Aqueous radiation-curable compositions for soft-feel applications

Abstract

An aqueous radiation curable composition comprising: a radiation curable polyurethane dispersion obtained by reacting a. a compound comprising at least two isocyanate groups; b. a polyol having a molecular weight of at least 500 g / mol; c. a compound comprising at least one group capable of reacting with an isocyanate group and at least one hydrophilic group; and d. an ethylenically unsaturated compound comprising at least one group capable of reacting with an isocyanate group and at least one ethylenically unsaturated group; a plurality of polyurethane particles having a median particle size D50 of 1 to 10 μm; and water.

Description

[Technical Field]

[0001] The present invention relates to an aqueous radiation-curable composition, a coating comprising the composition, a method for forming the composition, a method for forming the coating, and the use of the coating in the field of coating applications, more particularly to the use of the coating in the field of soft-feel applications, such as in automotive interiors. [Background technology]

[0002] The coating protects the surface from degradation that may occur due to chemicals and / or abrasion. Soft-feel coatings can have the added ability to transform the sometimes unattractive tactile feel of a surface (e.g., a plastic surface) into a comfortable feel similar to rubber, leather, or velvet. This allows manufacturers to use relatively inexpensive materials, such as plastic, and apply the coating to give them the appearance of high-end luxury goods. The coating can provide consumers with a high-quality and even luxurious appearance. The demand for soft-feel coatings is increasing. Such coatings can be used in many applications, including consumer electronics (e.g., laptop and mobile phone casings), home appliances (e.g., ovens and coffee makers), automotive interiors (e.g., panels, holders, and armrests), packaging materials (e.g., cosmetic bottles / caps and bags), and textured films for in-mold decoration / in-mold labeling (IMD / IML).

[0003] Current soft-feel coatings used in automobiles can be formed from conventional two-component aqueous compositions. Such soft-feel coatings typically lack the chemical resistance required specifically against sunscreens and insecticides (e.g., N,N-diethylmetotoluamide, i.e., DEET). Instead, the required chemical resistance is provided by a primer layer present beneath the soft-feel coating. Providing a primer layer requires additional time and expense.

[0004] Solvent-based curable compositions (where the solvent is typically a volatile organic compound) are commercially available (e.g., commercially available compositions EBECRYL® 8896 and EBECRYL® 8894). However, solvent-based compositions typically do not provide the soft touch required for automotive interiors. Furthermore, the coatings formed therefrom do not pass the necessary chemical tests, i.e., they do not possess the required chemical resistance.

[0005] Solvent-based curable compositions also have drawbacks from a regulatory standpoint. For example, the solvents are typically volatile organic compounds, which are undesirable from a sustainability perspective.

[0006] The market currently sees a demand for improvements to conventional coatings due to their poor chemical and scratch resistance. The introduction of water-based UV technology could revolutionize the soft-touch market.

[0007] Therefore, aqueous coating compositions with good soft-feel properties and chemical resistance are still needed in this field. [Overview of the project] [Problems that the invention aims to solve]

[0008] Therefore, an object of the present invention is to develop a radiation-curable composition and a coating formed from said composition that overcome some of the above-mentioned drawbacks, at least partially. [Means for solving the problem]

[0009] Compositions according to embodiments of the present invention and coatings formed from such compositions may have one or more of the following advantages: The embodiments of the composition are easier to apply compared to, for example, state-of-the-art two-component aqueous compositions. In particular, the application of a primer layer to the surface before applying the composition to the surface may not be necessary. Therefore, the method of applying the composition can be simple and cost-effective. High-performance equipment, such as a two-component spray gun, is typically not required for applying the composition. • Volatile organic compounds (e.g., organic solvents) are typically unnecessary in the composition. Furthermore, the amount of unreacted, i.e., free isocyanate groups in the composition can be small. This makes the composition a sustainable and safe choice from a regulatory standpoint. In addition, the absence of reactive free isocyanate groups typically extends the lifespan, i.e., pot life, of the composition. • The potential extension of the composition's lifespan, i.e., pot life, allows for the preparation of larger batches. This can lead to further cost savings. The composition can have good spray viscosity. Furthermore, the coating can be formed from the composition at low temperatures. Unlike conventional aqueous compositions, embodiments of the compositions of the present invention may not contain formaldehyde, alkylphenol ethoxylate (APEO), N-methylpyrrolidone (NMP), or N-ethylpyrrolidone (NEP). Because the composition is radiation-curable, the time required to cure the composition to form a coating can be short. For example, the curing may take less than a second, rather than an hour. The composition can provide a coating with a soft feel. Furthermore, the composition can provide a coating with good chemical stability and good to excellent chemical resistance to sunscreens and insecticides, such as N,N-diethylmetotoluamide (DEET). The composition according to the present invention can provide a coating with good adhesion.

[0010] In a first embodiment, the present invention relates to an aqueous radiation-curable composition comprising: a radiation-curable polyurethane aqueous dispersion, also called a radiation-curable polyurethane dispersion, obtained by reacting a: a compound containing at least two isocyanate groups; b: a polyol having a molecular weight of at least 500 g / mol; c: a compound containing at least one group capable of reacting with isocyanate groups and preferably a salt or capable of containing a salt after reaction with a neutralizing agent; and d: an ethylenically unsaturated compound containing at least one group capable of reacting with isocyanate groups and at least one ethylenically unsaturated group; a plurality of non-radiation-curable polyurethane particles having a median particle size D50 of 1 to 10 μm; and water.

[0011] In a second embodiment, the present invention relates to a coating formed by curing a composition according to an embodiment of the first embodiment.

[0012] In a third embodiment, the present invention relates to a method for forming a coating according to an embodiment of a second embodiment, comprising the steps of applying a composition according to an embodiment of a first embodiment to a surface and curing the composition to thereby form a coating.

[0013] In a fourth embodiment, the present invention relates to the use of coatings according to embodiments of the second embodiment for consumer electronics, home appliances, automotive interiors and exteriors, packaging materials, furniture, in-mold decoration, industrial applications, graphical applications, or in-mold labeling.

[0014] In a fifth aspect, the present invention relates to a method for forming an aqueous radiation-curable composition according to any embodiment of the first aspect of the present invention, comprising the step of mixing a compound for a radiation-curable polyurethane dispersion obtained by reacting a: a compound containing at least two isocyanate groups; b: a polyol having a molecular weight of at least 500 g / mol; c: a compound containing at least one group capable of reacting with an isocyanate group and preferably at least one hydrophilic group containing a salt or capable of containing a salt after reaction with a neutralizing agent; and d: an ethylenically unsaturated compound containing at least one group capable of reacting with an isocyanate group and at least one ethylenically unsaturated group; a plurality of non-radiation-curable polyurethane particles having a median diameter D50 of 1 to 10 μm; and water.

[0015] In the context of the present invention, an ethylenically unsaturated compound is a compound having at least one ethylenically unsaturated functional group. Ethylenelycols are typically suitable for radical polymerization, i.e., free radical polymerization. In the context of the present invention, "ethylenically unsaturated functional group" can refer to a group having at least one carbon-carbon double bond, i.e., a π bond, that can undergo radical polymerization under the influence of irradiation and / or an activating (photo) initiator. Polymerizable ethylenically unsaturated functional groups are generally selected from allyl groups, vinyl groups, and (meth)acryloyl groups. The double bond may be derived, instead or in addition, from, for example, an unsaturated acid, an unsaturated fatty acid, or an acrylamide. In preferred embodiments, the ethylenically unsaturated compound is a (meth)acrylated compound. In this specification, a (meth)acrylated compound is a compound containing one or more (meth)acryloyl groups.

[0016] In the context of the present invention, the term (meth)acrylic compound is understood to encompass both acrylated compounds and methacrylated compounds, or derivatives thereof, as well as mixtures thereof. In the context of the present invention, the term (meth)acrylate means encompassing both acrylate and methacrylate compounds. In preferred embodiments, the (meth)acrylate compound is an acrylated compound. Such a compound may contain at least one acrylate (CH2=CHCOO-) and / or methacrylate (CH2=CCH3COO-) group. Compounds containing only one (meth)acrylate functional group are preferred.

[0017] In the context of the present invention, the term "(meth)acrylic" encompasses the presence of acrylic and / or methacrylic groups on the compound either separately or as a mixture of acrylic and methacrylic groups.

[0018] In the context of the present invention, “water-dispersible compound,” “aqueous dispersion,” or “dispersion,” i.e., a dispersion of a self-water-dispersible compound, is a compound that, when mixed with water, forms a stable two-phase system of small particles dispersed in water without the help of additional emulsifiers or dispersants. A “water-dispersible compound” is a compound that is insoluble in water but can be dispersed in water without the need for the use of additional aids, such as emulsifiers or dispersants, and forms a water-dispersible compound (i.e., an aqueous dispersion). That is, when dispersed, it forms a stable two-phase system of small discrete particles or droplets dispersed in water. For example, in a “polyurethane dispersion,” the discrete particles are polyurethane polymers. The particles are the dispersion or internal phase, and the aqueous medium is the continuous or external phase. In this specification, “stable” means that there is substantially no coalescence (droplets) or coagulation (particles) resulting in phase separation, creaming, or sedimentation of the heterogeneous system after 1 day at 60°C, preferably 2 days or more, typically 4 days or more, and most preferably 10 days at 60°C.

[0019] In the context of this invention, the term "polyol" refers to a compound containing two or more hydroxyl groups per molecule.

[0020] In the context of the present invention, the term "polyamine" refers to a compound containing two or more primary or secondary amine groups per molecule.

[0021] In a first aspect, the present invention relates to an aqueous radiation-curable composition comprising: a. a compound containing at least two isocyanate groups; b. a polyol having a molecular weight of at least 500 g / mol; c. a compound containing at least one hydrophilic group capable of reacting with an isocyanate group and preferably containing a salt or capable of containing a salt after reaction with a neutralizing agent; and d. a radiation-curable polyurethane dispersion obtained by reacting a compound containing at least one group capable of reacting with an isocyanate group and at least one ethylenically unsaturated group with an ethylenically unsaturated compound, a plurality of polyurethane particles that are non-radiation-curable and have a median particle size D50 of 1 to 10 μm, and water.

[0022] In an embodiment of the first aspect, the radiation-curable polyurethane dispersion is obtained by reacting 10 to 60 parts by mass of compound a., 1 to 40 parts by mass of compound b., 2 to 25 parts by mass of compound c., and 15 to 85 parts by mass of compound d., and the parts by mass of compounds a., b., c., and d. total 100. Preferably, at least 15, for example at least 20 parts by mass of compound a. is present during the reaction. Preferably, a maximum of 50 parts by mass of compound a., more typically a maximum of 40 parts by mass of compound a. is present during the reaction. Preferably, 10 to 50, for example 20 to 40 parts by mass of compound a. is present during the reaction. In an embodiment, at least 80% by weight, preferably at least 85% by weight, more preferably at least 90% by weight of the compounds reacted to form the radiation-curable polyurethane dispersion consists of compounds a., b., c., and d. In an embodiment, at least 80% by weight, preferably at least 85% by weight, more preferably at least 90% by weight of the compounds reacted to form the radiation-curable polyurethane dispersion consists of compounds a., b., c., d., e. if present, and f. if present.

[0023] In an embodiment of the present invention, Compound a. includes an organic compound containing at least two, for example, 2 to 6 isocyanate groups. That is, Compound a. is a polyisocyanate compound. In an embodiment, Compound a. contains only 2 or 3 isocyanate groups, preferably only 2 isocyanate groups. In an embodiment, Compound a. is selected from aliphatic, alicyclic, aromatic and / or heterocyclic polyisocyanates or a combination thereof. In an embodiment, Compound a. contains an allophanate group, a biuret group and / or an isocyanurate group.

[0024] In an embodiment, the aliphatic or alicyclic polyisocyanate is at least one of 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 1,1'-methylenebis[4-isocyanatocyclohexane] (H12MDI), 5-isocyanato-1-isocyanatomethyl-1,3,3-trimethylcyclohexane (isophorone diisocyanate, IPDI) or pentamethylene diisocyanate (PDI). The aliphatic polyisocyanate containing more than 2 isocyanate groups is a derivative of the above-mentioned diisocyanate such as 1,6-diisocyanatohexane biuret and isocyanurate. Examples of aromatic polyisocyanates are 1,4-diisocyanatobenzene (BDI), 2,4-diisocyanatotoluene (2,4-TDI), 2,6-diisocyanatotoluene (2,6-TDI), 1,1'-methylenebis[4-isocyanatobenzene] (MDI), xylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), 1,5-naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI) and p-phenylene diisocyanate (PPDI).

[0025] Preferably, Compound a. includes an aliphatic or alicyclic polyisocyanate. In a preferred embodiment, Compound a. includes an aliphatic or alicyclic diisocyanate, for example, an alicyclic diisocyanate. 1,1'-methylenebis[4-isocyanatocyclohexane] (H12MDI) and / or isophorone diisocyanate (IPDI) are particularly preferred.

[0026] In the embodiment, compound a comprises a mixture of the compounds described with respect to compound a.

[0027] Preferably, the amount of polyol compound b used to prepare the radiation-curable polyurethane dispersion is 1 to 40 parts by mass.

[0028] In embodiments, polyol compound b. can be selected from polyols having a number-average molecular weight of at least 500 g / mol. In embodiments, compound b. has a number-average molecular weight of up to 5,000 g / mol, preferably up to 2,000 g / mol, and more preferably up to 1,000 g / mol, when calculated based on the hydroxyl index of the polyol. In this specification, the hydroxyl index can be calculated using the formula 56 × 2 × 1000 / (hydroxyl value of the polyol). In embodiments, polyol compound b. includes at least one of polyester polyols, polyether polyols, polycarbonate polyols, fatty dimergols, and polyacrylate polyols, as well as combinations thereof.

[0029] In the embodiment, the polyether polyol comprises at least one of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, or a block copolymer thereof.

[0030] In this embodiment, the fatty dimer ol is obtained from the hydrogenation of a dimer acid, preferably a dimer acid containing 36 carbon atoms.

[0031] In embodiments, polyacrylate polyols can be formed by radical polymerization of (meth)acrylic and / or (meth)acrylamide monomers, preferably initiated by a thermal radical initiator. Formation is preferably carried out in the presence of hydroxylated mercaptans. Terminal group transesterification with a diol, such as 1,4-butanediol, may follow the formation.

[0032] In a preferred embodiment of the first aspect, the polyol compound b is a polyester or polycarbonate.

[0033] Preferably, polyol compound b. is a polyester polyol. In embodiments, the polyester polyol is a hydroxyl-terminated reaction product of a polyhydric alcohol, preferably a dihydric alcohol, and a polycarboxylic acid, preferably a dicarboxylic acid or its corresponding anhydride. In embodiments, the polyester polyol is obtained from the ring-opening polymerization of a lactone. Preferably, the polycarboxylic acid used in the formation of the polyester polyol is aliphatic, alicyclic, aromatic, and / or heterocyclic, and these may be substituted, saturated, or unsaturated. Examples of dicarboxylic acids include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, hexahydrophthalic acid, isophthalic acid, terephthalic acid, orthophthalic acid, tetrachlorophthalic acid, 1,5-naphthalenedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, tetrahydrophthalic acid, trimellitic acid, trimesic acid, and pyromellitic acid or mixtures thereof. Polyester polyols may further contain air-drying components, such as long-chain unsaturated fatty acids, particularly fatty acid dimers.

[0034] Preferably, the polyhydric alcohol used in the preparation of the polyester polyol is selected from one or more diols described in the embodiment of diol compound e.

[0035] In a preferred embodiment, the polyester polyol is mainly produced from the polycondensation of (1) neopentyl glycol and (2) adipic acid and / or isophthalic acid.

[0036] In embodiments where compound b is a polycarbonate polyol, compound b may be a reaction product of a diol, such as ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, or tetraethylene glycol, with at least one of the following compounds: phosgene, dialkyl carbonate, such as dimethyl carbonate, diaryl carbonate, such as diphenyl carbonate, or cyclic carbonate, such as ethylene or propylene carbonate.

[0037] In the embodiment, compound b may include a mixture of the compounds described with respect to compound b.

[0038] Compound c is typically a compound containing at least one hydrophilic group capable of dispersing the radiation-curable polyurethane in an aqueous medium, such as a saturated organic compound. In embodiments, the radiation-curable polyurethane may be directly dispersible if, for example, the hydrophilic group is non-ionic or a salt. In alternative embodiments, the radiation-curable polyurethane is dispersible after reacting with a neutralizing agent to provide a salt. In embodiments, the hydrophilic group capable of dispersing the polyurethane in an aqueous medium may be ionic or nonionic. Preferably, the hydrophilic group is an ionic group, more preferably an anionic group, most preferably an acidic group or a corresponding salt. In embodiments, the acidic group is a carboxylic acid, sulfonic acid, or phosphonic acid group. In embodiments, the salt includes a counterion and a carboxylate, sulfonate, or phosphonate. Suitable counterions for the salt include ammonium, trimethylammonium, triethylammonium, sodium, potassium, lithium, etc. The nonionic group may include a hydrophilic moiety containing polyethylene oxide, polypropylene oxide, or block copolymers produced therefrom. Preferably, the hydrophilic group includes a carboxylic acid group and / or a salt thereof. Compound c is typically a hydrophilic compound.

[0039] In embodiments, at least one group capable of reacting with the isocyanate group can be selected from a list consisting of a hydroxyl group, a primary amino group, and a secondary amino group. In embodiments, compound c. is a hydroxylated and / or aminated compound. In embodiments, compound c. contains at least one, preferably at least two, hydroxyl groups, or at least one, preferably at least two, primary or secondary amino groups.

[0040] In a preferred embodiment, compound c. comprises a saturated hydroxycarboxylic acid containing at least one hydroxyl group and at least one carboxylic acid group. In an embodiment, the number of hydroxyl groups in compound c. is two or three. In an embodiment, the number of carboxylic acid groups in compound c. is up to three. Preferably, the hydroxycarboxylic acid is a saturated aliphatic hydroxycarboxylic acid having at least one hydroxyl group. Preferably, compound c. comprises an aliphatic saturated mono, di, and / or tricarboxylic acid or a mixture thereof having at least one hydroxyl group per molecule.

[0041] In preferred embodiments, compound c comprises an aliphatic saturated monocarboxylic acid containing at least one, for example, at least two hydroxyl groups. In embodiments, the saturated aliphatic hydroxycarboxylic acid is of the general formula (HO) x R(COOH) y It is represented by the following: R represents a linear or branched hydrocarbon portion having 1 to 12 carbon atoms. x is an integer from 1 to 3. y is an integer from 1 to 3. In embodiments, the sum of x + y is at most 5. In embodiments, the hydroxycarboxylic acid comprises at least one of citric acid, maleic acid, lactic acid, or tartaric acid. Preferably, y = 1 in the above general formula. In preferred embodiments, the hydroxycarboxylic acid comprises α,α-dimethylolalkanoic acid, such as 2,2-dimethylolpropionic acid and / or 2,2-dimethylolbutanoic acid, where x = 2 and y = 1 in the above general formula.

[0042] Compound c may contain at least one of the compounds c. discussed above. Compound c may contain a mixture of at least two of the compounds c. discussed above.

[0043] In embodiments, the aqueous radiation-curable composition of the present invention is an aqueous dispersion. In embodiments, compound c is used in an amount sufficient to make the radiation-curable polyurethane aqueous dispersible. In embodiments, the amount of compound c used in the synthesis of the radiation-curable polyurethane dispersion is in the range of 2 to 25 parts by mass, and the total amount of parts by mass of compounds a, b, c, and d is 100. In embodiments where the hydrophilic group is an ionic group, the amount of compound c is preferably in the range of 3 to 10 parts by mass, more preferably in the range of 3.5 to 8 parts by mass. In embodiments where the hydrophilic group is a nonionic group, preferably the amount of compound c is in the range of 5 to 25 parts by mass, more preferably in the range of 10 to 20 parts by mass.

[0044] In the embodiment, the ethylenically unsaturated compound d. contains at least one (meth)acrylic group. For example, the ethylenically unsaturated (meth)acrylic group can be introduced into compound d. via terminal and / or skeletal side groups, i.e., pendant groups, of compound d.

[0045] In embodiments, compound d. is selected from compounds containing at least one acrylic and / or methacrylic group. In embodiments, compound d. contains two or more nucleophiles (typically hydroxyl groups) capable of reacting with an isocyanate. Examples of such compound d. include polyester (meth)acrylates containing hydroxyl groups, polyether (meth)acrylates containing hydroxyl groups, polyester ester (meth)acrylates containing hydroxyl groups, and / or polyepoxy (meth)acrylates containing hydroxyl groups. In embodiments, compound d. is an acrylate. In embodiments, compound d. contains at least one linear compound containing an average of two hydroxyl groups per molecule. Such compounds are well known in the art. Preferably, compound d. contains polyester (meth)acrylates and / or polyepoxy (meth)acrylates having two or more, typically an average of two, hydroxyl groups. Preferably, compound d. contains an aliphatic compound.

[0046] Preferably, compound d comprises one or more ethylenically unsaturated functional groups (e.g., acrylic and / or methacrylic groups) and one nucleophilic functional group (typically a hydroxyl group) capable of reacting with an isocyanate. More preferably, compound d comprises a (meth)acryloyl monohydroxy compound, such as a poly(meth)acryloyl monohydroxy compound. Preferably, compound d comprises an acrylate. In embodiments, compound d comprises a mixture of at least two of the above compounds.

[0047] In alternative embodiments, compound d. comprises an aliphatic and / or aromatic polyol having 0.9 to 1.1, preferably 0.95 to 1.05 residual average hydroxyl functional groups, preferably an esterification product of an aliphatic polyol with (meth)acrylic acid. In preferred embodiments, compound d. comprises a partial esterification product of (meth)acrylic acid with a tri, tetra, penta, or hexavalent polyol or a mixture thereof. In embodiments, compound d. comprises a reaction product of a polyol with ethylene oxide and / or propylene oxide or a mixture thereof. In embodiments, compound d. comprises a reaction product of a polyol with a lactone that can react with the polyol in a ring-opening reaction. In embodiments, the lactone comprises γ-butyrolactone, δ-valerolactone, and ε-caprolactone, preferably at least one of δ-valerolactone and ε-caprolactone. Preferably, the alkoxylated polyol has up to 3 alkoxy groups per hydroxyl functional group and contains ε-caprolactone. Preferably, the polyol is partially esterified with acrylic acid, methacrylic acid, or a mixture thereof until a desirable residual hydroxyl functional group is reached.

[0048] Preferably, compound d comprises at least two (meth)acrylic functional groups, such as glycerol diacrylate, trimethylolpropane diacrylate, glycerol diacrylate, pentaerythritol triacrylate, ditrimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and (poly)ethoxylated and / or (poly)propoxylated equivalents thereof (any of these).

[0049] In the embodiment, compound d. is obtained from the reaction of (meth)acrylic acid with an aliphatic compound, an alicyclic compound, or an aromatic compound, and has an epoxy functional group and at least one (meth)acrylic functional group. In the embodiment, compound d. is obtained from the reaction of an aliphatic, alicyclic, or aromatic acid with an epoxy group containing (meth)acrylate, such as glycidyl (meth)acrylate.

[0050] Other suitable compounds that can be used for compound d are (meth)acrylic acid esters of linear and branched polyols in which at least one hydroxyl functional group can still freely react with an isocyanate group, such as hydroxyalkyl (meth)acrylates containing an alkyl group of 1 to 20 carbon atoms. For example, compound d may contain at least one of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate.

[0051] In some embodiments, compound d may include at least one of the compounds described with respect to compound d, for example, a mixture thereof.

[0052] In some embodiments, the adduct contains the functional groups of both compounds a. and d., i.e., it contains both compounds a. and d. The adduct can be formed by the reaction of an excess amount of one or more compounds a. and one or more compounds d. In another embodiment of the present invention, compounds a. and d. are provided as separate molecules.

[0053] In the embodiment, the amount of compound d used in the synthesis of the radiation-curable polyurethane is in the range of 15 to 85 parts by mass, preferably 15 to 70 parts by mass, more preferably 22 to 70 parts by mass, and most preferably 30 to 60 parts by mass, and the total amount of parts by mass of compounds a, b, c, and d is 100. When compounds a and d are included in the adduct, the amount of the adduct used in the synthesis of the radiation-curable polyurethane may be in the range of the sum of the lower limits of a and d as the lower limit, and the sum of the upper limits of a and d as the upper limit.

[0054] In the embodiment of the first aspect, the compounds reacted to obtain the radiation-curable polyurethane dispersion compound further include compound e, which is a diol having a molecular weight of up to 400 g / mol. In the embodiment, the total mass parts of compounds a, b, c, and d are 100, and compound e is added in an amount of 0 to 5 parts by mass, for example, 1 to 5 parts by mass.

[0055] In embodiments, compound e. comprises at least one of the following compounds: ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, dibutylene glycol, 2-methyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, bisphenol A, or an ethylene oxide adduct or propylene oxide adduct of hydrogenated bisphenol A, or a mixture thereof. In the embodiment, compound e. comprises at least one of the following compounds: glycerol, trimethylolethane, trimethylolpropane, ditrimethylolethane, ditrimethylolpropane, and pentaerythritol and / or dipentaerythritol.

[0056] In the embodiment of the first aspect, the compound reacted to obtain a radiation-curable polyurethane dispersion further comprises compound f., which contains at least two amino groups independently selected from primary and secondary amino groups. In the embodiment, compound f. has a molecular weight of up to 200 g / mol. Compound f. can function as a chain extender.

[0057] Chain-extended polyamines typically have an average of 2 to 4, more preferably 2 to 3, functional groups. Compound f. is a preferably water-soluble aliphatic, alicyclic, aromatic, or heterocyclic primary and / or secondary polyamine or hydrazine having up to 60, preferably up to 12, carbon atoms.

[0058] The amount of compound f added to the reaction to form a radiation-curable polyurethane can be determined from the amount of residue, i.e., unreacted isocyanate groups, present in the radiation-curable polyurethane prepolymer. In this specification, the radiation-curable polyurethane prepolymer is a compound obtained by the reaction of compounds a, b, c, and d, optionally e, and before the reaction with compound f. In embodiments, compound f is added after the reaction of compounds a, b, c, and d, optionally e. In embodiments, the ratio of amine groups in compound f to isocyanate groups in the prepolymer obtained after the reaction of compounds a, b, c, and d, optionally e, is in the range of 0.25 to 1.2, preferably 0.5 to 0.95. The residual isocyanate content is typically measured by isocyanate titration with an amine. The amount of amine groups is typically obtained by calculation. In an embodiment in which compound f. is reacted to obtain a radiation-curable polyurethane, compound f. can be added in an amount ranging from 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and the total amount of parts by mass of all compounds reacted to obtain the radiation-curable polyurethane is 100. In this embodiment, the total amount of parts by mass of compounds a., b., c., and d. is 100, and compound f. is added in an amount ranging from 1 to 15 parts by mass, preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass.

[0059] In embodiments, the chain-extended amine, i.e., compound f., includes at least one of the following compounds: hydrazine, ethylenediamine, piperazine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2-methylpentamethylenediamine, triethylenetriamine, isophoronediamine (or 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane), aminoethylethanolamine, polyethyleneamine, polyoxyethyleneamine, and polyoxypropyleneamine (e.g., Jeffamine from Huntsman), as well as mixtures thereof.

[0060] In embodiments, the composition contains a further ethylenically unsaturated compound. The further ethylenically unsaturated compound can be added to the composition before, during, or after the dispersion of the water-dispersible radiation-curable polyurethane. Typically, the further ethylenically unsaturated compound does not react, as it becomes part of the radiation-curable polyurethane dispersion. For example, the further ethylenically unsaturated compound is added to the composition only after the formation of the radiation-curable polyurethane dispersion. In embodiments containing a further water-dispersible, non-radiation-curable polyurethane, the further ethylenically unsaturated compound does not react, as it becomes part of the further water-dispersible, radiation-curable polyurethane. In other words, typically, unreacted further ethylenically unsaturated compounds are part of the composition. In embodiments, the further ethylenically unsaturated compound does not contain a functional group capable of reacting with an isocyanate group. In these embodiments, the further ethylenically unsaturated compound can be added before or during the step of reacting compounds a., b., c., and d. When the further ethylenically unsaturated compound is added before the radiation-curable polyurethane dispersion is dispersed in water, good dispersion stability is generally obtained. In embodiments, the further ethylenically unsaturated compound is different from compound d. In the embodiment, further ethylenically unsaturated compounds are also (meth)acrylated compounds.

[0061] In the embodiment, the further ethylenically unsaturated compound is independently selected from the (meth)acrylated compounds described above with respect to compound d. In the embodiment, the further ethylenically unsaturated compound may be any compound that is ethylenically unsaturated and does not contain any functional groups that can react with an isocyanate group.

[0062] In embodiments, the further ethylenically unsaturated compound preferably includes aliphatic and aromatic polyvalent polyols esterified with (meth)acrylic acid. Thereafter, preferably, the further ethylenically unsaturated compound does not contain residual hydroxyl functional groups. Preferably, the further ethylenically unsaturated compound is an esterification product of (meth)acrylic acid with a tri, tetra, v, and / or hexavalent polyol or a mixture thereof. In embodiments, the further ethylenically unsaturated compound is a reaction product of a tri, tetra, v, and / or hexavalent polyol with ethylene oxide and / or propylene oxide or a mixture thereof. In embodiments, the further ethylenically unsaturated compound is a reaction product of a tri, tetra, v, and / or hexavalent polyol with a lactone. Ethylene oxide, propylene oxide, and lactone can react with polyols in a ring-opening reaction. In embodiments, the lactone is γ-butyrolactone, δ-valerolactone, or ε-caprolactone, preferably δ-valerolactone or ε-caprolactone. In preferred embodiments, the polyol is an alkoxylated polyol having two or fewer alkoxy groups per hydroxyl functional group, or a polyol modified with ε-caprolactone. Preferably, the modified or unmodified polyol is esterified with acrylic acid, methacrylic acid, or a mixture thereof, preferably until no residual hydroxyl functional groups remain. In embodiments, further ethylenically unsaturated compounds include one or a mixture thereof of trimethylolpropane triacrylate, glycerol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, and their (poly)ethoxylated and (poly)propoxylated equivalents.

[0063] In embodiments, the further ethylenically unsaturated compound includes one of the following compounds: urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, or (meth)acrylic (meth)acrylate, or a mixture thereof. In preferred embodiments, the further ethylenically unsaturated compound is a polyurethane (meth)acrylate dispersion.

[0064] In embodiments, the further ethylenically unsaturated compound is an aqueous compound. The further ethylenically unsaturated compound may be water-dispersible or water-dilutable. Examples of urethane (meth)acrylate dispersions are UCECOAT® 7788, UCECOAT® 7655, UCECOAT® 7700, UCECOAT® 7230, UCECOAT® 7240, and UCECOAT® 7177. Examples of suitable water-dilutable urethane (meth)acrylates are, for example, UCECOAT® 6569, EBECRYL® 2002, and EBECRYL® 11. Such (meth)acrylate compounds are well known in the art. Methods for producing such (meth)acrylate compounds are also known in the art and have already been described in various patent applications. In this embodiment, a radiation-curable polyurethane dispersion and, if present, a further non-radiation-curable polyurethane dispersion are present in an amount of 100 parts by mass, and a further ethylenically unsaturated compound is present in an amount of 0 to 20 parts by mass, for example, 1 to 20 parts by mass.

[0065] In embodiments, the further ethylenically unsaturated compound may include at least one of the compounds described with respect to the further ethylenically unsaturated compound, for example, a mixture thereof.

[0066] In the embodiment of the first aspect, the polyurethane particles are not radiation-curable. The polyurethane particles have a median diameter D50 of 5 to 8 μm. In this specification, D50 is the micron diameter that divides the diameter distribution into half of the particles with a diameter greater than a micron and half of the particles with a diameter less than a micron. The polyurethane particles of the present invention may alternatively be described as polyurethane beads, polyurethane fillers, or polyurethane fine particles or microspheres. An advantage of the embodiments of the present invention is that the polyurethane particles can impart a soft touch to coatings formed with the composition.

[0067] In the first embodiment, the T of polyurethane particlesg That is, the glass transition temperature is a maximum of 0°C, preferably a maximum of -40°C, and more preferably a maximum of -50°C. An advantage of the embodiments of the present invention is that the polyurethane particles can be glassy at room temperature, which can impart a soft feel to coatings containing polyurethane particles. In the embodiments, the polyurethane particles are preferably insoluble in water at least. The polyurethane particles are chemically crosslinked polyurethane-based molecules. This distinguishes the particles from aggregates or micelles formed by physical interactions between molecules, such as hydrophobic / hydrophilic interactions. In the embodiments, the oil absorption of the polyurethane particles is a maximum of 120%, i.e., 120 grams of oil per 100 grams of polyurethane particles. In this specification, the oil absorption is preferably determined using ISO or ASTM techniques, for example, using ASTM D281.

[0068] In the embodiment, the polyurethane particles have a first volume before compression and a second volume, which is at least 90% of the first volume, determined using a microcompression tester-tester-Shimadzu MCT series, for example, after compression for 1 minute and subsequent relaxation using a force of 63 mN. An advantage of the embodiment of the present invention is that the polyurethane particles are soft and elastic. The softness and elasticity can impart a soft touch to coatings containing polyurethane particles. The polyurethane particles are solid, i.e., not liquid or gaseous.

[0069] Polyurethane particles are typically transparent, but the present invention is not limited thereto. In certain embodiments, the polyurethane particles may contain dyes or pigments.

[0070] In embodiments, polyurethane particles consist of at least 60%, preferably at least 80%, more preferably at least 90%, and most preferably at least 95% polyurethane. Typically, polyurethane particles are essentially made of polyurethane. In embodiments, the polyurethane of the polyurethane particles is aliphatic polyurethane. In embodiments, polyurethane particles are formed of polyols, the polyol preferably comprises at least one of polyester polyols, polycarbonate polyols, or polyether polyols. In preferred embodiments, polyurethane particles can be obtained from renewable plant sources. In preferred embodiments, polyurethane particles are obtained using a water-based method. In preferred embodiments, polyurethane particles are obtained using a method that does not contain solvents other than water, preferably organic solvents. An advantage of embodiments of the present invention is that polyurethane particles may not contain volatile organic compounds (VOCs), alkylphenol ethoxylates (APEOs), phthalates, formaldehyde, and heavy metals. In embodiments, polyurethane particles do not contain isocyanate groups. Suitable polyurethane particles for use in embodiments of the present invention include, for example, Decosphaera Transparent® HT8-20, MicroTouch® 850XF, and Addimat® 8FT.

[0071] In an embodiment of the first aspect, the composition comprises a further non-radiation-curable polyurethane dispersion obtained by reacting i. a compound containing at least two isocyanate groups, ii. a polyol having a molecular weight of at least 500 g / mol, iii. a compound containing at least one group capable of reacting with an isocyanate group and preferably at least one hydrophilic group containing a salt or capable of containing a salt after reaction with a neutralizing agent, and iv. a compound containing at least two amino groups selected from primary and secondary amino groups. In the embodiment, compound iv. has a molecular weight of up to 200 g / mol, for example, up to 150 g / mol.

[0072] In the embodiment, a further non-radiation-curable polyurethane dispersion is prepared by the steps of reacting compounds i. and ii. and preferably iii. to form a prepolymer, dispersing the prepolymer in an aqueous solvent, and extending the chain of the prepolymer by reacting the prepolymer with compound iv.

[0073] In this embodiment, compound i can be independently selected from any of the compounds described with respect to compound a.

[0074] Any polyol known to those skilled in the art can be used as polyol ii. In embodiments, compound ii. can be independently selected from any of the compounds described with respect to compound b. Typical polyols include, but are not limited to, glycols and polymer polyols. In embodiments, glycols include alkylene glycols, such as ethylene glycol; 1,2- and 1,3-propylene glycol; 1,2-, 1,3-, 1,4- and 2,3-butylene glycol; hexanediol; neopentyl glycol; 1,6-hexanediol; 1,8-octanediol; and other glycols, such as bisphenol-A, cyclohexanediol, cyclohexanedimethanol (1,4-bishydroxymethylcyclohexane), 2-methyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, caprolactonediol, dimelatediol, hydroxylated bisphenol, polyether glycol, halogenated diols, and mixtures thereof. However, the present invention is not limited to these.

[0075] In embodiments, the polymer polyol used in compound ii can be selected from polyester polyols, polyether polyols, polyhydroxypolyesteramides, hydroxyl-containing polycaprolactones, hydroxyl-containing acrylic interpolymers, hydroxyl-containing epoxides, polyalkylene ether polyols, polyhydroxypolycarbonates, polyhydroxypolyacetals, polyhydroxypolythioethers, polysiloxane polyols, ethoxylated polysiloxane polyols, polybutadiene polyols, and mixtures thereof. Representative polyols useful in the method of the present invention are those described in U.S. Patents 4,108,814 and 6,576,702, the contents of which are incorporated herein by reference.

[0076] In a preferred embodiment, polyol ii. includes polymer polyols. Preferred polymer polyols include polyester polyols, polyether polyols, and hydroxypolycarbonates.

[0077] Polyester polyols are esterification products prepared by reacting an organic polycarboxylic acid or its anhydride with a stoichiometric excess of a diol. In embodiments, the polyester polyol used in polyol ii. may include at least one of polyglycol azipart, isophthalate, orthophthalate, terephthalate, polycaprolactone polyol, sulfonated polyol, and mixtures thereof. In embodiments, polyester polyols can be formed from the diols described with respect to polyol b. Preferred diols for forming polyester polyols are ethylene glycol, butylene glycol, hexanediol, and neopentyl glycol. Suitable carboxylic acids for producing polyester polyols include, but are not limited to, dicarboxylic acids and tricarboxylic acids, as well as anhydrides such as maleic acid, maleic anhydride, succinic acid, glutaric acid, glutaric anhydride, adipic acid, suberic acid, pimelic acid, azelaic acid, sebacic acid, chloridenic acid, 1,2,4-butanetricarboxylic acid, phthalic acid, isomers of phthalic acid, phthalic anhydride, fumaric acid, dimer fatty acids, and mixtures thereof. Preferred polycarboxylic acids for forming polyester polyols include aliphatic or aromatic dibasic acids.

[0078] The hydroxypolyether can be selected from any hydroxypolyether known in the art. In embodiments, the hydroxypolyether is obtained by polymerization of epoxides, such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, or epichlorohydrin, or mixtures thereof. The epoxide can be polymerized in the presence or absence of a catalyst, such as BF3. The hydroxypolyether can be formed by adding an epoxide, or optionally a mixture of epoxides, to a component containing reactive hydrogen atoms, such as an alcohol or amine (e.g., water, ethylene glycol, 1,3- or 1,2-propylene glycol, 4,4'-dihydroxydiphenylpropane, or aniline).

[0079] In embodiments, hydroxypolythioethers are formed by condensing thiodiglycols by self-condensation and / or condensation with another glycol, dicarboxylic acid, formaldehyde, aminocarboxylic acid, or amino alcohol. Thus, hydroxypolythioethers may include polythio mixed ethers, polythioether esters, or polythioether ester amides. However, hydroxypolythioethers are not limited to these embodiments.

[0080] In some embodiments, the hydroxypolyacetal includes glycols, such as diethylene glycol, triethylene glycol, 4,4'-dioxyethoxydiphenyldimethylmethane, and reaction products of hexanediol with formaldehyde. In some embodiments, the hydroxypolyacetal is obtained by polymerization of a cyclic acetal. However, the hydroxypolyacetal is not limited to these embodiments.

[0081] The hydroxypolycarbonate may be any hydroxypolycarbonate known to those skilled in the art. In embodiments, the hydroxypolycarbonate is formed by reacting a diol, such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, or tetraethylene glycol, with a diaryl carbonate, such as diphenyl carbonate or phosgene.

[0082] In embodiments, hydroxypolyesteramides and hydroxypolyamides include mainly linear, for example, linear condensates, obtained from the reaction of saturated or unsaturated polycarboxylic acids or their anhydrides with polyhydric saturated or unsaturated amino alcohols, diamines, polyamines, or mixtures thereof.Preferred amino alcohols, diamines, and polyamines used to form polyesteramides and polyamides include 1,2-diaminoethane, 1,6-diaminohexane, 2-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 1,12-diaminododecane, 2-aminoethanol, 2-[(2-aminoethyl)amino]ethanol, piperazine, 2,5-dimethylpiperazine, and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexylethanolamine. Xane (isophorone diamine or IPDA), bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,4-diaminocyclohexane, 1,2-propylenediamine, hydrazine, urea, amino acid hydrazides, semicarbazide carboxylic acid hydrazides, bishydrazides and bissemicarbazides, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N,N,N-tris(2-aminoethyl)amine N-(2-piperazinoethyl)ethylenediamine, N,N'-bis(2-aminoethyl)piperazine, N,N,N'tris(2-aminoethyl)ethylenediamine, N-[N-(2-aminoethyl)-2-aminoethyl]-N'-(2-aminoethyl)piperazine, N-(2-aminoethyl)-N'-(2-piperazinoethyl)ethylenediamine, N,N-bis(2-aminoethyl)-N-(2-piperazinoethyl)amine, N,N-bis(2-piperazinoethyl)amine, polyethyleneimi Examples include, but are not limited to, iminobispropylamine, guanidine, melamine, N-(2-aminoethyl)-1,3-propanediamine, 3,3'-diaminobenzidine, 2,4,6-triaminopyrimidine, polyoxypropyleneamine, tetrapropylenepentamine, tripylenetetramine, N,N-bis(6-aminohexyl)amine, N,N'-bis(3-aminopropyl)ethylenediamine, and 2,4-bis(4'-aminobenzyl)aniline, as well as mixtures thereof.Other suitable diamines and polyamines include Jeffamine® D-2000 and D-4000 (commercially available from Huntsman Chemical Company), which are amine-terminated polypropylene glycols differing only in molecular weight. Polyhydroxyl compounds containing urethane and urea groups can be used. In certain embodiments, hydroxypolyamides are linear polyamides formed by reacting adipic acid with 1,6-diaminohexane. In certain embodiments, polyesteramides are formed by reacting adipic acid with 1,6-hexanediol and ethylenediamine.

[0083] However, polyol ii. is not limited to any of the embodiments described above. For example, polyol ii. can be selected from any polyol described in High Polymer, Vol. XVI, "Polyurethane, Chemistry and Technology" by Saunders-Frisch, Interscience Publisher, New York, London, Vol. I, 1962, pp. 32-42 and 44-54, and Vol. II, 1964, pp. 5-6 and 198-199, and Kunststoff-Handbuch, Vol. VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munich, 1966, e.g., pp. 45-71.

[0084] In embodiments, polyol ii. comprises two or more compounds described with respect to polyol ii. That is, polyol compound ii. may be a mixture. In preferred embodiments of the first embodiment, polyol compound ii. is a polyester or a polyether.

[0085] In this embodiment, compound iii can be independently selected from any of the compounds described with respect to compound c.

[0086] In this embodiment, compound iv. can be independently selected from any of the compounds described with respect to compound f.

[0087] In the embodiment of the first aspect, the non-radiation-curable further polyurethane dispersion accounts for 0.1 to 40% by weight of the total mass of the non-radiation-curable further polyurethane dispersion, the radiation-curable polyurethane dispersion, and the polyurethane particles. In the embodiment, the non-radiation-curable further polyurethane dispersion is provided as an aqueous dispersion. Preferably, the aqueous dispersion contains 30 to 45% by weight of the water-dispersible non-radiation-curable further polyurethane. Preferably, the aqueous dispersion has a kinematic viscosity of less than 1000 mPa·s, preferably less than 500 mPa·s, and more preferably less than 200 mPa·s. Preferably, the pH of the aqueous dispersion is 7 to 10. Preferably, the non-radiation-curable further polyurethane dispersion has a Tg of 0 to 100°C, for example 10 to 60°C. Preferably, the Mw of the water-dispersible non-radiation-curable further polyurethane is at least 100,000 g / mol, for example at least 1,000,000 g / mol. Examples of commercially available aqueous dispersions that may contain a suitable non-radiation-curable further polyurethane dispersion are Daotan® 6490, Daotan® 6491, and Daotan® 6493.

[0088] In the embodiment of the first aspect, the compound reacted to obtain a further non-radiation-curable polyurethane dispersion additionally includes compound v., which is a diol having a molecular weight of less than 500 g / mol, preferably up to 150 g / mol. Diol v. can be independently selected from any of the compounds described with respect to compound b., provided that diol v. has a Mw of 500 g / mol or less. In the embodiment of the first aspect, the mass ratio of the radiation-curable polyurethane dispersion in the composition to the further non-radiation-curable polyurethane dispersion is at least 1.5.

[0089] In the first embodiment, the plurality of polyurethane particles constitute 3 to 20% by mass of the composition as solid content. In the following embodiments, the amount of polyurethane particles as solid content may be independent of the amount of water in the composition and may depend only on the concentration of polyurethane present in the composition. In embodiments that do not include further non-radio-curable polyurethane dispersions, the mass ratio of the plurality of polyurethane particles to the radiation-curable polyurethane dispersion may be 0.08 to 1.0. In embodiments that include further radiation-curable polyurethane dispersions, the mass ratio of the plurality of polyurethane particles to the sum of the compounds in the radiation-curable polyurethane dispersion and the further radiation-curable polyurethane dispersion may be 0.08 to 1.0.

[0090] In a preferred embodiment, the composition comprises 7 to 25% by weight of a radiation-curable polyurethane dispersion, 0 to 15% by weight of a further non-radiation-curable polyurethane dispersion, 3 to 20% by weight of polyurethane particles, 0.1 to 5% by weight of a photoinitiator, 0 to 5% by weight of an additive other than the photoinitiator, for example, 0.1 to 5% by weight of an additive, and 30 to 80% by weight of water.

[0091] Radiation-curable polyurethane dispersions and non-radiation-curable polyurethane dispersions can be provided as dispersions in water. That is, radiation-curable polyurethane dispersions can be provided as radiation-curable polyurethane dispersions. Water-dispersible non-radiation-curable polyurethanes can be provided as non-radiation-curable polyurethane dispersions. Preferably, the dispersion contains 30 to 50% by mass of polyurethane, with the remainder being water. In these embodiments, preferably, the composition contains 30 to 85% by weight of radiation-curable polyurethane dispersion, 0 to 40% by weight of further dispersible polyurethane compound, 3 to 20% by weight of polyurethane particles, 0.1 to 5% by weight of a photoinitiator, 0.1 to 5% by weight of an additive different from the photoinitiator, and 0 to 20% by weight of additional water in addition to the water contained in the dispersion.

[0092] In embodiments, the composition of the first embodiment may further include at least one additive selected from rheological modifiers, thickeners, fusion aids, defoamers, wetting agents, adhesion promoters, flow and leveling agents, biocides, surfactants, stabilizers, antioxidants, waxes, further fillers different from polyurethane particles, polyurethane particles and nanoparticles different from radiation-curable and non-radiation-curable polyurethanes, matting agents, inert or functional resins, pigments, dyes, and tints. In preferred embodiments of the first embodiment, the composition further includes at least one of the following additives: catalysts, polymerization inhibitors, or photoinitiators.

[0093] In embodiments, at least one additive, such as a rheology modifier, anti-settling agent, wetting agent, leveling agent, anti-denting agent, defoaming agent, slip agent, flame retardant, UV protective agent, or adhesion promoter, is suitable for improving the application of the formulated dispersion to the substrate. Examples of suitable inhibitors include, but are not limited to, hydroquinone (HQ), methylhydroquinone (THQ), tert-butylhydroquinone (TBHQ), di-tert-butylhydroquinone (DTBHQ), hydroquinone monomethyl ether (MEHQ), and 2,6-di-tert-butyl-4-methylphenol (BHT). The inhibitor may also include phosphines, such as triphenylphosphine (TPP) and trisnonylphenylphosphite (TNPP), phenothiazine (PTZ), triphenylantimony (TPS), and mixtures thereof.

[0094] Aqueous radiation-curable compositions according to embodiments of the present invention may be curable by irradiation, for example, ultraviolet light. Preferably, the irradiation is carried out in the presence of a photoinitiator. Alternatively, the aqueous radiation-curable compositions may be cured by electron beam irradiation, which can result in good curing in the absence of a photoinitiator. Compositions according to embodiments of the present invention may be fast-curing. The compositions can be cured by, for example, UV LED and / or HUV.

[0095] In embodiments, the photoinitiators include low to non-yellowing photoinitiators, such as Omnirad® 1000 and Omnirad® 481 from IGM, DOUBLECURE® 200 from Comindex, Chemcure® 73, Chemcure® 73-w and Chemcure® 481 from Chembridge, and Irgacure® 184 and Darocure® 1173 from IGM. When the final use of the aqueous radiation-curable composition requires low migration and / or is in food packaging materials, polymer photoinitiators, such as Omnipol® grade from IGM, Irgacure® 2959 from IGM, or corrosion-preventive thioxanthone photoinitiators may be preferred. When different end uses of aqueous radiation-curable compositions are considered, such as inks, it may be preferable to use a photoinitiator together with an amine synergist, such as EBECRYL® P115, EBECRYL® P116, or DOUBLECURE® 225. When UV LED curing is used to cure the composition, it is preferable to use EBECRYL® LED01 or EBECRYL® LED02.

[0096] The radiation-curable polyurethane dispersion according to the embodiment of the first aspect may contain copolymerizable ethylenically unsaturated groups in an amount of at least 1 meq / g, typically at least 1.5 meq / g, preferably at least 2 meq / g. Herein, meq means milliequivalent and g means grams. Typically, this amount does not exceed 10 meq / g, more preferably not exceeding 7 meq / g, and most preferably not exceeding 5 meq / g. That is, the radiation-curable polyurethane dispersion may have some degree of unsaturation in the range of 1 to 10 meq of double bonds per gram of radiation-curable polyurethane dispersion, preferably 1.5 to 7 meq of double bonds per gram of radiation-curable polyurethane dispersion, and most preferably 2 to 5 meq of double bonds per gram of radiation-curable polyurethane dispersion.

[0097] The amount of ethylenically unsaturated groups in a radiation-curable polyurethane dispersion can be determined by nuclear magnetic resonance (NMR) spectroscopy. The amount of ethylenically unsaturated groups can be expressed in meq per gram of solid material. For determination, a dry sample of radiation-curable polyurethane, i.e., free of water and solvent, can be dissolved in N-methylpyrrolidone. The sample is then used to determine the molar concentration of ethylenically unsaturated groups. 1 The measurement is performed using 1H-NMR analysis, with, for example, 1,3,5-bromobenzene being used as an internal standard. Comparison of the peak assigned to the proton bonded to the aromatic ring of the internal standard with the peak assigned to the proton of the ethylenically unsaturated group in the radiation-curable polyurethane dispersion allows for the calculation of the molar concentration of the ethylenically unsaturated group. The molar concentration of the ethylenically unsaturated group can be assumed to be proportional to (A × B) / C, where A is the peak assigned to the proton of the ethylenically unsaturated group in the radiation-curable polyurethane dispersion. 1 This is the integral of the H peak. In this specification, B is the number of moles of the internal standard in the sample. In this specification, C is measured relative to the internal standard. 1 This is the integral of the H peak.

[0098] Alternatively, the amount of ethylenically unsaturated groups can be measured by titration after adding an excess amount of pyridinium dibromide sulfate relative to the ethylenically unsaturated groups. In this specification, for example, glacial acetic acid can be used as a solvent and mercury acetate can be used as a catalyst. The excess amount is liberated from iodine in the presence of potassium iodide, and the iodine is then titrated with sodium thiosulfate.

[0099] Typically, the radiation-curable polyurethane dispersion according to embodiments of the present invention contains a polymer or oligomer compound. In embodiments, the radiation-curable polyurethane dispersion according to the present invention has a number-average molecular weight (Mw) of 500 to 20,000 daltons, i.e., g / mol, preferably 800 to 10,000 daltons, and most preferably 1,000 to 5,000 daltons. The weight-average molecular weight (Mw) is typically measured by gel permeation chromatography. For example, gel permeation chromatography can be performed using THF as the eluent, a 3×PLgel 5μm Mixed-D LS 300×7.5mm column, suitable for an Mw range of 162 to 377,400 g / mol, and calibrated with a polystyrene standard at 40°C.

[0100] In embodiments, the aqueous radiation-curable composition according to embodiments of the present invention has a total solid content of 30 to 65% by weight, preferably 35 to 50% by weight. In this specification, the total solid content comprises a radiation-curable polyurethane dispersion, polyurethane particles, optionally a further non-radiation-curable polyurethane dispersion, and optionally solid additives. In embodiments, the non-solid content of the aqueous radiation-curable composition, such as the liquid content, includes, preferably, water. In embodiments, the aqueous radiation-curable composition has a viscosity measured at 25°C of up to 1,000 mPa·s, preferably up to 800 mPa·s, more preferably up to 500 mPa·s, and even more preferably up to 200 mPa·s. In embodiments, the aqueous radiation-curable composition has a pH of 6 to 11, preferably 6 to 8.5.

[0101] When aqueous radiation-curable polyurethanes are dispersed in water, they typically form nanoparticles. Typically, the average, or intermediate particle size, of radiation-curable polyurethanes is up to 200 nm, preferably up to 150 nm. Typically, the average, or intermediate particle size, of non-radiation-curable polyurethanes is up to 200 nm, preferably up to 150 nm.

[0102] In the embodiment, the radiation-curable polyurethane dispersion has a Tg of 0 to 100°C, for example, 10 to 60°C.

[0103] Any feature of any embodiment of the first aspect may be described independently, as correspondingly to any embodiment of any other aspect of the present invention.

[0104] In a second embodiment, the present invention relates to a coating formed by curing a composition according to an embodiment of the first embodiment. In the embodiment, the coating has a thickness of 2 to 200 μm perpendicular to the surface of the surface. In this specification, the thickness is the thickness of a dry coating typically obtained after removal of a water-containing liquid.

[0105] Any feature of any embodiment of the second aspect may be described independently, as correspondingly to any embodiment of any other aspect of the invention.

[0106] In a third embodiment, the present invention relates to a method for forming a coating according to an embodiment of a second embodiment, comprising the steps of applying a composition according to an embodiment of a first embodiment to a surface, and curing the composition to thereby form a coating. In embodiments, the composition can be applied to the surface by any possible method, for example, roller coating, spray application, inkjet or curtain coating. In embodiments, the method includes a further step of drying the coating to remove water, and optionally other solvents, contained in the composition. In embodiments, the composition is applied to a surface to form a coating having a surface thickness of 2 to 200 μm perpendicular to the surface of the surface. Hereinafter, thickness is the thickness of the dried coating.

[0107] In the third embodiment, the composition is applied to the surface at a temperature of 40 to 60°C. The composition can then be cured at a temperature of 10 to 50°C, for example, 20 to 40°C.

[0108] While specific uses of radiation-curable aqueous compositions for forming coatings are described, the present invention is not limited thereto. In fact, radiation-curable aqueous compositions according to the present invention can be used to form coatings (transparent and colored, glossy or matte), inks, paints, varnishes (such as overprint varnishes), and adhesives. Radiation-curable aqueous compositions can further be used to form composites, gel coats, 3D curing, and generally for creating 3D objects (e.g., 3D objects made from polyethylene, polypropylene, polycarbonate, polyvinyl chloride, and optionally pre-coated with other coatings, such as polyurethane).

[0109] Accordingly, the present invention relates to the use of radiation-curable aqueous compositions according to embodiments of the present invention for producing inks, varnishes (such as overprint varnishes), paints, coatings and adhesives, as well as to methods for producing inks, varnishes (such as overprint varnishes), coatings and adhesives, in which the compositions described herein are used.

[0110] In the embodiment, the surface is included in a substrate or article. In the embodiment, the coated substrate and article are prepared by an embodiment of the third embodiment, wherein the step of applying the composition to the surface includes the step of coating at least a portion of the substrate or article with the radiation-curable aqueous composition, and preferably the step of curing the radiation-curable aqueous composition. That is, the method of the third embodiment is (a) A step of providing a radiation-curable aqueous composition, (b) The step of applying the composition to the surface of an article or substrate, (c) Preferably a step of curing the composition by irradiating it with radiation, for example, chemical radiation. This could be a method of at least partially coating an article or substrate with a coating according to an embodiment of the second aspect, including the above.

[0111] In a secondary embodiment, the present invention relates to an article or substrate that is at least partially, for example, completely coated with a radiation-curable aqueous composition according to a first aspect of the present invention or with a coating according to an embodiment of a second aspect of the present invention. The substrate may be any substrate, such as wood, metal, paper, plastic, textile, fiber, ceramic, inorganic material (stone, brick), cement, plaster, glass, leather or leather-like material, concrete, and already printed or coated material (e.g., melamine panel, printed paper). The article may be any article, such as a 3D article. Preferably, the article or substrate is made of wood or plastic.

[0112] The composition can be applied as a single coat (monocoat) or as a topcoat.

[0113] Radiation-curable compositions are typically compositions that can be cured via radical-involved reactions. Curing is typically carried out by the application of radiation, but it can also be carried out, for example, by adding peroxides to the composition instead. A radiation-curable composition according to an embodiment of the first aspect may be curable by exposure to radiation due to the presence of ethylenically unsaturated functional groups in the radiation-curable polyurethane. These ethylenically unsaturated functional groups may be due to ethylenically unsaturated compounds used to form the radiation-curable composition. In a preferred embodiment, the radiation-curable aqueous composition is cured by irradiation with UV light, optionally UV LED light, or electron beam (EB). Low-energy curing (such as UV LED curing) is also possible. That is, the radiation-curable aqueous composition after application to a surface can be irradiated with chemical radiation, typically using UV light or electron beams. UV light is a suitable type of radiation for curing the radiation-curable composition according to the first aspect. Suitable wavelengths of UV light include 200-400 nm.

[0114] A typical suitable UV light source emits light at wavelengths of 200–800 nm and emits at least some radiation in the range of 200–400 nm.

[0115] A UV light source can be, for example, a UV light-emitting diode (UV-LED). UV-LEDs typically emit light in the strongest wavelength spectrum, in the range of 365–395 nm.

[0116] Any feature of any embodiment of the third aspect may be described independently, as correspondingly to any embodiment of any other aspect of the present invention.

[0117] In a fourth embodiment, the present invention relates to the use of coatings according to embodiments of the second embodiment for consumer electronics, home appliances, automotive interiors and exteriors, packaging materials, such as cosmetic packaging materials, furniture, in-mold decoration, industrial applications, graphical applications, or in-mold labeling, preferably for automotive interiors and exteriors, home appliances, consumer electronics, or cosmetic packaging materials.

[0118] A particular preferred use of the coating according to embodiments of the present invention is in automotive interiors and exteriors, preferably automotive interiors.

[0119] Any feature of any embodiment of the fourth aspect may be described independently, as correspondingly to any embodiment of any other aspect of the present invention.

[0120] In a fifth embodiment, the present invention relates to a method for forming an aqueous radiation-curable polyurethane dispersion obtained by reacting a: a compound containing at least two isocyanate groups; b: a polyol having a molecular weight of at least 500 g / mol; c: a compound containing at least one group capable of reacting with an isocyanate group and preferably a salt or capable of containing a salt after reaction with a neutralizing agent; and d: an ethylenically unsaturated compound containing at least one group capable of reacting with an isocyanate group and at least one ethylenically unsaturated group; a plurality of polyurethane particles having a median diameter D50 of 1 to 10 μm; and water, comprising the step of mixing these compounds.

[0121] Aqueous radiation-curable compositions according to embodiments of the present invention can be prepared in many ways. Radiation-curable polyurethane dispersions are typically provided in the form of aqueous solutions or aqueous dispersions. That is, water and radiation-curable polyurethane dispersions can be provided from a mixture containing water and radiation-curable polyurethane dispersions.

[0122] In embodiments, the formation of an aqueous radiation-curable composition comprises a first step involving the reaction of compounds a., b., c., and d., and optionally compound e. In this specification, compounds a., b., c., and d. can be reacted together simultaneously or in a multi-stage process. For example, compounds a., c., and optionally b. may react first, followed by compound d. Optionally, the method may further include a chain extension step by reaction with compound f. The reaction step with compound f. is preferably carried out after the reaction of a., b., c., and d., and optionally e, where compound f. reacts with any residual, i.e., unreacted isocyanate groups. This allows for the formation of a radiation-curable polyurethane dispersion according to embodiments of the present invention, preferably free of unreacted isocyanate groups. Optionally, further ethylenically unsaturated compounds can be added after the reaction has stopped. The residual isocyanate content is typically measured by isocyanate titration with an amine. The amount of NH2 groups is typically obtained by calculation. The reaction can be carried out by adding 5 to 40% by weight, preferably 15 to 25% by weight, of a solvent to reduce the viscosity of the prepolymer. Preferably, the solvent is acetone or methyl ethyl ketone.

[0123] Subsequently, in embodiments in which the hydrophilic groups provided by compound c. do not contain salts but may contain salts, the radiation-curable polyurethane dispersion can be reacted with a neutralizing agent to convert the hydrophilic groups to anionic salts. This can be done by adding an organic or inorganic neutralizing agent to the prepolymer or water. Suitable neutralizing agents include ammonia, volatile organic tertiary amines such as trimethylamine, triethylamine, triisopropylamine, tributylamine, N,N-dimethylcyclohexylamine, N,N-dimethylaniline, N-methylmorpholine, N-methylpiperazine, N-methylpyrrolidine and N-methylpiperidine, low-volatility alcohol amines such as dimethylaminoethanol, triethanolamine, dimethylaminoethylpropanolamine, and monovalent metal cations, preferably alkali metals such as lithium, sodium and potassium, and non-volatile inorganic bases such as anions, such as hydroxides, hydrides, carbonates and bicarbonates. Preferably, the neutralizing agent contains triethylamine and / or sodium hydroxide. The total amount of these neutralizing agents can be calculated according to the total amount of acid groups to be neutralized. In the embodiment, the neutralizing agent is added in a stoichiometric ratio of 0.5:1 to 1:1 relative to the acidic group of the neutralizing agent, such as a protonated hydrophilic group.

[0124] In embodiments, the radiation-curable polyurethane dispersion is dispersed in water, for example, by slowly adding a water-dispersible radiation-curable polyurethane to water, or conversely, by adding water to a prepolymer. Typically, dispersion is carried out using high-shear mixing.

[0125] In the embodiment, the neutralizing agent may be added before, during, or after the step of dispersing the water-dispersible radiation-curable polyurethane in water.

[0126] Typically, after the formation of a prepolymer dispersion, if the dispersion contains a volatile solvent, such as an organic solvent, having a boiling point below 100°C, the solvent is removed from the dispersion. This can be done under reduced pressure relative to atmospheric pressure and at a temperature of 20–90°C, preferably 40–70°C.

[0127] In some embodiments, the polyurethane particles are provided in powder form. In some embodiments, the polyurethane particles are provided as a dispersion or suspension. For example, the polyurethane particles can be provided in water.

[0128] The compositions according to embodiments of the present invention can be prepared in various ways. In embodiments, a radiation-curable polyurethane dispersion compound, polyurethane particles, water, optionally additives, and further compounds are blended and mixed. In embodiments, high-shear mixing is used for mixing. In embodiments, mixing can be carried out using a Cowles blade at a rotational speed of preferably 20 to 2000 revolutions per minute. For example, mixing can be carried out at room temperature under high shear at a rotational speed of 20 to 2000 revolutions per minute, for example, using a Cowles blade. In this specification, the rotational speed may depend on the diameter of the Cowles blade, the diameter of the container, and the volume being mixed.

[0129] In one embodiment, the mixing can result in an aqueous radiation-curable composition in which polyurethane particles are present in a suspension. In another embodiment, an anti-settling agent can be added to the aqueous radiation-curable composition to prevent the polyurethane particles from settling.

[0130] Any feature of any embodiment of the fifth aspect may be described independently, as correspondingly to any embodiment of any other aspect of the present invention.

[0131] One aspect of the present invention is shown below, but the present invention is not limited thereto. [Invention 1] Aqueous radiation-curable composition containing the following: • A radiation-curable polyurethane dispersion obtained by reacting the following: a. A compound containing at least two isocyanate groups, b. A polyol having a molecular weight of at least 500 g / mol, c. Compounds comprising at least one group capable of reacting with an isocyanate group, and at least one hydrophilic group, and d. An ethylenically unsaturated compound comprising at least one group capable of reacting with an isocyanate group and at least one ethylenically unsaturated group; • Multiple polyurethane particles that are non-radiation curable and have a median particle size D50 of 1 to 10 μm; and ·water. [Invention 2] The composition according to Invention 1, wherein a radiation-curable polyurethane dispersion is obtained by reacting 10 to 60 parts by mass of compound a, 1 to 40 parts by mass of compound b, 2 to 25 parts by mass of compound c, and 15 to 85 parts by mass of compound d, and the total parts by mass of compounds a, b, c, and d is 100. [Invention 3] The composition according to Invention 1 or 2, further comprising compound e., which is a diol having a molecular weight of up to 400 g / mol, as the compound reacted to obtain the radiation-curable polyurethane dispersion compound. [Invention 4] The composition according to any one of inventions 1 to 3, wherein the compound reacted to obtain a radiation-curable polyurethane dispersion additionally comprises compound f. having at least two amino groups independently selected from primary and secondary amino groups. [Invention 5] The composition according to any one of inventions 1 to 4, wherein polyol compound b. is polyester or polycarbonate. [Invention 6] A composition according to any one of inventions 1 to 5, wherein the polyurethane particles have a median diameter D50 of 5 to 8 μm. [Invention 7] A composition according to any one of inventions 1 to 6, comprising a further non-radiation-curable polyurethane aqueous dispersion obtained by reacting: i. Compounds containing at least two isocyanate groups; ii. Polyols having a molecular weight of at least 500 g / mol; iii. Compounds comprising at least one group capable of reacting with an isocyanate group, and at least one hydrophilic group; and iv. A compound comprising at least two amino groups selected from primary and secondary amino groups. [Invention 8] The composition according to Invention 7, wherein a further non-radiation-curable polyurethane dispersion accounts for 0.1 to 40% by weight of the total mass of the further non-radiation-curable polyurethane dispersion, the radiation-curable polyurethane dispersion, and the polyurethane particles. [Invention 9] The composition according to invention 7 or 8, further comprising compound v., which is a diol having a molecular weight of less than 500 g / mol, as the compound reacted to obtain a further non-radiation-curable polyurethane dispersion. [Invention 10] The composition according to any one of inventions 7 to 9, wherein polyol compound ii is polyester or polyether. [Invention 11] The composition according to any one of inventions 7 to 10, wherein the mass ratio of the radiation-curable polyurethane dispersion in the composition to a further non-radiation-curable polyurethane dispersion is at least 1.5. [Invention 12] A composition according to any one of Inventions 1 to 11, wherein multiple polyurethane particles constitute 3 to 20% by mass of the composition as solid content. [Invention 13] The composition according to any one of Inventions 1 to 12, further comprising: at least one of the following additives: a catalyst, a polymerization inhibitor, or a photoinitiator. [Invention 14] Polyurethane particles g A composition according to any one of inventions 1 to 13, wherein the maximum temperature is 0°C. [Invention 15] The composition according to any one of Inventions 1 to 14, wherein the amount of oil absorbed by the polyurethane particles is a maximum of 120 grams of oil per 100 grams of polyurethane particles. [Invention 16] A coating formed by curing a composition described in any one of Inventions 1 to 15. [Invention 17] The steps of applying a composition according to any one of inventions 1 to 15 to a surface, The step of curing the composition to form a coating. A method for forming the coating described in Invention 16, including the method described in Invention 16. [Invention 18] Use of the coating described in Invention 16 for consumer electronics, home appliances, automotive interiors and exteriors, packaging materials, furniture, in-mold decoration, industrial applications, graphical applications, or in-mold labeling. [Invention 19] A method for forming an aqueous radiation-curable composition according to any one of Inventions 1 to 15, comprising the step of mixing the following: Compounds of radiation-curable polyurethane dispersions obtained by reacting the following: a. A compound containing at least two isocyanate groups, b. A polyol having a molecular weight of at least 500 g / mol, c. Compounds comprising at least one group capable of reacting with an isocyanate group, and at least one hydrophilic group, and d. An ethylenically unsaturated compound comprising at least one group capable of reacting with an isocyanate group and at least one ethylenically unsaturated group; • Multiple polyurethane particles that are non-radiation curable and have a median diameter D50 of 1 to 10 μm; and · Water. The present invention will be described in detail below with reference to the following non-limiting examples, which are for illustrative purposes only. Unless otherwise indicated, the portions referred to in the examples are parts by weight. [Examples]

[0132] Radiation-curable polyurethane dispersion and non-radiation-curable polyurethane dispersion First radiation-curable polyurethane dispersion (UV PUD1) UV PUD1 is the commercially available product UCECOAT® 2804. It is a low-migration acrylated polyurethane translucent dispersion obtained from the reaction of a mixture of compounds a, b, c, d, and e. It had a viscosity of 60 mPas, a solids content of 34.7 wt%, a particle size of 96 nm, and a pH of 7.2.

[0133] Second radiation-curable polyurethane dispersion (UV PUD2) UV PUD2 contains 262.1g of EBECRYL® 4744 (d.), 13.4g of neopentyl glycol (e.), Ne Opentyl glycol、 Adipic acid and isophthalic acid 118.8g polyester (Mw635, b.), and a radiation-curable polyurethane dispersion obtained from the reaction of 35.1 g of dimethylolpropionic acid (c.), 0.3 g of dibutyltin dilaurate, 133.9 g of isophorone diisocyanate (a.), and 66.9 g of hexamethylene diisocyanate (a.). The resulting prepolymer had a residual NCO of 0.5 meq NCO / g. Next, 20.7 g of triethylamine was added. Finally, 11.8 g of ethylenediamine (f.) was added after the dispersion step. The final dispersion had a viscosity of 151 mPas, a solids content of 35.0 wt%, a particle size of 46 nm, and a pH of 7.9.

[0134] (Example 1c) Further non-radiation-curable polyurethane dispersions Three dispersions containing further polyurethanes that are water-dispersible and non-radiation-curable in water were used as examples: Daotan® 6490 (PUD1), Daotan® 6491 (PUD2), and Daotan® 6493 (PUD3). Each of these dispersions is commercially available. The properties of these dispersions are summarized in Table 0 below. [Table 0]

[0135] Preparation of aqueous radiation-curable compositions and coatings thereof For the sake of example, various compositions were prepared according to the following general method.

[0136] An aqueous radiation-curable polyurethane dispersion was poured into a 250 mL plastic mixing container. Optionally, a further non-radiation-curable polyurethane dispersion was added to the aqueous radiation-curable polyurethane dispersion. The dispersion was stirred at 600 rpm using a Cowles mixer blade (5 / 8 inch). Next, water and then additives were added to the aqueous dispersion to obtain a mixture. In the examples, Additol® VXW390 and Additol® VXW6580 were added as wetting agents and Irgacure® 500 was added as a photoinitiator. Finally, fillers, such as polyurethane particles or non-polyurethane particles, were added to the mixture. The mixture was stirred at 600 rpm for about 20 minutes. All steps were carried out at room temperature. The Cowles blade is preferred as it ensures good dispersion of the polyurethane particles, thereby obtaining a composition according to an embodiment of the present invention.

[0137] The relative amounts of the various compounds, additives and fillers used in each composition are shown in the following examples.

[0138] In the following examples, coatings were formed using the compositions immediately after preparation. For this purpose, each composition was applied to the surface of a plastic substrate (ABS: Magnum® 3616, ABS / PC: Bayblend® T85XF or T65XF). A bar coater was used to target a dry film thickness (DFT) of about 20 g / m 2 The applied composition was dried at 60 °C for 5 minutes. Thereafter, curing using UV radiation was carried out using two 120 W / cm Hg lamps (1000 - 1200 mJ / cm 2 ). The lamps passed once over the composition at a speed of 15 m / min (i.e., about 50 feet / min).

[0139] Analytical techniques Various analytical techniques were used to characterize the example compositions and coatings. These techniques are described below.

[0140] The hydrodynamic size of particles in various compositions was characterized using dynamic light scattering (DLS) measurements. Prior to DLS measurement, the concentrated composition was diluted with deionized distilled water to obtain a particle concentration of 0.05 w / w%. The diluted composition was filtered. DLS measurements were then performed at 23°C using a Beckman-Coulter DelsaNano-c particle analyzer. The incident monochromatic light used in the DLS measurement had a wavelength of λ = 658 nm. The scattered light was detected at an angle of 165° in a configuration close to backscattering. The z-mean particle size, along with the polydispersity index, was determined from the second-order cumulant analysis of the electric field autocorrelation function. The diffusion coefficient of a single particle was then estimated from the mean decay constant. From this, the median particle size D50 could be obtained using Stokes' relation.

[0141] The solid content was determined by gravimetric analysis. For radiation-curable polyurethane dispersions, gravimetric analysis included drying at 120°C for 2 hours. For further non-radiation-curable polyurethane dispersions, gravimetric analysis included drying at 125°C for 3 hours.

[0142] pH was measured according to DIN EN ISO 10390.

[0143] The viscosity of radiation-curable polyurethane dispersions and further non-radiation-curable polyurethane dispersions was measured using a cone and plate rheometer MCR092 (Paar-Physica) according to DIN EN ISO3219. (25 seconds) -1 A constant shear rate of 23°C was used.

[0144] The coating was tested for adhesion, soft feel, and DEET resistance.

[0145] For the soft-feel test, the example coating was compared to a commercially available WB 2k soft-feel coating from General Motors. The example coating was evaluated by three different observers regarding its softness. In the table, each coating is evaluated using a scale from 1 to 4, where 1 indicates a good soft feel and 4 indicates a poor soft feel. Preferably, the coating obtains a score of 1 or 2.

[0146] The resistance of each coating to DEET and sunscreen, i.e., chemical resistance, was also determined according to General Motors' sunscreen and insecticide resistance test procedure, e.g., GMW14445. The GMW14445 test was performed at 80°C. Other tests were performed at room temperature and ambient humidity. Each coating was evaluated using a scale of 1 to 4, where 1 indicates good resistance and 4 indicates poor resistance. Preferably, a coating obtains a score of 1.

[0147] The adhesion (ADH) of a coating to the surface of a plastic substrate is evaluated using a cross-hatch test. In all cases, first, five parallel cuts approximately 1 cm long and 1 mm apart are made in the coating using a knife. Next, five parallel cuts approximately 1 cm long and 1 mm apart are made transversely. Then, adhesive tape (Scotch®) is firmly pressed onto the cross-cut coating and rapidly removed. Damage to the cross-cut surface area of ​​the coating, i.e., due to adhesion loss, is expressed on a scale of 0 to 5, where 5 = best adhesion. Good adhesion is desirable to ensure a strong permanent bond between the coating and the surface.

[0148] Coatings and compositions Table A summarizes the parts by mass content of a series of compositions according to preferred embodiments of the present invention and the analysis results of the series of coatings formed thereby. Tables D, F, and H list the fillers used. Each of the coatings summarized in this table has a score of 1 for soft feel and chemical resistance, i.e., against sunscreen and DEET.

[0149] Coatings and compositions of curable polyurethane and non-curable further polyurethane at various concentrations. In further examples, the effect of the amount of PUD1 in a composition on the properties of a coating was tested. Table B summarizes the parts by mass content of a series of compositions and the analysis results of a series of coatings formed therefrom. Tables D and F list the fillers used. The last two columns of the tables show the weight percentages of radiation-curable polyurethane and non-radiation-curable polyurethane as a percentage of the total of radiation-curable and non-radiation-curable polyurethanes. For UV PUD1, it was observed that the soft feel was best when the composition for forming the coating contained PUD1. However, the amount of added PUD1 is preferably not too much. For example, the mass ratio of UV PUD1 to PUD is at least 1.5.

[0150] Coatings and compositions of various types of non-radiation-curable further polyurethane compounds In further examples, the effect of the type of PUD in the composition on the properties of the coatings was tested. The parts by mass content of a series of compositions and the analysis results of the series of coatings formed therefrom are summarized in Table C. For each PUD used in the examples, both soft feel and chemical resistance are preferred.

[0151] Coatings and compositions using various types of polyurethane particles In further examples, the influence of polyurethane particle characteristics on coating properties was tested. Table D summarizes the characteristics of various polyurethane particles tested. In this specification, D50 is the median particle size (μm). Table E summarizes the parts by mass content of a series of compositions and the analysis results of a series of coatings formed thereby. When the particle size is in the range of 1 to 10 μm, it can be observed from the examples that a soft feel is preferred in particular.

[0152] Coatings and compositions using various types of polymethylurea resin particles In further examples, the effect of using various types of particles on the properties of the coatings was tested. Table F summarizes the characteristics of the various particles used in the examples. In this specification, D50 is the median particle size (μm). Table G summarizes the parts by mass content of a series of compositions and the analytical results of the series of coatings formed therefrom. It can be observed that the results for polyurethane particles are better than those for polymethylurea resin particles. The results are similarly favorable when using mixtures containing at least polyurethane particles.

[0153] Coatings and compositions using various types of non-polyurethane particles The effects of using various types of particles on the properties of the coatings were further tested. Table H summarizes the characteristics of the various particles tested. In this specification, D50 is the median particle size (μm), and SC indicates the solid content in the form in which the filler is supplied by the manufacturer. Table I summarizes the parts by mass content of a series of compositions and the analytical results of a series of coatings formed thereby. It can be observed that the results for polyurethane particles are better than those for other particles, even when the diameter distribution is similar. This clearly demonstrates the advantageous effect of using polyurethane particles as used in this invention.

[0154] Coatings and compositions using polyurethane particles of various concentrations In further examples, the effects of using various amounts of polyurethane particles on the properties of coatings are tested. The parts by mass content of a series of compositions and the analysis results of the series of coatings formed therefrom are summarized in Table J. For compositions containing more than 20% by weight of polyurethane particles, the cosmetic properties and uniformity of the coatings are poor. This corresponds to the mass ratio of polyurethane particles to the sum of the non-radiation-curable further polyurethane dispersions and radiation-curable polyurethane dispersions exceeding 1.0. As mentioned in Table D, Addimat® 8FT is supplied in water and has a solid content of 36% by weight. Thus, 10 parts by weight of Addimat® 8FT in composition F13, mentioned in Table E, is equivalent to 3.6% by weight of polyurethane particles in composition F13. Thus, from these examples, it is assumed that the most favorable results are obtained when the polyurethane particle content of the composition is 3 to 20% by weight, or when the mass ratio of polyurethane particles to the sum of the water-dispersible non-radiation-curable further polyurethane dispersions and radiation-curable polyurethane dispersions is 0.08 to 1.0.

[0155] [Table A]

[0156] [Table B]

[0157] [Table C]

[0158] [Table D1]

[0159] [Table D2]

[0160] Table E

[0161] Table F

[0162]

Table G

[0163] Table H

[0164] Table I

[0165] Table J

Claims

1. the below described: • Radiation-curable polyurethane dispersion obtained by reacting the following: a. A compound containing at least two isocyanate groups, b. A polyol having a molecular weight of at least 500 g / mol, c. Compounds comprising at least one group capable of reacting with an isocyanate group, and at least one hydrophilic group, and d. An ethylenically unsaturated compound comprising at least one group capable of reacting with an isocyanate group and at least one ethylenically unsaturated group; - Multiple polyurethane particles that are non-radiation curable and have a median particle size D50 of 1 to 10 μm; and ·water, An aqueous radiation-curable composition comprising, The aqueous radiation-curable composition is as follows: i. Compounds containing at least two isocyanate groups; ii. Polyols having a molecular weight of at least 500 g / mol; iii. Compounds comprising at least one group capable of reacting with an isocyanate group, and at least one hydrophilic group; and iv. Compounds comprising at least two amino groups selected from primary and secondary amino groups, Further comprising a non-radiation-curable polyurethane aqueous dispersion obtained by reacting, The mass ratio of the radiation-curable polyurethane dispersion in the composition to a further non-radiation-curable polyurethane dispersion is at least 1.

5. Aqueous radiation curable composition.

2. The composition according to claim 1, wherein a radiation-curable polyurethane dispersion is obtained by reacting 10 to 60 parts by mass of compound a., 1 to 40 parts by mass of compound b., 2 to 25 parts by mass of compound c., and 15 to 85 parts by mass of compound d., and the total parts by mass of compounds a., b., c., and d. is 100.

3. The composition according to claim 1, further comprising compound e, which is a diol having a molecular weight of up to 400 g / mol, as the compound reacted to obtain the radiation-curable polyurethane dispersion compound.

4. The composition according to claim 1, wherein the compound reacted to obtain a radiation-curable polyurethane dispersion further comprises compound f., which contains at least two amino groups independently selected from primary and secondary amino groups.

5. The composition according to claim 1, wherein polyol compound b. is a polyester polyol or a polycarbonate polyol.

6. The composition according to claim 1, wherein the non-radiation-curable polyurethane particles have a median diameter D50 of 5 to 8 μm.

7. The composition according to claim 1, wherein a further non-radiation-curable polyurethane dispersion accounts for 0.1 to 40% by weight of the total mass of the further non-radiation-curable polyurethane dispersion, the radiation-curable polyurethane dispersion, and the polyurethane particles.

8. The composition according to claim 1, further comprising compound v., a diol having a molecular weight of less than 500 g / mol, which is reacted with a compound to obtain a further non-radiation-curable polyurethane dispersion.

9. The composition according to claim 1, wherein polyol compound ii is a polyester polyol or a polyether polyol.

10. The composition according to claim 1, wherein a plurality of non-radiation-curable polyurethane particles constitute 3 to 20% by mass of the composition as solid content.

11. The composition according to claim 1, further comprising at least one of the following additives: a catalyst, a polymerization inhibitor, or a photoinitiator.

12. Polyurethane particles that are not radiation-curable T ｇ The composition according to claim 1, wherein the temperature is 0°C at its maximum.

13. The composition according to claim 1, wherein the amount of oil absorbed by non-radiation-curable polyurethane particles is a maximum of 120 grams of oil per 100 grams of non-radiation-curable polyurethane particles, when determined using the ASTM D281 test method.

14. A coating formed by curing the composition according to any one of claims 1 to 13.

15. The steps include applying the composition to the surface, The step of curing the composition to form a coating. A method for forming the coating according to claim 14, including the method described in claim 14.

16. Use of the coating according to claim 14 for consumer electronics, home appliances, automotive interiors and exteriors, packaging materials, furniture, in-mold decoration, industrial applications, graphical applications, or in-mold labeling.

17. the below described: Compounds of radiation-curable polyurethane dispersions obtained by reacting the following: a. A compound containing at least two isocyanate groups, b. A polyol having a molecular weight of at least 500 g / mol, c. Compounds comprising at least one group capable of reacting with an isocyanate group, and at least one hydrophilic group, and d. An ethylenically unsaturated compound comprising at least one group capable of reacting with an isocyanate group and at least one ethylenically unsaturated group; - Multiple polyurethane particles that are non-radiation curable and have a median diameter D50 of 1 to 10 μm; and ・Water, A method for forming an aqueous radiation-curable composition according to any one of claims 1 to 13, comprising the step of mixing: The aqueous radiation-curable composition is as follows: v. Compounds containing at least two isocyanate groups; vi. Polyols having a molecular weight of at least 500 g / mol; vii. Compounds comprising at least one group capable of reacting with an isocyanate group, and at least one hydrophilic group; and viiii. Compounds comprising at least two amino groups selected from primary and secondary amino groups, Further comprising a non-radiation-curable polyurethane aqueous dispersion obtained by reacting, The mass ratio of the radiation-curable polyurethane dispersion in the composition to a further non-radiation-curable polyurethane dispersion is at least 1.

5. method.

Images