• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    WATER COATING COMPOSITION, METHOD OF FINISHING AN ARTICLE OR STRUCTURE, AND ARTICLE OR STRUCTURE. Aqueous coating composition which has 78 to 88% PVC and comprises, based on the total volume of solids of the dry coating, unless otherwise indicated: a. opacifying pigment particles comprising: i. 3 to 10% titanium dioxide; ii. from 0 to 20% of hollow polymeric particles; B. non-opacifying extensor particles comprising: i. magnesium and calcium carbonate; and / or ii. calcium carbonate; and / or iii. syenite nepheline; and / or iv. kaolin; where i + ii + iii + iv = 40 to 80% and iv is 0 to 20%; ç. polymer binder particles with Tg Fox calculated from 25 to 70 ° C which have an Acid value of 15 to 65 mg KOH / g polymer and in which the polymer particles are derived from acrylic monomers and optionally comprise styrene and / or its derivatives; d. dispersant that has an average molecular weight of at least 3500 Daltons; and is. fugitive coalescing solvent; wherein the composition is free of non-fugitive coalescing solvent.
    公开号:BR112012026737B1
    申请号:R112012026737-0
    申请日:2011-04-22
    公开日:2020-12-22
    发明作者:Stephen Arthur Wheeler；Javier PEREZ-AMOROS；Anthony David Woods；Simon Nicholas Emmett
    申请人:Akzo Nobel Coatings International B.V；
    IPC主号:
    专利说明:

    The present invention relates to pigmented coating compositions with reduced energy content, especially low to medium gloss pigment inks, also known as matte or low gloss paints. In particular, it refers to inks with a pigment volume content of 7 to 88%, which have a gloss of less than 30% when measured at 85 °.
    Pigmented inks with low coloring normally contain high levels of titanium dioxide, TiO2. This is because these pastels are predominantly white, with a small amount of color other than white added. Titanium dioxide is the best source of white due to its high refractive index compared to typical binders used in paints. Unfortunately, TiO2 requires large amounts of energy to be extracted from the soil and then purified. In fact, in paints with a high volume of pigment (PVC) with a light / pastel color, such as opaque whites and opaque light hues as described below, the high content of TiO2 (typically 10 to 20% by volume) used to achieve the desired color and opacity is the main contributor to the total energy content of the paint.
    By energy content, we indicate the energy required to extract, refine and manufacture the ingredients that comprise the ink and the energy necessary to manufacture the ink itself.
    Since most of the energy is generated by burning fossil fuel, high energy content usually results in high carbon dioxide emissions; hence the use of the alternative measure "built-in CO2" to indicate the energy content.
    The adverse effect of these emissions on the global environment, especially climate change, is generally accepted by the most serious commentators. There is, therefore, a need to reduce the energy consumed in the production of these paints.
    One approach is to reduce the TiO2 content of the paint. This simply reduces, however, the opacity of the dry coating, and although each dry paint coating may have a reduced energy content, additional coatings will be required to achieve opacity. Consequently, any benefit is lost or at least significantly reduced. Other approaches replace Ti02 in whole or in part with extending pigments, such as chalk. Although these extenders require less energy than TiO2 for their extraction and refining, the lower refractive index of these extenders is very close to the binders used in the paint. In this way, they do not diffuse light as well as TiO2 and, in order to compensate for the reduced amount of TiO2, more extender needs to be added to the paint to achieve the correct color and opacity. This, however, raises the PVC even further, eventually to the point where air is captured in the dry paint film. Although this increases opacity, it also usually results in lower resistance to wet friction.
    A possible solution to this dilemma is the use of calcined clay, as it has good opacity and is less harmful to resistance to friction. The manufacture of calcined clay requires, however, heating the clay to 1000 ° C in order to consume large amounts of energy. This clearly does not result in significant energy savings and is therefore not a preferred option.
    US Patent No. 4,277,385 describes paint compositions that have 75 to 85% PVC and also teaches that, to avoid cracking in high PVC paint films, the formulation must be free of non-opacifying inorganic pigments ( another name for extenders), essentially replacing them with solid, non-film-forming polymer particles. No attempt is made, however, to minimize the TiO2 content in these formulations and, therefore, the problem of high energy content and high CO2 emissions is not addressed.
    European Patent Application EP 0113435 describes an aqueous paint that contains a reduced content of 20 to 80% TiO2 in PVC. He teaches the use of mixtures that comprise pigmented vesiculated polymer spheres and larger opaque polymer particles that have microlaps, but not pigments, to replace TiO2, while maintaining resistance to friction and burning. As stated in that order, however, the pigmented vesiculated polymer spheres themselves contain TiO2 and therefore considerably increase the TiO2 content. This does little, when doing something, to reduce the total energy content of the paint.
    Pigmented vesiculated polymer spheres are polymer particles that contain both TiO2 and microlanks.
    There is, therefore, a need for improvement of paint compositions that contain reduced TiO2 content and, therefore, low energy content, while also having good opacity and good resistance to wet rubbing.
    Accordingly, an aqueous pigmented coating composition is provided which has 78 to 88% PVC and comprises, based on the total volume of solids in the dry coating, unless otherwise stated: a. opacifying pigment particles comprising: i. 3 to 10% titanium dioxide; ii. from 0 to 20% of polymeric particles; B. non-opacifying extensor particles comprising: i. magnesium and calcium carbonate; and / or ii. calcium carbonate; and / or iii. . syenite nepheline; and / or iv. kaolin; where i + ii + iii + iv = 40 to 80% and iv is 0 to 20%; ç. Tg polymer binder particles
    Fox calculated at 25 to 70 ° C which has an acid value of 15 to 65 mg KOH / g polymer and in which the polymer particles are derived from acrylic monomers and optionally comprise styrene and / or its derivatives; d. dispersant having an average molecular weight of at least 3500 Daltons; and is. fugitive coalescing solvent; wherein the composition is free of non-fugitive coalescing solvent.
    Preferably, the pigment volume content is 79 to 85, more preferably 80 to 85, most preferably greater than 80 to 84 and most preferably 81 to 83%. Any difference between real PVC and the sum of a and b is compensated for with other non-opacifying extending pigments, as defined below.
    Preferably, the opacifying pigment particles are white.
    Most preferably, the opacifying pigment particles consist of TiO2 and hollow polymer particles. Even more preferably, the opacifying pigment particles consist only of TiO2. TiO2 produced by means of the well-known chloride process is preferred in the present invention, as it requires less energy for its manufacture and, therefore, introduces less CO2 embedded in the coating.
    Titanium dioxide is preferentially in the form of rutile, as anatase is a less efficient diffuser and, therefore, a greater amount is needed to achieve the same degree of opacity.
    Preferably, TiO2 comprises from 3 to 9, more preferably from 3 to 8, preferably even greater from 5 to 8, preferably even greater from 6 to 8, preferably even greater, from 5 to 7 and, preferably more, from 6 to 7% by volume of the composition.
    Hollow polymeric particles, preferably spherical, can also be used to provide white opacity. Suitably, these particles contain a gap of 30 to 50% by volume of the particle. These particles are available in the form of aqueous dispersions under the trade name Ropaque®. . The composition preferably contains, however, less than 10% by volume of these white pigments with hollow polymeric spheres, as they contribute significantly to the energy content of the paint. In addition, they tend to provide unwanted shine to the dry ink film after drying. Most preferably, the composition is free of these hollow polymeric particles.
    Similarly, calcined clay, a white pigment, can be used as a partial substitute for TiO2. As the production of calcined clay, by itself, presents intensive energy consumption, however, care must be taken to limit the amount of calcined clay used in the formulation. To take full advantage of the energy savings to be made, it is preferred that the coating composition is free of calcined clay. Preferably, however, up to 30% by volume of calcined clay can be used, more preferably from 5 to 20% by volume and, preferably more, from 10 to 15% by volume. Pigmented vesiculated polymer spheres are also preferably avoided.
    Naturally, colored opacifying pigments with a different hue can also be added to the compositions according to the present invention, in addition to the other particles of opacifying pigments, to produce light / pastel colors, as discussed in more detail below.
    By non-opacifying extensor particles, inorganic particles are indicated that have a refractive index identical or similar to that of the polymeric binder. Since the opacifying strength of a particulate material is a consequence of the difference in the refractive index of the material and the medium in which it is dispersed and its particle size, these extenders are considered essentially non-opacifying; see pages 35 to 37, Paint and Surface Coatings - Theory and Practice, edited by R. Lambourne and published by John Wiley & Sons. This does not mean that they do not contribute to opacity, but that any contribution is small compared to TiO2.
    Extenders are usually not pure white and can provide some gray or yellow tint to the coating.
    Suitable examples of non-opacifying extensor particles include magnesium and calcium carbonate, calcium carbonate, syenite nepheline, kaolin, talc, silica, diatomaceous earth, mica and calcium sulfate. Preferably, the non-opacifying extender particles are selected from the group consisting of magnesium and calcium carbonate, calcium carbonate, syenite nepheline and kaolin. Preferably, the non-opacifying extensor particles are selected from the list consisting of magnesium and calcium carbonate, calcium carbonate, syenite nepheline and kaolin. Even more preferably, they are selected from the group consisting of magnesium and calcium carbonate, calcium carbonate and kaolin.
    The mineral known as dolomite is a convenient and effective source for its cost of magnesium and calcium carbonate, CaMg (CO3) 2. Dolomite is a preferred source of magnesium and calcium carbonate for use in the present invention. It is available in powder form with different average particle sizes.
    Suitable forms of calcium carbonate include calcite, including precipitated calcite. Socai P3 is an example of suitable precipitated calcium carbonate, in the form of calcite. An appropriate ground calcium carbonate is Omyacoat 850 OG.
    Syenite nepheline can be used to replace, in whole or in part, calcium carbonate.
    Kaolin, Al2Si2O5 (OH) 4, is a type of clay. The addition of kaolin above 20% by volume to the composition (calculated based on the dry coating) results in low resistance to wet rubbing. In addition, at these high levels of kaolin, the coating viscosity is too high to allow easy application using conventional application methods (such as rollers or brushes) and to allow the paint flow to produce an acceptable smooth finish. Conveniently, the amount of kaolin should be 0.5 to 20, more preferably 5 to 15, and preferably more, 6 to 12% by volume.
    Preferably, the non-opacifying extender particles comprise 60 to 75, more preferably 65 to 75 and, more preferably, 66 to 73% by volume of the dry coating.
    Conveniently, 20 to 50% of the total solids volume of the dry coating should comprise extending particles that have an average particle size ds0 of 2 microns. This ensures that the TiO2 particles are sufficiently spaced from each other, so that the diffusion is efficient and, therefore, the opacity is optimized.
    The particle sizes of the extenders are indicated as diameters d50. This means that 50% of the particles by volume are below this diameter.
    The binder comprises an aqueous dispersion of polymer binder particles, often called latex. Most preferably, these dispersions are made using emulsion polymerization methods.
    For simplicity, the word "polymer" in this specification is used to designate homopolymers and copolymers that comprise two or more variants of monomers.
    The polymer comprising the binder particles is preferably an acrylic-styrene polymer or a pure acrylic.
    By pure acrylic, it is indicated that the polymer is derived only from monomers selected from the esters of acrylic acid and methacrylic acid and from the acids themselves.
    By styrene-acrylic, it is indicated that some styrene and / or its copolymerizable derivatives are copolymerized in the polymer. Such suitable styrene derivatives include otomethyl styrene and vinyl toluene.
    Particles of acrylic polymer and styrene are most preferred, as they require the least amount of energy for their production compared to pure acrylics and, preferably superior, the polymer binder according to the present invention is derived from styrene, acrylate of butyl and a copolymerizable acid. Preferably higher, the copolymerizable acid is acrylic acid and / or methacrylic acid.
    Preferably, the level of binder in the coating is 5 to 20%, more preferably 5 to 15 and more preferably 8 to 15%, calculated on the volume of solids.
    Suitable acrylic monomers include alkyl esters of acrylic or methacrylic acid, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, n-octyl acrylate, lauryl methacrylate, of 2-ethylhexyl, nonyl acrylate, decyl acrylate, benzyl methacrylate, isobutyl methacrylate, isobornyl methacrylate and the hydroxyalkyl esters of these acids, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxyethyl methacrylate -hydroxypropyl. The acid value of the polymer is preferably 15 to 60, more preferably 15 to 55, more preferably 15 to 45 and most preferably 16 to 30 mg KOH / g of non-volatile polymer. Acid value below 15 mg KOH / g polymer produces dry paint with lower wet rub resistance, while more than 65 mg KOH / g polymer tends to degrade the wet rub resistance of dry paint. The acid value varies by copolymerizing acid functional monomers in the polymer comprising the particles. Such suitable monomers include acrylic acid, methacrylic acid and maleic acid or its anhydride. Preferably, the acid used is acrylic acid.
    Polymers with an average particle size of no more than 0.3 μm are preferred, as their joining of the particulate components of the composition together is better.
    Preferably, the average numerical particle size of the polymer particles is 0.05 to 0.30 μm, more preferably 0.07 to 0.15 μm and, more preferably, 0.08 to 0.14 μm . The number designates the diameter of the particles. The smallest particle size is preferred, as it results in greater resistance to friction, which is particularly important in the high PVC according to the present invention.
    The glass transition temperature, Tg, of the polymer binder can be adjusted by selecting monomers and the relative amounts of each that comprises the polymer.
    Preferably, Tg is from 26 to 70 ° C, more preferably from 26 to 55 ° C, more preferably from 26 to 45 ° C and most preferably from 27 to 35 ° C.
    For the avoidance of doubt, any reference to Tg in this specification describes designated Tg Fox, unless otherwise noted.
    When using polymers with higher Tg, more coalescing solvents and / or plasticizers are needed to allow the formation of a coherent coating film at a normal ambient temperature of about 20 to 25 ° C. Polymers with lower Tg are preferred, as they can effectively form film with reduced levels of solvents, in order to keep the volatile organic content of the ink and the energy content of the ink to a minimum.
    Pigment dispersants generally comprise a hydrophilic part and a hydrophobic part and, depending on the nature of the dispersing medium and the pigment surface, one part will have greater affinity for the pigment surface and the other part for the dispersion medium. In this way, a stable dispersion of pigment dispersed in the medium can be produced.
    In the present invention, the dispersant is necessary to disperse and stabilize non-polymeric opacifying pigments (including any colored pigments) and non-opacifying extending particles. The average molecular weight of the dispersant should be at least 3500 Daltons, preferably 4000, more preferably 5000 and, preferably greater, 6000 Daltons. The upper limit of the average molecular weight is preferably 50,000 Daltons, more preferably 40,000, preferably even greater 30,000, preferably even greater than 20,000 and most preferably 15,000 Daltons. The preferably higher average molecular weight of the dispersant is 3500 to 20,000 Daltons.
    Dispersants suitable for use in the present invention include Orotan® 681, Orotan® 731, Orotan 2002, Dispex HDN (a hydrophobic sodium salt of an acrylic copolymer) and Dispex N40 (a sodium salt of an acrylic polymer). Each of these has a molecular weight of more than 3,500 Daltons.
    Pastel colors are usually produced by adding small amounts of different colored pigments, in the form of a concentrated dispersion (also known as dyes or dyes), to a white paint.
    In order to achieve the desired frictional resistance, it is important that the coalescing solvent is fugitive, which means that it must leave the paint film. Depending on the solvent and the polymer composition of the binder, this can happen very quickly or it can take a few days. For guidance, we found that a coating such as Example 1 according to the present invention (2% by weight of Texanol over liquid paint) contains only 0.06% by weight of Texanol in the film after 24 hours of drying under ambient conditions of drying and only 0.01% by weight after an additional six days.
    Preferably, the fugitive coalescing solvent is capable of reducing the calculated Tg Fox of the polymer from -10 to -80 ° C, more preferably from -10 to -60 ° C, from
    even more preferably from -10 to -40 ° C and more preferably from -10 to -20 ° C. The reduction is preferably achieved using up to 4% by weight, more preferably up to 3% by weight, preferably even greater up to 2% by weight, preferably even greater up to 1% and more preferably up to 0.5% in weight, calculated on the liquid formulation.
    The extent to which a coalescing solvent reduces the calculated Tg Fox of a specific polymer can be calculated according to Equation 1: l / Tg = Vp / Tgp + o (Vs / Tgs Equation 1 where: Tgp and Tgs is the temperature glass transition temperature of the polymer and solvent, respectively; Tg is the glass transition temperature of the plasticized system; Vp and Vs are the volume fractions of the polymer and solvent, respectively; and α is a factor that compensates for small changes in the plasticization efficiency and is considered to be 1 for the purposes of the present invention.
    Suitable fugitive coalescent solvents include Lusolvan® FBH (diisobutyl ester from a mixture of dicarboxylic acids), Lusolvan® PP (diisobutyl ester from a mixture of dicarboxylic acids), Loxanol® EFC 300 (line ester), Buty Carbitol®, Butyl Cellosolve, Dowanol® EPh (phenyl ethylene glycol), Dowanol® PPh (propylene glycol phenyl ether), Dowanol TPnB (tripropylene glycol n-butyl ether), Dowanol® DPnB, DBE_9® (a mixture of dimethyl glutherate refined and dimethyl succinate), Eastman DB® solvent, Eastman EB® (ethylene glycol monobutyl ether), Texanol® (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate), Dapro® FX 511, Velate® 262, Arcosolve® DPNB, Arcosolve® TPnB and benzyl alcohol.
    A list of solvents and their glass transition temperatures can be found in the article An Applied Approach to Film Formation, by JW Taylor and TD Klots, presented at the 29th Annual Symposium on Powder Coatings, with High Content of Solids and Water Suspended .
    Some representative glass transition temperatures are listed below: Pamolyn® 300 -80 ° C Texanol® -84 ° C Arcosolv® PtB -88 ° C Carbitol® acetate -95 ° C Butyl carbitol® acetate -100 ° C Thickeners are used in coating compositions to control the rheology and viscosity profile of the compositions. Rheology modifiers suitable for use in the present invention include types of carboxymethyl cellulose such as Blanose® 731; hydroxyethyl cellulose such as Natrosol® 250 and Tylose® H grades; hydrophobically modified hydroxyethyl cellulose such as Natrosol® Plus and Tylose® HX grades; ethyl and ethylmethyl hydroxyethyl cellulose, such as Beromocoll® EHM grades; nonionic synthetic associative thickener (NSATs), such as Acrysol® RM825, Acrysol® SCT 275, Acrysol® RM2020, Aquaflow® NHS300, Coapur® 830W, Rheolate® 450, Bermodol® PUR grades; hydrophobically modified alkaline swellable emulsion thickeners (EASE), such as Acrysol® TT935, Acrysol® DR73, Ciba Rheovis®; swellable alkaline synthetic thickeners, such as Acrysol® ASE 60. NSAT, HASE, ASST and HEUR type thickeners are preferred over cellulosic types.
    The benefits of the present invention are conveniently achieved in colored coating compositions that normally require high levels of TiO2.
    These colors are gray and light-colored coatings, often called pastel or light colors, and, of course, white.
    These and all colors can be defined using the well-known Y, C *, h * system. In the system, any color can be represented by: i. its hue, illustrated by h *; ii. its saturation, C *; and iii. its brightness value, Y.
    These terms are defined scientifically by the Commission Internationale de 1'Eclairage (CIE) (see International Lighting Vocabulary, fourth edition, published by IEC / CIE 017.4-1987; ISBN 978 3 900734 07 7).
    For the avoidance of doubt, any reference to the coating color in this specification describes the color of the coating when dry, unless otherwise indicated.
    Hue is a measure of the color's proximity to red, yellow, green and blue. It is illustrated by the hue angle that varies from 0 to 360 °, where the angle defines the position of the hue in the coloring space, where red, yellow, green and blue are at angles of 0, 90, 180 and 270 °, respectively. The angles between these "cardinal points" indicate intermediate colors; a tint angle of 45 °, for example, is a reddish yellow (orange) color.
    Saturation is a measure of the intensity of the color, that is, the extent to which it is a pastel / light color, a strong color or something in between. Saturation can range from 0 to 100, with higher numbers indicating stronger colors. Colors that have a saturation value of 0 are "neutral" gray that rest on a black to white axis. The brightness value is a measure of the perceived lightness of the color, which ranges from 0 to 100, where 0 represents black and 100, white.
    Figure 1 shows a simplified representation of the Y, C *, h * system. It displays a slice of coloring space approximately at the midpoint of the light reflection value range, Y. The Y axis ranges from 0 to 100. Red, yellow, green and blue are displayed in their appropriate positions on the hue, circle . The C * axis runs from zero at the origin to 100 at the perimeter. At each Y value, additional slices of hue are associated, representing lighter and darker colors. At the dark and light ends of the Y scale, the colors are less intense and therefore saturation is inevitably low. For this reason, the coloring space is often illustrated in the form of a sphere, although in reality it is more of an irregularly shaped cylinder. Using the CIE notation, the gray or light colored compositions that most benefit from the present invention can be identified as the colors, including whites, which meet the following criteria: C * <Critical Equation 1 Y> mC * + 35 Equation 2 in which I take the values of Table 1 below. Table 1


    Above the Ccritico value / the color intensity is too high to be perceived as a pastel color.
    The values of m and Ccritic in intermediate hue angles can be calculated using linear interpolation.
    The table allows the calculation of C * and Y for any given hue and, therefore, white, gray or pastel / light tones are explicitly identified.
    Coatings that have a C * saturation of less than about 5 and a Y value of more than 95 are perceived by the human eye as white.
    The C *, Y and h * values of any color can be calculated from the color spectrum reflection curve,
    measured using a spectrophotometer according to the manufacturer's instructions. A suitable spectrophotometer is Datacolor Spectraflash SF 600.
    Preferably, the dry coating compositions according to the present invention satisfy Equations 1 and 2. Most preferably, the dry coating compositions have a saturation of less than 5 and a Y value of more than 85.
    Preferably, the brightness value of the dry coating is less than 30%, when measured at 85 °, more preferably less than 20%, preferably even greater less than 10%, preferably even greater less than 5%, and preferably from 2 to 8%.
    The coating composition may also contain other ingredients that are standard for coatings such as waxes, rheological modifiers, surfactants, defoamers, adhesion promoters, plasticizers, cross-linking agents, flow aids, biocides and clays.
    In a further aspect of the present invention, a method of coating an article or structure having a surface with a composition according to the present invention is provided which includes the steps of applying at least one liquid layer of the coating by means of a brush. , roller, pad or spray and allow a layer to dry and / or harden.
    In yet another aspect of the present invention, an article or structure is provided which has a surface coated with a composition according to the present invention. The present invention will now be illustrated by the following examples. The following ingredients were used in preparing the examples. Tioxide® TR92 is a rutile form of TiO2 (density 4.05 g / cm3) available from Huntsman Tioxide Europe Ltd., Hartlepool, Cleveland, United Kingdom. Microdol® H200 and H600 are both dolomites (density of 2.85 g / cm3) and are available through Omya (Omya House, Derby, United Kingdom). Social® P3 is precipitated calcium carbonate (density of 2.70 g / cm3) and is available from Solvay, Rheinberg, Germany. China Clay Supreme kaolin (density of 2.60 g / cm3) is available through Imerys. Ropaque® Ultra E is a 30% non-volatile dispersion of hollow polymeric spherical particles (density of 0.591 g / cm3) and is available from Rohm & Haas, Philadelphia, United States. Steabright® is a talc (density of 2.78 g / cm3) available through Rio Tinto PLC, London, United Kingdom. Texanol® is a coalescing ester alcohol available from Eastman Chemical Company, Tennessee, United States. TegMer® 804 is an ethylene glycol ester tetra available from Hallstar, 120 South Riverside Plaza, Suite 1620, Chicago, Illinois 60606, United States. Orotan® 731 A is a pigment dispersing agent (25% by weight non-volatile; the density of non-volatile is 1 g / cm3) available from Rohm & Haas, Philadelphia, United States. Disponil® A1580 is a surfactant (80% by weight of non-volatile; the density of non-volatile is 1.00 g / cm3) and is available from Cognis Deutschland GmbH & Co. KG, P. O. Box 130164, Germany. Dispex N40 is a dispersant available through Ciba. Dispelair® CF 823 is a defoamer (60% non-volatile by weight; density of non-volatile is 1.00 g / cm'3) and is available from Blackburn Chemicals Ltd., Whitebirk Industrial Estate, Blackburn, UK . Blanose® 7M 31C SCS 9554 (density 1.59 g / cm3) is available from Hercules GmbH, Dusseldorf, Germany. Natrosol Plus 331 is a cellulosic thickener available through Hercules Aqualon. Acticide CHR 0107, biocide, is available through Thor, Wincham Avenue, Wincham, Northwich, Cheshire, England. Aquaflow® NHS 3 00 (23% by weight of non-volatile; density of non-volatile is 1.00 g / cm3) is available from Hercules GmbH, Dusseldorf, Germany. China Clay Supreme (density of 2.60 g / cm3) is available through Imerys. Latex 1 is a copolymer of styrene, butyl acrylate and methacrylic acid with Tg of 10 ° C, acid value of 23.5 mg KOH / g polymer and solids content of 50% by weight. Latex 2 is a copolymer of styrene, butyl acrylate and methacrylic acid with 50 ° C Tg, acid value of 37.4 mg KOH / g polymer and solids content of 50% by weight. Latex 3 is a copolymer of styrene, butyl acrylate and acrylic acid with a Tg of 30 ° C, an acid value of 23.5 mg KOH / g polymer and a solids content of 50% by weight. Testing Procedures
    The following test methods were used to evaluate the examples: Molecular weight of dispersant
    Aqueous GPC configuration was used to measure the molecular weight. The equipment and conditions used were: Columns: two 30 cm GPC GMPWXL TSK columns from Tosoh. Eluent: 0.3 M sodium nitrate, 0.01 M sodium phosphate with pH adjusted to 7.5 using 0.1 M NaOH. Flow rate: 1.0 ml / min. Detector: Waters 410 differential refractive index detector. Software: Waters Millenium 32 v3.05.01. The instrument was calibrated with Dextran standards covering the range of 342 to 401000 g / mol. Samples were prepared by diluting 0.1 g in 10 ml of eluent and filtering through a 0.45 micron PVDF membrane. The injection volume was 100 μl. Opacity (contrast ratio)
    Opacity was measured according to BS 3900-D4. At least 90% are considered acceptable. The measured opacity is not linear in its relationship to how the eye perceives opacity. In this way, small differences in the measured opacity are observed by the eye as much larger differences. Brightness
    The brightness was measured according to BS EN ISO 2813, BS 3900-D5. Resistance to wet friction
    The frictional resistance of the dry film was measured according to BS EN ISO 11998 using two hundred cycles with the modification that the loss was recorded as mg / cm2. Loss of less than 6 mg / cm2 of removal is acceptable. High cut viscosity
    High-cut viscosity is measured at 25 ° C using an ICI cone and plate viscometer (available from Research Equipment London Ltd., London, TW2 5NX) operating at 10,000 s'1. Rotothinner viscosity (paint)
    The average cut viscosity is measured at 25 ° C using a Rotothinner viscometer (available from Sheen Instruments Ltd., Kingston-upon-Thames, Surrey, UK) equipped with a standard rotating disc rotor at about 562 rpm, which is equivalent to a cutting speed of about 250 s'1. Particle size of extenders
    The particle size of the extenders was measured using a Mastersizer according to ISO 13323, part 1 and 2. EXAMPLES
    The present invention will now be illustrated by the following examples. Numbered examples are in accordance with the present invention and comparative examples are indicated with letters. In all cases, the weight percentage of the formulation designates the liquid paint and the volume percentage for the dry coating. The following method was used to elaborate the paints in each case. Grinding base step
    Using a five liter metallic dispersion container, load water (1), Texanol, Orotan or Dispex, Disponil, Acticide and half the amount of Dispelair. Place the container under the High Speed Disperser equipped with a sawtooth blade. Shake at low speed so that no splashes are observed. Add Microdol H200 and H600, Socai P3, China Clay Supreme, Steabright and Tioxide TR92, drive for two minutes at low speed and then add Blanose or Natrosol thickener afterwards. After five minutes, slowly increase the speed as the ink becomes thicker. The unit should be driven at about 2500 rpm (depending on the volume), but without nozzles. Shake for an additional thirty minutes. Suspend the unit halfway to ensure that no pigment has adhered to the sides / base of the container through manual agitation. Turn the unit backwards at high speed and, after thirty minutes, reduce to low speed. Check the dispersion status of the grinding base for pieces sweeping over a plate. If the number of pieces is acceptable, add water (2), drive for an additional two minutes, then turn off the stirrer. The total amount of water displayed in the formulation example was the ratio of: water (1): water (2): water (3) = 45.5: 30.3: 24.2 Ink stage
    Load Latex 1 into an appropriately sized container and place under a stirrer equipped with a paddle blade.
    Load Ropaque, the rest of the Dispelair, the grinding base prepared above, water (3) and Aquaflow. Adjust the speed of the stirrer as the volume in the container increases, being careful to prevent sneezing.
    Shake for an additional fifteen minutes at low speed (about 500 rpm). Examples 1 and A
    Examples 1 and A are essentially identical, differing only by the Tg of the polymer binder particles. Example 1 according to the present invention using a latex that comprises polymer particles with 50 ° C Tg passes the wet friction test, while Comparative Example A, which uses polymer binder particles with 10 ° C Tg, is failed the wet friction test.
    5 The Tg of the polymer binder (Latex 2 with Tg 50 ° C) in the presence of the coalescing solvent is calculated using Equation 1 as discussed above. l / Tg = Vp / Tgp + o <Vs / Tgs Equation 1 The Tg of Texanol is -84 ° C. The volume fractions are calculated based on the polymer and the solvent alone. Thus, for Example 1, the total polymer% by weight is 3.25 (which is 50% of 6.5) and the solvent is 2.00. The specific gravity of the polymer and solvent is 1.08 and 0.95, respectively, and the volume fraction is, therefore, 0.151 and 0.84 9, respectively. Thus, the Tg of the polymer in the presence of Texanol is -23.0 ° C. Examples 2 and B
    These are essentially identical, except for PVC. Comparative Example B, in 90.3% PVC, fails the wet friction test.

    Examples 3 and C
    Example 3 and Comparative Example C are identical, except that the Tg of latex in the former is 30 ° C, while for the latter it is 10 ° C. The two coverings are in PVC greater than 1 and A.

    Examples 4a and 4b
    Effect of dispersant selection: The use of a hydrophobically modified dispersant (Orotan 731A) or a hydrophilic dispersant (Dispex N40) does not make a difference for wet friction.

    Example 5 and D
    Natrosol Plus is a hydrophotically modified thickener and Blanose 7M731 is a methylcellulose carboxy. Either can be used in the present invention.

    Examples 6 and E
    The effect of non-fugitive coalescing solvent (Archer RC) can be seen by the fact that Comparative Example E fails the wet friction test.
    权利要求:
    Claims (17)
    [0001]
    1. WATER COATING COMPOSITION, characterized by having PVC of 78 to 88% and comprising, based on the total volume of solids in the dry coating: a. opacifying pigment particles comprising: i. 3 to 10% titanium dioxide; ii. from 0 to 20% of hollow polymeric particles; B. non-opacifying extensor particles comprising: i. magnesium and calcium carbonate; and / or ii. calcium carbonate; and / or iii. syenite nepheline; and / or iv. kaolin; where i + ii + iii + iv = 40 to 80% and iv is 0 to 20%; ç. polymer binder particles with Tg Fox calculated from 26 to 70 ° C that have an acid value of 15 to 65 mg KOH / g of polymer and in which the polymer particles are derived from acrylic monomers and optionally comprise styrene and / or its derivatives; d. dispersant that has an average molecular weight of at least 3500 Daltons; and is. volatile coalescing solvent; wherein the composition is free of non-volatile coalescing solvent.
    [0002]
    2. COATING COMPOSITION, according to claim 1, characterized in that any difference between the real PVC and the sum of a and b is composed with other non-opacifying extending particles.
    [0003]
    COATING COMPOSITION according to either of claims 1 or 2, characterized in that the opacifying pigments are white.
    [0004]
    4. COATING COMPOSITION, according to claim 3, characterized in that the white opacifying pigments are selected from titanium dioxide and hollow polymeric particles.
    [0005]
    COATING COMPOSITION according to any one of claims 1 to 4, characterized in that the polymeric hollow spheres comprise less than 10% by volume.
    [0006]
    6. COATING COMPOSITION according to any one of claims 1 to 5, characterized in that the extending particles are selected from the group consisting of magnesium and calcium carbonate, calcium carbonate, syenite nepheline and kaolin.
    [0007]
    7. COATING COMPOSITION, according to claim 6, characterized in that 20 to 50% of the total volume of solids in the dry coating comprise extending particles with d50 <2 microns.
    [0008]
    COATING COMPOSITION according to any one of claims 1 to 7, characterized in that the polymer binder is derived from styrene, butyl acrylate and methacrylic acid.
    [0009]
    COATING COMPOSITION according to any one of claims 1 to 8, characterized in that the binder comprises from 5 to 20% of the dry coating.
    [0010]
    COATING COMPOSITION according to any one of claims 1 to 9, characterized in that the acidic value of the polymer binder is 15 to 60 mg KOH / g polymer.
    [0011]
    11. COATING COMPOSITION according to any one of claims 1 to 10, characterized in that the acidic component comprises acrylic acid and / or methacrylic acid and / or maleic acid and / or its anhydride.
    [0012]
    12. COATING COMPOSITION according to any one of claims 1 to 11, characterized in that it contains up to 4% by weight of volatile coalescing solvent based on the liquid formulation.
    [0013]
    13. COATING COMPOSITION according to any one of claims 1 to 12, characterized in that the coalescing solvent reduces the calculated Tg Fox of the polymer binder from -10 to -80 ° C.
    [0014]
    COATING COMPOSITION according to any one of claims 1 to 13, characterized in that it additionally contains colored pigments.
    [0015]
    COATING COMPOSITION, according to any one of claims 1 to 14, characterized in that it has a brightness of less than 15% when measured at 85 °.
    [0016]
    16. METHOD OF COATING AN ARTICLE OR STRUCTURE, characterized in that it has a surface with a composition, as defined in any one of claims 1 to 15, which includes the steps of applying at least one liquid layer of the coating by means of a brush , roller, pad or spray and allow a layer to dry and / or harden.
    [0017]
    17. ARTICLE OR STRUCTURE, characterized in that it has a surface coated with a composition, as defined in any one of claims 1 to 12.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112012026737B1|2020-12-22|aqueous coating composition, method of coating an article or structure, and article or structure
    BR112012026856B1|2020-11-24|aqueous coating composition, method of coating an article or structure, and article or structure
    EP2182033B1|2011-05-25|Low energy coatings
    RU2617630C2|2017-04-25|Improved energy-efficient solvent-free coating compositions
    CA2982058A1|2018-04-11|Hiding by using air voids encapsulated in hollow glass spheres
    TW201326332A|2013-07-01|Improved solvent-free low energy coatings
    同族专利:
    公开号 | 公开日
    CN102858888A|2013-01-02|
    ZA201207759B|2013-06-26|
    RU2553895C2|2015-06-20|
    US20110311801A1|2011-12-22|
    ES2427178T3|2013-10-29|
    AU2011246491B2|2014-08-07|
    EP2386610A1|2011-11-16|
    PL2563867T3|2016-03-31|
    UY33347A|2011-07-29|
    ES2556141T3|2016-01-13|
    MY160828A|2017-03-31|
    TN2012000474A1|2014-01-30|
    WO2011134908A1|2011-11-03|
    TW201141968A|2011-12-01|
    MA34104B1|2013-03-05|
    US8435340B2|2013-05-07|
    DK2386610T3|2013-09-23|
    EP2563867A1|2013-03-06|
    BR112012026737A2|2017-10-10|
    EP2563867B1|2015-09-30|
    RU2012149232A|2014-06-10|
    EP2386610B1|2013-06-19|
    PL2386610T3|2013-10-31|
    AR081184A1|2012-07-04|
    SG184827A1|2012-11-29|
    CN102858888B|2015-11-25|
    CA2795890A1|2011-11-03|
    AU2011246491A1|2012-10-11|
    DK2563867T3|2016-01-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1516802A|1976-03-02|1978-07-05|Scm Corp|Latex paint containing plastic pigment|
    US4277385A|1979-02-09|1981-07-07|Scm Corporation|High PVC latex paint|
    CA1226400A|1982-12-09|1987-09-01|Philip M. Smith|Opacification of paint|
    US4772332A|1987-04-21|1988-09-20|Engelhard Corporation|Use of mixture of high molecular weight sulfonates as auxiliary dispersant for structured kaolins|
    US4800107A|1987-10-15|1989-01-24|The Glidden Company|Dry fog sprayable latex paint|
    DE3736994C2|1987-10-31|1989-11-16|Bayer Ag, 5090 Leverkusen, De|
    US5201948A|1991-05-24|1993-04-13|Rohm And Haas Company|Method for improving scrub resistance|
    EP0525977A1|1991-06-28|1993-02-03|Morton International, Inc.|Fast dry waterborne traffic marking paint|
    DE19749643A1|1997-11-10|1999-05-12|Basf Ag|Dispersion paints containing polymers functionalized as binders with carbonyl groups|
    DE19811314A1|1998-03-16|1999-09-23|Basf Ag|Aqueous, pigment containing composition useful for production of dispersion dyes|
    DE19838850A1|1998-08-26|2000-03-02|Basf Ag|Aqueous pigmented film-forming polymeric coating composition for e.g. wood, glass or plastic comprises two different polymers, one of higher and one of lower glass transition temperatures|
    DE10049791A1|2000-10-09|2002-04-18|Basf Ag|Pigmented, water-based, solvent-free coating material, especially e.g. exterior emulsion paint, based on a dispersion of acrylic ester-based copolymer with a small content of polar comonomers, including unsaturated acid|
    AU785282B2|2001-06-20|2006-12-21|Rohm And Haas Company|Coating with improved hiding, compositions prepared therewith, and processes for the preparation thereof|
    GB0307246D0|2003-03-28|2003-04-30|Avecia Bv|Aqueous pigmented coating composition with improved open-time comprising crosslinkable oligomer and dispersed polymer|
    DE102004001990A1|2004-01-13|2005-08-04|Basf Ag|Aqueous coating compositions with high pigment volume concentration|
    AU2006201172B2|2005-04-04|2010-11-25|Rohm And Haas Company|Aqueous polymer dispersions|
    GB2432584A|2005-11-28|2007-05-30|Univ Sheffield|Particle stabilised foam|
    EP1942141A1|2006-12-22|2008-07-09|Rohm and Haas France SAS|Curable composition|
    EP1942142B1|2006-12-22|2010-02-17|Rohm and Haas Company|Curable composition|
    GB2449306A|2007-05-18|2008-11-19|Univ Sheffield|Composite particles|
    GB0808239D0|2008-05-07|2008-06-11|Tioxide Group Services Ltd|Compositions|
    ES2427130T3|2010-04-27|2013-10-28|Akzo Nobel Coatings International B.V.|Enhanced coatings with low titanium dioxide|
    EP2634151A1|2012-02-28|2013-09-04|Omya Development AG|Process for the preparation of cement, mortars, concrete compositions containing calcium carbonate-based filler - treated with ultrafine filler, compositions and cement products obtained and their applications|
    ES2640387T3|2013-08-06|2017-11-02|Basf Se|Dispersions of soundproofing polymers and masses with an emulsion polymer prepared in two stages|US8609761B1|2011-10-14|2013-12-17|Acrylall, LLC|Modified acrylic polymer coating and method|
    UY34399A|2011-10-26|2013-05-31|Akzo Nobel Coatings Int Bv|Enhanced Solvent-Free Low Cost Energy Coatings|
    FR3015474B1|2013-12-19|2016-01-01|Bostik Sa|WALL AND CEILING COATING COMPOSITION HAVING THERMAL INSULATION PROPERTIES|
    US9891350B2|2014-02-17|2018-02-13|Eastman Kodak Company|Light blocking articles having opacifying layers|
    RU2565203C1|2014-06-10|2015-10-20|Общество с ограниченной ответственностью "Яра"|Aqueous dispersion composition for finishing internal surfaces of buildings using reinforcing materials|
    US9469738B1|2015-06-04|2016-10-18|Eastman Kodak Company|Foamed aqueous composition|
    US10308781B2|2015-06-04|2019-06-04|Eastman Kodak Company|Method of making foamed, opacifying elements|
    US10233590B2|2015-06-04|2019-03-19|Eastman Kodak Company|Foamed, opacifying elements|
    US10138342B2|2016-08-18|2018-11-27|Eastman Kodak Company|Formable and foamed aqueous compositions|
    US9963569B2|2016-08-18|2018-05-08|Eastman Kodak Company|Method of making light-blocking high opacity articles|
    US10704192B2|2016-08-18|2020-07-07|Eastman Kodak Company|Light-blocking high opacity articles|
    US10233300B2|2016-08-18|2019-03-19|Eastman Kodak Company|Light-blocking articles with high opacifying layer|
    US20180094112A1|2016-10-03|2018-04-05|Eastman Kodak Company|Method and system for making light-blocking articles|
    US10145061B1|2017-05-09|2018-12-04|Eastman Kodak Company|Method for preparing thermally imaged opacifying elements|
    US10132031B1|2017-05-09|2018-11-20|Eastman Kodak Company|Foamed, opacifying elements with thermally transferred images|
    US10947360B2|2018-04-03|2021-03-16|Eastman Kodak Company|Method of making light-blocking high opacity articles|
    ES2886259T3|2019-03-12|2021-12-16|Theolaur Peintures|Aqueous paint composition containing hollow polymer particles and with a density less than 1 or 0.9|
    EP3926014A4|2020-06-19|2021-12-22|Theolaur Peintures|Composition for thermally insulating coating - associated coated surface|
    法律状态:
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: C09D 7/00 (2018.01) |
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-02-26| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-03-03| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-10-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/04/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    2022-02-15| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 11A ANUIDADE. |
    优先权:
    申请号 | 申请日 | 专利标题
    US32840110P| true| 2010-04-27|2010-04-27|
    EP20100161204|EP2386610B1|2010-04-27|2010-04-27|Improved low titanium dioxide coatings|
    EP10161204.2|2010-04-27|
    US61/328,401|2010-04-27|
    PCT/EP2011/056492|WO2011134908A1|2010-04-27|2011-04-22|Improved low titanium dioxide coatings|
    [返回顶部]