Red metal latex product

Abstract

The present application describes a latex or latex article having a red metal surface finish embedded at least in its surface in the latex or latex article, wherein the red metal surface finish comprises (a) one or more metal fillers comprising metal and / or metal oxide particles and (b) one or more red, purple and / or orange absorbent pigment particles, wherein the metal surface finish exhibits a red metal effect with the following features: a = 25-80 at 45 DEG; b = 10-40 at 45 DEG C; the FI is greater than or equal to 9.0 according to a formula (1).

Description

[0001] This invention relates to a latex product with a red metallic surface coating agent and a method for producing the same. Background of the Invention

[0003] For decorative or functional purposes, latex product manufacturers seek to differentiate their products, such as gloves, balloons, and other elastomer consumer goods. A metallic appearance is particularly desirable in many of these latex products, and this metallic appearance can be achieved in a variety of different colors. These colors are achieved by combining aluminum pigments with absorbent pigments. A preferred process involves blending an organic pigment dispersion of the target color with an aluminum pigment formulation in a latex tank, and then using it in a typical molding process for the desired latex product. The resulting latex product retains its metallic reflection with the absorbent color once fully cured. However, this does not apply to shades of red, where the blue reflection of aluminum shifts the color to a very blue tint within the red family, resulting in a magenta appearance unrelated to the pigment hue. To obtain pure red shades, latex product manufacturers must prepare a two-layer product, with an inner aluminum metal layer and an outer red layer, which minimizes blue reflection and allows for a pure red. However, this type of process introduces greater complexity, longer production time, and higher costs to latex product manufacturers than a single-layer process. One particular area where this problem is prevalent is in the manufacture and decoration of latex balloons, but this application is also suitable for use in other latex products. Other applications of the invention include latex products such as erasers, condoms and diaphragms, rubber household gloves, medical gloves, beach toys and other novelty products, catheters, dental products (wedges, orthodontic rubber bands), elastics for clothing, etc.

[0004] US2019 / 0192984 discloses an inflatable balloon made of a latex composition comprising latex and a passivated sheet made of a metal such as aluminum, nickel, iron, copper, lead, zinc, chromium, tin or a metal alloy and a metal chelate complex.

[0005] Achieving a pure red color in latex products using aluminum has been impossible until now. To address this issue, we discovered a method using iron oxide-coated aluminum in combination with red pigments to achieve a pure red metallic effect. This application provides a formulation for obtaining a pure red color with a metallic appearance desired by latex product manufacturers.

[0006] Therefore, the present invention relates to a latex article having a red metallic surface coating agent embedded at least in its surface, wherein the red metallic surface coating agent comprises one or more metal fillers comprising (a) metal and / or metal oxide particles and (b) one or more red, purple and / or orange absorbent pigment particles, wherein the metallic surface coating agent exhibits a red metallic effect having the following characteristics:

[0007] a =25-80 at 45°

[0008] b =10-40 at 45°

[0009] The angle-dependent color index (FI) is ≥ 9.0 according to formula (1):

[0010]

[0011] Where L 15. L 110 and L 45 is the color measurement value at the corresponding observation angle and a and b It is the color dimension of the Lab color space at 45°.

[0012] The Lab color space is a color contrast space, where dimension L represents lightness and a and b These represent the color-opposing dimensions of red-green and blue-yellow, respectively.

[0013] L 15. L 110 and L 45 is the color measurement value at the corresponding observation angle and is measured by "BYK-mac i", and this FI value is automatically calculated using the formula shown above.

[0014] The BYK-mac i objectively measures color, flare, and graininess at different viewing angles. Additionally, it detects and quantifies fluorescence in the visible light range and possesses the following characteristics:

[0015] Overall color impression:

[0016] - Five-angle color measurement for evaluating brightness variations: 15° / 25° / 45° / 75° / 110°

[0017] - Additional color measurements after glossiness for angle-dependent colorimetric analysis: -15°

[0018] - Flash and grain size measurements for thin-film characterization

[0019] - Detect and quantify fluorescence (luminescence intensity) excited in the visible light range.

[0020] Color measurement:

[0021] ●Color geometry conditions: 45° illumination; non-mirror observation at -15°, 15°, 25°, 45°, 75°, and 110°.

[0022] ●Measuring area diameter 23mm

[0023] ● Spectral range (colorimetric method): 400-700nm, 10nm resolution

[0024] ● Measurement range: 0-600% reflectance

[0025] ●Color repeatability: 0.01 ΔE (Measure the white color 10 times consecutively)

[0026] ●Color reproduction: Gray BCRA II color swatch: Average ΔE < 0.10, Color BCRA II swatch: Average ΔE < 0.25

[0027] ●Color scale ΔE ; ΔE CMC; ΔE 94; ΔE 2000; ΔE 99; ΔE DIN6175-2019 and customer-defined scales

[0028] ●Color Index: Different colors depending on the angle, Int-Em

[0029] ●Light source A; C; D50; D65; F2; F7; F11; F12; CIE 015:2018 LED light source

[0030] ●Observer 2°; 10°

[0031] Effect measurement:

[0032] ●Effective geometry conditions: 15°, 45°, 75° and diffused illumination; vertical observation with camera.

[0033] ●Effect parameter ΔS; ΔS_a; ΔS_i; ΔG

[0034] ●Effect repeatability S_a / S_i: 5% or > 0.50 / G = ± 0.05

[0035] ●Effect reproducibility S_a / S_i: 10% or > 1.00 / G = ± 0.15

[0036] Furthermore, this objective is achieved by a method for producing a latex article having a red metallic surface coating of any of the preceding claims as follows: mixing a liquid or fluid natural and / or synthetic latex with a red metallic surface coating comprising one or more metal fillers (a) containing metal and / or metal oxide particles and one or more red, purple, and / or orange absorbent pigment particles (b), or mixing with a particulate composition containing (a) and (b), and forming a latex article from the mixture thus obtained, such that the red metallic surface coating is embedded at least in its surface within the latex article and has a red metallic appearance. The effect is achieved by first forming a latex article from a liquid or fluid natural and / or synthetic latex and then applying a mixture of a liquid or fluid natural and / or synthetic latex and a red metallic surface coating agent comprising one or more metal fillers (a) containing metal and / or metal oxide particles and one or more red, purple and / or orange absorbent pigment particles (b) to a dried article, or by applying a particle composition containing (a) and (b) to the latex article, and forming a latex coating on the latex article by the mixture, such that the red metallic surface coating agent is embedded in the latex article at least in its surface and has a red metallic effect.

[0037] Preferably, the liquid or fluid latex and / or the particulate composition containing (a) and (b) contains water and one or more additives selected from non-silicone defoamers, polyalkylene glycols, nonionic surfactants, preferably alcohol ethoxylates, rheology modifiers, preferably acrylic polymers and / or acrylic copolymer emulsions, preferably in water.

[0038] Furthermore, this objective is achieved through red metallic latex products obtained by the method described above.

[0039] Furthermore, this objective is achieved by a particulate composition comprising:

[0040] (a) One or more metal fillers comprising metal and / or metal oxide particles as defined in any one of claims 1-11, and

[0041] (b) One or more red, purple, and / or orange absorbent pigment particles as defined in any one of claims 1-11

[0042] The particulate composition produces a red metallic surface coating on at least the surface of a latex article containing the particulate composition, wherein the metallic surface coating exhibits a red metallic effect with the following characteristics in the latex article:

[0043] a =25-80 at 45°

[0044] b =10-40 at 45°

[0045] The angle-dependent color index (FI) is calculated according to formula (1) as FI ≥ 9.0.

[0046]

[0047] Where L 15. L 110 and L 45 is the color measurement value at the corresponding observation angle and a and b It is the color dimension of the Lab color space at 45°.

[0048] Furthermore, this objective is achieved by using the particulate composition as a red metallic surface coating agent for at least the surface of a latex article (wherein the latex article, the metallic surface coating agent exhibits a red metallic effect with the above characteristics) and by using particulate or pigment dispersions as defined above to color photosensitive resist formulations, printing inks, liquid inks, coating compositions, paints, plastics, films, or fibers used in the manufacture of color filters.

[0049] Furthermore, this objective is achieved by a particulate or pigment dispersion comprising a particulate composition as defined above and further comprising a polymeric dispersant.

[0050] There are two types of aluminum sheets in the Paliocom series. One is the "corn chip type" and the other is the "silver dollar type".

[0051] Regarding particle size, D50 is 10-22 micrometers, preferably 20 micrometers. PALIOCROM GOLD L2158 (NV 72.5%) has a particle size D50 of 17 micrometers and the composition of the slurry is aluminum (about 28%), silica (about 13%), and iron oxide (about 32%) plus solvent (about 27%).

[0052] Detailed description

[0053] The inventors of this invention have discovered that by changing the hue of metallic colors from silver aluminum pigments to metallic pigments in the color space of gold, red, or orange, preferably multilayer metallic pigments, a pure red can be obtained using a single-layer latex material. This type of pigment—component (a) of this invention, metallic and / or metal oxide particles—is preferably designed as or comprises a substrate coated with one or more metal oxides with a refractive index preferably different from that of the substrate. For example, an aluminum substrate can be coated with iron oxide (Fe2O3), thereby making the particles (a) black, brown, gold, red, orange, or yellow. Alternatively or preferably additionally, one or more other coatings such as SiO2, TiO2, SnO2, ZnO, Al2O3, and / or other metal oxides known to those skilled in the art may be present. Other substrates may also be used, such as mica, glass, Al2O3, copper, silver, nickel, stainless steel, and alloys of various metals such as zinc and copper. The coating is preferably based on the coating pigment (a) or alternatively on the substrate of the coating pigment (a) comprising 5-95% by weight, more preferably 10-80% by weight, and most preferably 20-70% by weight.

[0054] The shape of pigment (a) can be freely chosen. Preferably, the pigment is thinner in one spatial direction than in the other two: the preferred shape is flake-shaped, coin-shaped, (corn) flake-shaped, or multicolored fragment-shaped. Silver coin-shaped and (corn) flake-shaped are preferred.

[0055] The particle size D50 is preferably 5-100 micrometers, more preferably 10-50 micrometers, most preferably 10-35 micrometers, for example 10-22 micrometers, and more preferably 15-22, most preferably 17-20 micrometers.

[0056] Latex manufacturing for balloons, gloves, and other products typically takes place in aqueous latex tanks. Before a latex article is formed on a mold by immersing it in the latex solution, the pigment must be fully dispersed in the latex tank. The color of the pigment in the latex solution must remain stable over a long period. Therefore, the pigment is provided as a formulation to maximize the color value of the final latex product.

[0057] The pigment (a) of the above type must be compatible with the latex solution and other components in the storage tank. Additionally, the pigment should maintain its color value once added to the storage tank. For this purpose, the pigment is preferably surface-treated with a stabilizer to improve its stability in the latex solution. Such stabilizer surface treatments include, but are not limited to, polymer encapsulation, silica encapsulation, passivation with molybdic acid, vanadium, chromium, phosphate esters, phosphonic acid, and other chemicals known to those skilled in the art. Other useful passivating chemicals include amines, carboxylic acids, or organophosphate esters, as well as polymers having groups that complex with iron oxide.

[0058] Optionally, the pigment can be provided as a pre-formulated formulation or concentrate. The pigment formulation can be solid or liquid, preferably in the form of a liquid dispersion of the pigment, preferably a dispersion in water. Liquid formulations can be prepared using additional dispersants such as nonionic surfactants, anionic surfactants, or polymeric dispersants, or mixtures thereof. Surfactants or combinations of surfactants and polymers can also be used in said formulations. Examples of surfactants are alcohol ethoxylates, fatty acid ethoxylates, polyethylene glycol ethers, and alkylbenzene sulfonates.

[0059] Therefore, the pigment(a) dispersion preferably comprises pigment(a), a liquid dispersion medium, preferably water, and at least one dispersant, preferably selected from nonionic surfactants, anionic surfactants, or polymeric dispersants or mixtures thereof. The amount of dispersant based on the pigment(a) dispersion is preferably 0.1-10% by weight, more preferably 0.5-5% by weight, and most preferably 0.5-3% by weight.

[0060] Alternatively, solid formulations that are easily dispersed or stirred into water are also acceptable. These solid formulations include pigments (a) and solid carriers compatible with aqueous systems. Carriers include phosphates, phosphate esters, and phosphonic acids, which possess certain hydrophilic properties that allow the product to be easily incorporated into aqueous latex solutions. Pigment concentrations are typically in the range of 40-95% by weight. The carrier is typically present at a concentration of 5-60% by weight.

[0061] The method for preparing latex articles consists of a pre-dispersion process, a dispersion process, and a molding process including a dry process. In the pre-dispersion process, a pH-adjusted pigment (a) dispersion and natural latex are thoroughly mixed together. Additional natural latex and colored pigment (b) are added to the pre-dispersion and thoroughly mixed. A mold, for example for balloons or gloves, is immersed in a coagulant such as calcium nitrate and dried. The dried mold is then immersed in the natural latex solution and subsequently baked at 60-120°C, preferably 80-100°C, until cured.

[0062] In this invention, 1-5% by weight of an iron oxide coating metallic pigment (a) such as Paliocom (from Sun Chemical), Stellar (from CQV), Zenexo (from Schlenk), Meoxal (from Merck), etc., preferably aluminum; and 0.1-5.0% by weight of an organic pigment (b) are incorporated into a natural latex to obtain a red metallic target color having the following characteristics:

[0063] a =25-80 at 45°

[0064] b =10-40 at 45°

[0065] The angle-dependent color index (FI) is calculated according to equation (1) ≥ 9.0.

[0066]

[0067] Where L 15. L 110 and L 45 is the color measurement value at the corresponding observation angle and a and b It is the color dimension of the Lab color space at 45°.

[0068] Angle-dependent coloration is the change in lightness, hue, or chroma of dried ink, paint, or other colored coatings when viewed from different angles. For example, the color may match the test panel well when viewed from the front, but change when moved 45° or 60° to the left or right.

[0069] There are two types of aluminum flakes in the Paliocom series. One is "corn flake type" and the other is "silver coin type". Regarding particle size, D50 is 10-22 micrometers, preferably 20 micrometers.

[0070] Table 1: Amount of iron oxide relative to substrate in various iron oxide metallic effect pigments

[0071]

[0072] PALIOCROM GOLD L2158 (NV 72.5%) has a particle size D50 of 17 micrometers and the composition of the slurry is aluminum (approximately 28%), silica (approximately 13%), and iron oxide (approximately 32%) plus solvent (approximately 27%).

[0073] Red, purple, and / or orange absorbing pigment particles (b) reflect red, purple, and / or orange. The absorbing pigment (b), preferably the red absorbing pigment (b), can be an inorganic pigment or, preferably, an organic pigment or a mixture of two or more thereof. Preferably, it is selected from quinacridone pigments, diketopyrrolopyrrolidone pigments, azo red pigments, azo orange pigments, and dioxinone pigments. Azide pigments, naphthol pigments, diaryl compound pigments, perylene pigments, diazo orange pigments, benzimidazolone pigments, pyrazolone pigments, violet ketone pigments, azomethyl alkali pigments, anthraquinone pigments, triaryl carbon pigments Pigments, including thioindole pigments, isoindoline pigments, substituted pigments having a common chemical structure, inorganic mixed metal and mixed metal oxide red pigments and their blends. More preferably, the red absorbent pigment is selected from Pigment Red 122, Pigment Red 202, Pigment Red 188, Pigment Red 269, Pigment Red 254, Pigment Red 57:1, Pigment Red 48:2, Pigment Violet 23 and their blends.

[0074] The average particle size of the red, purple, and / or orange absorbent pigment particles (b) can be freely chosen, but is typically in the nanometer range. In other embodiments, the particles may have an average diameter of 0.1-200 nanometers or 0.1-15 nanometers. The particle size can be measured using a camsizer or other optical instrument.

[0075] Depending on the desired final color effect and color depth or density, the amount and weight ratio of components (a) and (b) in the latex or latex article can be freely chosen. The amount of component (a) in the latex is preferably 0.1-20% by weight, more preferably 0.5-10% by weight, and most preferably 1-5% by weight, based on 100% by weight of the final latex.

[0076] The amount of component (b) in the latex is preferably 0.01-20% by weight, more preferably 0.1-10% by weight, and most preferably 0.25-7.5% by weight, based on 100% by weight of the final latex.

[0077] The appropriate or preferred weight ratio of pigment (b) to (a) is illustrated by the following examples.

[0078] Any reference or identification of any document in this application is not an endorsement of prior art representing the present invention.

[0079] Implementation Plan

[0080] This invention is further illustrated by the following set of paragraphs or embodiments, as well as combinations of paragraphs or embodiments derived from the indicated dependencies and retrospective references. It is particularly noteworthy that in the various instances where a scope of embodiments is mentioned, for example with the term "the method of any one of embodiments 1-5," it is intended to explicitly disclose to a skilled person each embodiment within that scope, i.e., the wording of the term should be understood by a skilled person as synonymous with "the method of any one of embodiments 1, 2, 3, 4, and 5." Furthermore, it should be clearly noted that the following set of paragraphs and embodiments is not the set of claims defining the scope of protection, but rather represents appropriate components of the specification relating to the general and specific aspects of the invention.

[0081] 1. A method for providing a latex article with a red metallic coating, said coating comprising a printing ink having one or more metallic fillers and one or more red, purple, or orange absorbent pigments, wherein the metallic coating exhibits a red metallic effect having the following characteristics:

[0082] a =25-80 at 45°

[0083] b =10-40 at 45°

[0084] The color difference index (FI) is ≥9.0 according to equation (1).

[0085] 2. The method of implementation scheme 1, wherein the metal filler comprises one or more layers of metal or metal oxide.

[0086] 3. The method of implementation scheme 2, wherein the weight of the metal filler is 0.5-10% by weight.

[0087] 4. The method of any one of embodiments 1-3, wherein the metal filler comprises one or more layers of metal or metal oxide and one or more layers of iron oxide.

[0088] 5. The method of embodiment 4, wherein the metal filler comprises 30-250 times (by weight) iron oxide relative to the metal or metal oxide substrate.

[0089] 6. The method according to any one of embodiments 1-5, wherein the red absorbent pigment is selected from quinacridone pigments, diketopyrrolopyrrolidone pigments, azo red pigments, azo orange pigments, and dioxinone pigments. Azide pigments, naphthol pigments, diaryl compound pigments, perylene pigments, diazo orange pigments, benzimidazolone pigments, pyrazolone pigments, violet ketone pigments, azomethyl alkali pigments, anthraquinone pigments, triaryl carbon pigments Pigments, sulfur-indigo pigments, isoindoline pigments, including substituted compounds with a common chemical structure, inorganic mixed metal and mixed metal oxide red pigments and their blends.

[0090] 7. The method of any one of embodiments 1-6, wherein the red absorbent pigment is selected from Pigment Red 122, Pigment Red 202, Pigment Red 188, Pigment Red 269, Pigment Red 254, Pigment Red 57:1, Pigment Red 48:2, Pigment Violet 23 and blends thereof.

[0091] 8. The method of any one of Implementation Schemes 1-7, wherein the latex product is selected from balloons, gloves and erasers.

[0092] 9. A red metallic latex article which can be obtained by any one or more of the methods described in embodiments 1-7.

[0093] 10. A latex or latex article having a red metallic surface coating agent embedded at least in its surface, wherein the red metallic surface coating agent comprises:

[0094] (a) One or more metal fillers comprising metal and / or metal oxide particles, and

[0095] (b) One or more red, purple, and / or orange absorbent pigment particles,

[0096] The metal surface coating agent exhibits a red metallic effect with the following characteristics:

[0097] a =25-80 at 45°

[0098] b =10-40 at 45°

[0099] The angle-dependent color index (FI) is calculated according to formula (1) as FI ≥ 9.0.

[0100]

[0101] Where L 15. L 110 and L 45 is the color measurement value at the corresponding observation angle and a and b It is the color dimension of the Lab color space at 45°.

[0102] 11. The latex or latex article of embodiment 10, wherein the metal filler (a) comprises a surface layer (a2) of one or more metals and / or metal oxides.

[0103] 12. The latex or latex article of embodiment 10 or 11, wherein the amount of metal filler (a) in the latex or latex article is 0.5-10% by weight based on the latex or latex article having a red metallic surface coating.

[0104] 13. The latex or latex article of any one of embodiments 10-12, wherein the metal filler (a) comprises a metal oxide preferably selected from mica, glass, Al2O3 and / or a metal preferably selected from aluminum, copper, silver, nickel, zinc, stainless steel or alloys of two or more of these metals as a base material (a1).

[0105] 14. The latex or latex article of embodiment 13, wherein the metal filler (a) comprises one or more surface layers (a2) selected from one or more metal or metal oxide surface layers different from iron oxide on a substrate (a1) and / or one or more iron oxide surface layers, wherein the metal and metal oxide are different from the metal and metal oxide of the substrate.

[0106] 15. The latex or latex article of embodiment 14, wherein the iron oxide contained in the surface layer (a2) by the metal filler (a) is 30 to 250 times the weight of the metal and / or metal oxide substrate (a1).

[0107] 16. A latex or latex product according to any one of embodiments 10-15, wherein the red absorbent pigment (b) is selected from quinacridone pigments, diketopyrrolopyrrolidone pigments, azo red pigments, azo orange pigments, and dioxinone pigments. Azide pigments, naphthol pigments, diaryl compound pigments, perylene pigments, diazo orange pigments, benzimidazolone pigments, pyrazolone pigments, violet ketone pigments, azomethyl alkali pigments, anthraquinone pigments, triaryl carbon pigments Pigments, sulfur indigo pigments, isoindoline pigments, including substituted products having the aforementioned common chemical structure, inorganic mixed metal and / or mixed metal oxide red pigments and their blends.

[0108] 17. The latex or latex product of any one of embodiments 10-16, wherein the red absorbent pigment (b) is selected from Pigment Red 122, Pigment Red 202, Pigment Red 188, Pigment Red 269, Pigment Red 254, Pigment Red 57:1, Pigment Red 48:2, Pigment Violet 23 and blends thereof.

[0109] 18. The latex or latex product of any one of embodiments 10-17, wherein the latex is selected from natural rubber latex and / or synthetic rubber latex.

[0110] 19. Latex or latex articles of any one of embodiments 10-18, wherein the latex articles are selected from balloons, gloves, preferably rubber household gloves and medical gloves, condoms and diaphragms, beach toys, catheters, dental products, preferably wedges and orthodontic rubber bands, and elastic materials for clothing.

[0111] 20. A latex or latex article according to any one of embodiments 10-19, wherein the red metallic surface coating agent comprising one or more metal fillers (a) containing metal and / or metal oxide particles and one or more red, purple and / or orange absorbent pigment particles (b) is part of a printing ink for applying the red metallic surface coating agent to the latex or latex article.

[0112] 21. A method for producing a latex article having a red metallic surface coating according to any one of embodiments 10-20, comprising:

[0113] A liquid natural and / or synthetic latex dispersion is mixed with a red metallic surface coating agent comprising one or more metal fillers (a) containing metal and / or metal oxide particles and one or more red, purple, and / or orange absorbent pigment particles (b), and the mixture is used to form a latex article, such that the red metallic surface coating agent is embedded in the latex article at least in its surface and has a red metallic effect.

[0114] Alternatively, a latex article may first be formed from a liquid natural and / or synthetic latex dispersion and then the dried article may be coated with a mixture of the liquid natural and / or synthetic latex dispersion and a red metallic surface coating agent comprising one or more metal fillers (a) containing metal and / or metal oxide particles and one or more red, purple and / or orange absorbent pigment particles (b), and a latex coating may be formed on the article by the mixture, such that the red metallic surface coating agent is embedded in the latex article at least in its surface and has a red metallic effect.

[0115] 22. The method of embodiment 21, wherein the latex and / or the mixture contains water and one or more additives selected from non-silicone defoamers, polyalkylene glycols, nonionic surfactants, preferably alcohol ethoxylates, rheology modifiers, preferably acrylic polymers and / or acrylic copolymer emulsions, preferably in water.

[0116] 23. A red metallic latex article which can be obtained by or derived from the method of embodiment 21 or 22.

[0117] 24. A particulate composition comprising:

[0118] (a) One or more metal filler particles comprising metal and / or metal oxide particles, and

[0119] (b) One or more red, purple, and / or orange absorbent pigment particles as defined in any of embodiments 10-20,

[0120] The particulate composition produces a red metallic surface coating on at least the surface of a latex article containing the pigment composition, wherein the metallic surface coating exhibits a red metallic effect with the following characteristics in the latex article:

[0121] a =25-80 at 45°

[0122] b =10-40 at 45°

[0123] The angle-dependent color index (FI) is calculated according to formula (1) as FI ≥ 9.0.

[0124]

[0125] Where L 15. L 110 and L 45 is the color measurement value at the corresponding observation angle and a and b It is the color dimension of the Lab color space at 45°.

[0126] 25. Use of a particulate composition, at least in its surface, as a red metallic surface coating agent for latex articles, the particulate composition comprising:

[0127] (a) One or more metal fillers comprising metal and / or metal oxide particles, and

[0128] (b) One or more red, purple, and / or orange absorbent pigment particles as defined in any of embodiments 10-20,

[0129] In latex products, this metallic surface coating exhibits a reddish metallic effect with the following characteristics:

[0130] a =25-80 at 45°

[0131] b =10-40 at 45°

[0132] The angle-dependent color index (FI) is calculated according to formula (1) as FI ≥ 9.0.

[0133]

[0134] Where L 15. L 110 and L 45 is the color measurement value at the corresponding observation angle and a and b It is the color dimension of the Lab color space at 45°.

[0135] The particulate (pigment) composition of the present invention can be appropriately dispersed with a polymer dispersant to form a pigment dispersion.

[0136] Therefore, the present invention relates to, in another aspect, the following:

[0137] 26. A particulate or pigment dispersion comprising a particulate composition as defined in embodiment 24 and a polymeric dispersant.

[0138] Two or more polymer dispersants can also be added.

[0139] Suitable polymeric dispersants improve pigment dispersion and reduce interparticle attraction within the dispersion. Improved dispersion refers to a smaller average particle size with a narrower particle size distribution (or particle size reduction achieved in a shorter grinding time). The dispersions are significantly more stable against flocculation and agglomeration compared to those produced by conventional methods. Suitable polymeric dispersants have a two-component structure comprising polymer chains and anchoring groups. A specific combination of these contributes to their effectiveness.

[0140] The polymer dispersant can be a statistical (e.g., random), alternating, gradient, grafted, or block copolymer. The polymer dispersant is typically added based on particles (a) and pigments (b), and optionally other pigments, in an amount of 1-50% by weight, preferably up to 35% by weight.

[0141] Suitable polymer dispersants are copolymers such as cationic copolymers, anionic copolymers, amphoteric copolymers, or nonionic copolymers.

[0142] The copolymer may, for example, have repeating units derived from polymerizable or polycondensable acids, esters, glycols, nitriles, amides, imides, olefins, epoxides, or aziridines, such as acrylic acid or methacrylic acid or their esters, amides or nitriles, terephthalates, caprolactam, ethylene, propylene, isobutylene, styrene, ethylene oxide, or ethyleneimine. Graft and block copolymers are preferred.

[0143] It can be used as a cationic, anionic, amphoteric, or nonionic copolymer, for example under the trade name Disperbyk. ® 111, 160, 161, 162, 163, 164, 166, 170, 171, 182, 2000, 2001, 2070, 2150, 2163; EFKA ® Dispex ® Ultra 4585, Solsperse ® 24000, 32550, Ajisper ® Those obtained from PB-821, PB-822, PB-823 and their combinations.

[0144] The polymeric dispersant typically affects the viscosity of the pigment dispersion. Therefore, it is preferable to use a polymeric dispersant that results in a low viscosity of the particle / pigment dispersion, such as an amphoteric copolymer or, in particular, a cationic copolymer.

[0145] Particles or pigment dispersions can be prepared by various methods. For example, a pigment composition, solvent, and polymer dispersant, along with optional pigment synergists, can be dispersed in predetermined amounts via a dispersion step. This dispersion step can be carried out using a paint mixer, sand mill, ball mill, roller mill, stone mill, jet mill, or homogenizer. Other colorants may also be added, if present. If desired, other suitable additives or base resins of the composition to be used in the final application may be present during the dispersion step. The base resin may be added partially or completely. The dispersion time can be adjusted appropriately depending on the equipment used. The dispersion temperature can be varied, for example, 0°C or higher, at room temperature, or up to 100°C.

[0146] The particle / pigment composition or particle / pigment dispersion of the present invention can be used in a variety of applications, such as for coloring organic materials of any natural or synthetic origin, such as photoresist formulations for making color filters, printing inks, liquid inks, coating compositions, paints, plastics, films or fibers.

[0147] Therefore, the present invention relates to, in another aspect, the following:

[0148] 27. Use of the particulate composition as defined in embodiment 24 or the particulate or pigment dispersion as defined in embodiment 26 in the coloring of photoresist formulations for the manufacture of color filters, printing inks, liquid inks, coating compositions, paints, plastics, films or fibers.

[0149] Based on the organic material to be colored, this particle / pigment composition is typically used in amounts of 0.01-30% by weight.

[0150] The present invention, including its various embodiments, has been described in detail. However, it should be understood that those skilled in the art can make changes and / or modifications to the invention that fall within the scope and spirit of this disclosure when considering it.

[0151] Example

[0152] The present invention is further described by the following non-limiting embodiments, which further illustrate the invention and are not intended, nor should they be construed, as limiting the scope of the invention.

[0153] The following compositions were used in the examples:

[0154] Compal WS4468 (A1 88.0%): D 50 15μm

[0155] PR122 dispersion Sunsperse QPD0122 (40.2 wt% PR122)

[0156] PR269 dispersion RPD-2690 (37.61 wt% PR269)

[0157] PR57:1 dispersion RFD-9587 (38.0 wt% PR57:1)

[0158] PR254 dispersion RFD-0254 (48.10 wt% PR254)

[0159] PV23 dispersion VFD-1157 (46.90 wt% PV23)

[0160] Compal WS4468 metallic effect pigment (SunChemical) (Al 88.0%)

[0161] All of the following implementations are prepared stepwise as described above.

[0162] Invention Example 1—Dispersion and Latex Solution

[0163] 1. Weigh 502.4g of PALIOCROM GOLD L2024 (non-volatile matter (NV) = 60.0%), 136.7g of non-silicone defoamer, 23.9g of polypropylene glycol, 215.3g of deionized (DI) water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0164] 2. Add 102.5g of acrylic emulsion and stir for 30 minutes.

[0165] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 10.0g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0166] 4. Add the PR122 dispersion Sunsperse QPD0122 (40.2 wt% PR122) to mixture #3 in the amounts shown in Table 2. Mix at 3000 RPM for 3 min using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0167] Invention Example 2—Dispersions and Latex Solutions

[0168] 1. Weigh 502.4g of PALIOCROM GOLD L2024 (NV 60.0%), 136.7g of non-silicone defoamer, 23.9g of polypropylene glycol, 215.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0169] 2. Add 102.5g of acrylic emulsion and stir for 30 minutes.

[0170] 3. Weigh 89.3g of latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 10.0g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0171] 4. Add PR269 dispersion RPD-2690 (37.61 wt% PR269) to mixture #3 in the amounts shown in Table 2.

[0172] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0173] Invention Example 3—Dispersions and Latex Solutions

[0174] 1. Weigh 502.4g of PALIOCROM GOLD L2024 (NV 60.0%), 136.7g of non-silicone defoamer, 23.9g of polypropylene glycol, 215.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0175] 2. Add 102.5g of acrylic emulsion and stir for 30 minutes.

[0176] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 10.0g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0177] 4. Add the PR57:1 dispersion RFD-9587 (38.0 wt% PR57:1) in the amounts shown in Table 2.

[0178] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0179] Invention Example 4—Dispersions and Latex Solutions

[0180] 1. Weigh 502.4g of PALIOCROM GOLD L2024 (NV 60.0%), 136.7g of non-silicone defoamer, 23.9g of polypropylene glycol, 215.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0181] 2. Add 102.5g of acrylic emulsion and stir for 30 minutes.

[0182] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 10.0g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0183] 4. Add PR254 dispersion RFD-0254 (48.10 wt% PR254) to mixture #3 in the amounts shown in Table 2.

[0184] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0185] Invention Example 5—Dispersions and Latex Solutions

[0186] 1. Weigh 415.8g of PALIOCROM GOLD L2158 (NV 72.5%), 136.7g of non-silicone defoamer, 32.6g of polypropylene glycol, 293.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0187] 2. Add 102.53g of acrylic emulsion and stir for 30 minutes.

[0188] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 3.1g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0189] 4. Add PR57:1 dispersion RFD-9587 (38.0 wt% PR57:1) to mixture #3 in the amounts shown in Table 2.

[0190] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0191] Invention Example 6—Dispersions and Latex Solutions

[0192] 1. Weigh 415.8g of PALIOCROM GOLD L2158 (NV 72.5%), 136.7g of non-silicone defoamer, 32.6g of polypropylene glycol, 293.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0193] 2. Add 102.53g of acrylic emulsion and stir for 30 minutes.

[0194] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 3.1g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0195] 4. Add PR269 dispersion RPD-2690 (37.61 wt% PR269) to mixture #3 in the amounts shown in Table 2.

[0196] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0197] Invention Example 7—Dispersions and Latex Solutions

[0198] 1. Weigh 415.8g of PALIOCROM GOLD L2158 (NV 72.5%), 136.7g of non-silicone defoamer, 32.6g of polypropylene glycol, 293.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0199] 2. Add 102.53g of acrylic emulsion and stir for 30 minutes.

[0200] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 10.0g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0201] 4. Add PR122 dispersion QPD-0122 (40.2 wt% PR-122) to mixture #3 in the amounts shown in Table 2.

[0202] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0203] Invention Example 8—Dispersions and Latex Solutions

[0204] 1. Weigh 415.8g of PALIOCROM GOLD L2158 (NV 72.5%), 136.7g of non-silicone defoamer, 32.6g of polypropylene glycol, 293.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0205] 2. Add 102.53g of acrylic emulsion and stir for 30 minutes.

[0206] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 10.0g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0207] 4. Add PR57:1 dispersion RFD-9587 (38.0 wt% PR57:1) to mixture #3 in the amounts shown in Table 2.

[0208] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0209] Invention Example 9—Dispersions and Latex Solutions

[0210] 1. Weigh 415.8g of PALIOCROM GOLD L2158 (NV 72.5%), 136.7g of non-silicone defoamer, 32.6g of polypropylene glycol, 293.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0211] 2. Add 102.53g of acrylic emulsion and stir for 30 minutes.

[0212] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 10.0g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0213] 4. Add PR269 dispersion RPD-2690 (37.61 wt% PR269) to mixture #3 in the amounts shown in Table 2.

[0214] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0215] Invention Example 10—Dispersions and Latex Solutions

[0216] 1. Weigh 415.8g of PALIOCROM GOLD L2158 (NV 72.5%), 136.7g of non-silicone defoamer, 32.6g of polypropylene glycol, 293.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0217] 2. Add 102.53g of acrylic emulsion and stir for 30 minutes.

[0218] 3. Weigh 53.6g of natural latex, 0.4g of rheology modifier (acrylic copolymer emulsion), and 10.8g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0219] 4. Add PR57:1 dispersion RFD-9587 (38.0 wt% PR57:1) to mixture #3 in the amounts shown in Table 2.

[0220] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0221] Invention Example 11—Dispersions and Latex Solutions

[0222] 1. Weigh 415.8g of PALIOCROM GOLD L2158 (NV 72.5%), 136.7g of non-silicone defoamer, 32.6g of polypropylene glycol, 293.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0223] 2. Add 102.53g of acrylic emulsion and stir for 30 minutes.

[0224] 3. Weigh 53.6g of natural latex, 0.4g of rheology modifier (acrylic copolymer emulsion), and 10.8g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0225] 4. Add PR269 dispersion RPD-2690 (37.61 wt% PR269) to mixture #3 in the amounts shown in Table 2.

[0226] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0227] Invention Example 12—Dispersions and Latex Solutions

[0228] 1. Weigh 405.7g of PALIOCROM RED L3258 (NV 74.3%), 136.7g of non-silicone defoamer, 41.2g of polypropylene glycol, 302.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0229] 2. Add 102.5g of acrylic emulsion and stir for 30 minutes.

[0230] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 3.1g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0231] 4. Add PR57:1 dispersion RFD-9587 (38.0 wt% PR57:1) to mixture #3 in the amounts shown in Table 2.

[0232] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0233] Invention Example 13—Dispersions and Latex Solutions

[0234] 1. Weigh 405.7g of PALIOCROM RED L3258 (NV 74.3%), 136.7g of non-silicone defoamer, 41.2g of polypropylene glycol, 302.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0235] 2. Add 102.5g of acrylic emulsion and stir for 30 minutes.

[0236] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 3.1g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0237] 4. Add PR269 dispersion RPD-2690 (37.61 wt% PR269) to mixture #3 in the amounts shown in Table 2.

[0238] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0239] Invention Example 14—Dispersions and Latex Solutions

[0240] 1. Weigh 405.7g of PALIOCROM RED L3258 (NV 74.3%), 136.7g of non-silicone defoamer, 41.2g of polypropylene glycol, 302.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0241] 2. Add 102.5g of acrylic emulsion and stir for 30 minutes.

[0242] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 10.0g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0243] 4. Add PR122 dispersion QPD-0122 (40.2 wt% PR122) to mixture #3 in the amounts shown in Table 2.

[0244] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0245] Invention Example 15—Dispersions and Latex Solutions

[0246] 1. Weigh 405.7g of PALIOCROM RED L3258 (NV 74.3%), 136.7g of non-silicone defoamer, 41.2g of polypropylene glycol, 302.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0247] 2. Add 102.5g of acrylic emulsion and stir for 30 minutes.

[0248] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 10.0g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0249] 4. Add PR269 dispersion RPD-2690 (37.61 wt% PR269) to mixture #3 in the amounts shown in Table 2.

[0250] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0251] Invention Example 16—Dispersions and Latex Solutions

[0252] 1. Weigh 405.7g of PALIOCROM RED L3258 (NV 74.3%), 136.7g of non-silicone defoamer, 41.2g of polypropylene glycol, 302.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0253] 2. Add 102.5g of acrylic emulsion and stir for 30 minutes.

[0254] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 10.0g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0255] 4. Add PR57:1 dispersion RFD-9587 (38.0 wt% PR57:1) to mixture #3 in the amounts shown in Table 2.

[0256] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0257] Invention Example 17—Dispersions and Latex Solutions

[0258] 1. Weigh 405.7g of PALIOCROM RED L3258 (NV 74.3%), 136.7g of non-silicone defoamer, 41.2g of polypropylene glycol, 302.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0259] 2. Add 102.5g of acrylic emulsion and stir for 30 minutes.

[0260] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 10.0g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0261] 4. Add PR254 dispersion RFD-0254 (48.10 wt% PR254) to mixture #3 in the amounts shown in Table 2.

[0262] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0263] Invention Example 18—Dispersions and Latex Solutions

[0264] 1. Weigh 405.7g of PALIOCROM RED L3258 (NV 74.3%), 136.7g of non-silicone defoamer, 41.2g of polypropylene glycol, 302.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0265] 2. Add 102.5g of acrylic emulsion and stir for 30 minutes.

[0266] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 10.0g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0267] 4. Add PV23 dispersion VFD-1157 (46.90 wt% PV23) to mixture #3 in the amounts shown in Table 2.

[0268] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0269] Invention Example 19—Dispersions and Latex Solutions

[0270] 1. Weigh 405.7g of PALIOCROM RED L3258 (NV 74.3%), 136.7g of non-silicone defoamer, 32.6g of polypropylene glycol, 293.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0271] 2. Add 102.53g of acrylic emulsion and stir for 30 minutes.

[0272] 3. Weigh 53.6g of natural latex, 0.4g of rheology modifier (acrylic copolymer emulsion), and 10.8g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0273] 4. Add PR122 dispersion QPD-0122 (40.2 wt% PR122) to mixture #3 in the amounts shown in Table 2.

[0274] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0275] Invention Example 20—Dispersions and Latex Solutions

[0276] 1. Weigh 405.7g of PALIOCROM RED L3258 (NV 74.3%), 136.7g of non-silicone defoamer, 32.6g of polypropylene glycol, 293.3g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0277] 2. Add 102.53g of acrylic emulsion and stir for 30 minutes.

[0278] 3. Weigh 53.6g of natural latex, 0.4g of rheology modifier (acrylic copolymer emulsion), and 10.8g of Paliocolon dispersion (from step 1) into separate containers and stir for 30 minutes.

[0279] 4. Add PR269 dispersion RPD-2690 (37.61 wt% PR269) to mixture #3 in the amounts shown in Table 2.

[0280] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0281] Invention Example 21—Dispersions and Latex Solutions

[0282] 1. Weigh 301.4g of SunMICA gold 284-1219, 136.7g of non-silicone defoamer, 44.0g of polypropylene glycol, 396.2g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0283] 2. Add 102.53g of acrylic emulsion and stir for 30 minutes.

[0284] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 10.0g of SunMICA dispersion (from step 1) into separate containers and stir for 30 minutes.

[0285] 4. Add PR122 dispersion QPD-0122 (40.2 wt% PR122) to mixture #3 in the amounts shown in Table 2.

[0286] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0287] Invention Example 22—Dispersions and Latex Solutions

[0288] 1. Weigh 301.4g of SunMICA gold 284-1219, 136.7g of non-silicone defoamer, 44.0g of polypropylene glycol, 396.2g of deionized water, and 17.9g of alcohol ethoxylated nonionic surfactant into a 2L beaker and stir for 30 minutes.

[0289] 2. Add 102.53g of acrylic emulsion and stir for 30 minutes.

[0290] 3. Weigh 89.3g of natural latex, 0.7g of rheology modifier (acrylic copolymer emulsion), and 10.0g of SunMICA dispersion (from step 1) into separate containers and stir for 30 minutes.

[0291] 4. Add PR269 dispersion RPD-2690 (37.61 wt% PR269) to mixture #3 in the amounts shown in Table 2.

[0292] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0293] Comparative Example 23—Dispersion and Latex Solution (without iron oxide)

[0294] 1. Weigh 25.0g of Compal WS4468 metallic effect pigment (SunChemical) (Al 88.0%) and 50.0g of deionized water into a 100ml beaker and stir for 30min.

[0295] 2. Use a buffer system to adjust the pH to 9.2.

[0296] 3. Weigh 78.6g of natural latex, 10.0g of rheology modifier (acrylic copolymer emulsion), and 10.5g of premix Compal WS4468 (from step 1) into separate containers and stir for 30 minutes.

[0297] 4. Add PR122 dispersion QPD-0122 (40.2 wt% PR122) to mixture #3 in the amounts shown in Table 3.

[0298] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0299] Comparative Example 24—Dispersions and Latex Solutions (without iron oxide)

[0300] 1. Weigh 25.0g of Compal WS4468 (Al 88.0%) and 50.0g of deionized water into a 100ml beaker and stir for 30min.

[0301] 2. Use a buffer system to adjust the pH to 9.2.

[0302] 3. Weigh 78.6g of natural latex, 10.0g of rheology modifier (acrylic copolymer emulsion), and 10.5g of premix Compal WS4468 (from step 1) into separate containers and stir for 30 minutes.

[0303] 4. Add PR269 dispersion RPD-2690 (37.6 wt% PR269) to mixture #3 in the amounts shown in Table 3.

[0304] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0305] Comparative Example 25—Dispersions and Latex Solutions (without iron oxide)

[0306] 1. Weigh 25.0g of Compal WS4468 (Al 88.0%) and 50.0g of deionized water into a 100ml beaker and stir for 30min.

[0307] 2. Use a buffer system to adjust the pH to 9.2.

[0308] 3. Weigh 78.6g of natural latex, 10.0g of rheology modifier (acrylic copolymer emulsion), and 10.5g of premix Compal WS4468 (from step 1) into separate containers and stir for 30 minutes.

[0309] 4. Add PR57:1 dispersion RFD-9587 (38.0 wt% PR57:1) to mixture #3 in the amounts shown in Table 3.

[0310] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0311] Comparative Example 26—Dispersions and Latex Solutions (without iron oxide)

[0312] 1. Weigh 25.0g of Compal WS4468 (Al 88.0%) and 50.0g of deionized water into a 100ml beaker and stir for 30min.

[0313] 2. Use a buffer system to adjust the pH to 9.2.

[0314] 3. Weigh 78.6g of natural latex, 10.0g of rheology modifier (acrylic copolymer emulsion), and 10.5g of premix Compal WS4468 (from step 1) into separate containers and stir for 30 minutes.

[0315] 4. Add PR254 dispersion RFD-0254 (48.1 wt% PR254) to mixture #3 in the amounts shown in Table 3.

[0316] 5. Mix for 3 minutes at 3000 RPM using a high-speed mixer DAC 150 FVZ-K (Flack Tec., Inc.) to provide the final mixture.

[0317] The coatings of each embodiment were prepared on a primer-coated aluminum plate (4×6 inches) using a 25mil applicator and baked at 80°C for 30 minutes.

[0318] Color measurement using BYK-mac i

[0319] F-index (FI value). The FI value is calculated according to formula (1):

[0320]

[0321] Table 2: Color measurement values ​​of the invention examples, using filler (a) and pigment (b)

[0322]

[0323]

[0324] The weight percentage of red pigment refers to the actual amount of pigment in each embodiment, not the amount of pigment dispersion (for example, in Invention Example 1, 0.77 weight percentage of red pigment requires 1.74 parts of Sunsperse QPD0122. 40.2 × 1.74 = 0.77 red pigment).

[0325] Table 2 shows that all invention examples meet the red metal color target.

[0326] Table 3: Color Measurement Values ​​for Comparative Examples

[0327]

[0328] The weight percentage of red pigment refers to the actual amount of pigment in each embodiment, not the amount of pigment dispersion (for example, in Invention Example 1, 0.77 weight percentage of red pigment requires 1.74 parts of Sunsperse QPD0122. 40.2 × 1.74 = 0.77 red pigment).

[0329] Table 3 shows that the proportion did not meet the red metallic color target.

Claims

1. A latex or latex article having a red metallic surface coating agent embedded at least in its surface, wherein the red metallic surface coating agent comprises: (a) One or more metal fillers comprising metal and / or metal oxide particles, and (b) One or more red, purple, and / or orange absorbent pigment particles, The metal surface coating agent described herein exhibits a red metallic effect with the following characteristics: a =25-80 at 45° b =10-40 at 45° The angle-dependent color index (FI) is calculated according to formula (1) as FI ≥ 9.

0. Where L 15. L 110 and L 45 is the color measurement value at the corresponding observation angle and a and b It is the color dimension of the Lab color space at 45°.

2. The latex or latex article of claim 1, wherein the metal filler (a) comprises one or more metal and / or metal oxide surface layers (a2).

3. The latex or latex article of claim 1 or 2, wherein the amount of the metal filler (a) in the latex or latex article is 0.5-10% by weight based on the latex or latex article having a red metallic surface coating.

4. The latex or latex article of any one of claims 1-3, wherein the metal filler (a) comprises a metal oxide preferably selected from mica, glass, Al2O3 and / or a metal preferably selected from aluminum, copper, silver, nickel, zinc, stainless steel or alloys of two or more of these metals as a base material (a1).

5. The latex or latex article of claim 4, wherein the metal filler (a) comprises one or more surface layers (a2) selected from one or more metal or metal oxide surface layers different from iron oxide and / or one or more iron oxide surface layers on the substrate (a1), wherein the metal and metal oxide are different from the metal and metal oxide of the substrate.

6. The latex or latex article of claim 5, wherein the iron oxide contained in the surface layer (a2) by the metal filler (a) is 30 to 250 times the weight of the metal and / or metal oxide substrate (a1).

7. The latex or latex article of any one of claims 1-6, wherein the red absorbent pigment (b) is selected from quinacridone pigments, diketopyrrolopyrrolidone pigments, azo red pigments, azo orange pigments, and di... Azide pigments, naphthol pigments, diaryl compound pigments, perylene pigments, diazo orange pigments, benzimidazolone pigments, pyrazolone pigments, violet ketone pigments, azomethyl alkali pigments, anthraquinone pigments, triaryl carbon pigments Pigments, sulfur indigo pigments, isoindoline pigments, including substituted products having the aforementioned common chemical structure, inorganic mixed metal and / or mixed metal oxide red pigments and their blends.

8. The latex or latex article of any one of claims 1-7, wherein the red absorbent pigment (b) is selected from Pigment Red 122, Pigment Red 202, Pigment Red 188, Pigment Red 269, Pigment Red 254, Pigment Red 57:1, Pigment Red 48:2, Pigment Violet 23 and blends thereof.

9. The latex or latex article of any claim, wherein the latex is selected from natural rubber latex and / or synthetic rubber latex.

10. The latex or latex article of any one of claims 1-9, wherein the latex article is selected from balloons, gloves, preferably rubber household gloves and medical gloves, condoms and diaphragms, beach toys, catheters, dental products, preferably wedges and orthodontic rubber bands, and elastics for clothing.

11. The latex or latex article of any one of claims 1-10, wherein the red metallic surface coating comprising one or more metal fillers (a) containing metal and / or metal oxide particles and one or more red, purple and / or orange absorbent pigment particles (b) is part of a printing ink for applying the red metallic surface coating to the latex or latex article.

12. A method for producing a latex article having a red metallic surface coating agent according to any one of claims 1-11, comprising the following steps: A liquid or fluid natural and / or synthetic latex is mixed with a red metallic surface coating agent comprising one or more metal fillers (a) containing metal and / or metal oxide particles and one or more red, purple, and / or orange absorbent pigment particles (b), or with a particle composition containing (a) and (b), and the mixture thus obtained is used to form a latex article, such that the red metallic surface coating agent is embedded at least in its surface into the latex article and has a red metallic effect. Alternatively, a latex article may first be formed from a liquid or fluid natural and / or synthetic latex and then coated with a mixture of the liquid or fluid natural and / or synthetic latex and a red metallic surface coating agent comprising one or more metal fillers (a) containing metal and / or metal oxide particles and one or more red, purple and / or orange absorbent pigment particles (b), or with a particle composition containing (a) and (b). Furthermore, the mixture forms a latex coating on the latex article, thereby embedding the red metallic surface coating agent at least in its surface into the latex article and giving it a red metallic effect.

13. The method of claim 12, wherein the liquid or fluid latex and / or the particulate composition containing (a) and (b) contains water and one or more additives selected from non-silicone defoamers, polyalkylene glycols, nonionic surfactants, preferably alcohol ethoxylates, rheology modifiers, preferably acrylic polymers and / or acrylic copolymer emulsions, preferably in water.

14. A red metallic latex article which can be obtained by or derived from the method of claim 12 or 13.

15. A particulate composition comprising: (a) One or more metal fillers comprising metal and / or metal oxide particles as defined in any one of claims 1-11, and (b) One or more red, purple, and / or orange absorbent pigment particles as defined in any one of claims 1-11 The particulate composition produces a red metallic surface coating in at least its surface of a latex article containing the particulate composition, wherein the metallic surface coating exhibits a red metallic effect with the following characteristics in the latex article: a =25-80 at 45° b =10-40 at 45° The angle-dependent color index (FI) is calculated according to formula (1) as FI ≥ 9.

0. Where L 15. L 110 and L 45 is the color measurement value at the corresponding observation angle and a and b It is the color dimension of the Lab color space at 45°.

16. Use of a particulate composition, at least in its surface, as a red metallic surface coating agent for latex articles, said composition comprising: (a) One or more metal fillers comprising metal and / or metal oxide particles as defined in any one of claims 1-11, and (b) One or more red, purple, and / or orange absorbent pigment particles as defined in any one of claims 1-11 In the latex product, the metallic surface coating agent exhibits a red metallic effect with the following characteristics: a =25-80 at 45° b =10-40 at 45° The angle-dependent color index (FI) is calculated according to formula (1) as FI ≥ 9.

0. Where L 15. L 110 and L 45 is the color measurement value at the corresponding observation angle and a and b It is the color dimension of the Lab color space at 45°.

17. A particulate or pigment dispersion comprising the particulate composition as defined in claim 15 and further comprising a polymeric dispersant.

18. Use of the particulate composition as defined in claim 15 or the particulate or pigment dispersion as defined in claim 17 in the coloring of photoresist formulations for the manufacture of color filters, printing inks, liquid inks, coating compositions, paints, plastics, films, or fibers.

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