Modified polyisocyanate

Abstract

The present invention relates to modified polyisocyanates and their use, particularly as crosslinking components in water-soluble or water-dispersible coatings. The modified polyisocyanates are obtained by the reaction of a system containing the following components: at least one aminosulfonic acid; at least one polyisocyanate; at least one tertiary amine; and optionally a polyether alcohol containing ethylene oxide groups. The modified polyisocyanates contain at least one iminooxadiazinedione structure and at least one isocyanurate structure, with the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure being 1:300 to 1:5. The amount of sulfonate groups in the modified polyisocyanates is 0.75% to 1.1% by weight, based on the amount of the modified polyisocyanate taken as 100% by weight. The viscosity of the modified polyisocyanates is measured at 23°C and 10 s according to DIN EN ISO 3219:1994-10. -1 The shear strength is determined at a shear rate of 500 mPa·s to 10,000 mPa·s. A coating containing the modified polyisocyanate of the present invention can be sufficiently stirred by hand, and the resulting coating layer has high gloss and good transparency.

Description

Technical Field

[0001] The present invention relates to modified polyisocyanates and their use, in particular their use as crosslinking components in water-soluble or water-dispersible coatings.

Background Art

[0002] In recent years, water-dispersible modified polyisocyanates have become increasingly important in various fields of application in response to increasingly stringent environmental regulations in various countries. Water-dispersible modified polyisocyanates are often used as crosslinking components in aqueous two-component coatings or aqueous dispersion adhesives and sealants. Water-dispersible modified polyisocyanates are used for fabric finishing or formaldehyde-free fabric printing inks for crosslinking of aqueous dispersions and, in addition, are used as auxiliaries for wet strengthening treatment of paper (see, for example, EP-A0959087 and the documents cited herein).

[0003] Currently, water-dispersible modified polyisocyanates can be broadly classified into two types: non-ionic modified types and ionic modified types. Non-ionic modified polyisocyanates, especially polyether-modified polyisocyanates, are widely used, but they still have many drawbacks. For example, since very high viscosities have to be overcome during dispersion, only relatively high shear forces (e.g., high-speed stirring) can be applied to obtain a uniform dispersion in water. In another example, when such polyether-modified polyisocyanates are used as crosslinking agents in aqueous two-component coatings, generally a relatively large amount of polyether is introduced in order to achieve better dispersibility. On the other hand, the water resistance of the coating layer formed from the coating is continuously affected. On the other hand, the concentration of isocyanate in the polyether-modified polyisocyanate is significantly reduced and the crosslinking density is decreased.

[0004] In order to overcome the above-mentioned drawbacks, attempts have been made to use ionic modified polyisocyanates.

[0005] Water-dispersible carboxylic acid group-modified polyisocyanates can be obtained, for example, by introducing carboxylic acid groups into the polyisocyanate structure (EP-A0443138, EP-A0510438, and EP-A0548669). The carboxylic acid group-modified polyisocyanates can be dispersed in water by stirring without using high shear forces. However, their storage stability is relatively poor, especially after the carboxylic acid groups are neutralized. This is because carboxylate groups have certain catalytic activities that lead to the polymerization of isocyanate groups at room temperature, involving, for example, trimerization to polyisocyanurates or the formation of α-polyamide structures. This causes gelation of the carboxylic acid group-modified polyisocyanates and results in poor storage stability.

[0006] Another example is water-dispersible sulfonic acid group-modified polyisocyanates obtained by modifying polyisocyanates with sulfonic acid groups. CN101754990A discloses a method for modifying polyisocyanates using 4-aminotoluene-2-sulfonic acid containing a benzene ring. The resulting sulfonic acid group-modified polyisocyanates have better water dispersibility than carboxylic acid group-modified polyisocyanates. However, the benzene ring present in them reduces the yellowing resistance of the formed coating layer. CN1190450C discloses the preparation of modified polyisocyanates using 3-cyclohexylaminopropanesulfonic acid and 2-(cyclohexylamino)-ethanesulfonic acid as hydrophilic modifiers, and tertiary amines and neutralizing agents as phase transfer catalysts. CN104448232 discloses the preparation of modified polyisocyanates by using 4-(cyclohexylamino)-butanesulfonic acid as a hydrophilic modification reagent and tertiary amines as phase transfer catalysts to obtain modified polyisocyanates.

[0007] The above-mentioned sulfonic acid group-modified polyisocyanate can be dispersed in water without very high shear force. However, in actual operation, the operator still needs to first dilute the sulfonic acid group-modified polyisocyanate with a solvent to about 70 to 80% to reduce its viscosity in order to obtain a coating, and then mix it with other coating components and disperse it by manual stirring. The addition of the solvent can significantly increase the VOC content of the coating and may cause damage to the environment and the human body.

[0008] Therefore, there is a need in the art for a modified polyisocyanate that can be manually stirred sufficiently and exhibits good dispersibility without solvent dilution.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Summary of the Invention

[0010] An object of the present invention is to provide a modified polyisocyanate and its use, particularly its use as a crosslinking component of a water-soluble or water-dispersible coating.

[0011] The modified polyisocyanate of the present invention comprises the following components: a. Formula I

Chemical Formula

[0012] According to one aspect of the present invention, there is provided a process for producing a modified polyisocyanate of the present invention, wherein components a, b and optionally component d react in the presence of component c to give the aforementioned modified polyisocyanate.

[0013] According to a further aspect of the present invention, there is provided the use of the modified polyisocyanate of the present invention as an initiating component in the preparation of polyurethanes.

[0014] According to a further aspect of the present invention, there is provided the use of the modified polyisocyanate of the present invention as a crosslinking component in a water-soluble or water-dispersible coating, adhesive or sealant.

[0015] According to a further aspect of the present invention, there is provided the use of the modified polyisocyanate of the present invention as an initiating component for the preparation of a blocked polyisocyanate blocked with a blocking agent.

[0016] According to yet another aspect of the present invention, there is provided a coating, adhesive or sealant comprising the modified polyisocyanate of the present invention.

[0017] According to yet another aspect of the present invention, there is provided a substrate coated with a coating, adhesive or sealant of the present invention.

[0018] According to yet another aspect of the present invention, there is provided the use of the modified polyisocyanate of the present invention to improve the manual stirring behavior of a coating, adhesive or sealant.

[0019] According to yet another aspect of the present invention, there is provided the use of the modified polyisocyanate of the present invention as a crosslinking component in a water-soluble or water-dispersible two-component aqueous coating.

[0020] According to yet another aspect of the present invention, there is provided a two-component aqueous coating comprising at least one aqueous hydroxy resin dispersion, at least one modified polyisocyanate of the present invention, optionally auxiliaries and optionally additives.

[0021] According to yet another aspect of the present invention, an aqueous hydroxy resin dispersion, optionally an auxiliary agent, and optionally an additive are mixed in any manner to obtain a mixture, and the modified polyisocyanate of the present invention and the aforementioned mixture are mixed and manually stirred to obtain an aqueous two-component coating. A method for preparing an aqueous two-component coating is provided, which includes the step of obtaining an aqueous two-component coating.

[0022] According to yet another aspect of the present invention, a product is provided that includes a substrate and a coating formed by applying the aqueous two-component coating of the present invention to the substrate. The product is preferably furniture.

[0023] According to still another aspect of the present invention, a method for manufacturing a product is provided, which includes the steps of applying the aqueous two-component coating of the present invention to a substrate and subsequently curing and drying it.

[0024] The modified polyisocyanate of the present invention can be directly mixed with other coating components without solvent dilution, and can be uniformly dispersed in the resin system by simple manual stirring to obtain a coating. The coating layer formed from the coating has good gloss and transparency.

[0025] During the preparation by mixing a coating, an adhesive, or a sealant containing the modified polyisocyanate of the present invention, the addition of a solvent is not required for the dispersion of the modified polyisocyanate. Therefore, the resulting coating, adhesive, or sealant has a low VOC content.

[0026] Therefore, the present invention actually provides a modified polyisocyanate that can be sufficiently stirred manually and has good dispersibility. The coating layer formed from the coating containing the aforementioned modified polyisocyanate has high gloss and good transparency.

Embodiments for Carrying Out the Invention

[0027] The present invention relates to the following components: a. Formula I [ka] (where: R1 and R2 independently represent hydrogen, a substituted or unsubstituted and / or heteroatom-containing aliphatic group having 1 to 18 carbon atoms, a substituted or unsubstituted and / or heteroatom-containing cycloaliphatic group having 3 to 18 carbon atoms, a substituted or unsubstituted and / or heteroatom-containing aromatic group having 1 to 18 carbon atoms; R1 and R2 can react with each other to form a cycloaliphatic group having 3 to 8 carbon atoms, or a heterocyclic group having 3 to 8 carbon atoms substituted with an oxygen atom or a nitrogen atom; R3 represents a linear or branched aliphatic group having 2 to 8 carbon atoms. at least one aminosulfonic acid represented by: b. at least one polyisocyanate; c. at least one tertiary amine; and d. optionally, a polyether alcohol containing ethylene oxide groups; A modified polyisocyanate obtained by a reaction of a system comprising: The modified polyisocyanate contains at least one iminooxadiazinedione structure and at least one isocyanurate structure, and the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure is 1:300 to 1:5; the sulfonate group of the modified polyisocyanate (the sulfonate group is a SO3 having a molar weight of 80 g / mol) is 1:300 to 1:5; - (meaning that the amount of the modified polyisocyanate is 0.75% by weight to 1.1% by weight, based on the amount of the modified polyisocyanate as 100% by weight; and the viscosity of the modified polyisocyanate is 23° C. and 10 s according to DIN EN ISO 3219:1994-10 -1 The modified polyisocyanate has a shear modulus of 500 mPa·s to 10,000 mPa·s, determined at a shear rate of 100 / s.

[0028] The present invention also provides a method for preparing a modified polyisocyanate, for preparing a water-soluble or water-dispersible coating, adhesive or sealant for preparing a polyurethane or a blocked polyisocyanate blocked with a blocking agent, and for improving the manual stirring behavior of a coating, adhesive or sealant, the use of a modified polyisocyanate, a coating, adhesive or sealant containing a modified polyisocyanate, in particular the use of a modified polyisocyanate in a wood coating, a method for preparing an aqueous two-component coating, a product obtained by applying the aforementioned coating to a substrate, and a method for manufacturing the product.

[0029] Modified polyisocyanate The modified polyisocyanate of the present invention may also refer to a mixture of modified polyisocyanates.

[0030] The iminooxadiazinedione structure is represented by Formula II.

Chemical formula

[0031] The isocyanurate structure is represented by Formula III.

Chemical formula

[0032] R4, R5, R6, R7, R8, and R9 may each independently be the same or different.

[0033] The weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified polyisocyanate is preferably from 1:200 to 1:5, preferably from 1:100 to 1:5, more preferably from 1:100 to 1:6, still more preferably from 1:30 to 1:7, and most preferably from 1:30 to 1:20.

[0034] The total weight of the iminooxadiazinedione structure and the isocyanurate structure of the modified polyisocyanate is 5% by weight or more based on the amount of the modified polyisocyanate as 100% by weight.

[0035] The amount of the sulfonate group (the sulfonate group means SO3 having a molar weight of 80 g / mol) of the modified polyisocyanate is preferably from 0.75% by weight to 1.0% by weight based on the amount of the modified polyisocyanate as 100% by weight. - is meant)

[0036] The viscosity of the modified polyisocyanate is in accordance with DIN EN ISO 3219:1994-10 at 23 °C and 10 s -1It is determined by the shear rate, preferably 500 mPa·s to 7000 mPa·s, preferably 1000 mPa·s to 7000 mPa·s, and most preferably 3000 mPa·s to 7000 mPa·s.

[0037] Aminosulfonic acid R1 and R2 can preferably react with each other to form a cycloaliphatic group having 3 to 8 carbon atoms or a heterocyclic group having 3 to 8 carbon atoms substituted with an oxygen atom or a nitrogen atom, and the aforementioned heterocyclic group is preferably further substituted.

[0038] R3 preferably represents a linear or branched aliphatic group having 2 to 4 carbon atoms, more preferably a linear or branched aliphatic group having 2 to 3 carbon atoms, and most preferably a linear or branched aliphatic group having 3 carbon atoms.

[0039] The aminosulfonic acid may be any mixture of one or more aminosulfonic acids represented by Formula I.

[0040] The aminosulfonic acid is preferably one or more of the compounds 3-cyclohexylaminopropane-1-sulfonic acid, 4-cyclohexylamino-1-butanesulfonic acid, and 2-cyclohexylaminoethane-1-sulfonic acid, more preferably one or more of the compounds 3-cyclohexylaminopropane-1-sulfonic acid and 4-cyclohexylamino-1-butanesulfonic acid, and most preferably 3-cyclohexylaminopropane-1-sulfonic acid.

[0041] The amount of the aminosulfonic acid is preferably 1.5% by weight to 3.5% by weight, more preferably 2% by weight to 3% by weight, and most preferably 2.2% by weight to 2.9% by weight based on the amounts of components a and b as 100% by weight.

[0042] Polyisocyanate The polyisocyanate in the present invention refers to a raw material component for preparing a modified polyisocyanate.

[0043] The polyisocyanate contains at least one iminooxadiazinedione structure and at least one isocyanurate structure.

[0044] The iminooxadiazinedione structure is represented by Formula II.

Chemical formula

[0045] The isocyanurate structure is represented by Formula III.

Chemical formula

[0046] R4, R5, R6, R7, R8, and R9 may each independently be the same or different.

[0047] The weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified polyisocyanate is preferably from 1:300 to 1:5, more preferably from 1:200 to 1:5, even more preferably from 1:100 to 1:5, even more preferably from 1:100 to 1:6, even more preferably from 1:30 to 1:7, and most preferably from 1:30 to 1:20.

[0048] The total weight of the iminooxadiazinedione structure and the isocyanurate structure is 5% by weight or more based on the amount of the polyisocyanate as 100% by weight.

[0049] The content of the monomeric diisocyanate in the polyisocyanate is preferably less than 1% by weight, most preferably less than 0.5% by weight.

[0050] The viscosity of the polyisocyanate is determined at a temperature of 23 °C and a shear rate of 10 s -1 in accordance with DIN EN ISO 3219:1994-10, and is preferably 100 mPa·s to 9000 mPa·s, more preferably 500 mPa·s to 8000 mPa·s, and most preferably 500 mPa·s to 6000 mPa·s.

[0051] The amount of the polyisocyanate is preferably 5% by weight or more based on the components of the reaction for preparing the modified polyisocyanate as 100% by weight.

[0052] The polyisocyanate is preferably one or more of the following compounds: aliphatic polyisocyanate, cycloaliphatic polyisocyanate, araliphatic polyisocyanate and aromatic polyisocyanate.

[0053] In addition to the isocyanurate structure and the iminooxadiazinedione structure, the polyisocyanate may further contain one or more of the following structural units: urethane, biuret, uretdione and allophanate.

[0054] The polyisocyanate preferably consists of at least two diisocyanates and is prepared, for example, by the modification of simple aliphatic, cycloaliphatic, araliphatic and / or aromatic diisocyanates as described in the following documents: J.Prakt.Chem. 336 (1994) 185 - 200, DE - A1670666, DE - A1954093, DE - A2414413, DE - A2452532, DE - A2641380, DE - A3700209, DE - A3900053 and DE - A3928503, or EP - A0336205, EP - A0339396 and EP - A0798299. The diisocyanate can be prepared by phosgenation in the liquid or gas phase or by a phosgene - free process, for example, by thermal urethane cleavage.

[0055] The weight - average molecular weight of the diisocyanate is preferably from 140 to 400.

[0056] The diisocyanate is preferably one or more of the following compounds: 1,4 - diisocyanatobutane, 1,5 - diisocyanatopentane (pentamethylene diisocyanate, PDI), 1,6 - diisocyanatohexane (hexamethylene diisocyanate, HDI), 2 - methyl - 1,5 - diisocyanatopentane, 1,5 - diisocyanato - 2,2 - dimethylpentane, 2,2,4 - trimethyl - 1,6 - diisocyanatohexane, 2,4,4 - trimethyl - 1,6 - diisocyanatohexane, 1,10 - diisocyanatodecane, 1,3 - diisocyanatocyclohexane, 1,4 - diisocyanatocyclohexane, 1,3 - bis(isocyanatomethyl) - cyclohexane, 1,4 - bis(isocyanatomethyl) - cyclohexane, 1 - isocyanato - 3,3,5 - trimethyl - 5 - isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4’ and 4,4’ - diisocyanatodicyclohexylmethane (H 12-MDI), 1-isocyanato-1-methyl-4(3)isocyanato-methylcyclohexane, bis(isocyanatomethyl)-norbornane, 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanato-propane-2-yl)-benzene (TMXDI), 2,4- and 2,6-diisocyanatotoluene (TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI) and 1,5-diisocyanatonaphthalene (NDI).

[0057] The polyisocyanate is preferably one or more of the following compounds: aliphatic polyisocyanates and cycloaliphatic polyisocyanates, more preferably aliphatic polyisocyanates, still more preferably derivatives containing an isocyanurate structure and an iminooxadiazinedione structure, which are based on one or more of the following compounds: hexamethylene diisocyanate, isophorone diisocyanate and 4,4'-diisocyanatodicyclohexylmethane, still more preferably derivatives containing an isocyanurate structure and an iminooxadiazinedione structure, which are based on one or more of the following compounds: hexamethylene diisocyanate and isophorone diisocyanate, and most preferably derivatives containing an isocyanurate structure and an iminooxadiazinedione structure, which are based on hexamethylene diisocyanate.

[0058] Tertiary amine The tertiary amine of the present invention is used to neutralize the sulfonic acid group of the aminosulfonic acid.

[0059] The tertiary amine is preferably one or more of the following compounds: tertiary monoamines, tertiary diamines, and other tertiary amines containing groups reactive with isocyanates.

[0060] The tertiary monoamine is preferably one or more of the following compounds: trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, N-methylpiperidine and N-ethylpiperidine and N,N-dimethylcyclohexylamine.

[0061] The tertiary diamine is preferably one or more of the following compounds: 1,3-bis-(dimethylamino)-propane, 1,4-bis-(dimethylamino)-butane, and N,N'-dimethylpiperazine.

[0062] The tertiary amine is most preferably N,N-dimethylcyclohexylamine.

[0063] Other tertiary amines containing groups reactive towards isocyanates are preferably alkanolamines such as, for example, dimethylethanolamine, methyldiethanolamine and / or triethanolamine.

[0064] The molar equivalent ratio of the tertiary amine to the sulfonate group of the aminosulfonic acid is preferably from 0.3 to 1.9, most preferably from 0.6 to 1.4.

[0065] The amount of the tertiary amine is an amount sufficient to catalyze the reactions of components a, b and optionally component d. However, other conventional catalysts known in polyurethane chemistry may optionally be used to accelerate the reactions in the process of the present invention. The conventional catalysts are preferably one or more of the following compounds: other tertiary amines and metal salts.

[0066] The other tertiary amines are preferably one or more of the following compounds: triethylamine, pyridine, methylpyridine, benzyldimethylamine, N,N-endethylene piperazine, N-methylpiperidine, pentamethyldiethylenetriamine, N,N-dimethylaminocyclohexane and N,N'-dimethylpiperazine.

[0067] The metal salt is preferably one or more of the following compounds: ferric chloride, aluminum tris(ethylacetoacetate), zinc chloride, zinc n-octoate, zinc 2-ethyl-1-hexanoate, zinc 2-ethylcaproate, zinc stearate, zinc naphthenate, zinc acetylacetonate, tin n-octoate, tin 2-ethyl-1-hexanoate, tin ethylhexanoate, tin laurate, tin palmitate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin maleate, dibutyltin dilaurate, dioctyltin diacetate, and molybdenum glycolate.

[0068] The amount of the normal catalyst is preferably 0.001% to 2% by weight, most preferably 0.005% to 0.5% by weight, based on the amount of the components of the reaction as 100% by weight.

[0069] Polyether alcohol containing ethylene oxide groups The polyether alcohol containing an ethylene oxide group is used in an amount of 0 to 17% by weight, preferably 0 to 13% by weight, most preferably 0 to 5% by weight, based on the amount of the components of the reaction as 100% by weight, in the method for producing the modified polyisocyanate of the present invention.

[0070] The polyether alcohol containing an ethylene oxide group preferably contains a statistical average of 5 to 30, most preferably 7 to 25, ethylene oxide groups per molecule.

[0071] The polyether alcohol containing an ethylene oxide group can be obtained by alkoxylation of appropriate raw material molecules by known methods, for example, as described in Ullmanns Encyclopaedie der technischen Chemie, 4th edition, volume 19, Verlag Chemie Weinheim, pages 31 - 38.

[0072] Suitable starting materials are preferably one or more of the following compounds: saturated monohydric alcohols, unsaturated alcohols, aromatic alcohols, araliphatic alcohols, secondary monoamines, and heterocyclic secondary amines.

[0073] Saturated monohydric alcohols are preferably one or more of the following compounds: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, isomeric pentanols, hexanol, octanol, nonanol, n-decyl alcohol, n-dodecyl alcohol, n-tetradecyl alcohol, n-hexadecanol, n-octadecyl alcohol, cyclohexanol, isomeric methylcyclohexanols, hydroxymethylcyclohexane, 3-ethyl-3-oxetanemethanol, and tetrahydrofurfuryl alcohol.

[0074] Unsaturated alcohols are preferably one or more of the following compounds: allyl alcohol, 1,1-dimethyl-allyl alcohol, and oleyl alcohol.

[0075] Aromatic alcohols are preferably one or more of the following compounds: phenol, isomeric cresols, and methoxyphenols.

[0076] Araliphatic alcohols are preferably one or more of the following compounds: benzyl alcohol, anisyl alcohol, and cinnamyl alcohol.

[0077] Secondary monoamines are preferably one or more of the following compounds: dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine, diisobutylamine, bis(2-ethylhexyl)-amine, N-methylcyclohexylamine, N-ethylcyclohexylamine, and dicyclohexylamine.

[0078] Heterocyclic secondary amines are preferably one or more of the following compounds: morpholine, pyrrolidine, piperidine, and 1H-pyrazole.

[0079] Suitable raw material molecules are more preferably saturated monohydric alcohols having 1 to 4 carbon atoms, and most preferably methanol.

[0080] Alkylene oxides suitable for the alkoxylation reaction, particularly ethylene oxide and / or propylene oxide, can be used in any order or as a mixture in the alkoxylation reaction.

[0081] The polyether alcohol containing an ethylene oxide group may be any mixture of one or more polyether alcohols containing an ethylene oxide group.

[0082] The alkylene oxide units in the polyether alcohol containing an ethylene oxide group preferably contain 30 mol% or more, and most preferably 40 mol% or more of ethylene oxide groups.

[0083] The polyether alcohol containing an ethylene oxide group is most preferably a polyethylene glycol-methyl ether alcohol containing statistically an average of 7 to 30, most preferably 7 to 25 ethylene oxide groups per molecule.

[0084] The polyether alcohol containing an ethylene oxide group according to the present invention may be further added. Alternatively, the polyisocyanate may already contain ethylene oxide polyether units. When the polyisocyanate already contains ethylene oxide polyether units, the polyisocyanate is a polyisocyanate modified to be hydrophilic with an ethylene oxide polyether alcohol, for example, a polyisocyanate prepared by the method described in EPA0959087, page 2, lines 25 to 46.

[0085] Solvent The components of the reaction for preparing the modified polyisocyanate may further include a solvent.

[0086] The solvent is a conventional solvent known to be useful in the preparation of modified polyisocyanates and is preferably one or more of the following compounds: ethyl acetate, butyl acetate, 1-methoxypropan-2-yl acetate, 3-methoxy-n-butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, xylene, chlorobenzene, petroleum solvents, more highly substituted aromatic compounds, carbonates, lactones, propylene glycol diacetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, N-methylpyrrolidone and N-methylcaprolactam.

[0087] The more highly substituted aromatic compounds are preferably solvent naphthas of the trade names Solvesso, Isopar, Nappar and Shellsol.

[0088] The carbonates are preferably one or more of the following compounds: dimethyl carbonate, diethyl carbonate, 1,2-ethylene carbonate, and 1,2-propylene carbonate.

[0089] The lactones are preferably one or more of the following compounds: β-propiolactone, γ-butyrolactone, ε-caprolactone, and ε-methylcaprolactone.

[0090] The modified polyisocyanate preferably has the following components: a. Formula I

Chemical formula

[0091] The modified polyisocyanate is more preferably the following components: a. 3-cyclohexylaminopropanesulfonic acid; b. A derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure; and c. A tertiary amine; obtained by the reaction of a system containing The weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified polyisocyanate is 1:30 to 1:7. The amount of the sulfonate group (the sulfonate group means SO3 having a molar weight of 80 g / mol) of the modified polyisocyanate is 0.75% by weight to 1.1% by weight based on the amount of the modified polyisocyanate as 100% by weight; the viscosity of the modified polyisocyanate is determined according to DIN EN ISO 3219:1994-10 at a temperature of 23 °C and a shear rate of 10 s - and is 500 mPa·s to 10,000 mPa·s. -1

[0092] The tertiary amine is preferably N,N-dimethylcyclohexylamine.

[0093] The weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified isocyanate is preferably 1:30 to 1:20.

[0094] The amount of the sulfonate group (the sulfonate group means SO3 having a molar weight of 80 g / mol) of the modified polyisocyanate is preferably 0.75% by weight to 1.0% by weight based on the amount of the modified polyisocyanate as 100% by weight. -

[0095] The viscosity of the modified polyisocyanate is at a temperature of 23 °C and a shear rate of 10 s according to DIN EN ISO 3219:1994-10 -1 ​​Measured at a shear rate, preferably 500 mPa·s to 7000 mPa·s, more preferably 1000 mPa·s to 7000 mPa·s, and most preferably 3000 mPa·s to 7000 mPa·s.

[0096] The molar equivalent ratio of the tertiary amine to the sulfonate group of 3-cyclohexylaminopropanesulfonic acid is preferably 0.3 to 1.9.

[0097] The amount of 3-cyclohexylaminopropanesulfonic acid is 2% to 3% by weight based on the amounts of components a and b as 100% by weight.

[0098] The weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure is preferably 1:30 to 1:7, and most preferably 1:30 to 1:20.

[0099] The modified polyisocyanate is most preferably the following components: a. 3-cyclohexylaminopropanesulfonic acid (where the amount of 3-cyclohexylaminopropanesulfonic acid is 2% to 3% by weight based on the amounts of components a and b as 100% by weight); b. A derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure (where the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure is preferably 1:30 to 1:20); and c. N,N-dimethylcyclohexylamine having a molar equivalent ratio of 0.3 to 1.9 to the sulfonate group of 3-cyclohexylaminopropanesulfonic acid; obtained by the reaction of a system containing The weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified polyisocyanate is from 1:30 to 1:20; the amount of the sulfonate group (the sulfonate group means SO3 having a molar weight of 80 g / mol) of the modified polyisocyanate is from 0.75% by weight to 1.0% by weight based on the amount of the modified polyisocyanate as 100% by weight; the viscosity of the modified polyisocyanate is determined at a temperature of 23 °C and a shear rate of 10 s in accordance with DIN EN ISO 3219:1994-10 and is from 3000 mPa·s to 7000 mPa·s. - which means) is from 0.75% by weight to 1.0% by weight based on the amount of the modified polyisocyanate as 100% by weight; the viscosity of the modified polyisocyanate is determined at a temperature of 23 °C and a shear rate of 10 s -1 in accordance with DIN EN ISO 3219:1994-10 and is from 3000 mPa·s to 7000 mPa·s.

[0100] Method for preparing modified polyisocyanate The method for preparing the modified polyisocyanate includes a step of carrying out a reaction at a temperature of 40 °C to 150 °C in the presence of component a, component b, component c and optionally component d, and maintaining the molar equivalent ratio of the groups reactive with the NCO groups to the NCO groups at 2:1 to 400:1.

[0101] The reaction temperature is preferably from 50 °C to 130 °C.

[0102] The molar equivalent ratio of the groups reactive with the NCO groups to the NCO groups is preferably from 4:1 to 250:1, and most preferably until the theoretically calculated NCO content is achieved in the reaction.

[0103] The modified polyisocyanate is transparent, colorless or almost colorless.

[0104] Use The modified polyisocyanate is preferably used in the form of an aqueous emulsion.

[0105] The polyisocyanate of the present invention is preferably used as a crosslinking component for a water-soluble or water-dispersible coating, adhesive or sealant having a group reactive with an isocyanate group, particularly a hydroxyl group, and is used in the production of a coating layer based on such an aqueous coating, adhesive or sealant.

[0106] When the modified polyisocyanate of the present invention is used as a crosslinking component for components of a water-soluble or water-dispersible coating, the molar ratio of the NCO groups of the modified polyisocyanate to the groups reactive with the NCO groups, particularly hydroxyl groups, is preferably 0.5:1 to 2:1.

[0107] When the modified polyisocyanate of the present invention is used as a crosslinking component in a water-soluble or water-dispersible adhesive or sealant, it may be incorporated, if necessary, in a relatively small amount into a non-functional water-soluble or water-dispersible adhesive or sealant, and as a result, very specific properties can be obtained, for example, as an additive for improving adhesiveness. For example, it is used as a papermaking aid or additive that does not contain absorbent halides, or for inorganic building materials such as concrete or mortar.

[0108] The coating, adhesive or sealant containing the above-mentioned modified polyisocyanate may further contain a polyisocyanate different from the above-mentioned modified polyisocyanate. The polyisocyanate different from the above-mentioned modified polyisocyanate is preferably added to the above-mentioned modified polyisocyanate before the above-mentioned modified polyisocyanate is mixed with the resin component.

[0109] The polyisocyanate different from the above-mentioned modified polyisocyanate is preferably used in an amount such that the properties of the coating, adhesive or sealant containing the aqueous hydroxy resin dispersion and the modified polyisocyanate are not affected. For this combination, the modified polyisocyanate of the present invention acts as an emulsifier for the polyisocyanate different from the above-mentioned modified polyisocyanate.

[0110] Use in the preparation of polyurethane The modified polyisocyanate can also be used in the form blocked with a blocking agent in an aqueous one-component polyurethane system. Suitable blocking agents are, for example, diethyl malonate, ethyl acetoacetate, acetoxime, butanone oxime, ε-caprolactam, 3,5-dimethylpyrazole, 1,2,4-triazole, dimethyl-1,2,4-triazole, imidazole or any mixture of these blocking agents.

[0111] The modified polyisocyanate has excellent emulsifiability in water and can be uniformly distributed. The coating layer formed from the polyurethane of the aforementioned modified polyisocyanate has excellent optical properties, particularly high surface gloss and high transparency.

[0112] Manufacturing method of products The coating can be carried out using mechanical tools known to those skilled in the art or using a two-component spray gun.

[0113] The substrate can be any substrate, preferably metal, wood, alloy, inorganic material, glass, stone, ceramic raw material, concrete, hard synthetic material, soft synthetic material, fabric, leather or paper, most preferably wood, metal, alloy or inorganic material.

[0114] The substrate may optionally have a normal primer before being coated.

[0115] Water-based two-component coating The aqueous hydroxy resin dispersion is preferably a dispersion of a hydroxyl group-containing polyacrylate, and most preferably a dispersion of a hydroxyl group-containing polyacrylate having a weight average molecular weight of 1000 to 10000.

[0116] Generally, all compounds that are soluble or dispersible in water and contain groups reactive towards isocyanates are suitable as reaction partners for the aqueous two-component coatings of the present invention, for example as polyurethanes or polyureas dispersed in water, where the active hydrogen atoms are present in urethane or urea groups and the polyurethanes or polyureas can be crosslinked with modified polyisocyanates.

[0117] The aqueous two-component coatings may optionally contain one or more of the following substances, which are common auxiliaries and additives in the field of coatings: flow aids, coloring pigments, fillers, defoamers, co-solvents, matting agents, and emulsifiers.

[0118] The coating layer formed by drying the aqueous two-component coating at room temperature has good properties.

[0119] The aqueous two-component coatings may also be dried at elevated temperatures, or may be dried at temperatures up to 260 °C.

[0120] The aqueous two-component coatings may be wood coatings, textile coatings, plastic coatings, architectural coatings or metal coatings, most preferably wood coatings.

Examples

[0121] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art of the present invention. In case of conflict between the definitions of terms herein and the commonly understood meaning by one of ordinary skill in the art, the definitions provided herein shall prevail.

[0122] Unless otherwise specified, all numbers expressing amounts of ingredients, reaction conditions, etc. used in this specification and the claims are to be understood as being modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximate values that can vary as desired depending on the properties.

[0123] Unless otherwise specified, as used herein, "a," "an," and "the" mean "at least one" or "one or more." For example, "a component" refers to one or more components, and thus two or more components are contemplated, used, or can be used in the practice of embodiments.

[0124] As used herein, "and / or" refers to one or all of the recited elements.

[0125] As used herein, "including" and "comprising" include cases where only the recited elements are present and cases where other unrecited elements are present in addition to the recited elements.

[0126] All percentages in the present invention are weight percentages unless otherwise specified.

[0127] The analytical measurements of the present invention were carried out at 23 °C unless otherwise specified.

[0128] The weight ratio of the iminooxadiazinedione structure to the isocyanurate structure in the polyisocyanate is 13 determined by 13C NMR. The test apparatus was a Bruker DPX-400. The weight ratio of the iminooxadiazinedione structure:isocyanurate structure = 1:(integration area @ 148.4 ppm) / (integration area @ 147.9 ppm + integration area @ 144.5 ppm + integration area @ 135.3 ppm).

[0129] In the reaction for preparing a modified polyisocyanate from the polyisocyanate of the present invention, the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure in the modified polyisocyanate is the same as the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure in the polyisocyanate.

[0130] Viscosity was determined in accordance with DIN EN ISO 3219:1994-10 at a temperature of 23 °C and a shear rate of 10 s -1 using an MV-DIN rotor. The isocyanate group (NCO) content was determined in accordance with DIN-EN ISO 11909:2007-05. The measurement data refer to the free and potentially free NCO content. Standard for color value test: DIN-EN1557:1997-03. Standard for gloss test: GB / T 9754-2007. Standard for haze test: ASTM E430-11.

[0131] Raw materials and reagents Polyisocyanate P1: A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen injection tube and dropping funnel was placed under a nitrogen atmosphere. 850 g of hexamethylene diisocyanate (HDI) was added thereto and heated to 65 °C with stirring. Next, 5.5 g of trimethyl-2-methyl-2-hydroxyethylammonium hydroxide (a solution diluted to 5 wt% with isobutanol) was added as a catalyst. When the NCO content of the reaction solution reached 45.6 wt%, 1.1 g of di-n-butyl phosphate was added to stop the reaction. Unreacted monomers were removed by a thin-film evaporator at 140 °C and a vacuum of 0.05 mbar. A polyisocyanate P1 with a non-volatile content of 100 wt%, a viscosity of 1200 mPa·s (23.5 °C), an NCO content of 23.0 wt%, an HDI monomer concentration of 0.25 wt%, and a weight ratio of iminooxadiazinedione structure to isocyanurate structure of 1:27.57 was obtained.

[0132] Polyisocyanate P2: The preparation method of P1 was carried out. The reaction was terminated when the NCO content of the reaction solution reached 38%. Unreacted monomers were removed by a thin-film evaporator at 140 °C and a vacuum of 0.05 mbar. A polyisocyanate P2 with a non-volatile content of 100 wt%, a viscosity of 3000 mPa·s (23.5 °C), an NCO content of 21.7 wt%, an HDI monomer concentration of 0.25 wt%, and a weight ratio of iminooxadiazinedione structure to isocyanurate structure of 1:20.28 was obtained.

[0133] The preparation method of polyisocyanate P3:P1 was carried out. The reaction was terminated when the NCO content of the reaction solution reached 32%. The unreacted monomer was removed by a thin-film evaporator at 140 °C and a vacuum of 0.05 mbar. Polyisocyanate P3 with a non-volatile content of 100% by weight, a viscosity of 16000 mPa·s (23.5 °C), an NCO content of 20.0% by weight, an HDI monomer concentration of 0.25% by weight, and a weight ratio of iminooxadiazinedione structure to isocyanurate structure of 1:27.57 was obtained.

[0134] The preparation method of polyisocyanate P4:P1 was carried out. A tetrabutylphosphonium hydrogen difluoride solution was used as the catalyst (diluted to 50% with an isopropanol / methanol solvent with a weight ratio of 2:1). Dibutyl phosphate was added to terminate the reaction when the NCO content of the reaction solution reached 32%. Polyisocyanate P4 with a non-volatile content of 100% by weight, a viscosity of 700 mPa·s (23.5 °C), an NCO content of 23.4% by weight, an HDI monomer concentration of 0.25% by weight, and a weight ratio of iminooxadiazinedione structure to isocyanurate structure of 1:1.28 was obtained.

[0135] Tolonate HDT-LV2: A commercially available product based on hexamethylene diisocyanate, with an NCO content of 23.0% by weight and an HDI monomer concentration of less than 0.5% by weight, and a weight ratio of iminooxadiazinedione structure to isocyanurate structure below the detection limit, available from VENCOREX. Tetrabutylphosphonium hydrogen difluoride solution: Purchased from Jinjinle Chemical Company. Isopropanol: Purchased from Sigma-Aldrich. Methanol: Purchased from Sigma-Aldrich. 3-Cyclohexylaminopropanesulfonic acid: Purchased from Sigma-Aldrich. N,N-Dimethylcyclohexylamine: Purchased from Sigma-Aldrich. Trimethyl-2-methyl-2-hydroxyethylammonium hydroxide: Purchased from Sigma-Aldrich. Bayhydrol A 2470: An aqueous hydroxyacrylate dispersion available from Covestro, Germany. BYK028: A silicone defoamer (a mixture of foam-breaking polysiloxane and hydrophobic particles in polyethylene glycol) purchased from BYK, Germany. BYK346: A wetting and leveling agent (a polyether-modified siloxane solution) available from BYK, Germany. BUTYL CELLOSOLVE: A co-solvent, ethylene glycol butyl ether, purchased from Dow Chemical, USA. RHEOVIS PU 1291: A rheology additive, an associative thickener: a hydrophobically modified ethoxylated urethane, purchased from BASF, Germany.

[0136] Modified polyisocyanate 1 27 g (0.14 eq) of polyisocyanate P2, 100 g (0.53 eq) of Tolonate HDT-LV2, 3.6 g (0.016 eq) of 3-cyclohexylaminopropanesulfonic acid and 2.08 g (0.016 mol) of dimethylcyclohexylamine were stirred at 80 °C for 4 hours under dry nitrogen and then cooled to room temperature. The modified polyisocyanate of the present invention was obtained with the following characteristic data. The aforementioned modified polyisocyanate was in the form of a colorless transparent solution: Solid content: 100 wt% NCO content: 20.78 wt% Viscosity (23 °C): 2907 mPa·s Color value (Hazen): 57 Sulfonate group content: 0.98 wt% (The sulfonate group has a molar weight of 80 g / mol of SO3 - is meant) Iminooxadiazinedione / isocyanurate: 1:100 Ethylene oxide group content: 0.0 wt%

[0137] Modified polyisocyanate 2 215.44 g (1.10 eq) of polyisocyanate P2, 502.5 g (2.72 eq) of polyisocyanate P1, 20.3 g (0.09 eq) of 3 - cyclohexylaminopropanesulfonic acid and 11.7 g (0.09 mol) of dimethylcyclohexylamine were stirred at 80 °C for 4 hours under dry nitrogen and then cooled to room temperature. The modified polyisocyanate of the present invention was obtained with the following characteristic data. The aforementioned modified polyisocyanate was in the form of a colorless and transparent solution: Solid content: 100 wt% NCO content: 21.32 wt% Viscosity (23 °C): 3293 mPa·s Color value (Hazen): 18 Sulfonate group content: 0.98 wt% (The sulfonate group means SO3 having a molar weight of 80 g / mol) - (means) Iminooxadiazinedione / isocyanurate: 1:26.07 Ethylene oxide group content: 0.0 wt%

[0138] Modified polyisocyanate 3 1705 g (8.74 eq) of polyisocyanate P2, 48.3 g (0.22 eq) of 3 - cyclohexylaminopropanesulfonic acid and 27.8 g (0.22 mol) of dimethylcyclohexylamine were stirred at 80 °C for 4 hours under dry nitrogen and then cooled to room temperature. The modified polyisocyanate of the present invention was obtained with the following characteristic data. The aforementioned modified polyisocyanate was in the form of a colorless and transparent solution: Solid content: 100 wt% NCO content: 20.47 wt% Viscosity (23 °C): 5992 mPa·s Color value (Hazen): 7 Sulfonate group content: 0.98 wt% (The sulfonate group means SO3 having a molar weight of 80 g / mol) - (means) Iminooxadiazinedione / isocyanurate: 1:21.2 Ethylene oxide group content: 0.0 wt%

[0139] Modified polyisocyanate 4 657 g (3.37 eq) of polyisocyanate P2, 69.8 g (0.39 eq) of polyisocyanate P4, 20.6 g (0.09 eq) of 3 - cyclohexylaminopropanesulfonic acid and 11.9 g (0.09 mol) of dimethylcyclohexylamine were stirred at 80 °C for 4 hours under dry nitrogen and then cooled to room temperature. The modified polyisocyanate of the present invention was obtained with the following characteristic data. The aforementioned modified polyisocyanate was in the form of a colorless transparent solution: Solid content: 100% by weight NCO content: 20.11% by weight Viscosity (23 °C): 6645 mPa·s Color value (Hazen): 18 Sulfonate group content: 0.98% by weight (the sulfonate group means SO3 having a molar weight of 80 g / mol) - means) Iminooxadiazinedione / isocyanurate: 1:11.35 Ethylene oxide group content: 0.0% by weight

[0140] Modified polyisocyanate 5 565.01 g (2.90 eq) of polyisocyanate P2, 131 g (0.73 eq) of polyisocyanate P4, 19.7 g (0.09 eq) of 3 - cyclohexylaminopropanesulfonic acid and 11.9 g (0.09 mol) of dimethylcyclohexylamine were stirred at 80 °C for 4 hours under dry nitrogen and then cooled to room temperature. The modified polyisocyanate of the present invention was obtained with the following characteristic data. The aforementioned modified polyisocyanate was in the form of a colorless transparent solution: Solid content: 100% by weight NCO content: 20.7% by weight Viscosity (23 °C): 4690 mPa·s Color value (Hazen): 17 Sulfonate group content: 0.98% by weight (the sulfonate group means SO3 having a molar weight of 80 g / mol) - means) Iminooxadiazinedione / Isocyanurate: 1:7.67 Ethylene oxide group content: 0.0 wt%

[0141] Modified polyisocyanate 6 718 g (3.68 eq) of polyisocyanate P2, 16.3 g (0.07 eq) of 3 - cyclohexylaminopropanesulfonic acid and 8.82 g (0.07 mol) of dimethylcyclohexylamine were stirred at 80 °C for 4 hours under dry nitrogen and cooled to room temperature. A mixture of the modified polyisocyanates of the present invention was obtained with the following characteristic data. The aforementioned mixture of modified polyisocyanates was in the form of a colorless transparent solution: Solid content: 100 wt% NCO content: 20.6 wt% Viscosity (23 °C): 5743 mPa·s Color value (Hazen): 20 Sulfonate group content: 0.79 wt% (The sulfonate group has a molar weight of 80 g / mol for SO3 - is meant) Iminooxadiazinedione / Isocyanurate: 1:21.03 Ethylene oxide group content: 0.0 wt%

[0142] Modified polyisocyanate 7 125 g (0.6 eq) of modified polyisocyanate 3, 1.92 g (0.005 mol) of a monofunctional polyethylene oxide polyether alcohol starting from methanol and having an average molecular weight of 350 were stirred at 95 °C for 4 hours under dry nitrogen and cooled to room temperature. Modified polyisocyanates were obtained with the following characteristic data. The aforementioned modified polyisocyanates were in the form of a colorless transparent solution: Solid content: 100 wt% NCO content: 19.46 wt% Viscosity (23 °C): 9839 mPa·s Color value (Hazen): 0 Sulfonate group content: 0.96 wt% (The sulfonate group has a molar weight of 80 g / mol for SO3 - is meant) Iminooxadiazinedione / Isocyanurate: 1:21.3 Ethylene oxide group content: 1.4 wt%

[0143] Comparative modified polyisocyanate 1 718.21 g (3.68 eq) of polyisocyanate P2, 12.78 g (0.06 eq) of 3-cyclohexylaminopropanesulfonic acid and 7.72 g (0.06 mol) of dimethylcyclohexylamine were stirred at 80 °C for 4 hours under dry nitrogen and then cooled to room temperature. A comparative modified polyisocyanate was obtained with the following characteristic data. The aforementioned comparative modified polyisocyanate was in the form of a colorless transparent solution: Solid content: 100 wt% NCO content: 20.85 wt% Viscosity (23 °C): 5296 mPa·s Color value (Hazen): 14 Sulfonate group content: 0.62 wt% (the sulfonate group has a molar weight of 80 g / mol for SO3 - is meant) Iminooxadiazinedione / Isocyanurate: 1:20.89 Ethylene oxide group content: 0.0 wt%

[0144] Comparative modified polyisocyanate 2 718.02 g (3.68 eq) of polyisocyanate P2, 15.24 g (0.07 eq) of 3-cyclohexylaminopropanesulfonic acid and 8.82 g (0.07 eq) of dimethylcyclohexylamine were stirred at 80 °C for 4 hours under dry nitrogen and then cooled to room temperature. A comparative modified polyisocyanate was obtained with the following characteristic data. The aforementioned comparative modified polyisocyanate was in the form of a colorless transparent solution: Solid content: 100 wt% NCO content: 20.26 wt% Viscosity (23 °C): 7012 mPa·s Color value (Hazen): 20 Sulfonate group content: 0.73 wt% (the sulfonate group has a molar weight of 80 g / mol for SO3 - is meant) Iminooxadiazinedione / Isocyanurate: 1:20.98 Ethylene oxide group content: 0.0 wt%

[0145] Comparative modified polyisocyanate 3 718.1 g (3.68 eq) of polyisocyanate P2, 24 g (0.11 eq) of 3 - cyclohexylaminopropanesulfonic acid, and 14.01 g (0.11 mol) of dimethylcyclohexylamine were stirred at 80 °C for 4 hours under dry nitrogen and then cooled to room temperature. A comparative modified polyisocyanate was obtained with the following characteristic data. The aforementioned comparative modified polyisocyanate was in the form of a colorless transparent solution: Solid content: 100 wt% NCO content: 19.76 wt% Viscosity (23 °C): 9361 mPa·s Color value (Hazen): 18 Sulfonate group content: 1.15 wt% (The sulfonate group has a molar weight of 80 g / mol for SO3 - is meant) Iminooxadiazinedione / Isocyanurate: 1:21.41 Ethylene oxide group content: 0.0 wt%

[0146] Comparative modified polyisocyanate 4 717.9 g (3.42 eq) of polyisocyanate P3, 20.31 g (0.09 eq) of 3 - cyclohexylaminopropanesulfonic acid, and 11.7 g (0.09 mol) of dimethylcyclohexylamine were stirred at 80 °C for 4 hours under dry nitrogen and then cooled to room temperature. A comparative modified polyisocyanate was obtained with the following characteristic data. The aforementioned comparative modified polyisocyanate was in the form of a colorless transparent solution: Solid content: 100 wt% NCO content: 17.64 wt% Viscosity (23 °C): 32740 mPa·s Color value (Hazen): 24 Sulfonate group content: 0.98 wt% (The sulfonate group has a molar weight of 80 g / mol for SO3 -(meaning Iminooxadiazinedione / Isocyanurate: 1:27.57 Ethylene oxide group content: 0.0 wt%

[0147] Comparative modified polyisocyanate 5 428.7 g (2.20 eq) of polyisocyanate P2, 285.12 g (1.58 eq) of polyisocyanate P4, 20.32 g (0.09 eq) of 3 - cyclohexylaminopropanesulfonic acid, and 11.7 g (0.09 mol) of dimethylcyclohexylamine were stirred at 80 °C for 4 hours under dry nitrogen and then cooled to room temperature. A comparative modified polyisocyanate was obtained with the following characteristic data. The aforementioned comparative modified polyisocyanate was in the form of a colorless transparent solution: Solids content: 100 wt% NCO content: 20.9 wt% Viscosity (23 °C): 3501 mPa·s Color value (Hazen): 16 Sulfonate group content: 0.98 wt% (The sulfonate group has a molar weight of 80 g / mol for SO3 - (meaning Iminooxadiazinedione / Isocyanurate: 1:4.15 Ethylene oxide group content: 0.0 wt%

[0148] Method for preparing water-based two-component coatings of examples and comparative examples Formulation of Component A: According to the formulation shown in Table 1, an antifoaming agent, a leveling agent, a co - solvent, a rheology additive, and water were continuously added to a hydroxyacrylic resin or a hydroxypolyurethane resin. It was dispersed at a high speed of 1500 rpm for 20 minutes. Component A was thus obtained.

[0149] [Table 1]

[0150] 50 g of Component A and the modified polyisocyanate of the present invention or a comparative modified polyisocyanate (the molar ratio of isocyanate groups to hydroxyl groups was 1.5:1) were mixed and manually stirred for 30 seconds using a wooden stick. In this way, the aqueous two-component coatings of the examples and comparative examples were obtained.

[0151] Test method for water dispersibility 7.5 g of water was added to the aqueous two-component coating. The mixture was manually stirred uniformly and filtered through a 100-mesh filter sieve. The residue on the filter sieve was visually observed. The less residue present on the filter sieve, the better the dispersibility of the modified polyisocyanate in the resin system. According to the amount of residue on the filter sieve, the dispersibility of the modified polyisocyanate in the resin system was graded from 1 to 3. 1 means a large amount of residue on the filter sieve; 2 means a relatively large amount of residue on the filter sieve; 3 means almost no residue on the filter sieve. 1 means the worst and 3 means the best.

[0152] Test conditions for gloss and haze 7.5 g of water was added to the aqueous two-component coating. The mixture was manually stirred uniformly and filtered through a 100-mesh filter sieve. The filtered coating was applied to a black plastic plate with a wet film thickness of 120 μm and dried in air. In this way, a coating layer was obtained, and its gloss and haze were measured.

[0153] Evaluation criteria for gloss and haze: 60° gloss > 80, haze value < 100. The larger the 60° gloss value, the higher the gloss of the coating layer, and the larger the haze value, the lower the transparency of the coating layer. Table 2 shows the formulations and test results of the aqueous two-component coatings of Examples 1 to 5 and Comparative Example 1. Table 3 shows the formulations and test results of the aqueous two-component coatings of Examples 3, 6 and Comparative Examples 2 to 4. Table 4 shows the formulations and test results of the aqueous two-component coatings of Examples 3, 7 and Comparative Example 5. Table 5 shows the formulations and test results of the aqueous two-component coatings of Examples 3 and 8 and Comparative Examples 1 and 6.

[0154]

Table 2

[0155] The weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified polyisocyanate contained in the aqueous two-component coatings of Examples 1 to 5 was 1:300 to 1:5. In particular, at 1:100 to 1:5, the aqueous two-component coating had almost no residue on the filter sieve, and the modified polyisocyanate showed good dispersibility in the coating components, that is, the coating could be sufficiently stirred manually, and the coating layer formed by the coating showed excellent transparency and gloss.

[0156] The weight ratio of the iminooxadiazinedione structure to the isocyanurate structure in the comparative modified polyisocyanate contained in the comparative aqueous two-component coating of Comparative Example 1 was 1:4.15. The coating layer formed by the coating showed excellent transparency and gloss. However, the aqueous two-component coating had a large amount of residue on the filter sieve, and the comparative modified polyisocyanate showed insufficient dispersibility in the coating components, that is, its ability to stir the coating manually was insufficient.

[0157]

Table 3

[0158] The sulfonate group content of the modified polyisocyanate contained in the aqueous two-component coatings of Examples 3 and 6 was 0.75 wt% to 1.1 wt%. The aqueous two-component coatings had almost no residue on the filter sieve. The modified polyisocyanate had good dispersibility in the coating components, that is, the coating could be sufficiently stirred manually, and the coating layer formed by the coating had excellent transparency and gloss.

[0159] The sulfonate group content of the comparative modified polyisocyanate contained in the comparative aqueous two-component coatings of Comparative Examples 2 to 4 was less than or more than 0.75 wt% to 1.1 wt%. The aqueous two-component coatings had relatively more residues on the filter sieve. The comparative modified polyisocyanate showed insufficient dispersibility in the coating components, that is, its ability to stir the coating manually was insufficient. Alternatively, the coating layer formed by the coating showed insufficient transparency and gloss.

[0160]

Table 4

[0161] The viscosity of the modified polyisocyanate contained in the aqueous two-component coatings of Examples 3 and 7 was 500 mPa·s to 10,000 mPa·s. The aqueous two-component coatings had almost no residue on the filter sieve. The modified polyisocyanate showed good dispersibility in the coating components, that is, the coating could be sufficiently stirred manually. The coating layer formed by the coating showed excellent transparency and gloss.

[0162] The modified polyisocyanate contained in the comparative aqueous two-component coating of Comparative Example 5 had a viscosity exceeding 10,000 mPa·s. The coating layer formed by that coating exhibited insufficient transparency and gloss. The aqueous two-component coating had a relatively large amount of residue on the filter sieve. The comparative modified polyisocyanate showed insufficient dispersibility in the coating components, that is, its ability to manually stir the coating was insufficient.

[0163]

Table 5

[0164] Regardless of whether the modified polyisocyanate contained in the aqueous two-component coating was diluted with an organic solvent, the aqueous two-component coating had almost no residue on the filter sieve. The modified polyisocyanate showed good dispersibility in the coating components, that is, the coating could be sufficiently stirred manually. The coating layer formed by that coating exhibited excellent transparency and gloss.

[0165] The comparative modified polyisocyanate contained in the comparative aqueous two-component coating of Comparative Example 1 showed insufficient dispersibility in the coating components. After diluting the comparative modified polyisocyanate with an organic solvent (Comparative Example 6), its dispersibility was significantly improved.

[0166] It is obvious to those skilled in the art that the present invention is not limited to the above-mentioned specific details and may be implemented in other specific forms without departing from the spirit or main features of the present invention. Therefore, the embodiments should be regarded as illustrative in all respects and not restrictive. Therefore, the scope of the present invention is defined by the scope of the claims rather than the foregoing description. Therefore, any changes within the meaning and scope of the equivalents of the claims are considered to belong to the present invention.

Claims

1. The following components: a. Formula I 【Chemical 1】 (wherein R1 and R2 are each independently hydrogen, an aliphatic group having 1 to 18 carbon atoms which may or may not be substituted and / or contains a heteroatom, a cycloaliphatic group having 3 to 18 carbon atoms which may or may not be substituted and / or contains a heteroatom, an aromatic group having 6 to 18 carbon atoms which may or may not be substituted and / or contains a heteroatom; R1 and R2 can react with each other to form a cycloaliphatic group having 3 to 8 carbon atoms, or a heterocyclic group having 3 to 8 carbon atoms substituted with an oxygen atom or a nitrogen atom; R3 represents a linear or branched aliphatic group having 2 to 8 carbon atoms) at least one aminosulfonic acid represented by; b. At least one polyisocyanate; c. At least one tertiary amine; and d. Optionally, a polyether alcohol containing an ethylene oxide group; A modified polyisocyanate obtained by the reaction of a system containing, the modified polyisocyanate contains at least one iminooxadiazinedione structure and at least one isocyanurate structure, and the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure is 1:300 to 1:5; the amount of sulfonate groups in the modified polyisocyanate is 0.75% by weight to 1.1% by weight based on the amount of the modified polyisocyanate as 100% by weight; the viscosity of the modified polyisocyanate is determined according to DIN EN ISO 3219:1994-10 at a temperature of 23 °C and a shear rate of 10 s －１ and is 500 mPa·s to 10,000 mPa·s, a modified polyisocyanate.

2. The modified polyisocyanate is characterized in that the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure is 1:200 to 1:5, and the modified polyisocyanate according to claim 1.

3. The viscosity of the modified polyisocyanate is determined according to DIN EN ISO 3219:1994-10 at a temperature of 23 °C and a shear rate of 10 s －１ and is 500 mPa·s to 7000 mPa·s, and the modified polyisocyanate according to claim 1.

4. The amount of the sulfonate group of the modified polyisocyanate is 0.75% by weight to 1.0% by weight based on the amount of the modified polyisocyanate as 100% by weight, and the modified polyisocyanate according to claim 1.

5. R3 represents a linear or branched aliphatic group having 2 to 4 carbon atoms, and the modified polyisocyanate according to any one of claims 1 to 4.

6. The aminosulfonic acid is one or more of compounds of 3-cyclohexylaminopropanesulfonic acid, 4-(cyclohexylamino)-1-butanesulfonic acid and 2-(cyclohexylamino)ethanesulfonic acid, and the modified polyisocyanate according to any one of claims 1 to 4.

7. The amount of the aminosulfonic acid is 1.5% by weight to 3.5% by weight based on the amounts of components a and b as 100% by weight, and the modified polyisocyanate according to any one of claims 1 to 4.

8. The polyisocyanate contains at least one iminooxadiazinedione structure and at least one isocyanurate structure, and the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure is 1:300 to 1:5, and the modified polyisocyanate according to any one of claims 1 to 4.

9. The modified polyisocyanate according to any one of claims 1 to 4, characterized in that the polyisocyanate is one or more of compounds of aliphatic polyisocyanates and cycloaliphatic polyisocyanates.

10. The modified polyisocyanate according to any one of claims 1 to 4, characterized in that the polyether alcohol containing an ethylene oxide group has an ethylene oxide group content of 0 to 17% by weight based on the amount of the components of the reaction as 100% by weight.

11. The modified polyisocyanate is obtained by a reaction of a system containing the following components: a. 3 - cyclohexylaminopropanesulfonic acid; b. A derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure; and c. A tertiary amine; and is obtained by a reaction of a system containing the following components: The weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified polyisocyanate is 1:30 to 1:7, and the amount of the sulfonate group of the modified polyisocyanate is 0.75% to 1.1% by weight based on the amount of the modified polyisocyanate as 100% by weight; the viscosity of the modified polyisocyanate is determined according to DIN EN ISO 3219:1994 - 10 at a temperature of 23 °C and a shear rate of 10 s －１ and is 500 mPa·s to 10,000 mPa·s, which is the modified polyisocyanate according to claim 1 or 2.

12. The modified polyisocyanate is obtained by a reaction of a system containing the following components: a. 3 - cyclohexylaminopropanesulfonic acid (where the amount of 3 - cyclohexylaminopropanesulfonic acid is 2% to 3% by weight based on the amounts of components a and b as 100% by weight); b. A derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure; and c. N,N-dimethylcyclohexylamine present in a molar equivalent ratio of 0.3 to 1.9 with respect to the sulfonate group of 3-cyclohexylaminopropanesulfonic acid; obtained by the reaction of a system containing the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified polyisocyanate is 1:30 to 1:20; the amount of the sulfonate group of the modified polyisocyanate is 0.75% by weight to 1.0% by weight based on the amount of the modified polyisocyanate as 100% by weight; the viscosity of the modified polyisocyanate is determined according to DIN EN ISO 3219:1994-10 at a temperature of 23 °C and a shear rate of 10 s －１ and is 3000 mPa·s to 7000 mPa·s, the modified polyisocyanate according to any one of claims 1 to 4.

13. Use of the modified polyisocyanate according to any one of claims 1 to 12 as an initial component in the preparation of polyurethanes.

14. Use of the modified polyisocyanate according to any one of claims 1 to 12 as a crosslinking component in a water-soluble or water-dispersible coating, adhesive or sealant.

15. Use of the modified polyisocyanate according to any one of claims 1 to 12 as an initial component for the preparation of a blocked polyisocyanate blocked with a blocking agent.

16. A coating, adhesive or sealant comprising the modified polyisocyanate according to any one of claims 1 to 12.

17. A substrate coated with the coating, adhesive or sealant according to claim 16.

18. Use of the modified polyisocyanate according to any one of claims 1 to 12 to improve the manual stirring behavior of a coating, adhesive or sealant.

19. Use of the modified polyisocyanate according to any one of claims 1 to 12 as a crosslinking component in a water-soluble or water-dispersible aqueous two-component coating.

20. An aqueous two-component coating comprising at least one aqueous hydroxy resin dispersion, at least one modified polyisocyanate according to any one of claims 1 to 12, optionally an auxiliary agent, and optionally an additive.

21. A method for preparing an aqueous two-component coating, comprising the steps of mixing an aqueous hydroxy resin dispersion, optionally an auxiliary agent, and optionally an additive in any manner to obtain a mixture, mixing the modified polyisocyanate according to any one of claims 1 to 12 and the mixture, and manually stirring to obtain an aqueous two-component coating.

22. A product comprising a substrate and a coating formed by applying the aqueous two-component coating according to claim 20 to the substrate.

23. The product according to claim 22, wherein the substrate is wood, metal, alloy or inorganic material.

24. The product according to claim 22, wherein the product is furniture.

25. A method for manufacturing a product, comprising the steps of applying the aqueous two-component coating according to claim 20 to a substrate, and subsequently curing and drying.

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