CN112898896B - Photocurable aqueous coating composition - Google Patents
Photocurable aqueous coating composition Download PDFInfo
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- CN112898896B CN112898896B CN202110177633.XA CN202110177633A CN112898896B CN 112898896 B CN112898896 B CN 112898896B CN 202110177633 A CN202110177633 A CN 202110177633A CN 112898896 B CN112898896 B CN 112898896B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
A photocurable aqueous coating composition is disclosed, comprising a 2-functional urethane acrylate, a 6-functional urethane acrylate, and an acrylate diluent. Also disclosed is a method of preparing the photo-curable aqueous coating composition comprising mixing a 2-functionality urethane acrylate, a 6-functionality urethane acrylate and an acrylate diluent at 10-35 ℃ and 500-1200 rpm. Also disclosed are the use of the photocurable aqueous coating composition and the photocurable coating composition prepared by the above method for coating a substrate and the substrate coated therewith.
Description
Technical Field
The invention relates to the field of coatings, in particular to a photocureable water-based coating.
Background
Photocured coatings are coating compositions that utilize the energy of ultraviolet light to initiate a crosslinking reaction between a polymer and a reactive monomer diluent in the coating, thereby forming a hardened paint film. Generally, photocurable coating compositions have the advantages of short curing time, low curing temperature, and energy savings. For this reason, photocurable coatings are becoming a hot spot of recent development.
Moreover, under the influence of continuous upgrading of environmental protection policies, domestic automobile coatings are gradually switched from solvent-based coatings to water-based coatings after 2014. With the release of new environmental regulations, the restrictions on the VOC of the water-based coating are becoming more severe, and the VOC requirements are also being upgraded to a level of no water VOC <420g/L.
Therefore, in order to realize energy saving and meet environmental regulations, there is an urgent need to develop a novel photocurable aqueous coating. For example, solvent-based coatings are widely used in the market for automotive interior coatings, but a few photo-curable water-based coatings are difficult to compare with solvent-based coatings in terms of appearance, chemical resistance (e.g., sunscreen), aging resistance, and the like, and cannot meet the requirements of high-grade automotive interior paints.
Therefore, there is a need to develop a photo-curable aqueous coating composition having excellent physicochemical properties.
Disclosure of Invention
The present inventors have conducted extensive studies and developed a photocurable aqueous coating composition having a low VOC content, excellent appearance, high hardness, substrate adhesion, and chemical and aging resistance.
The invention provides a photo-curing water-based paint composition which comprises 2-functionality polyurethane acrylate, 6-functionality polyurethane acrylate and acrylate diluent.
The present invention also provides a method of preparing a photocurable aqueous coating composition comprising mixing 2-functionality urethane acrylate, 6-functionality urethane acrylate and an acrylate diluent at 10 to 35 ℃ and 500 to 1200 rpm.
The present invention also provides for the use of a photocurable aqueous coating composition for coating a substrate, wherein the photocurable aqueous coating composition comprises a 2-functional urethane acrylate, a 6-functional urethane acrylate, and an acrylate diluent.
The present invention further provides a coated substrate comprising at least one coating layer formed from a photocurable aqueous coating composition, wherein the photocurable aqueous coating composition comprises a 2-functional urethane acrylate, a 6-functional urethane acrylate, and an acrylate diluent.
The features and advantages of the present invention will be presented in more detail in the following detailed description of embodiments.
Detailed Description
As used herein, unless otherwise expressly specified, the numbers expressing, for example, numbers, ranges, amounts, or percentages used in the specification and claims are to be understood as being modified in all instances by the term "about", even if the term is not expressly recited. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims herein are approximations that may vary depending upon the desired properties to be obtained by the present invention.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently has certain errors. This error is a corollary to the standard deviation found in its corresponding measurement method.
Moreover, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
In this application, the use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise. In addition, in this application, the use of "or" means "and/or" unless explicitly stated otherwise, even though "and/or" may be explicitly used in some cases. In addition, in this application, the use of "a" means "at least one" unless explicitly stated otherwise. For example, "a" polymer, "a" coating, and the like refer to one or more of any of these items. And features of one embodiment may be used with other embodiments as will be recognized by those skilled in the art, even if not explicitly stated herein.
As used herein, the term "photocure," also known as "UV/UV cure," refers to a coating composition that utilizes primarily the energy of ultraviolet light to initiate a crosslinking reaction between a polymer and a reactive monomer diluent in a coating to form a paint film. As used herein, the term "cure" refers to the process of a material becoming "fixed" to form an irreversible crosslinked network, no longer flowing, melting, or dissolving. The term "curing" is used interchangeably herein with "crosslinking".
As used herein, the term "waterborne" refers to a coating composition that includes at least 50% by weight water in a solvent.
The photocurable aqueous coating composition according to the present invention is a one-component coating composition. The single component is the single-package coating, and has the advantages of being ready to use and convenient to store and construct.
The photocurable aqueous coating composition according to the invention is a single-layer coating composition. As used herein, the term "monolayer" refers to a single coating, i.e., a coating formed by a single application. Herein, the film thickness of the single layer coating is 20 to 40 μm, such as 30 to 35 μm.
The photocurable aqueous coating composition according to the invention has a low VOC content. As used herein, the term "VOC (volatile organic compound)" refers to any organic compound having a boiling point of less than or equal to 250 ℃ (482 ° f) measured at standard atmospheric pressure of 101.3 kPa. Organic solvents are typically the major source of VOCs. The VOC content (free of water) of the photo-curing water-based coating composition provided by the invention is lower than 420g/L, and the requirement of new national environmental regulations on the VOC content of the water-based coating is met. The VOC value can be obtained by detecting the contents of the respective organic compound components in the paint by gas chromatography and then adding the contents of the respective components. The VOC content (free of water) of the photocurable waterborne coating composition according to the present invention can be up to about 400g/L.
The photocurable aqueous coating composition according to the present invention may be suitably used for plastic substrates. For example, the photocurable aqueous coating composition according to the present invention may be used for coating automotive interiors.
The photocurable aqueous coating composition according to the present invention may include pigments such as color pastes and/or effect pigments, etc. to form coatings of various colors. The photocurable aqueous coating composition according to the present invention can form a high gloss black coating. The "high gloss black coating" may have the following parameter values based on the L a b color system specified in JIS Z8729: at 45 degrees, L <2,a is-0.3, b is-0.3; at 20 ℃ the gloss is > 85 and the DOI (distinctness of image) > 90. The parameter values can be obtained by BYK color difference instrument, gloss instrument and orange peel instrument.
The invention provides a photo-curing water-based paint composition which comprises 2-functionality polyurethane acrylate, 6-functionality polyurethane acrylate and an acrylate diluent.
As used herein, the term "functionality" refers to the average functionality of the monomers forming the polymer, i.e., the average number of functional groups per monomer.
As used herein, the term "urethane acrylate" refers to a polymer whose repeating units include both carbamate-based functionality and acrylic functionality.
Herein, the "acrylate diluent" refers to an acrylate monomer for participating in a curing reaction in a photo-curable coating system. The acrylate diluent can reduce the viscosity of the system, affecting the curing kinetics, the degree of crosslinking, and the properties of the coating formed.
The 2-functional urethane acrylate used in the photo-curable aqueous coating composition according to the present invention may include 2-functional polyether urethane acrylate and 2-functional polyester urethane acrylate. Suitably, the weight ratio of the 2-functional polyether urethane acrylate to the 2-functional polyester urethane acrylate may be from about 0.1 to 1.2, for example from about 0.1 to 1.0, such as from about 0.1 to 0.8.
The 2-functional polyether urethane acrylate can be prepared from the following components: isocyanate and polyether polyol. The isocyanate includes one or more selected from isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI), and diphenylmethane diisocyanate (MDI). The polyether polyol includes a polyether diol.
Suitably, the 2-functional polyether urethane acrylate has a number average molecular weight of about 3000 to 6000, which can be determined by gel permeation chromatography using appropriate standards such as polystyrene standards. The 2-functional polyether urethane acrylate may contain about 10 to 20wt% polyether moieties.
The 2-functional polyether urethane acrylate may be in the form of an emulsion having a solids content of about 35 to 45wt%. The "solid content" refers to the mass remaining after evaporation of the solution as a percentage of the mass of the original emulsion.
The 2-functionality polyester urethane acrylate can be prepared by the following components: isocyanate and polyester polyol. The isocyanate includes one or more selected from isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI), and diphenylmethane diisocyanate (MDI). The polyester polyol includes a polyester diol.
Suitably, the 2-functional polyester urethane acrylate has a number average molecular weight of about 3000 to 6000, which can be determined by gel permeation chromatography using appropriate standards such as polystyrene standards.
The 2-functional polyester urethane acrylate may be in the form of an emulsion having a solids content of about 35 to 45wt%. The "solid content" refers to the mass remaining after evaporation of the solution as a percentage of the mass of the original emulsion.
The coating composition may include about 8wt% or more, such as about 10wt% or more or about 12wt% or more, of the 2-functional urethane acrylate, or may include about 25wt% or less, such as about 20wt% or less or about 18wt% or less, of the 2-functional urethane acrylate, based on the total weight of the aqueous photocurable coating composition. The 2-functional urethane acrylate may be present in the coating composition in a range of about 8 to 25wt%, such as about 10 to 20wt% or about 12 to 18wt%, or any other combination of these extremes, based on the total weight of the aqueous photocurable coating composition.
The 6-functional urethane acrylate used in the photocurable aqueous coating composition according to the present invention may be prepared from components comprising one or more of the following organic units: simple diols such as butanediol, polyester diols, polyether diols, polycarbonate diols, and the like. Suitably, the 6-functional urethane acrylate has a number average molecular weight of about 1000 to 2000, which can be determined by gel permeation chromatography using appropriate standards such as polystyrene standards.
The 6-functional urethane acrylate may be in the form of an emulsion having a solids content of about 40 to 50 wt.%. The "solid content" refers to the mass remaining after evaporation of the solution as a percentage of the mass of the original emulsion.
The coating composition may include about 5wt% or more, such as about 8wt% or more or about 10wt% or more, of the 6-functional urethane acrylate, or may include about 20wt% or less, such as about 18wt% or less or about 15wt% or less, of the 6-functional urethane acrylate, based on the total weight of the aqueous photocurable coating composition. The 6-functional urethane acrylate may be present in the coating composition in a range of about 5 to 20 weight percent, such as about 8 to 18 weight percent or about 10 to 15 weight percent, based on the total weight of the aqueous photocurable coating composition, or any other combination using these extremes.
In the photocurable aqueous coating composition according to the present invention, the weight ratio of the 2-functional urethane acrylate to the 6-functional urethane acrylate may be about 0.1 to 6. The weight ratio of the 2-functional urethane acrylate to the 6-functional urethane acrylate may be about 0.2 to 5. The weight ratio of the 2-functionality urethane acrylate to the 6-functionality urethane acrylate may be about 0.5 to 2.
The acrylate diluent used in the photocurable aqueous coating composition according to the present invention may include a multifunctional acrylate diluent. The term "multifunctional" means that the diluent contains three or more reactive groups that can participate in the photocuring reaction. Suitably, the acrylate diluent used in the photo-curable aqueous coating composition of the present invention may comprise one or more selected from the group consisting of: ethoxylated trimethylolpropane triacrylate (ETPTA), pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol hexaacrylate (DPHA). The acrylate diluent used in the photocurable aqueous coating composition according to the present invention may include ethoxylated trimethylolpropane triacrylate. The acrylate diluent used in the photocurable aqueous coating composition according to the present invention may include ethoxylated trimethylolpropane triacrylate and dipentaerythritol hexaacrylate.
The coating composition may include about 5wt% or more, such as about 8wt% or more or about 10wt% or more, of the acrylate diluent, or may include about 25wt% or less, such as about 22wt% or less or about 20wt% or less, of the acrylate diluent, based on the total weight of the aqueous photocurable coating composition. The acrylate diluent may be present in the coating composition in a range of about 5 to 25 wt.%, such as about 8 to 22 wt.% or about 10 to 20 wt.%, or any other combination using these extremes, based on the total weight of the aqueous photocurable coating composition.
The photocurable aqueous coating composition according to the present invention also includes one or more photoinitiators to promote photocuring. As used herein, the term "photoinitiator" refers to a material that is capable of decomposing under uv irradiation and causing cross-linking polymerization of polymers and/or monomers to form a three-dimensional network. Examples of suitable photoinitiators include, but are not limited to, IRGACURE 1173, IRGACURE 184, from BASF, and the like. Generally, the photocurable aqueous coating composition according to the present invention includes about 1 to 5wt% of a photoinitiator based on the total weight of the coating composition.
The photocurable aqueous coating composition according to the present invention may further include 5-10 wt% of a co-solvent based on the total weight of the coating composition. The cosolvent can improve the appearance of a paint film and improve the workability. Suitable co-solvents include, but are not limited to, alcoholic solvents such as ethylene glycol butyl ether, dipropylene glycol methyl ether (DPM), propylene glycol methyl ether, and the like.
The photo-curable aqueous coating composition according to the present invention may further include 35 to 70wt% of water based on the total weight of the coating composition.
The photocurable aqueous coating composition according to the present invention may further include a pigment to form a coating layer having a desired color. The pigment may include effect pigments such as aluminum powder, pearl powder, etc., and/or mill base of organic and inorganic pigments.
The pigment used in the photocurable aqueous coating composition of the present invention may include high pigment carbon black to form a high light black coating layer. As used herein, the term "high pigment carbon black" refers to carbon black pigments having a jetness value (My) of greater than 100 and a hue value (dM) of greater than 10, the "jetness value" and "hue value" being determined in accordance with DIN55979 standard. The high prime carbon black used in the photocurable aqueous coating composition of the present invention may have an average particle size of less than about 15nm, which may be determined by electron microscopy.
The effect pigments and/or mill bases used in the photocurable aqueous coating compositions of the present invention are commercially available. Examples of suitable effect pigments and/or mill bases include, but are not limited to, effect pigments and/or mill bases from merck, basf, ekart, toyo aluminum k. Generally, the photo-curable aqueous coating composition according to the present invention may include 0 to 10wt% of a pigment based on the total weight of the coating composition.
The photocurable aqueous coating composition according to the present invention may also include one or more other auxiliary ingredients including, but not limited to: the substrate wetting agent can improve the surface tension and permeability of the coating composition, can better wet a substrate and improve the adhesion of the coating; an antifoaming agent which can suppress the formation of foam in the coating composition; thickeners which can increase the paint viscosity and improve the wet film thickness and protect the paint from settling and delamination; a dispersant that promotes compatibility of the ingredients in the coating composition; a fragrance that provides a pleasant odor to the coating; waxes which can improve scratch resistance and improve touch; and so on. When these auxiliary ingredients are present, each auxiliary ingredient is present in an amount of up to about 2 wt-%, based on the total weight of the coating composition.
The present invention provides a method of preparing a photocurable aqueous coating composition comprising mixing a 2-functionality urethane acrylate, a 6-functionality urethane acrylate and an acrylate diluent at 10 to 35 ℃ and 500 to 1200 rpm.
The method for preparing a photocurable aqueous coating composition according to the present invention may comprise:
(1) Mixing 2-functional polyether urethane acrylate, 2-functional polyester urethane acrylate and 6-functional urethane acrylate at the temperature of 10-35 ℃ and the rotating speed of 500-1200 rpm;
(2) Adding ethoxylated trimethylolpropane triacrylate and optional dipentaerythritol hexaacrylate into the mixture in the step (1) at the temperature of 10-35 ℃ and the rotating speed of 500-1200 rpm, and then stirring for 20-30 minutes;
(3) At the temperature of 10-35 ℃ and the rotating speed of 500-1200 rpm, adding optional auxiliary agents, pigments and/or color pastes and water into the mixture obtained in the step (2).
The invention also provides the use of a photo-curable aqueous coating composition for coating a substrate, wherein the photo-curable aqueous coating composition comprises a 2-functional urethane acrylate, a 6-functional urethane acrylate and an acrylate diluent. The substrate comprises a plastic substrate.
The present invention further provides a coated substrate comprising at least one coating layer formed from a photocurable aqueous coating composition, wherein the photocurable aqueous coating composition comprises a 2-functional urethane acrylate, a 6-functional urethane acrylate, and an acrylate diluent. The substrate comprises a plastic substrate.
The photocurable aqueous coating compositions of the present invention can be applied by any standard method known in the art, such as spraying, dipping, rolling, brushing, and the like, and then cured under ultraviolet light irradiation to form a coating. The ultraviolet irradiation condition may include UV energy of 700-900mJ/cm 2 The light intensity is 100-300mW/cm 2 The UV irradiation is performed at the irradiation intensity of (a). The photo-curing water-based paint composition can be dried and desolventized before being cured by ultraviolet irradiation, namely, baked for 10 to 15 minutes at a temperature of between 60 and 80 ℃.
The photocurable aqueous coating composition according to the present invention can be applied to a dry film thickness of 20 to 40 μm.
Examples
The following examples are provided to further illustrate the invention but are not to be construed as limiting the invention to the details set forth in the examples. All parts and percentages in the following examples are by weight unless otherwise indicated.
Preparation of Photocurable Water-based coating composition according to the present invention
The photocurable aqueous coating compositions Ex1-4 provided by the present invention were prepared using the components and contents listed in table 1 below.
TABLE 1 photo-curable waterborne coating compositions Ex1-4 according to the invention
a Comprising about 10 to 20 weight percent of a polyether moiety having a number average molecular weight of about 3000 to 6000, in the form of an emulsion, having a solids content of about 35 to 45 weight percent;
b a number average molecular weight of about 3000 to 6000, in emulsion form, a solid content of about 35 to 45wt%;
c a number average molecular weight of about 1000 to 2000, in emulsion form, with a solids content of about 40 to 50wt%;
d IRGACURE 1173 selected from BASF, IRGACURE 184;
e high-pigment carbon blacks selected from the group of pigments of the merck (Merk), basf, ekart (Eckart), eastern aluminum industry (Toyo aluminum k.k.);
f Tego 4100；
g Byk 028；
h Tego 3030；
i ethylene glycol butyl ether, DPM, and/or propylene glycol methyl ether.
Preparation of comparative coating compositions
(a) Comparative coating compositions CE1-5 with different polymers
Comparative coating compositions CE1-5 were prepared using the components and amounts listed in table 2 below.
TABLE 2 comparative coating compositions CE1-5
a In the form of an emulsion, the solid content is about 35%, the Tg is about 50-80 ℃, and the number average molecular weight is 3000-8000;
b comprising about 10 to 20 weight percent of a polyether moiety having a number average molecular weight of about 3000 to 6000, in the form of an emulsion, having a solids content of about 35 to 45 weight percent;
c a number average molecular weight of about 3000 to 6000, in emulsion form, a solid content of about 35 to 45wt%;
d a number average molecular weight of about 1000 to 2000, in emulsion form, with a solids content of about 40 to 50wt%;
e IRGACURE 1173 selected from BASF, IRGACURE 184;
f high-pigment carbon blacks selected from the group of pigments of the merck (Merk), basf, ekart (Eckart), eastern aluminum industry (Toyo aluminum k.k.);
g Tego 4100；
h Byk 028；
i Tego 3030；
j selected from ethylene glycol butyl ether, DPM, and/or propylene glycol methyl ether.
(b) Comparative coating compositions CE6-8 with different reactive diluents
Comparative coating compositions CE6-8 were prepared using the components and levels listed in table 3 below.
TABLE 3 comparative coating compositions CE6-8
a Comprising about 10 to 20 weight percent of a polyether moiety having a number average molecular weight of about 3000 to 6000, in the form of an emulsion, having a solids content of about 35 to 45 weight percent;
b a number average molecular weight of about 3000 to 6000, in emulsion form, a solid content of about 35 to 45wt%;
c a number average molecular weight of about 1000 to 2000, in emulsion form, with a solids content of about 40 to 50wt%;
d IRGACURE 1173, IRGACURE 184 from BASF;
e high pigments selected from the group of pigments of the merck (Merk), pasteur, eka (Eckart), toyo aluminum K.K.)Carbon black;
f Tego 4100；
g Byk 028；
h Tego 3030；
i ethylene glycol butyl ether, DPM, and/or propylene glycol methyl ether.
Performance testing
Firstly, the photo-curing water-based paint composition Ex1-4 provided by the invention and the paint composition CE1-8 of the comparative example are coated on a plastic substrate, baked for 10-15 minutes at 60-80 ℃ to evaporate the solvent, and then UV energy is 700-900mJ/cm 2 The light intensity is 100-300mW/cm 2 The UV irradiation is performed at the irradiation intensity of (a).
The coated substrate was then subjected to the following performance tests:
1-VOC content
Herein, the VOC (water-free, g/L) content of the photocurable aqueous coating compositions Ex1-4 according to the present invention was calculated by the following method:
1. the mass m of each component in the composition was measured separately i Mass m of water in the composition w Density of composition p s ；
2. Calculated according to the formula
Where ρ is w Is the density of water at 23 ℃.
2-hardness
The "hardness" reflects the ability of the coating to resist external forces without itself being damaged. The hardness of the coatings is determined in this context according to the GB/T6739-1996 standard.
And (3) testing equipment: mitsubishi pencil, standard load cart.
The technical parameters are as follows: scratching the paint film with Mitsubishi pencils of different hardness grades at an angle of about 45 degrees for at least 7mm under a load of 750 g; pencil hardness grade 2H >.
And (3) testing results: the hardest pencil hardness rating at which no scratch was produced was recorded in comparison at various curing times (room temperature standing).
3-substrate adhesion
The term "adhesion" refers to the ability of the coating to adhere to the surface of the substrate as well as the ability of the coating to agglomerate itself. The adhesion of the coating is determined here according to the GB/T9286 standard.
The sample surface was scribed with NT knife at 6X6 scribe lines (25 with 1mm 2 Squares, score lines and base), keeping the test surface as flat as possible (keeping the edge sharp). If the sample is too small and does not have enough space for grid division, the sample is divided into 45-degree cross grids. Nichiban tape (No. 405), scotch tape (No. 610) or other tapes of the same type (18 mm wide, tape tack should be 5.3N/18mm wide or more) were adhered to the sample surface, and the tape was compacted with an eraser to make the tape sufficiently contact with the test surface and left to stand for 3 minutes. The tape was quickly torn off in the 90-degree direction and the test surface was visually inspected and rated with reference to ISO standards.
ISO standard rating:
level 0: 5B
The edges of the cuts were completely smooth without any peeling of the grid edges.
Level 1: 4B
And small pieces are stripped at the intersection of the cuts, and the actual damage in the grid cutting area is less than or equal to 5 percent.
Stage 2: the edge or the intersection of the 3B cut is stripped, and the area of the 3B cut is 5% -15%.
And 3, level: 2B, partial peeling or whole-large peeling is carried out along the edge of the cut, or partial lattices are peeled by whole grids, and the peeling area is 15-35 percent.
4, level: the 1B cut edge is larger than the peel or some squares are partially or totally peeled, and the area of the 1B cut edge is 35-65%.
Stage 5: 0B, a piece of paint falls off at the scribing edge and the intersection, and the total falling-off finish paint is more than 65 percent.
4-resistance to boiling in water
By "boil-resistant" is meant the ability of the coating to maintain constant properties in a boiling environment. In the text, the resistance of the coating to boiling was determined as follows:
the adhesion of the coating was evaluated after the coating was boiled in water at 100 ℃ for 2 hours. The method of determining the adhesion and the rating criteria are as described above. The boiling resistance of the coating is reflected by the adhesion of the coating after boiling.
5-hydrolysis resistance
The "hydrolysis resistance" refers to the ability of the coating to maintain constant performance in high humidity and high heat environments. In the text, the resistance of the coating to hydrolysis is determined as follows:
the adhesion of the coating was evaluated after the coating was left at 90-95% RH for 72 hours. The method of determining the adhesion and the rating criteria are as described above. The hydrolysis resistance of the coating is embodied by the coating adhesion under high-heat high-humidity conditions.
6-chemical resistance
The "chemical resistance" refers to the resistance of the coating to chemicals (e.g., sun cream, etc.). In the text, the chemical resistance of the coating is determined as follows:
a chemical, such as a sunscreen, is applied to the surface of the coating and then left at 60 c for about 24 hours. The appearance of the coating was evaluated after wiping off the chemicals with a dry cotton fabric. The batch was then aged at room temperature for about 4 hours and then tested for scratch resistance under various loadings.
Chemical resistance is considered to be present if the coating satisfies the following requirements at the same time:
7-resistance to ageing
By "aging resistance" is meant the ability of the coating to maintain its original properties in use against the adverse effects of light, moisture, high temperature, etc. In the text, the resistance of the coating to ageing is determined as follows:
the appearance and substrate adhesion of the coatings were evaluated after the coatings were left at 100 ℃ for about 7 days.
The coating is considered to have aging resistance if it simultaneously satisfies the following requirements:
8-emulsion stability
After the coating composition was left at 40 ℃ for 30 days, the appearance of the coating composition was evaluated, i.e., whether or not the coating composition was delaminated and the fineness was changed was observed. The coating composition is stable if there is no delamination and no significant change in fineness.
| Performance testing | Ex1 | Ex2 | Ex3 | Ex4 | CE1 | CE2 | CE3 | CE4 | CE5 | CE6 | CE7 | CE8 |
| Adhesion force | Level 0 | Level 0 | Level 0 | Level 0 | Level 1 | Level 1 | Level 0 | Stage 2 | Grade 0 | Grade 0 | Level 0 | Level 0 |
| Hardness of | H | H | H | H | H | F | H | F | H | H | H | H |
| Boiling adhesion | Level 0 | Level 0 | Level 0 | Level 0 | Stage 2 | Grade 3 | Level 0 | 4 stage | Grade 0 | Level 0 | Grade 0 | Level 0 |
| Hydrolytic adhesive force | Level 0 | Level 0 | Level 0 | Level 0 | 4 stage | 4 stage | Level 1 | Grade 5 | Level 1 | Level 0 | Level 0 | Level 0 |
| Chemical resistance | OK | OK | OK | OK | NG | NG | NG | NG | NG | OK | OK | OK |
| Aging resistance | OK | OK | OK | OK | OK | OK | OK | OK | OK | OK | OK | OK |
| Emulsion stability | OK | OK | OK | OK | OK | OK | OK | OK | OK | NG | NG | NG |
While particular aspects of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (12)
1. A photo-curable aqueous coating composition comprising 2-functional urethane acrylate, 6-functional urethane acrylate and an acrylate diluent, wherein the 2-functional urethane acrylate comprises 2-functional polyether urethane acrylate and 2-functional polyester urethane acrylate, wherein the weight ratio of the 2-functional polyether urethane acrylate to the 2-functional polyester urethane acrylate is 0.1 to 0.8,
wherein the 2-functionality polyether urethane acrylate has a number average molecular weight of 3000 to 6000 and contains 10 to 20wt% of polyether part, the 2-functionality polyester urethane acrylate has a number average molecular weight of 3000 to 6000, the 6-functionality urethane acrylate has a number average molecular weight of 1000 to 2000,
wherein the acrylate diluent comprises a multifunctional acrylate diluent comprising ethoxylated trimethylolpropane triacrylate,
the thickness of a coating formed by the photo-curing water-based paint composition is 20 to 40 mu m.
2. The photocurable aqueous coating composition of claim 1 wherein the weight ratio of 2-functionality urethane acrylate to 6-functionality urethane acrylate is from 0.1 to 6.
3. The photocurable aqueous coating composition of claim 1 wherein the multifunctional acrylate diluent comprises ethoxylated trimethylolpropane triacrylate and dipentaerythritol hexaacrylate.
4. The photocurable aqueous coating composition of claim 1 further comprising a pigment.
5. The photocurable aqueous coating composition of claim 4 wherein the pigment comprises a high pigment carbon black.
6. The photocurable aqueous coating composition of claim 1, wherein said coating composition has a VOC value of no more than 400g/L as measured by the absence of water.
7. The photocurable aqueous coating composition of claim 1 wherein the coating composition is a single layer coating composition.
8. A process for producing the photocurable aqueous coating composition according to any one of claims 1-7, which comprises mixing 2-functional urethane acrylate, 6-functional urethane acrylate and an acrylate diluent at 10 to 35 ℃ and 500 to 1200 rpm.
9. Use of a photocurable aqueous coating composition according to any one of claims 1-7 and a photocurable aqueous coating composition prepared according to the process of claim 8 for coating a substrate.
10. The use of claim 9, wherein the substrate comprises a plastic.
11. A coated substrate comprising at least one coating layer formed from the photocurable aqueous coating composition of any one of claims 1-7 and the photocurable aqueous coating composition prepared according to the method of claim 8.
12. The coated substrate of claim 11, wherein the substrate comprises plastic.
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| CN100448939C (en) * | 2004-12-20 | 2009-01-07 | 比亚迪股份有限公司 | Coating material solidified by ultraviolet light and prepartion method |
| CN102212311A (en) * | 2011-05-09 | 2011-10-12 | 中国工程物理研究院化工材料研究所 | Colorful ultraviolet (UV) light solidifying paint |
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