methacrylate (CAS No. 32360-05-7); • 9% to 13% by weight of eicosyl acrylate (CAS No. 48076-38-6) and / or eicosyl methacrylate (CAS No. 45294-18-6); 42% to 46% by weight of docosyl acrylate (CAS No. 18299-85-9) and / or docosyl methacrylate (CAS No. 16669-27-5); • 0.3% to 1.5% by weight of hexadecyl acrylate (CAS No. 13402-02-3) and / or hexadecyl methacrylate (CAS No. 2495-27-4).

[0031] Preferably, the behenyl (meth)acrylate comprises or consists of a mixture of the indicated amount of the acrylate.

[0032] Preferably, with respect to the amounts of (A) to (F) in the polymer (the following amounts are expressed as weight % of each compound relative to the total weight of (A) to (F)): (A) is present in an amount of 10% to 90% by weight, preferably 30% to 80% by weight, and more preferably 45% to 75% by weight; (B) is present in an amount of 0% to 30% by weight, preferably 2% to 23% by weight, and more preferably 5% to 22% by weight; (C) is present in an amount of 0.1% to 30% by weight, preferably 1% to 20% by weight, and more preferably 1.5% to 17% by weight; (D) is present in an amount of 0% to 50% by weight, preferably 3% to 35% by weight, and more preferably 7% to 33% by weight; (E) is present in an amount of 0% to 25% by weight, preferably 2% to 20% by weight, and more preferably 3% to 15% by weight; (F) is present in an amount of 0% to 15% by weight, preferably 0% to 10% by weight, and more preferably 0% to 8% by weight.

[0033] According to a preferred embodiment, the polymer comprises or consists of (AI), optionally (BI), (C), optionally (D), optionally (E), and optionally (F), preferably comprising or consisting of (AI), optionally (BI), (C), (D), optionally (E), and optionally (F), more preferably comprising or consisting of (AI), (BI), (C), and (D), optionally comprising or consisting of (E) and optionally (F).

[0034] In a particularly preferred embodiment, the polymer contains or consists of the following compounds in the amounts shown in Table 1.A below.

[0035] [Table 1.A]

[0036] More preferably, the polymer contains or consists of the following compounds in the amounts shown in Table 1.B, Table 1.C, Table 1.D, or Table 1.E below.

[0037] [Table 1.B]

[0038] [Table 1.C]

[0039] [Table 1.D]

[0040] [Table 1.E]

[0041] The polymerization is preferably a radical reaction in an organic or aqueous liquid phase (preferably in a dispersion or (micro)emulsion), in an inert atmosphere (e.g., a nitrogen atmosphere), and in the presence of at least one organic or inorganic peroxide or hydroperoxide type radical initiator, azo, or ultraviolet-activated initiator, and optionally a redox initiator.

[0042] Preferably, the radical initiator is selected from the group consisting of benzoyl peroxide, lauroyl peroxide, acetyl peroxide, succinyl peroxide, tert-thiobutyl perpivalate; cumene hydroperoxide, t-butyl hydroperoxide, t-amyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide; ammonium persulfate, potassium persulfate; azo-2,2-bis(isobutyronitrile), azo-2,2-bis-(2,4-dimethyl-4-methoxy-valeronitrile), azo-4-4-bis-(4-cyanopentanoic acid), azodicarbonamide; benzophenone, 2-methylanthraquinone or 2-chlorothioxanthone, and mixtures thereof.

[0043] More preferably, the radical initiator is 2,2'-azobis(isobutyronitrile) (AIBN) or 2,2'-azobis(2-methylpropionamidine) dihydrochloride.

[0044] If present, the redox initiator is primarily used at the end of the process to complete the reaction and reduce the concentration of unreacted monomers.

[0045] Preferably, the redox initiator is a mixture of a sodium salt of hydroxymethylphosphate, a disodium salt of 2-hydroxy-2-sulfinatoacetic acid, and an oxidizing agent such as hydrogen peroxide, tert-butyl hydroperoxide, or ammonium persulfate. Such mixtures can be obtained, for example, as Bruggolite® E28 (Brugemann Chemicals; Heilbronn; Germany).

[0046] The amount of the radical initiator is preferably 0.01% to 5% by weight, and more preferably 0.1% to 1.5% by weight, relative to the total weight of compounds (A) to (F).

[0047] The polymerization temperature is preferably 40°C to 90°C, preferably 45°C to 60°C, or 60°C to 85°C.

[0048] According to one embodiment, downstream of polymerization, one or more of the technical additives described below are uniformly mixed with the polymer in the liquid phase.

[0049] According to another embodiment, a second solvent is added downstream of polymerization in the presence of a first organic solvent, and the first organic solvent is then at least partially removed by distillation. The second solvent preferably has a high boiling point (T e The temperature must be >70°C (suitable for safe transport and / or application) and retain the polymer in the solution / emulsion. The second solvent may be an organic solvent or water.

[0050] If the liquid phase is aqueous, one or more surfactants and optionally one or more organic cosolvents may be used in polymerization. As an example, the surfactants are selected from the following, which can ultimately be used individually or in combination: - Nonionic surfactants; - Cationic surfactant; - Anionic surfactant; - Amphoteric surfactants (e.g., dodecylbetaine or aminocarboxylic acid).

[0051] Preferably, the surfactant is present in an amount of 0.1% to 100% by weight relative to the weight of the monomer.

[0052] The nonionic surfactant is preferably poly(ethylene glycol) lauryl ether, poly(ethylene glycol) tridecyl ether, poly(ethylene glycol) cetyl ether, poly(ethylene glycol)-co-poly(propylene glycol) cetyl ether, poly(ethylene glycol) stearyl ether, poly(ethylene glycol) oleyl ether, poly(ethylene glycol) nonylphenol ether, poly(ethylene glycol) octylphenol ether, poly(ethylene glycol) monolaurate, poly(ethylene glycol) monostearate, poly(ethylene glycol) monooleate, or sorbitan monolaurate. Selected from the group consisting of sorbitan monostearate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, poly(ethylene glycol)sorbitan monolaurate, poly(ethylene glycol)sorbitan monopalmitate, poly(ethylene glycol)sorbitan monostearate, poly(ethylene glycol)sorbitan monooleate, poly(ethylene glycol)-co-poly(propylene glycol), fatty acid esters of polyglycerin, polyether-modified silicone oils and perfluoroalkyl ether adducts, and mixtures thereof.

[0053] The cationic surfactant is preferably selected from the group consisting of ammonium compounds based on amines of saturated and unsaturated fatty acids, such as octadecylammonium acetate and dodecyltrimethylammonium chloride; ammonium compounds based on polyethoxylates and polypropoxylates having amino functional groups and their interpolymers, such as polyoxyethylene laurylmonomethylammonium chloride; ammonium compounds based on arylamines, such as biphenyltrimethylammonium chloride and imidazoline derivatives, such as ammonium salts formed from animal fat and imidazoline; and silicone-based cationic surfactants and fluorine-based cationic surfactants.

[0054] The anionic surfactant is preferably selected from the group consisting of aliphatic alcohol sulfates, such as sodium dodecyl sulfate and poly(ethylene glycol) lauryl ether sulfate; alkyl sulfonates, such as sodium lauryl sulfonate; alkylbenzene sulfonates, such as nonylphenol ether sulfate; sulfosuccinates, such as sodium sulfosuccinate hexyl diether; aliphatic alcohol phosphates, such as sodium lauryl phosphate and fatty acid salts, such as sodium stearic acid salt.

[0055] Preferably, a liquid phase (solvent and / or co-solvent) having a boiling point of less than 120°C is used for polymerization. Examples include ketones, polyalcohols, glycols, esters, and hydrocarbons.

[0056] As further examples, solvents are selected from the group consisting of ketones, e.g., acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohols, e.g., ethanol, isopropanol, and butanol; polyalcohols, e.g., 1,3-butanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, dipropylene glycol, tripylene glycol, and glycerol; ethers and esters of polyalcohols, e.g., dipropylene glycol monomethyl ether, tripylene glycol monomethyl ether, triethylene glycol dimethyl ether, and diethylene glycol monobutyl ether acetate; esters, e.g., ethyl acetate, propyl acetate, butyl acetate, dibutyl adipate, and dibutyl succinate; and hydrocarbons and halogenated hydrocarbons, e.g., toluene, xylene, octane, perchloroethylene, and 1,3-dichloro-2,2,3,3,3-pentalolopropane.

[0057] One or more chain transfer agents, such as alkyl mercaptans (e.g., n-dodecyl mercaptan, n-octyl mercaptan, tert-thio-dodecyl mercaptan), can be optionally used in polymerization. The amount of the chain transfer agent is preferably 0.01% to 3% by weight, and preferably 0.05% to 0.5% by weight, relative to the total weight of compounds (A) to (F).

[0058] Downstream of polymerization, the polymer preparation may contain diisocyanate or polyisocyanate additives in the presence of at least one suitable non-aqueous solvent and at least one catalyst, such as bismuth neodecanoate, tris(2-ethylhexanoate)bismuth, and zinc(II) acetylacetonate, or 1,4-diazabicyclo[2.2.2]octane (DABCO), to increase the molecular weight of the polymer. The isocyanate is preferably selected from the group consisting of the following: (a) 1,5-pentamethylene diisocyanate (PDI) and its polymers, preferably trimers, optionally of biological origin; (b) Toluene diisocyanate (TDI) and its adducts, preferably TDI trimers; (c) Polyisocyanates derived from hexamethylene diisocyanates (HDI) obtained by trimerization, biuretization, and / or allophanate processes; (d) Polyisocyanates derived from isophorone diisocyanates (IPDIs) obtained by trimerization, biuretization, and / or allophanation processes; (e) 4,4'-Methylenedicyclohexyl diisocyanate (H12MDI); (f) Trimethylhexamethylene diisocyanate (TMDI); (g) 1,4-Cyclohexyl diisocyanate (CHDI); (h) Tetramethylxylene diisocyanate (TMXDI); and (i) Any two or more mixtures selected from (a) to (h).

[0059] Furthermore, an object of the present invention is a composition comprising the polymer and one or more technical additives.

[0060] The composition is preferably in liquid form. More preferably, the composition is a solution, dispersion, or emulsion.

[0061] The one or more technical additives are selected from the following group: (i) One or more polymers configured to obtain a composition having a wetting effect, higher abrasion resistance, and / or better adhesion to a substrate, and / or flame retardancy, and / or antibacterial properties, and / or film-forming properties; and / or (ii) Further polymers that may be silicones, such as alkylpolysiloxanes (CAS No. 200074-76-6); or paraffins (e.g., available from supplier Iberceras) or blocked isocyanates with a melting point of 40°C to 100°C, preferably 50°C to 70°C; and / or (iii) Nanoparticles of silica and / or cerium oxide, titania, alumina, zirconia, or combinations thereof; and / or (iv) Any combination of (i) to (iii).

[0062] In this specification, the term “blocked isocyanate” means mono-, di-, and polyisocyanates in which the isocyanate group has reacted with a blocking agent, releasing the isocyanate and blocking agent upon heating. Suitable blocking agents, such as amines, amides, compounds having active hydrogen atoms, or alcohols, are known in the art. Better adhesion can be obtained by heating in the presence of a compound having a functional group that can react with isocyanate groups, such as hydroxyl groups or amine groups, of a suitable substrate, such as fibers. As a result, the blocked isocyanates, particularly the blocked polyisocyanates, present in preferred embodiments of the present invention can enhance adhesion to substrates having groups such as amino groups or hydroxyl groups that can react with the blocked isocyanate. Such blocked isocyanates are commercially available, for example, Arkophob DAN, Arkophob SR, and Cassurit FF (all from Archroma); Phobol XAN (Huntsman); and Ruco-Guard WEB (Rudolf).

[0063] In this specification, the term "nanoparticle" means a particle having an average particle size distribution of 1 nm to 100 nm (this distribution is preferably determined by dynamic laser light scattering).

[0064] In embodiment (iii), nanoparticles can optionally be surface-functionalized to further enhance their compatibility in the composition to which they are added. The combined action of the polymer (alone or in combination with alkylpolysiloxane or paraffin (ii)) which is the subject of the present invention, which modifies the chemical composition of the surface, and the nanoparticles which modify its geometric structure to create nanoroughness of the surface, significantly increases the hydrophobicity and oleophobicity of the surface. Such a surface has properties such as self-cleaning, anti-icing, and / or anti-biological contamination. Furthermore, some types of nanoparticles can limit surface degradation and degradation of deposited organic molecules caused by the action of solar ultraviolet light.

[0065] Furthermore, an object of the present invention is the use of the polymer or composition as a water-repellent and / or oil-repellent and / or anti-fouling agent and / or anti-graffiti agent for substrates.

[0066] The base material is preferably selected from the group consisting of paper, cardboard, natural fibers, synthetic fibers, carpet (i.e., rug or carpet, preferably carpet), leather, eco-leather, leather, and construction materials; preferably, the construction material is one of brick, tile, natural stone, recycled stone, ceramics, gypsum, concrete, cement, mortar, wood, glass, metal, and plastic.

[0067] Preferably, in this application, the polymer or composition can be diluted with a suitable solvent, applied, and dried. Application can be done by dipping, spraying, rolling, sponge, and / or brushing. Drying can be done at room temperature or by heating.

[0068] The present invention will be described here based on examples provided as purely non-limiting examples. [Examples]

[0069] Example 1 (Reference) (LAB140721) The following ingredients are added to a 250 ml four-necked flask placed in a temperature-controlled oil bath equipped with a mechanical stirrer, thermometer, and droplet condenser.

[0070] [Table 2]

[0071] The reaction mixture is heated to 80°C under a nitrogen atmosphere. After reacting for approximately 3 hours, the second dose of 0.17 g (0.00104 mol) of AIBN is added.

[0072] Approximately 1638cm -1The progress of the reaction, accompanied by a decrease in the characteristic peak of the methacrylic group, is confirmed by IR analysis.

[0073] After adding the second dose of AIBN (0.170g; 0.0010 mol) and allowing the reaction to continue for approximately 2 hours, IR analysis was performed to confirm the disappearance of the characteristic peak of the methacrylic group. Subsequently, heating was stopped, the mixture was cooled to 60°C, and approximately 50g of butyl acetate was added to bring the solution concentration to 25%.

[0074] In Example 1, only (B) is present.

[0075] Example 2 (Reference) (LAB310522) Add the indicated amounts of the following substances to the flask and process them in the same manner as in Example 1.

[0076] [Table 3]

[0077] In Example 2, (A) is absent.

[0078] Example 3 (LAB130721) Add the indicated amounts of the following substances to the flask and process them in the same manner as in Example 1.

[0079] [Table 4]

[0080] Example 4-1 (T1A~T16A) Place the indicated amount of the following substance into the flask and process it in the same manner as in Example 1. (Sample T1A)

[0081] [Table 5]

[0082] Repeat the synthesis in the same manner as in Example 1, using the amounts (in grams) shown in Table 6.

[0083] [Table 6]

[0084] Example 4-2 (LAB250722A) Add the indicated amounts of the following substances to the flask and process them in the same manner as in Example 1.

[0085] [Table 7]

[0086] Example 4-2.A (LAB290124) Add the indicated amounts of the following substances to the flask and process them in the same manner as in Example 1.

[0087] [Table 7.A]

[0088] Example 4-2.B (LAB 200324) Place the indicated amounts of the following substances into a flask and allow to react for approximately 4 hours. Then, add the second dose of AIBN and proceed as in Example 1.

[0089] [Table 7.B]

[0090] Example 4-2.C (LAB210324) Place the indicated amounts of the following substances into a flask and allow to react for approximately 4 hours. Then, add the second dose of AIBN and proceed as in Example 1.

[0091] [Table 7.C]

[0092] Example 4-3 (LAB270722) Add the indicated amounts of the following substances to the flask and process them in the same manner as in Example 1.

[0093] [Table 8]

[0094] Example 4-4 (LAB280722) Add the indicated amounts of the following substances to the flask and process them in the same manner as in Example 1.

[0095] [Table 9.A]

[0096] Examples 4-5 (LAB130721A) Add the indicated amounts of the following substances to the flask and process them in the same manner as in Example 1.

[0097] [Table 9.B]

[0098] Example 5 (LAB141022) Add the indicated amounts of the following substances to the flask and process them in the same manner as in Example 1.

[0099] [Table 10]

[0100] Approximately two hours after the second addition of AIBN, IR analysis was performed to confirm the disappearance of the characteristic peak of the methacrylic group. Then, heating was stopped, and the mixture was cooled to 60°C. 1.1 g (0.0183 mol) of glacial acetic acid and 0.6 g of 35% hydrogen peroxide solution dissolved in 70.4 g of desalinated water were added. The mixture was heated to 80°C and stirred for 2 hours. The IPA was removed over approximately 3 hours under a nitrogen atmosphere at 80°C.

[0101] Finally, add 30.6g of desalted water to bring the product concentration to 25%.

[0102] Example 6 (LAB181022) Add the indicated amounts of the following substances to the flask and process them in the same manner as in Example 1.

[0103] [Table 11]

[0104] After adding the second dose of AIBN, perform an IR analysis approximately 2 hours later to confirm that the characteristic peak of the (meth)acrylic group has disappeared. Then, stop heating, cool to 60°C, add 1.64 g (0.0184 mol) of 2-amino-2-methyl-1-propanol, and stir for at least 15 minutes.

[0105] Finally, add 50.0g of desalted water to bring the product concentration to 25%.

[0106] Example 7 (LAB191022) Add the indicated amounts of the following substances to the flask and process them in the same manner as in Example 1.

[0107] [Table 12]

[0108] Approximately two hours after the addition of the second dose of AIBN, IR analysis was performed to confirm the disappearance of the characteristic peak of the (meth)acrylic group. Then, heating was stopped, and the mixture was cooled to 60°C. After that, a 65°C heated solution, in which 0.685 g (0.017 moi) of sodium hydroxide was dissolved in 67.93 g of desalted water, was added. This solution was stirred for 30 minutes.

[0109] IPA is removed under reduced pressure and a nitrogen stream at 80°C for approximately 3 hours.

[0110] Table 13 below summarizes the composition of the polymers obtained according to previous examples in synthetic form.

[0111] [Table 13]

[0112] In this regard, please note that the quotation marks around the monomers in Table 13 above indicate the type of monomer used in each of the previous samples, and the same quotation marks are used in each of the tables from Table 1 to 12 (e.g., (D) 2 =Stearyl methacrylate; (C) 2 = Methacrylic acid; (E) 1 (=2-dimethylaminoethyl methacrylate).

[0113] Example 6: Evaluation of antifouling effect on stone The product in the 25% solution obtained in the previous example was diluted with butyl acetate or water (Example 5 only) to concentrations of 2.5%, 5%, and 10%.

[0114] Apply the solution to the Serene stone, Vicenza stone, and White Carrara marble using a sponge. Before application, wash the Vicenza stone and White Carrara marble with hot water, while the Serene stone is acid-washed with a 1:4 perchloric acid solution and then rinsed with running water. Allow the washed stones to dry before application.

[0115] After applying the product, wait 24 hours, then apply drops of water, oil, and coffee to the treated surface. After 8 hours, remove the drops and evaluate the antifouling effect.

[0116] The table below shows the results of contact angle tests on stones treated with a 2.5% butyl acetate polymer solution. The contact angles to water and hexadecane were evaluated after 20 seconds. The values ​​shown in Table 14 are the average of five measurements. The abbreviation "am" stands for active substance.

[0117] [Table 14]

[0118] Figure 1 shows samples T1A (upper left quadrant), T2A (lower left quadrant), T3A (upper right quadrant), and T4A (lower right quadrant) with three drops of coffee added to each sample. Figure 2 shows the effectiveness of the antifouling effect after droplet removal, where the quadrant arrangement is the same as in Figure 1.

[0119] Attached Figures 4 and 5 show samples of selenium treated with LAB290124, with water, oil, and coffee droplets applied immediately after application (Figure 4), and the droplets left on the stone for 5 hours, then removed, and the sample taken 24 hours later (Figure 5).

[0120] Figures 6 and 7 attached show samples of selene stone treated with LAB200324, with water, oil, and coffee droplets applied immediately after application (Figure 6) and immediately after the droplets were removed from the stone after being left on it for 5 hours (Figure 7).

[0121] Figures 8 and 9 attached show samples of selenium treated with LAB210324, with water, oil, and coffee droplets applied immediately after application (Figure 8) and immediately after the droplets were removed from the stone after being left on it for 5 hours (Figure 9).

[0122] Conclusions regarding the contact angle test: All polymers that are the subject of this invention (including those applied to samples not shown in the figures) were shown to have good or excellent water repellency against the three types of stones tested. The best samples in this test were T3A, T5A, T9A, and T12A.

[0123] Tests on LAB130721 and LAB130721A samples, which contain only compound (AI) or only compound (A.II) and no compound (B), show that results similar to those obtained with T1A-T16A samples can be obtained as long as the concentration increases. In these tests, concentrations between 4.0% am and 6.0% am were considered favorable, and no increase in contact angle was observed in tests conducted at 10% am.

[0124] Furthermore, in addition to (A), an acceptable contact angle was also obtained in tests using the LAB280722 sample, which also contained monomethacryloxypropyl-terminated polydimethylsiloxane (B.II). As shown in Table 14 above, in the presence of 2.5% of the active substance, the angle to hexadecane in the LAB130721 test was 24.7°, and in the LAB130721A test it was 26.1°. When the same tests were performed using monomethacryloxypropyl-terminated monomer (B.II) or (BI) (LAB140721 and LAB310522 tests, respectively), the angle did not exceed 10°.

[0125] Comparing LAB130721 to tests with LAB270722 and LAB280722, the introduction of a secondary silicone monomer such as monomethacryloxypropyl-terminated polydimethylsiloxane (B.II) or 3-[tris(trimethylsiloxy)silyl]propyl methacrylate (BI) improved the angle to hexadecane (better oleophobicity). The angle was better when using (BI) (48.9°).

[0126] While the LAB290124 sample exhibited excellent antifouling properties, its contact angle with hexadecane was not the best among the tests.

[0127] For the LAB200324 and LAB210324 samples, excellent contact angles with water and hexadecane were observed. While the LAB200324 sample showed room for improvement in its antifouling effect, no significant fouling was observed in the LAB210324 sample.

[0128] Example 7: Evaluation of stain-resistant effect on textiles The products of samples T3A, T5A, T9A, T12A, and T14A are diluted with butyl acetate to a concentration of 2% by weight.

[0129] Furthermore, the products of samples T5A and LAB290124 are diluted with butyl acetate to a concentration of 2.5% by weight.

[0130] The solutions of samples T3A, T5A (2%), T9A, T12A, and T14A are cotton fabrics, polyamide fabrics, suede leather, and eco-leather applied using low-pressure spray coating.

[0131] In the solutions of Sample T5A (2.5%) and LAB290124, they are brown suede leather, orange nubuck leather, and light blue nubuck leather.

[0132] After drying at room temperature for 24 hours, the appearance and feel, water repellency, and oil repellency were evaluated according to AATCC193 (water-repellent and liquid-repellent) and AATCC118-2002 (hydrocarbon-resistant) standards. These standards are effective as of the filing date or priority date of this application.

[0133] The results for samples T3A, T5A (2%), T9A, T12A, and T14A are shown in Tables 15 to 18.

[0134] The results for samples T5A (2.5%) and LAB290124 are shown in Tables 18.A to 18.D.

[0135] [Table 15]

[0136] [Table 16]

[0137] [Table 17]

[0138] [Table 18]

[0139] All samples tested according to the AATCC193 standard showed satisfactory results.

[0140] In tests conducted according to the AATCC118-2002 standard, samples T5A (2%) and T9A were found to provide acceptable oil repellency. Sample T5A (2.5%) provided the best oil repellency in the tests.

[0141] [Table 18.A]

[0142] [Table 18.B]

[0143] [Table 18.C]

[0144] [Table 18.D]

[0145] The results in Table 19 below pertain to tests performed on stones using the LAB130721 sample.

[0146] [Table 19]

[0147] Furthermore, LAB130721 (regardless of concentration), LAB250722A, LAB270722, and LAB280722 provided acceptable oil repellency. Sample T14A achieved 3 / 4 oil repellency. LAB130721A showed results consistent with LAB130721.

[0148] Example 8: Fabric Treatment - Synthesis of Polymers 1-3 - The formulations defined above were applied to emulsion polymerization for textile processing.

[0149] Polymer 1: An emulsion of the polymer according to the present invention, prepared by emulsifying twice a mixture formed by the following components in a Manton-Gorin apparatus (400 bar, 60°C).

[0150] [Table 20] *Available from companies such as Sigma Aldrich, for example.

[0151] The emulsion is placed in a 1000 ml four-necked flask in a temperature-controlled oil bath equipped with a mechanical stirrer, thermometer, droplet condenser, and nitrogen stream. After reaching 30°C, 11 g of 1,1-dichloroethene is added, and then, after reaching an intermediate temperature of 40°C, a predetermined amount of catalyst consisting of 14 g of water and 1 g of 2,2-azobis(2-methylpropionamidine) dihydrochloride is added and the mixture is heated to 60°C. After slow stirring at 60°C for 2 hours, a predetermined amount of radical catalyst of the same composition and quantity as the initial catalyst is added. The polymerization time is 5 hours at 60°C. At the end of the reaction, the excess vinyl chloride is vacuum-distilled at 50°C under a residual pressure of 100 mg bar. The resulting dispersion has a solid content of approximately 30% by weight.

[0152] Polymer 2: The mixture formed by the following components is placed in a flask and treated in the same manner as for polymer 1.

[0153] [Table 21] *Available from companies such as Sigma Aldrich, for example.

[0154] The flask contains 193.9 g of an aqueous 55% wax emulsion (cationic emulsion, density 0.94 g / ml at 25°C) with a wax melting point of 55-60°C. 9.4 g of 1,1-dichloroethene is added at 30°C, and the mixture is heated to 60°C. After reaching an intermediate temperature of 40°C, a predetermined amount of catalyst consisting of 14 g of water and 1 g of 2,2'-azobis(2-methylpropionamidine) dihydrochloride is added. After slow stirring at 60°C for 2 hours, a further predetermined amount of radical catalyst of the same composition and quantity as the initial catalyst is added. The polymerization time is 5 hours at 60°C. At the end of the reaction, the excess vinyl chloride is vacuum-distilled at 50°C under a residual pressure of 100 millibars. The resulting dispersion has a solid content of approximately 40% by weight.

[0155] Polymer 3: The mixture formed by the following components is placed in a flask and treated in the same manner as for polymer 1.

[0156] [Table 22] *Available from companies such as Sigma Aldrich, for example.

[0157] The emulsion is placed in a 1000 ml four-necked flask set in a temperature-controlled oil bath equipped with a mechanical stirrer, thermometer, droplet condenser, and nitrogen stream. Once the temperature stabilizes at 30°C, 11 g of 1,1-dichloroethene is added. The mixture is then heated to 60°C, and after reaching an intermediate temperature of 40°C, a predetermined amount of catalyst consisting of 10.3 g of water and 1 g of 2,2-azobis(2-methylpropionamidine) dihydrochloride is added. After slow stirring at 60°C for 2 hours, a predetermined amount of radical catalyst of the same composition and quantity as the initial catalyst is added. The polymerization time is 5 hours at 60°C. At the end of the reaction, the excess vinyl chloride is vacuum-distilled at 50°C under a residual pressure of 100 mg / L. The resulting dispersion has a solid content of approximately 30% by weight.

[0158] Example 9: Fiber treatment - Substrate treatment The substrate was processed using the following procedure.

[0159] (I) Cut a piece of material (e.g., leather or a woven fabric such as cotton, polyester, polyamide, etc.) measuring approximately 60 cm x 20 cm;

[0160] (II) Weigh the dried substrate using an analytical scale;

[0161] (III) Set the roller pressure to 3 bar and the rotation speed to 0.60 cm / min, and switch on the Foulard device (Figure 3; Model 20FL500, Manufacturer: Off.Elettromeccanica Gavazzi);

[0162] (IV) Attach a bath of moistening solution containing a protective agent to the front of the Foulard apparatus and fill it with the moistening solution (capacity of half a liter to one liter);

[0163] (V) Start the rollers of the Foulard apparatus and immerse it in the bath of wetting solution, then place the substrate in between;

[0164] (VI) Slide the substrate off the rollers and place it back between the two rollers for the next step (avoid placing the substrate into the bath filled with the wetting solution);

[0165] (VII) Weigh the wet substrate and evaluate the amount of wet solution remaining on the substrate according to the following formula (substrate pickup rate). Pickup rate = ((Final material weight - Initial material weight) / Initial material weight) * 100

[0166] (VIII) Place the substrate in an oven at 120°C for 1.5 minutes to perform the drying process;

[0167] (IX) Place the substrate in a 150°C oven for 3 minutes to perform the crosslinking process (curing);

[0168] (X) Remove the dried substrate and perform the evaluation test.

[0169] Example 9: Fiber treatment - Evaluation by AATCC test Oil droplets with different surface tensions are applied to a treated substrate. After 30 seconds, the oil droplets are removed, and the absorption of the droplets by the treated surface is evaluated. The oil-repellent grade is identified as the highest test grade among those that are not completely absorbed within 30 seconds. Table 23 below shows the grades of the applied oils.

[0170] [Table 23]

[0171] The following table schematically shows the results of tests conducted in accordance with AATCC118-2002 and the contact angle with water (using the Drop Shape Analyzer-DSA100 tool).

[0172] [Table 24]

[0173] [Table 25]

[0174] Clear oil repellency was confirmed in fiber treatment using polymer 1 in an aqueous emulsion.

[0175] Polymer 1 exhibits good water repellency. The contact angle with water was 127.6° for cotton and 136.1° for polyamide.

[0176] Water repellency was improved by using a wax (polymer 2) in an aqueous emulsion along with the selected monomer. The contact angle with water was 137.6° for cotton and 139.0° for polyamide. With polymer 2, water repellency was improved even when compound (A) was present in smaller amounts.

[0177] In polymer 3, water and oil repellency are improved by increasing the weight percentages of monomers (Al) and (BI) and introducing methyl methacrylate along with behenyl acrylate, without using emulsifying waxes.

[0178] The present invention has the following advantages.

[0179] Advantageously, the polymers and compositions that are the subject of this invention have reversible water-repellent and oil-repellent properties.

[0180] Advantageously, the significance of applying the polymers and compositions that are the subject of this invention lies in their ability to exhibit low molecular weight cohesive energy, and consequently, their ability to exhibit low surface energy properties, such as reducing surface tension in aqueous or organic environments. For example, surface tension values ​​may range from about 15 dyn / cm to about 30 dyn / cm, and particularly from 19 dyn / cm to about 25 dyn / cm.

[0181] Advantageously, the significance of applying the subject matter of the polymers and compositions of the present invention lies in its ability to reduce surface tension to a value comparable to that of fluorinated acrylic polymers having a similar structure.

[0182] In particular, the polymers and compositions that are the subject of this invention are highly noteworthy because they exhibit and can impart high surface properties.

[0183] Advantageously, the polymers and compositions that are the subject of this invention can be used to obtain solutions of any concentration, even at concentrations close to their purity.

[0184] Nevertheless, the polymers and compositions that are the subject of this invention exhibit extremely excellent performance even at low concentrations.

[0185] Advantageously, the polymers and compositions that are the subject of this invention are "fluorine-free," and therefore are effective as alternatives to fluorinated polymers, which are characterized by objective environmental problems.

[0186] Advantageously, the above-mentioned additional components can significantly improve the hydrophobic-oleophobic properties of the treated surface, and therefore the described polymers and compositions are also high performance in terms of these properties.

[0187] Advantageously, the polymers and compositions that are the subject of this invention have good adhesion to the surface being treated.

[0188] Advantageously, the polymers and compositions that are the subject of this invention have good permeability to water vapor.

[0189] Advantageously, the polymers and compositions that are the subject of this invention have good chemical and physical compatibility with the substrate being treated.

[0190] Advantageously, the polymers and compositions that are the subject of this invention have good chemical, physical, thermal, and photo-oxidative stability.

[0191] Advantageously, the polymers and compositions that are the subject of this invention have good solubility in environmentally friendly solvents.

[0192] Advantageously, the polymers and compositions that are the subject of this invention did not cause discoloration of the substrate.

[0193] Although not previously specified, those skilled in the art can envision, using typical expertise in the art, modifying or substituting some of the above embodiments with other technically equivalent elements.

[0194] These examples of modifications or substitutions also fall within the scope defined by the following claims.

[0195] Furthermore, each alternative example shown in relation to a particular embodiment can be carried out independently of the other modifications described.

Claims

1. at least, (A) or a combination of (A) and (B); and (C), (D), (E), (F) (optionally), and at least two selected from combinations thereof; A polymer obtained by polymerization between, Here, (A) is a compound of general formula (A.I) or (A.II), or a mixture of (A.I) and (A.II): 【Chemistry 1】 (A.I.) 【Chemistry 2】 (A.II) In the formula, R3 is independently hydrogen or methyl; (B) is a compound of general formula (B.I) or (B.II), or a mixture of (B.I) and (B.II): 【Transformation 3】 (B.I) In the formula, R1 is either hydrogen or methyl; 【Chemistry 4】 (B.II) In the formula, n is an integer from 3 to 15, preferably from 3 to 10; (C) is (meth)acrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, monomers containing hydroxyl groups, for example, 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl methacrylate, poly(ethylene glycol) mono(meth)acrylate, poly(propylene glycol) mono(methacrylate), poly(ethylene glycol)-co-poly(propylene glycol) mono(methacrylate), polytetrahydrofuran mono(methacrylate), N-hydroxymethyl (methacrylamide), hydroxybutyl vinyl ether, N-hydroxymethyl (meth)acrylamide, vinyl (meth)acrylate, allyl (meth)acrylate, N-methoxymethylacrylamide, N-isopropoxy-methylacrylamide, N-butoxy-methylacrylamide At least one selected from the group consisting of N-isobutoxymethylacrylamide, glycidyl (meth)acrylate, 2-carboxyethyl acrylate, and (α,α-dimethyl-m-isopropenylbenzyl) isocyanate, phenol, ketoxime, isocyanate-terminated alkyl (meth)acrylate compounds blocked by pyrazole, and mixtures thereof; (D) is a compound of general formula (D.I): Rh-OCOC(R2)=CH2 (D.I) During the ceremony, R2 is either hydrogen or methyl; Rh is a benzyl radical or a linear or branched alkyl radical having 1 to 30 carbon atoms, preferably an alkyl radical having 1 to 20 carbon atoms; (E) is a compound of general formula (E.I) and: R5R6N-Rp-OCOC(R4)=CH2 (E.I) During the ceremony, R4 is either hydrogen or methyl; Rp is a C1 to C10 alkylene radical optionally substituted with at least one hydroxyl and / or halogen group; R5 and R6 are independently hydrogen, a benzyl radical, or a linear or branched alkyl radical having 1 to 10 carbon atoms; (F) is at least one selected from the group consisting of vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl stearate, N-vinylpyrrolidinone, vinyl chloride, vinylidene chloride, trimethylvinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, and mixtures thereof. polymer.

2. (A) is a compound of general formula (A.I), where R3 is preferably methyl; (B) is a compound of general formula (B.I), where R1 is preferably methyl; (C) is selected from 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, glycidyl methacrylate, acrylic acid, methacrylic acid, 2-carboxyethyl acrylate and mixtures thereof; (D) is at least one selected from the group consisting of decyl (meth)acrylate, isobornyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, tridecyl (meth)acrylate, behenyl (meth)acrylate, C18-longer-chain (meth)acrylates, and mixtures thereof; more preferably, (D) is stearyl (meth)acrylate, tridecyl methacrylate, or a mixture thereof; In the compound of general formula (E.I), Rp is an alkylene radical having 2 to 5 carbon atoms, and R5 and R6 are independently hydrogen or a linear or branched alkyl radical having 1 to 5 carbon atoms. The polymer according to claim 1.

3. (E) is selected from the group consisting of 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl acrylate, 2-diethylaminoethyl methacrylate, and mixtures thereof. The polymer according to claim 1 or 2.

4. The polymer comprises or consists of the following: Table 1 The polymer according to any one of claims 1 or 3.

5. The polymer comprises or consists of the following: Table 2 The polymer according to claim 4.

6. The polymer comprises or consists of the following: Table 3 The polymer according to claim 4.

7. The polymer comprises or consists of the following: Table 4 The polymer according to claim 4.

8. A composition comprising a polymer according to any one of claims 1 or 7, and one or more technical additives, wherein the composition is a solution, dispersion or emulsion; Preferably, the one or more technical additives are selected from the following group. (i) One or more polymers configured to obtain a composition having a wetting effect, higher abrasion resistance, and / or better adhesion to a substrate, and / or flame retardancy, and / or antibacterial properties, and / or film-forming properties; and / or (ii) Further polymers that may be silicones, such as alkylpolysiloxanes; or paraffins or blocked isocyanates having a melting point of 40°C to 100°C, preferably 50°C to 70°C; and / or (iii) Nanoparticles of silica and / or cerium oxide, titania, alumina, zirconia, or combinations thereof; and / or (iv) Any combination of (i) to (iii) A composition that is

9. The composition according to claim 8, wherein the nanoparticles (iii) have an average particle size distribution of 1 nm to 100 nm, and the average distribution is determined by dynamic laser light scattering.

10. Uses of the polymer according to any one of claims 1 to 7 or the composition according to claim 8 or 9 as a water-repellent and / or oil-repellent agent and / or anti-fouling agent and / or anti-graffiti agent for a substrate; Preferably, the base material is selected from the group consisting of paper, cardboard, natural fibers, synthetic fibers, carpet, leather, eco-leather, and construction materials; preferably, the construction material is one of brick, tile, natural stone, recycled stone, ceramics, gypsum, concrete, cement, mortar, wood, glass, metal, and plastic. Use.

Images