Acrylic-urethane aqueous dispersion composition

Abstract

The present disclosure provides an acrylic-urethane aqueous dispersion composition having excellent mixing stability and particularly excellent coating properties on a plastic material due to comprising an acrylic-based copolymer and polyurethane, and provides a coating layer having excellent coating properties, excellent water resistance, and excellent blocking resistance by using same, and a water-resistant article comprising same.

Description

Acrylic-urethane water dispersion composition

[0001] The present disclosure provides an acrylic-urethane water dispersion composition having excellent mixing stability and a coating layer having excellent water resistance, adhesion, and blocking resistance using the same.

[0002] An ink composition containing a water-dispersed paint and pigment is coated on a metal, ceramic or plastic substrate to provide effects such as excellent water resistance, surface hardness or chemical resistance, thereby preventing deterioration of the material's properties due to corrosion and improving the style.

[0003] Among these, plastic materials are widely used in high-tech fields such as automobiles, aerospace / aviation, interior / exterior, or mobile phones, as well as in daily necessities, and the technology for coating surfaces and the technology for water-dispersed paints used are increasing for reasons of aesthetics or improvement of physical properties.

[0004] When coating plastic materials, the most important factors are application properties and adhesion. To apply water-dispersible paints to conventional plastic materials and form a coating layer, a surface energy modification process, such as corona treatment, is essential. This is because untreated plastic materials have very low surface energy, making application of water-dispersible paints difficult and causing the coating layer formed by water-dispersible coatings to easily disappear. Consequently, coating conventional plastic materials with water-dispersible paints is very complex and increases process costs.

[0005] Therefore, there is a need for a new paint that has excellent applicability to plastic materials without a surface energy modification process, and the formed coating layer has excellent adhesion, excellent water resistance, and excellent blocking resistance.

[0006] One aspect of the present disclosure is to provide an acrylic-urethane water dispersion composition having excellent applicability to a plastic material.

[0007] One aspect of the present disclosure is to provide an acrylic-urethane water dispersion composition having excellent storage stability without formation of long-term aggregates even when an acrylic emulsion and a urethane emulsion are mixed.

[0008] As one aspect of the present disclosure, there is provided a coating layer having excellent adhesion to a substrate, particularly excellent adhesion to a plastic material, and an article including the same, using the acrylic-urethane water dispersion composition.

[0009] One aspect of the present disclosure provides an article in which the coating of the aqueous dispersion composition does not separate even when stored for a long period of time, in the case of an article coated using the acrylic-urethane aqueous dispersion composition.

[0010] In one aspect of the present disclosure, there is provided an acrylic-urethane dispersion composition comprising an acrylic copolymer having a degree of crosslinking of 50 to 60%, which is prepared from a monomer composition comprising a reactive emulsifier composition comprising 50 wt% or more of methyl methacrylate and a reactive emulsifier containing two or more unsaturated groups, and a polyurethane having a spectrum area ratio of methylene groups to carbonyl groups of 1:1.5 to 2.5 as measured by infrared spectroscopy.

[0011] In another aspect of the present disclosure, the polyurethane may have a spectrum area ratio of a methylene group to a carbonyl group of 1.5 to 2.0 in a spectrum measured by infrared spectroscopy.

[0012] As one aspect of the present disclosure, the monomer composition may further comprise one or more comonomers selected from C3-C6 alkyl(meth)acrylate, (meth)acrylic acid, and (meth)acrylonitrile.

[0013] As one aspect of the present disclosure, the acrylic-urethane water dispersion composition may have a solids content of 10 to 50%.

[0014] As one embodiment of the present disclosure, the acrylic-urethane water dispersion composition may have an acrylic copolymer and polyurethane in a weight ratio of 1:0.1 to 0.5.

[0015] As one aspect of the present disclosure, the acrylic-urethane water dispersion composition may be such that, when applied once by Meyer bar coating on an ASA (Acrylonitrile styrene acrylate copolymer) film, there are no uncoated pores observed with the naked eye.

[0016] As one aspect of the present disclosure, the reactive emulsifier may have a substituent including one or more unsaturated groups and an ether group (*-O-*).

[0017] As one embodiment of the present disclosure, the reactive emulsifier may include one or more selected from the following chemical formulae 1 to 3.

[0018] [Chemical Formula 1]

[0019]

[0020] [Chemical Formula 2]

[0021]

[0022] [Chemical Formula 3]

[0023]

[0024] (In the above chemical formulas 1 to 3, R1, R2 and R3 are each independently a straight chain or branched chain C 10 -C 50 alkyl, and X1, X2 and X3 are each independently an anionic hydrophilic group.)

[0025] As one aspect of the present disclosure, the monomer composition may further comprise a (meth)acrylate crosslinking agent comprising two or more (meth)acrylic groups.

[0026] In one aspect of the present disclosure, a coating layer formed from the acrylic-urethane water dispersion composition can be provided.

[0027] As one aspect of the present disclosure, the coating layer may have a peel strength of 5B as measured by ASTM D3359.

[0028] In one embodiment of the present disclosure, the coating layer may exhibit minimal or no blocking as measured by KS A 1024.

[0029] One aspect of the present disclosure can provide a waterproof article having a substrate and a coating layer as described above formed on the surface of the substrate.

[0030] In one aspect of the present disclosure, the substrate may be plastic.

[0031] As one aspect of the present disclosure, the substrate may be a film, a sheet, or an injection-molded article.

[0032] As one embodiment of the present disclosure, the acrylic-urethane water dispersion composition has excellent mixing stability with very little occurrence of agglomeration even during long-term storage.

[0033] As one aspect of the present disclosure, the acrylic-urethane water dispersion composition can have excellent applicability even without corona treatment of a plastic material, thereby reducing the volume of manufacturing equipment and production cost.

[0034] As one embodiment of the present disclosure, the acrylic-urethane water dispersion composition can form a very excellent coating layer having a peel strength of 5B as measured by ASTM D3359, even without corona treatment of a plastic material.

[0035] As one embodiment of the present disclosure, a water-resistant article manufactured using the acrylic-urethane water dispersion composition exhibits very little or no blocking in a blocking test measured according to KS A 1024, so that the article can be delivered to a consumer without the coating layer peeling off and becoming detached even when loaded or transported for a long period of time.

[0036] Figure 1 is a spectrum measured by FT-IR of water-dispersed polyurethane (Alberdinkg Boley, U 3251).

[0037] Figure 2 is a spectrum measured by FT-IR of water-dispersed polyurethane (COVESTRO, IMPRANIL DLC-T).

[0038] Figure 3 is a spectrum measured by FT-IR of water-dispersed polyurethane (COVESTRO, IMPRANIL DLC-F).

[0039] Figure 4 is a spectrum measured by FT-IR of water-dispersed polyurethane (COVESTRO, IMPRANIL DLU).

[0040] Figure 5 is a spectrum measured by FT-IR of water-dispersed polyurethane (Alberdinkg Boley, U 400N).

[0041] Hereinafter, the acrylic-urethane aqueous dispersion composition will be described. Unless otherwise defined, the technical and scientific terms used herein have the meanings commonly understood by those of ordinary skill in the art to which this invention pertains. In the following description, descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention will be omitted.

[0042] Additionally, the singular forms used in this disclosure may be intended to include the plural forms as well, unless the context specifically indicates otherwise.

[0043] In addition, units used in the present disclosure without special mention are based on weight, and for example, units of % or ratio mean weight% or weight ratio, and weight% means the weight% that any one component of the entire composition occupies in the composition unless otherwise defined.

[0044] Additionally, the numerical ranges used in this disclosure include lower and upper limits and all values ​​within the range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of upper and lower limits of numerical ranges defined in different shapes. Unless otherwise specifically defined in the specification of this disclosure, values ​​outside the numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0045] The term "includes" in this disclosure is an open-ended description having an equivalent meaning to expressions such as "comprises," "contains," "has," or "characterizes," and does not exclude additional elements, materials, or processes not listed.

[0046] The term '(meth)acrylate' in this article may refer to either acrylate or methacrylate.

[0047] Hereinafter, the acrylic-urethane water dispersion composition of the present disclosure will be described.

[0048] As one aspect of the present disclosure, the acrylic-urethane water dispersion composition may include an acrylic copolymer and polyurethane.

[0049] The above acrylic-urethane water dispersion composition may be a mixture of an acrylic emulsion containing an acrylic copolymer in deionized water and a water-dispersed polyurethane containing polyurethane in deionized water.

[0050] In general, when a conventional acrylic emulsion and a water-dispersed polyurethane are mixed, coagulation occurs, and a paint manufactured by mixing them has low applicability and is not commercially available. However, in one embodiment of the present disclosure, an acrylic emulsion including an acrylic copolymer satisfying the following properties and a water-dispersed polyurethane including polyurethane are mixed, thereby solving this problem.

[0051] In one embodiment of the present invention, the acrylic copolymer included in the acrylic-urethane water dispersion composition satisfies a crosslinking degree of 50 to 60%, and the polyurethane has a spectrum (1710 cm) of a carbonyl group (*-C=0-*) when the spectrum area of ​​a methylene group (*-CH2) is 1 in a spectrum measured by infrared spectroscopy (FT-IR). -1 The peak) area ratio can be characterized as being 1.5 to 2.5.

[0052] The degree of crosslinking of the acrylic copolymer above can be measured as follows.

[0053] The above crosslinking degree measurement method was performed by placing 10 g of a crosslinked acrylic copolymer in a beaker containing 200 ml of ethyl acetate at 25°C and leaving it for 24 hours. After leaving it for 24 hours, the crosslinked acrylic copolymer was completely dried, its mass was measured, and the degree of crosslinking was calculated using the following formula.

[0054] [ceremony]

[0055] Crosslinking degree (%) = Mass of crosslinked acrylic copolymer left in ethyl acetate (g) / 10 (g) X 100

[0056] The above acrylic-urethane water dispersion composition may include an acrylic copolymer having a crosslinking degree in the above range and a polyurethane satisfying the above spectral area ratio.

[0057] The above-mentioned acrylic-urethane water dispersion composition exhibits excellent mixing stability with no aggregation even after long-term storage, and can exhibit remarkable applicability to plastic substrates. Furthermore, even without corona treatment of the plastic substrate, it can be applied very smoothly, and the formed coating layer can have an excellent appearance, excellent adhesion, and excellent blocking resistance.

[0058] As another aspect of the present disclosure, the acrylic-urethane water dispersion composition may preferably include an acrylic copolymer having a crosslinking degree of 55 to 60%, in terms of having better mixing stability and excellent coatability.

[0059] As one embodiment of the present disclosure, the acrylic copolymer may be prepared from a monomer composition comprising a reactive emulsifier composition comprising 50 wt% of methyl methacrylate and a reactive emulsifier containing two or more unsaturated groups.

[0060] The above reactive emulsifier may be an emulsifier containing two or more unsaturated groups and simultaneously having an ether group. By having the ether group, it has excellent miscibility with water-dispersed polyurethane, allowing for uniform mixing and also increasing adhesion to the substrate.

[0061] Furthermore, since the reactive emulsifier contains an unsaturated group, it can participate in the reaction as a monomer in the polymerization of an acrylic copolymer. Furthermore, since the reactive emulsifier may contain two or more unsaturated groups, an acrylic copolymer manufactured by including the reactive emulsifier can have a crosslinking degree within the above range. Furthermore, it can exhibit adhesion and coating properties to substrates such as plastic substrates, and long-term mixing stability when mixed with the polyurethane, thereby effectively demonstrating overall properties.

[0062] The unsaturated group of the above reactive emulsifier may mean a carbon double bond, and in terms of an acrylic copolymer containing the same having higher polymerization reactivity, it may mean a vinyl group (*-CH=CH2).

[0063] As one embodiment of the present disclosure, the reactive emulsifier composition may include one or two or more reactive emulsifiers selected from the following chemical formulae 1 to 3, and is not particularly limited as long as it includes a reactive emulsifier capable of crosslinking by containing two or more functional groups capable of radical reaction.

[0064] [Chemical Formula 1]

[0065]

[0066] [Chemical Formula 2]

[0067]

[0068] [Chemical Formula 3]

[0069]

[0070] (In the above chemical formulas 1 to 3, R1, R2 and R3 are each independently a straight chain or branched chain C 10 -C 50 alkyl, X1, X2 and X3 are each independently an anionic hydrophilic group, and n1, n2 and n3 are each independently an integer from 4 to 20.)

[0071] The above anionic hydrophilic group is not particularly limited as long as it is recognizable by a person skilled in the art, and as an example, a carboxylic acid group (*-COO - M + ), sulfonic acid group (*-SO3 - M + ), sulfate ester base (*-OSO3 - M + ) and phosphate ester base (*-PO3 - Na 2+ ) can be any one of the following.

[0072] Since the above reactive emulsifier composition has already been disclosed in many products, a detailed description thereof will be omitted.

[0073] In one embodiment of the present disclosure, the reactive emulsifier composition may contain the reactive emulsifier (chemical formula 2 and chemical formula 3) containing two or more unsaturated groups in an amount of 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, up to 40 wt%, 25 wt% or less, or 15 wt% or less, based on the total content, for example, 5 to 30 wt%, 10 to 20 wt%, or 15 to 20 wt%.

[0074] However, if the acrylic copolymer manufactured above has a crosslinking degree of 50 to 60%, this is not necessarily limited.

[0075] As one aspect of the present disclosure, the monomer composition may further include various comonomers in addition to methyl methacrylate.

[0076] Examples of the above comonomers include, but are not limited to, one or more selected from C3-C6 alkyl(meth)acrylate, (meth)acrylic acid, and (meth)acrylonitrile.

[0077] An acrylic copolymer manufactured by further including the above monomer can have better adhesive strength as a paint, and in terms of better adhesive strength, butyl (meth)acrylate may be more preferred as the C3-C6 alkyl (meth)acrylate, but this is not necessarily limited thereto.

[0078] As one aspect of the present disclosure, the monomer composition may further comprise a multifunctional (meth)acrylate crosslinker comprising two or more (meth)acrylate groups.

[0079] The above multifunctional monomer may include, but is not limited to, various monomers such as pentaerythritol tetraacrylate, propylene glycol dimethacrylate, and polyalkylene glycol dimethacrylate having a number average molecular weight of 200 to 1000 g / mol.

[0080] For example, the crosslinking agent may be present in an amount of 5 wt% or less, 3 wt% or less, 1 wt% or less, 0.01 wt% or more, or 0.1 wt% or more, based on the total weight of the entire reactive compound (monomer, crosslinking agent, reactive emulsifier), and for example, 0.01 to 5 wt%, or 0.1 to 1 wt%, but is not limited thereto.

[0081] The method for producing the above acrylic copolymer and the monomer composition will be described in detail in the method for producing an acrylic-urethane water dispersion composition described below.

[0082] In one embodiment of the present disclosure, the polyurethane may have a spectrum area ratio of a methylene group to a carbothyl group of 1:1.5 to 2.5 in a spectrum measured by infrared spectroscopy, and in another embodiment, may have a spectrum area ratio of 1:1 to 2.0.

[0083] The above spectral area ratio was measured using an infrared spectroscopy meter (Btuker, Lumos). First, a water-dispersed polyurethane containing polyurethane was dried under reduced pressure at 80°C for 24 hours to produce a film with a thickness of 3 μm, and then measured. Afterwards, the measured spectrum was confirmed, and the methylene (*-CH2-*) spectrum (symmetrical vibration: 2853 cm -1 Peak and asymmetric vibration 2926 cm -1 ) was obtained, and the carbonyl group (*-C=O-*) spectrum (1710 cm -1 The area of ​​the peak was calculated, and the carbonyl group spectrum area ratio was calculated for the methylene spectrum area ratio of 1.

[0084] Polyurethane having a spectral area ratio in the above range has excellent miscibility with the acrylic copolymer described above, and an acrylic-urethane water dispersion composition manufactured including these can have excellent mixing stability without causing long-term agglomeration.

[0085] Therefore, as described above, the acrylic-urethane water dispersion composition has particles of an acrylic copolymer and polyurethane dispersed with excellent miscibility, and not only does it not easily coagulate even when stored for a long period of time, but also has remarkably excellent applicability on a plastic substrate, so it can be usefully used as a paint or coating for a plastic material.

[0086] In addition, the above-mentioned acrylic-urethane water dispersion composition may be preferred because it contains an acrylic copolymer having a crosslinking degree of 50 to 60% for an unknown reason and contains a polyurethane satisfying a spectral area ratio in the above range, so that it has excellent applicability to a plastic substrate, excellent mixing stability, and the formed coating layer can have excellent water resistance and excellent blocking resistance.

[0087] In one embodiment of the present invention, the acrylic-urethane water dispersion composition may have a solid content of 10 to 50 wt%, preferably 10 to 40 wt%, 20 to 40 wt%, and more preferably 25 to 35 wt%.

[0088] An acrylic-urethane aqueous dispersion composition satisfying the solid content in the above range not only has excellent applicability, but also shortens the time for the applied acrylic-urethane aqueous dispersion composition to dry and form a coating layer, so that a coating process using the acrylic-urethane aqueous dispersion composition can be preferred because it can have excellent workability overall.

[0089] The method for measuring the solid content of the above acrylic-urethane aqueous dispersion composition may be to completely dry the acrylic-urethane aqueous dispersion composition to evaporate all water, and the content of the remaining solid content may be the percentage (%) of the content of the initial acrylic-urethane aqueous dispersion composition.

[0090] In addition, the solid content of the acrylic-urethane water dispersion composition can be controlled by the solid content and mixing ratio of the acrylic emulsion containing the acrylic copolymer and the water dispersion polyurethane containing the polyurethane in the manufacturing method described below.

[0091] Therefore, the above-described acrylic-urethane water dispersion composition is prepared by mixing the acrylic emulsion and water-dispersed polyurethane described above, and thus may be in the form of an acrylic copolymer and polyurethane dispersed in water.

[0092] In one embodiment of the present disclosure, the acrylic-urethane water dispersion composition may include an acrylic copolymer and polyurethane in a weight ratio of 1:0.1 to 0.5, and in another embodiment, the weight ratio may be 1:0.1 to 0.4, or 1:0.1 to 0.3.

[0093] An acrylic-urethane water dispersion composition satisfying the above weight ratio may be preferred because it has better mixing stability, does not cause clouding when a coating layer formed therefrom and a water-resistant article formed with the coating layer come into contact with water, has very low water absorption, and has excellent blocking resistance.

[0094] In one embodiment of the present disclosure, the acrylic copolymer and polyurethane may be in the form of particles, which may be prepared by mixing an acrylic emulsion prepared by emulsion polymerization and a urethane emulsion prepared by emulsion polymerization. In addition, the emulsion may be prepared by microemulsion polymerization, but is not limited thereto.

[0095] In one embodiment of the present disclosure, the acrylic copolymer may have an average particle diameter (D50) of 0.1 to 1 ㎛, 0.1 to 0.5 ㎛, or 0.1 to 0.2, and the polyurethane may have an average particle diameter (D50) of 0.05 to 1 ㎛, 0.05 to 0.5 ㎛, but this is not necessarily limited as long as it does not impair the physical properties of the acrylic-urethane dispersion composition including the same.

[0096] The average particle diameter (D50) of the above acrylic copolymer may be measured using a laser diffraction particle size distribution measuring device (Malvern, MASTERSIZER 3000 hydro) and the average particle diameter and Span value (average particle distribution width) based on a wet measurement method. However, any measurement method that is recognizable to a person skilled in the art may be used without limitation.

[0097] In addition, the average particle diameter (D50) of the above acrylic copolymer is the D50 value, which is the average particle diameter by volume-based measurement (when Dn means the diameter of particles corresponding to n% in terms of the integrated fraction, “D50” may mean a value corresponding to 50% in terms of the integrated fraction in terms of volume).

[0098] As one aspect of the present disclosure, when the acrylic-urethane water dispersion composition is filtered through a 300 mesh (0.046 mm) nylon filter, no filtered aggregates may be generated.

[0099] The above acrylic-urethane water dispersion composition is capable of mixing an acrylic copolymer and polyurethane, and as described above, has excellent mixing stability, thereby preventing a decrease in applicability due to aggregates generated by agglomeration of the acrylic copolymer and polyurethane.

[0100] As one aspect of the present disclosure, the acrylic-urethane water dispersion composition may be free of voids that are not applied and are observed with the naked eye when applied to a substrate in the measured method defined in the present disclosure.

[0101] The above acrylic-urethane water dispersion composition can have excellent applicability even when coated on a plastic substrate with very low surface energy without surface treatment such as corona treatment, and thus can be preferred because the processability of the manufacturing process of a water-resistant article in which a coating layer is formed by applying and drying the composition can be very excellent.

[0102] As one aspect of the present disclosure, the acrylic-urethane water dispersion composition may be prepared by mixing an acrylic emulsion and a urethane emulsion.

[0103] In one aspect of the present disclosure, the method for producing the acrylic-urethane water dispersion composition may include the steps of producing an acrylic emulsion from a monomer composition including a reactive emulsifier composition including 50 wt% or more of methyl methacrylate and a reactive emulsifier containing two or more unsaturated groups in the presence of water, and the steps of mixing the acrylic emulsion with a water-dispersed polyurethane including polyurethane.

[0104] The acrylic copolymer included in the above acrylic emulsion may have a crosslinking degree of 50 to 60% as described above, and the polyurethane included in the above water-dispersed polyurethane may have a spectrum area ratio of methylene groups and carbonyl groups of 1.5 to 2.5 in a spectrum measured by infrared spectroscopy.

[0105] In one embodiment of the present disclosure, the step of preparing the acrylic emulsion may be to add 50 to 200 parts by weight of the monomer composition to 100 parts by weight of water and perform emulsion polymerization. In another embodiment, the monomer composition may be added in an amount of 50 to 150 parts by weight, or 100 parts by weight, but this is not necessarily limited as long as it is recognizable by a person skilled in the art.

[0106] In one embodiment of the present disclosure, the monomer composition may be, as described above, 50 wt% or more based on the total content, and the upper limit is not limited thereto, but may be 80 wt% or less, 70 wt% or less, or 60 wt% or less, but is not necessarily limited thereto.

[0107] An acrylic emulsion manufactured by including methyl methacrylate in the above range of content and an acrylic-urethane water dispersion composition comprising the same can be used as a water-based paint with excellent color quality including pigments, and the appearance of a coating layer formed by the acrylic-urethane water dispersion composition can be excellent, so it may be preferred, but this is not necessarily limited thereto.

[0108] As one aspect of the present disclosure, the monomer composition may further comprise one or more comonomers selected from C3-C6 alkyl(meth)acrylate, (meth)acrylic acid, and (meth)acrylonitrile, as described above.

[0109] In the above monomers, C3-C6 alkyl(meth)acrylate may be preferred as it can further improve the adhesiveness of the acrylic-urethane water dispersion composition being manufactured.

[0110] In one embodiment of the present disclosure, the comonomer may comprise 70 to 90 wt% of C3-C6 alkyl(meth)acrylate, 2 to 10 wt% of meth)acrylic acid, and 7 to 17 wt% of (meth)acrylonitrile, based on the total content.

[0111] When the above-described comonomer satisfies the above-described composition, the acrylic-urethane water dispersion composition manufactured by including it has excellent applicability and adhesiveness, etc., and can be more usefully used as a paint suitable for plastic materials, but this is not necessarily limited thereto.

[0112] In one embodiment of the present disclosure, the monomer composition may comprise 0.01 to 5 wt% of the reactive emulsifier composition, and in another embodiment, 0.1 to 3 wt%.

[0113] An acrylic copolymer manufactured by including a reactive monomer in the above range of contents satisfies a crosslinking degree of 50 to 60%, and thus an acrylic-urethane water dispersion composition including the same can be preferred because it satisfies physical properties such as excellent mixing stability and excellent application properties.

[0114] In one embodiment of the present invention, the monomer composition may further include a (meth)acrylate-based crosslinking agent containing two or more (meth)acrylate groups.

[0115] The acrylic copolymer manufactured by further including the above (meth)acrylate crosslinking agent can further strengthen crosslinking, but this is not necessarily limited as long as the degree of crosslinking described above is satisfied.

[0116] In one embodiment of the present disclosure, the acrylic emulsion may have a solids content of 20 to 60%, and in another embodiment, 30 to 60%, 40 to 60%, or 45 to 55%.

[0117] In one embodiment of the present disclosure, the water-dispersed polyurethane may have a solids content of 10 to 50 wt%, and in another embodiment, 20 to 50 wt%, 30 to 50 wt%, or 35 to 45 wt%.

[0118] The above acrylic emulsion and water-dispersed polyurethane have a solid content within the above-described range, so that not only can they maintain a viscosity that is easy to stir in a mixing process, but they can also easily satisfy the weight ratio of the acrylic copolymer and the polyurethane of the acrylic-urethane water-dispersed composition to be manufactured, and the solid content of the acrylic-urethane water-dispersed composition to be manufactured can also be easily controlled, making them preferable.

[0119] As one aspect of the present disclosure, the step of mixing the urethane emulsion may be mixing an acrylic emulsion and a water-dispersed polyurethane at a weight ratio of 1:0.2 to 1, or may be mixing them at a weight ratio of 1:0.2 to 0.5.

[0120] An acrylic-urethane water dispersion composition prepared by mixing an acrylic emulsion and a water-dispersed polyurethane so as to satisfy the above range can have a weight ratio of the included acrylic copolymer and polyurethane controlled so as to satisfy the above range.

[0121] As one aspect of the present disclosure, the step of mixing the urethane emulsion may further include a non-silicone-based defoaming agent.

[0122] The above mixing step may be preferred because it further includes a non-silicone-based defoaming agent, enabling the production of an acrylic-urethane aqueous dispersion composition without bubbles by using an acrylic emulsion and an aqueous polyurethane, and because it enables the production of an acrylic-urethane aqueous dispersion composition containing an acrylic copolymer and polyurethane with excellent dispersion.

[0123] As one embodiment of the present disclosure, the water-dispersed polyurethane may be a commercially available product, for example, U 3251 from Alberdinkg Boley, IMPRANIL DLC-F or IMPRANIL DLC-T from COVESTRO, etc. However, as long as the polyurethane included satisfies the spectral area ratio of the methylene and carbonyl groups described above, it may be used without limitation, and thus, it is not necessarily limited thereto.

[0124] In one aspect of the present disclosure, a waterproof article can be provided in which a substrate and a coating layer are formed on the surface of the substrate.

[0125] The above waterproof article may be formed by applying the above acrylic-urethane water dispersion composition onto a substrate and drying it to form a coating layer on the substrate.

[0126] As one aspect of the present disclosure, the substrate may be metal, floor, ceramic, plastic, etc., and in particular, since the acrylic-urethane water dispersion composition can have excellent applicability and adhesiveness even without surface treatment of the plastic material, it can be usefully used for coating a plastic substrate.

[0127] As one aspect of the present disclosure, the substrate may be a film, a sheet, an injection-molded product, or the like.

[0128] The above acrylic-urethane water dispersion composition can be applied to form a coating layer regardless of the shape of the substrate, and in particular, has excellent applicability even without surface energy treatment of the plastic substrate, so that it can be easily manufactured as a waterproof article in which a coating layer is formed on the surface of a plastic substrate having a large area.

[0129] As one embodiment of the present disclosure, the coating layer may have a peel strength of 5B as measured by ASTM D3359, so that a waterproof article having the coating layer formed thereon can maintain excellent appearance and excellent water resistance for a long period of time without the coating layer peeling off even when damaged by external scratches or the like.

[0130] In one aspect of the present disclosure, the coating layer may exhibit a small amount of blocking or no blocking at all, as measured by KS A 1024, and preferably no blocking at all.

[0131] The above blocking may refer to a phenomenon in which the coating layer separates when a waterproof article having a coating layer formed thereon is laminated in a natural humidity and temperature environment, a constant pressure is applied for a long period of time, and then the laminated waterproof article is removed again, as will be described in detail in the examples below.

[0132] That is, the above-mentioned waterproof product can be delivered to the consumer intact without the coating layers separating from each other even when loaded and transported for a long period of time.

[0133] The acrylic-urethane aqueous dispersion composition will be described in more detail through the following examples. However, the following examples are merely a reference for further illustrating the present disclosure and are not intended to limit the present disclosure, which may be implemented in various forms. Furthermore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. Furthermore, the terminology used in the description of this disclosure is merely for the purpose of effectively describing specific embodiments and is not intended to limit the present disclosure.

[0134] [measurement method]

[0135] 1. Fourier transform infrared (FT-IR) spectroscopy measurement

[0136] The measurement was performed using an infrared spectroscopy meter (Bruker, Lumos). The water-dispersed polyurethane was dried under reduced pressure at 80°C for 3 minutes to produce a film with a thickness of 3 μm, and the measurement was performed. After that, the measured spectrum was confirmed, and the methylene (*-CH2-*) spectrum (symmetric vibration: 2853 cm -1 Peak and asymmetric vibration 2926 cm -1 The area of ​​the peak was obtained, and the carbonyl group (*-C=O-*) spectrum (1710 cm -1 The area of ​​the peak was calculated, and the carbonyl group spectrum area ratio was calculated for the methylene spectrum area ratio of 1.

[0137] 2. Cross-linking degree measurement

[0138] 10 g of a cross-linked acrylic copolymer was placed in a beaker containing 200 ml of ethyl acetate at 25°C and left to stand for 24 hours. After the cross-linked acrylic copolymer was left to stand for 5 hours, it was completely dried, its mass was measured, and the degree of cross-linking was calculated using the following formula.

[0139] [ceremony]

[0140] Crosslinking degree (%) = Mass of crosslinked acrylic copolymer left in ethyl acetate (g) / 10 (g) X 100

[0141] 3. Measurement of mixing stability

[0142] The aqueous dispersion solution was passed through a nylon filter having 300 mesh (0.046 mm) pores. Afterwards, the coagulants filtered through the nylon filter were visually inspected and expressed according to the following conditions.

[0143] ○: No agglomeration, good mixing stability

[0144] △: Small amount of aggregates, poor mixing stability

[0145] X: Large amount of aggregates, poor mixing stability

[0146] 4. Measurement of applicability

[0147] An aqueous dispersion solution was applied once on an ABS (Acrylonitrile butadiene styrene copolymer) film using Meyer bar coating. Afterwards, the aqueous dispersion solution applied on the film was observed with the naked eye. If the entire surface was completely coated, it was marked with ○. If 1 to 5 holes were formed without application, it was marked with △. If more than 5 holes were formed without application, it was marked with X.

[0148] 5. Water resistance measurement

[0149] When the coated measurement sample was immersed in water at 25℃ for 6 hours, the white turbidity phenomenon of the coating was observed at 10-minute intervals for the first 30 minutes, and then the white turbidity phenomenon was observed at 1-hour intervals for 6 hours. If white turbidity did not occur for 6 hours, it was indicated as X, and if white turbidity occurred, the time was recorded.

[0150] Additionally, 45 g of the aqueous solution was placed in a Teflon mold and dried until a film was formed. The weight of the dried film was measured, then immersed in water at 25°C for 24 hours and reweighed. The water uptake was calculated as the ratio of the weight increase to the initial weight.

[0151] 6. Measurement of anti-blocking properties

[0152] Measurement samples were prepared according to KS A 1024, and each measurement sample was brought into contact with the waterproof coating side and the uncoated side, and then maintained for 24 hours at a humidity of 75%, a temperature of 40 (tolerance temperature ±1) ℃, a weight of 45 Х30 mm 500 g, and a pressure of 10 kgf / ㎡. When the contact surfaces were separated, the degree of tearing of each side was visually judged, and if there was no blocking, it was marked as ○, if a small amount of blocking occurred, it was marked as △, and if a large amount of blocking occurred and the shape of the coating was significantly damaged, it was marked as Х.

[0153] 7. Adhesion Measurement (Cross-Cut Adhesion Test)

[0154] Measurements were made in accordance with ASTM D3359, and the measurement samples were prepared in the same manner as the measurement samples prepared in the above-mentioned coating appearance evaluation. The measurement samples were scratched in a grid pattern with a cross-cutting machine, adhered with standard tape, and peeled off to measure the degree of peeling of the waterproof coating. Depending on the area of ​​the waterproof coating peeled off, the following standard grades were indicated.

[0155] 5B: The grid lines are clean,

[0156] 4B: The area of ​​the peeled coating film is less than 5% of the total area,

[0157] 3B: The area of ​​the peeled coating film is less than 5-15% of the total area,

[0158] 2B: The area of ​​the peeled coating film is less than 15-35% of the total area,

[0159] 1B: The area of ​​the peeled coating film is less than 35-65% of the total area,

[0160] 0B: The area of ​​the peeled coating film exceeds 65% of the total area.

[0161] Preparation of acrylic emulsion with acrylic copolymer dispersed therein

[0162] [Manufacturing Example 1]

[0163] For 100 parts by weight of deionized water in a reactor, 50 parts by weight of methyl methacrylate, 40 parts by weight of butylacrylate, 3 parts by weight of methacrylic acid, 2 parts by weight of acrylonitrile, and 2 parts by weight of a reactive emulsifier (Adka, SR-10) were stirred for 1 hour to mix and emulsify the monomers.

[0164] Thereafter, the reactor was heated to 75°C at a constant rate, and 0.2 parts by weight of azobicisobutyronitrile was added dropwise to 100 parts by weight of the deionized water over 4 hours, followed by emulsification polymerization for an additional 1 hour to produce an acrylic emulsion. The acrylic emulsion was completely dried, and the measured solid content was confirmed to be 50%.

[0165] Afterwards, the degree of crosslinking of the acrylic emulsion was measured and shown in Table 1 below.

[0166] [Manufacturing Example 2]

[0167] In the above Manufacturing Example 1, an acrylic emulsion was manufactured by emulsification polymerization in the same manner as in the above Manufacturing Example 1, except that 2 parts by weight of pentaerythritol tetraacrylate (PETA) was further added to 100 parts by weight of deionized water.

[0168] Afterwards, the degree of crosslinking of the acrylic emulsion was measured and shown in Table 1 below.

[0169] [Manufacturing Example 3]

[0170] In the above Manufacturing Example 1, an acrylic emulsion was manufactured by the same emulsion polymerization process except that 2 parts by weight of Sodium Dodecyl Benzen Sulfonate (SDBS) and 1 part by weight of Pentaerythritol Tetraacrylate (PETA) were included for 100 parts by weight of deionized water without adding a reactive emulsifier.

[0171] Afterwards, the degree of crosslinking of the acrylic emulsion was measured and shown in Table 1 below.

[0172] Preparation of acrylic-urethane water dispersion composition

[0173] [Example 1]

[0174] 80 g of the acrylic emulsion of Preparation Example 1 having a solid content of 50% was added to a stirrer, and while stirring, 20 g of an aqueous polyurethane dispersion having a solid content of 40% (Alberdinkg Boley, U 3251) was added and stirred for 10 minutes. Thereafter, 0.1 g of a non-silicone-based defoaming agent was further added to the stirrer, and stirring was performed for another 10 minutes. 60 g of distilled water was added, and stirring was performed for 30 minutes, thereby producing an acrylic-urethane aqueous dispersion composition having a solid content of 30%.

[0175] Afterwards, the acrylic-urethane water dispersion composition was applied to a thickness of 7 μm on an ASA (Acrylonitrile styrene acrylate copolymer) film using a Meyer bar coater, and dried at 80°C for 3 minutes to prepare a measurement sample with a 2 μm coating formed.

[0176] The manufactured acrylic-urethane water dispersion composition and measurement sample were measured using the above measurement method, and are shown in Table 2 below.

[0177] [Example 2]

[0178] In the above Example 1, an acrylic-urethane water dispersion composition and a measurement sample were prepared in the same manner as in Example 1 except that 50 g of water-dispersed polyurethane (Alberdinkg Boley, U 3251) and 70 g of distilled water were added to adjust the solid content to 30%.

[0179] The manufactured acrylic-urethane water dispersion composition and measurement sample were measured using the above measurement method, and are shown in Table 2 below.

[0180] [Example 3]

[0181] In the above Example 1, an acrylic-urethane water dispersion composition and a measurement sample were prepared in the same manner as in Example 1 except that 100 g of water-dispersed polyurethane (Alberdinkg Boley, U 3251) and 87 g of distilled water were added to adjust the solid content to 30%.

[0182] The manufactured acrylic-urethane water dispersion composition and measurement sample were measured using the above measurement method, and are shown in Table 2 below.

[0183] [Example 4]

[0184] In the above Example 1, an acrylic-urethane dispersion composition and a measurement sample were prepared in the same manner as in Example 1, except that a urethane dispersion polyurethane (COVESTRO, IMPRANIL DLC-T) was used instead of a water-dispersed polyurethane (Alberdinkg Boley, U 3251).

[0185] The manufactured acrylic-urethane water dispersion composition and measurement sample were measured using the above measurement method, and are shown in Table 2 below.

[0186] [Example 5]

[0187] In the above Example 1, an acrylic-urethane water dispersion composition and a measurement sample were prepared in the same manner as in Example 1, except that a water dispersion polyurethane (COVESTRO, IMPRANIL DLC-F) was used instead of a water dispersion polyurethane (Alberdinkg Boley, U 3251).

[0188] The manufactured acrylic-urethane water dispersion composition and measurement sample were measured using the above measurement method, and are shown in Table 2 below.

[0189] [Comparative Example 1]

[0190] In the above Example 1, only the acrylic emulsion of Manufacturing Example 1 was used, and 53.3 g of distilled water was added to adjust the solid content to 30%, and then, in the same manner, a measurement sample was prepared and measured using the above measurement method, and the results are shown in Table 2 below.

[0191] [Comparative Example 2]

[0192] In the above Example 1, instead of using the acrylic emulsion of Manufacturing Example 1, only 100 g of water-dispersed polyurethane (Alberdinkg Boley, U 3251) was used, and 33.3 g of distilled water was added to adjust the solid content to 30%. Afterwards, a measurement sample was prepared in the same manner and measured using the above measurement method, and the results are shown in Table 2 below.

[0193] [Comparative Example 3]

[0194] In the above Example 1, an acrylic-urethane aqueous dispersion composition and a measurement sample were prepared in the same manner as in Preparation Example 2, except that the acrylic emulsion containing an acrylic copolymer having a crosslinking degree of 78% was used.

[0195] The manufactured acrylic-urethane water dispersion composition and measurement sample were measured using the above measurement method, and are shown in Table 2 below.

[0196] [Comparative Example 4]

[0197] In the above Example 1, an acrylic-urethane water dispersion composition and a measurement sample were prepared in the same manner as in Preparation Example 3, except that the acrylic emulsion containing an acrylic copolymer having a crosslinking degree of 44% was used.

[0198] The manufactured acrylic-urethane water dispersion composition and measurement sample were measured using the above measurement method, and are shown in Table 2 below.

[0199] [Comparative Example 5]

[0200] In the above Example 1, an acrylic-urethane water dispersion composition and a measurement sample were prepared in the same manner as in Example 1, except that a urethane emulsion (COVESTRO, IMPRANIL DLU) was used instead of a urethane emulsion (Alberdinkg Boley, U 3251).

[0201] The manufactured acrylic-urethane water dispersion composition and measurement sample were measured using the above measurement method, and are shown in Table 2 below.

[0202] [Comparative Example 6]

[0203] In the above Example 1, an acrylic-urethane water dispersion composition and a measurement sample were prepared in the same manner as in Example 1, except that water dispersion polyurethane (Alberdinkg Boley, U 3251) was not used, but water dispersion polyurethane (Alberdinkg Boley, U 400N) was used.

[0204] The manufactured acrylic-urethane water dispersion composition and measurement sample were measured using the above measurement method, and are shown in Table 2 below.

[0205] Acrylic copolymerPolyurethaneAcrylic-urethane water dispersion compositionProductCrosslinking degree(%)Methylene group:Carbonyl group(FT-IR area)Solid content(%)Acrylic copolymer:Urethane copolymer(weight ratio)Example 1Preparation example 1581:2.0301:0.2Example 2Preparation example 1581:2.0301:0.5Example 3Preparation example 1581:2.0301:1Example 4Preparation example 1581:1.8301:0.2Example 5Preparation example 1581:1.6301:0.2Comparative example 1Preparation example 158Not used30XComparative example 2Not used1:2.030XComparative example 3Preparation example 2781:2.0301:0.2Comparative example Manufacturing Example 4 3441:2.0 301:0.2 Comparative Example 5 Manufacturing Example 1581:0.8 301:0.2 Comparative Example 6 Manufacturing Example 1581:0.6 301:0.2

[0206] Mixing stability, application, cloudiness, moisture absorption rate (wt%), adhesive strength, blocking resistance, Example 1○○X35B○, Example 2○○X105B○, Example 3○○X155B△, Example 4○○X45B○, Example 5○○X35B○, Comparative Example 1-XX45B○, Comparative Example 2-○X205BX, Comparative Example 3△XX23B○, Comparative Example 4△△X105B△, Comparative Example 5△△1 hour135B△, Comparative Example 6XX40 minutes204BX

[0207] In the above Table 2, Examples 1 to 5 were prepared by mixing water-dispersed polyurethanes including polyurethanes satisfying a methylene group:carbonyl group spectral area ratio of 1:1.5 to 2.5 and Preparation Example 1 including an acrylic copolymer satisfying a crosslinking degree of 58%, and confirming that the back pressure stability, coatability, water resistance, and blocking resistance were at commercially acceptable levels or were excellent, and the adhesive strength was very excellent at 5B. In particular, it was confirmed that the acrylic-urethane aqueous dispersions of Examples 1, 2, 4, and 5, in which the weight ratio of the acrylic copolymer and the polyurethane was 1:0.1 to 0.5, except for Example 3, had better water absorption and blocking resistance than the acrylic-urethane aqueous dispersion of Example 3.

[0208] In contrast, looking at Comparative Examples 1 and 2 in Table 2 above, it was confirmed that when acrylic emulsion and water-dispersed polyurethane were used alone, neither the applicability nor the water resistance could be excellent, and the adhesive strength and blocking resistance were also very poor. Comparative Examples 3 and 4 above included Preparation Examples 2 and 3 in which the crosslinking degree was not 50 to 60%, and for unknown reasons, the applicability, adhesive strength, and blocking resistance were very poor.

[0209] The above Comparative Examples 5 and 6 contained polyurethane having a methylene group:carbonyl group spectral area ratio of 1:0.8 or 1:0.6, respectively, and had very poor mixing stability and poor water resistance and blocking resistance.

[0210] Therefore, as one aspect of the present disclosure, the acrylic-urethane water dispersion is a mixture of an acrylic emulsion including an acrylic copolymer having a specific degree of crosslinking and a water-dispersed polyurethane including a polyurethane having a spectrum area ratio of methylene groups and carbonyl groups of an infrared spectroscopy-measured spectrum of 1:1.5 to 2.5, thereby having excellent mixing stability and applicability to a plastic material, and a coating layer formed therefrom can have excellent adhesive strength, excellent water resistance, and excellent blocking resistance.

[0211] As described above, the present disclosure has been described by specific matters and limited examples and comparative examples, but these are provided only to help a more general understanding of the present disclosure, and the present disclosure is not limited to the above examples, and those of ordinary skill in the art to which the present disclosure pertains can make various modifications and variations based on this description.

[0212] Therefore, the idea of ​​the present invention should not be limited to the described embodiments, and all things that are equivalent or equivalent to the claims described below as well as the claims are considered to fall within the scope of the idea of ​​the present invention.

Claims

1. An acrylic copolymer having a crosslinking degree of 50 to 60% prepared from a monomer composition comprising a reactive emulsifier composition comprising 50 wt% or more of methyl methacrylate and a reactive emulsifier containing two or more unsaturated groups; and An acrylic-urethane water dispersion composition comprising a polyurethane having a spectrum area ratio of methylene groups to carbonyl groups of 1:1.5 to 2.5 in a spectrum measured by infrared spectroscopy.

2. In paragraph 1, The above polyurethane is an acrylic-urethane water dispersion composition having a spectrum area ratio of methylene groups to carbonyl groups of 1.5 to 2.0 in a spectrum measured by infrared spectroscopy.

3. In paragraph 1, An acrylic-urethane water dispersion composition, wherein the monomer composition further comprises one or more comonomers selected from C3-C6 alkyl(meth)acrylate, (meth)acrylic acid, and (meth)acrylonitrile.

4. In paragraph 1, The above acrylic-urethane water dispersion composition is an acrylic-urethane water dispersion composition having a solid content of 10 to 50%.

5. In paragraph 1, The above acrylic-urethane water dispersion composition is an acrylic-urethane water dispersion composition in which the acrylic copolymer and polyurethane have a weight ratio of 1:0.1 to 0.

5.

6. In paragraph 1, The above acrylic-urethane water dispersion composition is an acrylic-urethane water dispersion composition in which, when applied once by Meyer bar coating on an ASA (Acrylonitrile styrene acrylate copolymer) film, there are no uncoated voids observed with the naked eye.

7. In paragraph 1, An acrylic-urethane water dispersion composition wherein the reactive emulsifier has a substituent including at least one unsaturated group and an ether group (*-O-*).

8. In paragraph 7, An acrylic-urethane water dispersion composition, wherein the reactive emulsifier comprises at least one selected from the following chemical formulae 1 to 3. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] (In the above chemical formulas 1 to 3, R1, R2 and R3 are each independently a straight chain or branched chain C 10 -C 50 alkyl, X1, X2 and X3 are each independently an anionic hydrophilic group, and n1, n2 and n3 are each independently an integer from 4 to 20.) 9. In paragraph 1, An acrylic-urethane water dispersion composition, wherein the monomer composition further comprises a (meth)acrylate crosslinking agent containing two or more (meth)acrylic groups.

10. A coating layer formed from an acrylic-urethane water dispersion composition selected from any one of claims 1 to 9.

11. In paragraph 10, The above coating layer is a coating layer having a peel strength of 5B as measured by ASTM D3359.

12. In paragraph 10, The above coating layer is a coating layer that exhibits minimal or no blocking as measured by KS A 1024.

13. Description; and A water-resistant article having a coating layer of clause 10 formed on the surface of the above-mentioned article.

14. In paragraph 13, The above description is a water-resistant plastic article.

15. In paragraph 13, The above description refers to a water-resistant article in the form of a film, sheet, or injection molded product.

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